Black SH e Ed Laser Ablation Effects and Applications

LASERS AND ELECTRO-OPTICS RESEARCH AND TECHNOLOGY
LASER ABLATION: EFFECTS

AND APPLICATIONS

No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or
by any means. The publisher has taken reasonable care in the preparation of this digital document, but makes no
expressed or implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of information
contained herein. This digital document is sold with the clear understanding that the publisher is not engaged in
rendering legal, medical or any other professional services.

LASERS AND ELECTRO-OPTICS
RESEARCH AND TECHNOLOGY

Additional books in this series can be found on Novas website
under the Series tab.

Additional E-books in this series can be found on Novas website
under the E-books tab.

LASERS AND ELECTRO-OPTICS RESEARCH AND TECHNOLOGY

LASER ABLATION: EFFECTS
AND APPLICATIONS

SHARON E. BLACK
EDITOR

Nova Science Publishers, Inc.
New York

Copyright 2011 by Nova Science Publishers, Inc.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system or
transmitted in any form or by any means: electronic, electrostatic, magnetic, tape, mechanical
photocopying, recording or otherwise without the written permission of the Publisher.

For permission to use material from this book please contact us:
Telephone 631-231-7269; Fax 631-231-8175
Web Site: http://www.novapublishers.com

NOTICE TO THE READER
The Publisher has taken reasonable care in the preparation of this book, but makes no expressed or
implied warranty of any kind and assumes no responsibility for any errors or omissions. No
liability is assumed for incidental or consequential damages in connection with or arising out of
information contained in this book. The Publisher shall not be liable for any special,
consequential, or exemplary damages resulting, in whole or in part, from the readers use of, or
reliance upon, this material. Any parts of this book based on government reports are so indicated
and copyright is claimed for those parts to the extent applicable to compilations of such works.

Independent verification should be sought for any data, advice or recommendations contained in
this book. In addition, no responsibility is assumed by the publisher for any injury and/or damage
to persons or property arising from any methods, products, instructions, ideas or otherwise
contained in this publication.

This publication is designed to provide accurate and authoritative information with regard to the
subject matter covered herein. It is sold with the clear understanding that the Publisher is not
engaged in rendering legal or any other professional services. If legal or any other expert
assistance is required, the services of a competent person should be sought. FROM A
DECLARATION OF PARTICIPANTS JOINTLY ADOPTED BY A COMMITTEE OF THE
AMERICAN BAR ASSOCIATION AND A COMMITTEE OF PUBLISHERS.

Additional color graphics may be available in the e-book version of this book.

LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Laser ablation : effects and applications / editor, Sharon E. Black.
p. cm.
Includes index.
ISBN 978-1-61209-189-1 (eBook)
1. Laser ablation. I. Black, Sharon E.
TA1715.L367 2010
621.36'6--dc22
2010041370

Published by Nova Science Publishers, Inc. New York

CONTENTS

Preface vii
Chapter 1 Double-Pulse Laser Ablation of Solid Targets
in Ambient Gas: Mechanisms and Effects 1
G. Cristoforetti

and V. Palleschi
Chapter 2 Assessing Hunter-Gatherer Mobility in Cis-Baikal,
Siberia Using LA-ICP-MS: Methodological Correction
for Laser Interactions with Calcium Phosphate Matrices
and the Potential for Integrated LA-ICP-MS Sampling
of Archaeological Skeletal Materials 45
Ian Scharlotta, Andrzej Weber, S. Andy DuFrane,
Olga I. Goriunova and Robert Creaser
Chapter 3 Modeling of Laser Ablation Induced by Nanosecond
and Femtosecond Laser Pulses 99
Tatiana E. Itina, Mikhail E. Povarnitsyn
and Konstantin V. Khishchenko
Chapter 4 Fabrication of Silicon Nanocrystal Based Structures
with Nanosecond Laser Ablation Processings
in Liquid Media 127
V. vrek
Chapter 5 Ho:YAG Laser Lithotripsy 143
Jinze Qiu, Thomas E. Milner

and Joel M. H. Teichman
Chapter 6 Computer Modelling of Femtosecond Laser Ablation
of Semiconductors and Dielectrics 153
D. P. Korfiatis and K.-A. Th. Thoma
Chapter 7 Thermophysical Effects of Femtosecond Laser Ablation
of Metal Target 163
Ranran Fang and Hua Wei

Contents vi
Chapter 8 Formation of Nanoparticles under Laser Ablation
of Solids in Liquids 191
G. A. Shafeev
Chapter 9 Nanodiamonds from Laser Ablation in Liquid 227
G. W. Yang
Index 267

PREFACE

Laser ablation is the process of removing material from a solid (or occasionally liquid)
surface by irradiating it with a laser beam. At low laser flux, the material is heated by the
absorbed laser energy and evaporates or sublimates. At high laser flux, the material is
typically converted to a plasma. Usually, laser ablation refers to removing material with a
pulsed laser, but it is possible to ablate material with a continuous wave laser beam if the laser
intensity is high enough. This book presents current research in the study of laser ablation
from across the globe. Topics discussed herein include double-pulse laser ablation of solid
targets in ambient gas; using laser ablation ICP-MS and its potential in sampling
archaeological skeletal materials; and numerical modeling of laser-matter interactions.
Chapter 1 - Laser Ablation (LA) is used in a widespread range of applications, among
them it is employed as sampling procedure for the elementary chemical analysis of materials.
With this aim, many analytical techniques makes use of LA - such as LA Ion Mobility
Spectrometry, Resonant LA, LA-Atomic Fluorescence Spectrometry and LA-Microwave
Induced Plasma-Atomic Emission Spectrometry among them the most popular ones are
probably the Laser-Ablation Inductively Coupled Plasma (LA-ICP) techniques and the Laser
Induced Breakdown Spectroscopy (LIBS).
In all these cases, it is desirable to attain the largest possible mass removal from the target
in order to lower the Limit Of Detection (LOD) of the technique. Such intent is particularly
true in the LIBS case, where LODs for solid samples are usually in the range of ppm or tens
of ppm, which are often inadequate for many applications.
One of the possible ways to overcome this problem is the use of two laser pulses,
temporally separated by a suitable delay, for the laser ablation. In this scheme, the laser
beams can be arranged in a collinear geometry, where both the beams are aligned normally to
the target and are focused on its surface, or in an orthogonal geometry (pre-ablation
configuration), where the first pulse runs parallel to the target surface and is focused in the
ambient gas in front of it, while the latter is aligned perpendicularly and ablates the target. In
case of ns-laser ablation, in both these configurations, a substantial enhancement of mass
removal and of its atomization with respect to the case where a single pulse with equal total
energy has been observed, where these phenomena lead to an improvement of both the LODs
and the reproducibility of measurements. Such experimental configurations lead also to a
different thermodynamic and dynamic evolution of the plasma, which can be useful in case of
LIBS analysis.
Sharon E. Black viii
Many works have been dedicated to Double Pulse (DP) Laser ablation, aimed to establish
the optimal experimental conditions to be used in different applications and to understand the
physical mechanisms, still not clear, leading to the observed mass removal enhancement [1].
The aim of the present chapter is presenting and resuming the ns-ns DP state of art,
discussing the occurring physical processes. Experimental results of the authors, as well as of
other scientists, will be shown and discussed to validate and run down hypotheses on the
mechanisms involved.
In particular, the interpretation of the lower plasma shielding, due to a rarefied ambient
environment, experienced by the second laser pulse will be presented. The reduction of
plasma shielding allows a larger part of the laser energy to reach the target surface, resulting
in an enhancement of the mass removal. Besides, such an improved laser-matter coupling
produces a stronger heating, which could lead the molten pool near the thermodynamic
critical temperature and drive the onset of phase explosion mechanism.
A summary of the effects produced in DP configuration by using short and ultrashort
laser pulses is also mentioned, together with a brief discussion of the mechanisms involved.
Chapter 2 - Micro-sampling and analysis of tooth enamel from faunal samples in the
archaeological record has enabled research into the mobility and seasonality of animals
in prehistory. However, studies on human tooth samples have failed to yield similar results. It
is well understood that human tooth enamel does not fully mineralize in a strictly linear
fashion, but rather entails five recognizable stages of mineralization. Until the enamel matrix
fully crystallizes, the matrix remains an open chemical system, thus at each stage of
mineralization, the geochemical composition of the enamel matrix can be altered. At present
it is unclear if failure to mirror the results from faunal teeth with human teeth is a factor of
mineralization rates or simply the result of the difference in enamel volume and formation
time between human and herbivore teeth. Therefore, the applicability of chemical analyses to
human teeth is a balance between micro-sampling analytical techniques and generating
archaeologically relevant data. Yet limited case studies have been performed to examine the
scale and extent of this problem in human teeth using laser-ablation ICP-MS. Five human
molars from an Early Bronze Age cemetery on the shores of Lake Baikal, Siberia
were serially sampled and analyzed by means of laser-ablation quadrupole and multicollector
ICP-MS in order to examine the nature of geochemical changes within the enamel matrix.
This sampling was performed in order to generate a statistically significant dataset to assess
the effectiveness of two approaches along with published methodologies to counter known
problems with attempts to assess Sr87. Recent research has demonstrated that among the
methodological problems, there is isobaric interference at mass 87 caused by the formation of
calcium phosphate (Ca40PO) in response to interaction between the laser and the enamel
matrix. Correction procedures using Zr91 in tandem with Ba/Sr ratios are examined.
Additionally, serial sampling of teeth from hypothesized mobile hunter-gatherers provides
useful insight into the dynamic interplay between physical sampling limitations and the scale
at which useful geochemical data can be recovered from organic minerals. Traditional
utilization of geochemical data for mobility has relied on a local/non-local dichotomy in
population level analyses; however, this approach is of limited utility with regard to mobile
populations. The authors ability to effectively analyze skeletal materials at a micro scale
provides their best hope at addressing the rift between recognition of an indirect relationship
between biological intakes, mineral formation and being able to generate relevant analytical
data.
Preface ix
Chapter 3 - The chapter considers the problem of numerical modeling of laser-matter
interactions. The main objective is to clarify the mechanisms of this extremely complex
process.
Comparison of femtosecond and nanosecond laser ablation is first presented. Thermal
model is used for nanosecond ablation. The physical phenomena involved into the interaction
of a laser-generated plasma plume with a background environment are furthermore studied. A
three-dimensional combined model is developed to describe the plasma plume formation and
its expansion in vacuum or into a background gas. The proposed approach takes advantages
of both continuous and microscopic descriptions. The simulation technique is suitable for the
simulation of high-rate laser ablation for a wide range of the background pressure. The model
takes into account the mass diffusion and the energy exchange between the ablated and
background species, as well as the collective motion of the ablated species and the
background gas particles. The developed approach is used to investigate the ablation of
aluminum in the presence of a background gas. The influence of the background gas on the
expansion dynamics of the laser-generated plume is examined. Experimental density
distributions are explained based on the simulation results.
A detailed analysis of material decomposition in femtosecond regime is then performed
by using a hydrodynamic model with a thermodynamically complete equation of state. As a
result, several ablation mechanisms are observed. A major fraction of the ablated material is
found to originate from the metastable liquid region, which is decomposed either thermally in
the vicinity of the critical point into a liquid-gas-mixture or mechanically at high strain rate
and negative pressure into liquid droplets and chunks. The calculation results agree with the
results of previous molecular dynamics simulations and explain recent experimental findings.
In addition, effects of the ultra-short laser excitations of wide band gap materials need a
particular attention. In this case, material ionization through multi-photon excitation and
electron-impact ionization should be considered. Laser interactions are simulated with a
particular focus on the control over laser plume expansion process. The properties of the
laser-generated plasma plume are shown to be strongly affected by the laser-mater interaction
mechanism
Chapter 4 - In this chapter a nanosecond (ns) laser ablation and fragmentation processing
in water, pure and doped spin on glass (SOG) polymer-based solutions are discussed. The
confinement of laser-generated plasma in liquids allows the silicon nanocrystals (Si-ncs)
formation with a quantum confinement size effects. The author demonstrates that ns laser
processes in liquid can be efficiently applied for the fabrication and tuning the optoelectronic
properties of Si-ncs based nanostructures. The laser fragmentation in water induces the self-
assembly and allows formation of closely-packed stable luminescent Si-ncs over ~ 200 m.
Contrary to the water, the laser ablation and fragmentation in pure and doped SOG solutions
inhibit aglomeration and enhance the Si-ncs luminescence properties. Finally, the authior
disccusses physics and dynamics of Si-ncs formation through the serial growth processes that
occurred in liquid media confined ns laser generated plasma.
Chapter 5 - The long-pulse Ho:YAG laser has been used for intracorporeal laser
lithotripsy of urinary calculi since the mid-1990s and is considered the gold standard
modality for endoscopic laser lithotripsy. The authors present an overview of Ho:YAG laser
lithotripsy. They begin with an introduction of the ablative mechanism of Ho:YAG laser
lithotripsy, and compare to short-pulse (< 10 usec) laser lithotripsy. Ablative properties of
Sharon E. Black x
Ho:YAG laser lithotripsy are reviewed and the authors summarize several practical problems
and safety issues of existing optical fibers for Ho:YAG lithotripsy.
Chapter 6 - Ultrafast laser ablation has proved to be a powerful tool for material
processing. Combination of both experimental and theoretical efforts can lead to the
determination of optimum values of laser parameters for the improvement of accuracy which
is a most crucial aspect in micromachining.
Besides experiment and theory, numerical simulation can also provide a significant
research tool in the field for the calculation of parameters of great importance which influence
the micromachining process. Such parameters are ablation threshold as a function of the laser
wavelength, pulse duration and the properties of the particular material. Especially, the
prediction through numerical simulation of the geometry and the dimensions of the craters
formed and the damaged surrounding surface for known laser and material properties can lead
to control and optimization of the micromachining process. Furthermore, numerical
simulation can drop light to the microscopic processes through which femtosecond laser
damage occurs.
In this chapter, the numerical techniques currently used for the simulation of femtosecond
laser ablation of semiconductors and dielectrics are presented and discussed. These
techniques include molecular dynamics simulation, the Fokker-Planck approach and two
temperature models.
Chapter 7 - The electron-phonon relaxation time as a function of pulse width and fluence
of femtosecond laser is studied based on the two-temperature model. The satisfactory
agreement between our numerical results and experimental data indicates that the electron-
phonon relaxation time is reasonably accurate with the influences of pulse width and fluence
of femtosecond laser. An improved two-temperature model to describe femtosecond laser
ablation of metal target is also presented. The temperature-dependent heat capacity and
thermal conductivity of the electron, as well as electron temperature-dependent absorption
coefficient and absorptivity are all considered in this tailored two-temperature model. The
satisfactory agreement between our numerical results and experimental data indicates that the
temperature dependence of heat capacity, thermal conductivity, absorption coefficient and
absorptivity in femtosecond laser ablation of metal target must not be neglected. This chapter
finally presents a unified thermal model, which can describe the thermophysical effects with
laser pulse width ranges from nanosecond to femtosecond. The satisfactory agreement
between the authors numerical results and experimental results of vaporization threshold
indicates that the unified thermal model is correct and reasonable.
Chapter 8 - The process of nanoparticle formation under laser ablation of solids in liquids
is described. Critical parameters are discussed that govern the properties of nanoparticles
ejected into the surrounding liquid. These parameters are laser wavelength, pulse duration,
interaction of individual nanoparticles with laser beam inside the liquid. A review of previous
results is presented on the properties of nanoparticles of noble metals. Recent data on laser-
assisted generation of other metals is given, including the formation of alloyed nanoparticles.
Micro- and nanostructuring of the target upon its laser ablation in liquid environment is
discussed. Examples are given of the influence of the surrounding liquid on the chemical
composition of generated nanoparticles. The laser control over the size distribution of
nanoparticles in liquids is demonstrated either by spatial profiling of laser beam intensity or
proper tuning of laser wavelength into plasmon resonance of nanoparticles. Recent results are
Preface xi
given on excitation of high energy levels of media under laser exposure to laser pulses of
picosecond range of duration.
Chapter 9 - Laser ablation in liquid, i.e. pulsed-laser induced liquid-solid interface
reaction (PLIIR) has been developed to synthesize diamond nanocrystals. Chemical and
physical mechanisms of the nanodiamonds synthesis upon PLIIR are addressed based on the
nucleation thermodynamics and growth kinetics. The authors studies showed that PLIIR
could be expected to be a general route to synthesize the nanocrystals with the metastable
phases.

In: Laser Ablation: Effects and Applications ISBN: 978-1-61122-466-5
Editor: Sharon E. Black 2011 Nova Science Publishers, Inc.
Chapter 1
DOUBLE-PULSE LASER ABLATION
OF SOLID TARGETS IN AMBIENT GAS:
MECHANISMS AND EFFECTS
G. Cristoforetti
1
and V. Palleschi
2

1
National Institute of Optics, Research Area of National Research Council,
Via G.Moruzzi, 1 56124 Pisa (ITALY)
2
Applied Laser Spectroscopy Laboratory, Institute of Chemistry
of Organometallic Compounds, Research Area of National
Research Council, Via G.Moruzzi, 1 56124 Pisa (ITALY)
ABSTRACT
Laser Ablation (LA) is used in a widespread range of applications, among them it is
employed as sampling procedure for the elementary chemical analysis of materials. With
this aim, many analytical techniques makes use of LA - such as LA Ion Mobility
Spectrometry, Resonant LA, LA-Atomic Fluorescence Spectrometry and LA-Microwave
Induced Plasma-Atomic Emission Spectrometry among them the most popular ones are
probably the Laser-Ablation Inductively Coupled Plasma (LA-ICP) techniques and the
Laser Induced Breakdown Spectroscopy (LIBS).
In all these cases, it is desirable to attain the largest possible mass removal from the
target in order to lower the Limit Of Detection (LOD) of the technique. Such intent is
particularly true in the LIBS case, where LODs for solid samples are usually in the range
of ppm or tens of ppm, which are often inadequate for many applications.
One of the possible ways to overcome this problem is the use of two laser pulses,
temporally separated by a suitable delay, for the laser ablation. In this scheme, the laser
beams can be arranged in a collinear geometry, where both the beams are aligned
normally to the target and are focused on its surface, or in an orthogonal geometry (pre-
ablation configuration), where the first pulse runs parallel to the target surface and is
focused in the ambient gas in front of it, while the latter is aligned perpendicularly and
ablates the target. In case of ns-laser ablation, in both these configurations, a substantial
enhancement of mass removal and of its atomization with respect to the case where a
single pulse with equal total energy has been observed, where these phenomena lead to
G. Cristoforetti and V. Palleschi 2
an improvement of both the LODs and the reproducibility of measurements. Such
experimental configurations lead also to a different thermodynamic and dynamic
evolution of the plasma, which can be useful in case of LIBS analysis.
Many works have been dedicated to Double Pulse (DP) Laser ablation, aimed to
establish the optimal experimental conditions to be used in different applications and to
understand the physical mechanisms, still not clear, leading to the observed mass removal
enhancement [1].
The aim of the present chapter is presenting and resuming the ns-ns DP state of art,
discussing the occurring physical processes. Experimental results of the authors, as well
as of other scientists, will be shown and discussed to validate and run down hypotheses
on the mechanisms involved.
In particular, the interpretation of the lower plasma shielding, due to a rarefied
ambient environment, experienced by the second laser pulse will be presented. The
reduction of plasma shielding allows a larger part of the laser energy to reach the target
surface, resulting in an enhancement of the mass removal. Besides, such an improved
laser-matter coupling produces a stronger heating, which could lead the molten pool near
the thermodynamic critical temperature and drive the onset of phase explosion
mechanism.
A summary of the effects produced in DP configuration by using short and ultrashort
laser pulses is also mentioned, together with a brief discussion of the mechanisms
involved.
1. INTRODUCTION
In the last decade, many papers, especially aimed at improving LIBS and LA-ICP figures
of merit, focussed their attention on Double Pulse Laser Ablation [1]. However, the
pioneering works on the subject go back to the seventies, where effects similar to those
recently investigated had been already observed and discussed.
The double pulse approach was firstly studied by Piepmeier and Malmstadt [2,3]. In both
works a multiple spikes irradiation over an aluminium target in air from a Q-switched ruby
laser ( = 694.3 nm, 50 ns), with a separation between the pulses of 500 ns, was
performed. The observed enhancement of Al II and Al III lines was associated to the
absorption of the second pulse by the plasma ignited by the first pulse, resulting in a further
excitation of the aluminium species.
Maher and Hall [4] studied the effects produced by focussing two CO
2
laser pulses,
separated by a suitable temporal delay, on the same spot on different targets. When the delay
between the pulses was in the 30-70 s window, they observed a pulse-target coupling
stronger with respect to that produced by a single pulse, resulting in a higher impulse
delivered onto the target surface. In order to understand the reasons of such effect, the focal
spots were slightly moved, so that they did not overlap; also in that case, the results obtained
were very similar to the ones observed with overlapping spots, suggesting that a possible
thermal explanation of the observed phenomena, based on the pre-heating of the target
surface, could be ruled out. High-speed photographs, interferometric observations, target
damage evaluations and impulse measurements led the authors to conclude that the stronger
laser-target coupling is produced by a pronounced reduction in local medium density caused
by shocks expanding from the first laser pulse interaction resulting in a more difficult ignition
Double-Pulse Laser Ablation of Solid Targets in Ambient Gas 3
of Laser Supported Detonation (LSD) regime and then in a weaker shielding of the second
laser pulse.
Pershin and coworkers [5-7] in the eighties studied the effects produced by focussing two
Q-switched Nd:YAG pulses of 20 ns-duration, separated by 25 s, on an aluminium target
and on laser glasses in air, observing an intensity enhancement of target element lines and, at
the same time, a reduction of line intensity from atmospheric species with respect to the
signal obtained with a single laser pulse. The authors suggested that by an appropriate spatial
selection of plasma emission acquisition should then be possible to enhance the spectral line
signal-to-background and improve the limits of detections (LODs) of the analysis. The
formation of a plasma mirror and/or of self-focussing of the radiation in the plasma, which
both could be possible causes of the observed effects, were excluded by the experimental
results. Scattering and transmission coefficients were measured for the plasmas produced by
the first and the second pulse, finding a much lower intensity of scattered light in the latter
case [6]. Such results, together with the lower emission from atmospheric species [7], led the
author to the conclusion that double-pulse effects are produced by a reduction in the gas
density following the interaction with the first laser pulse, allowing the radiation of the
second pulse to reach the heated surface of the target and generate a more efficient
breakdown.
An interesting variant of the method, consisting of DP ablation of samples immersed in a
liquid environment, was introduced by Nyga and Neu [8] and developed by Pichahchy et al.
[9]. In this case, the first laser pulse produces a cavitation bubble on the target surface which
expands, reaching the maximum extension after about 400 s, and then collapses again; the
plasma produced inside the bubble is rapidly quenched and the emitted lines are considerably
broadened by pressure effects. If a second pulse is focussed onto the target in the
correspondence of the cavitation bubble, a plasma plume is ignited and expands into the
bubble vapour environment, in a condition similar to that of plasmas generated in ambient
gas, resulting in emission lines much narrower and in a strong line intensity enhancement,
which can reach up to two orders of magnitude. Such method was proposed for the
elementary analysis of samples submerged in water (e.g. for geological samples located under
water).
From the nineties up to now, different experimental configurations for the double and
multiple pulses approach have been tested and a large amount of papers have been published
on the topic, modifying the geometry of the laser pulses; the duration, energy and wavelength
of the pulses, including combinations between femtosecond, picosecond and nanosecond
lasers, and the delay between them; the environment where the ablation is ignited and finally
the target composition. Many of such works were devoted to a better understanding of the
mechanisms underlying the DP effects, by means of a large variety of techniques for plasma
diagnostics and for the examination of laser crater on the target, including spectroscopic
analysis of plasma emission, direct or shadowgraphic imaging of the plume, interferometric
analysis, microscopic target analysis, etc.
Many other works focussed their attention on the possible applications of DP benefits,
and most of them pointed to the improvement of reproducibility and sensitivity of LIBS and
LA-ICP techniques. Such works were devoted mainly to the description of DP effects and to
the determination of the most suitable experimental conditions and apparatus for their
application. However, other applications were proposed, as for example the production of
nanoparticles by means of DP laser ablation of metal targets in liquid environment. Burakov
et al. [10] showed that DP-LA provides a more effective ablation, and then a larger amount of
nanoparticles with respect to SP-LA. Moreover, the mean size and the stability of
nanoparticles could be controlled by a proper selection of the temporal delay between the
laser pulses, which affects the decay time of the plasma plume and then the temporal window
where the nucleation and growth of nanocrystals occur.
Basically, three different laser beam geometries have been up to now investigated in the
literature and will be considered here, despite other, more exotic configurations, have been
also tested [11]. Most research efforts have been focused on the collinear configuration,
which is certainly the easiest to arrange experimentally. In this configurations both beams are
aligned normally to the target and are focused on its surface (Figure 1a). However, a large
amount of works have been published dealing with an orthogonal arrangement of the beams;
here, the first pulse (pre-ablation scheme) (Figure 1b) or the second one (reheating scheme)
(Figure 1c) is directed parallel to the target surface and focused in the atmosphere in front of
it, while the other is perpendicular and ablates the target.
All such configurations, when utilized with a proper choice of experimental conditions,
may result in an enhancement of plasma emission, which can be fruitfully used for the
improvement of LIBS technique figures of merit. However, while the first two arrangements,
with appropriate choice of experimental parameters, produce also a substantial increment of
the mass ablated, the last one turns out only in a re-heating of the plasma produced by the
absorption of the first laser pulse, so that, strictly speaking, it can not be classified as DP-LA
method. Nevertheless, also the results obtained by such configuration will be rapidly
summarized in the following for the completeness of the subject.
Another important criterion of classification between the experimental configurations is
the duration of the laser pulses, since the mechanisms occurring during the DP-LA are
noticeably different depending on the pulse length. In most of the works, two nanoseconds
pulses are used, whose utilization is certainly more accessible for portable instruments and
stand-off applications; however, also combinations of nanosecond with ultrashort pulses have
been tested [12,13].
A summary of the effects produced by DP-LA in the different experimental
configurations and a critical review of the mechanisms proposed in the corresponding cases
are reported in the following sections. Particular emphasis will be given to the lower
shielding mechanism, which is in our opinion the main reason of signal and mass removal
enhancement in case of nanosecond-nanosecond pulses.
The attention will be focussed mainly on the nanosecond-nanosecond laser ablation,
which appears to be more accessible for applications, and whose mechanisms are noticeably
different from those occurring in femtosecond and picosend DP-LA; however, a brief
description of results, mechanisms and references related to combinations of laser pulses with
different duration will also be given.

Figure 1. experimental geometries used in DP experiments

Finally, the present chapter is focussed to the case of DP-LA of solid targets, mainly
metals, in ambient gas, although the technique has been successfully applied to solid targets
immersed in a liquid environment [14,15], with important potential applications going from
the target sampling and analysis to the synthesis of nanoparticles of controllable size
distribution. DP-LA of liquids, gases and aerosols is not treated in the present chapter.
2. NANOSECOND-NANOSECOND PULSES
COMBINATION: EFFECTS OF DP-LA
a) Collinear Beams Configuration
The collinear configuration, where both laser beams are aligned perpendicularly to the
target surface, has been widely tested and studied and, from a practical point of view, is the
most suitable for standoff applications [16,17]. Some works published in literature utilize also
slightly different configurations, where the laser beams hit the target at non-normal angles of
incidence [11]; however, since both the laser pulses produce the ablation of the sample and
the physical processes involved are similar to those occurring in the collinear perpendicular
configuration, such cases are included in the present section. The paragraph is subdivided in
four parts, dealing with the effects of collinear DP-LA on the plasma emission, on the plasma
dynamics, on the ablation mechanisms and on the relationship between ambient gas
conditions and DP effects.
Effects on plasma emission
All the works dealing with the spectroscopic analysis of plasmas induced by a ns-ns
laser pulses combination evidence a large enhancement, depending on the matrix of the
target, of the line intensities produced both by target atoms and ions, which can reach two
orders of magnitude [18-23]. At the opposite, the intensity of spectral lines emitted by atoms
and ions deriving from ambient gas (e.g. N and O species in ambient air) is markedly
reduced. An example of plasma spectra in the range 250-400 nm obtained in SP and in
collinear DP configuration by a Fe-Mn alloy is shown in Figure 2, taken from Ref.[25]; all
the lines in the spectral range shown in the figure belong to Fe and Mn atomic and ionic
species and exhibit an evident enhancement of 1-2 orders of magnitude.
It is worth to emphasize, however, that the signal enhancement found in collinear DP-LA
is dependent on the detector field of view [24], that can be easily explained by the different
plasma volume and dynamics obtained in SP and DP configuration. It is also important to
note that, usually, the enhancement is obtained by calculating the ratio of the line intensities
observed in the same temporal acquisition window both in SP and in DP configurations;
clearly, the value so-calculated depends strongly on the different dynamical and
thermodynamic evolution of the SP and DP plumes which can be very different, so that such
method is, to some extent, arbitrary and misleading. This should be taken into account for
example when the comparison of plasma temperature and electron density values in the two
cases is done.
The observed enhancement results in a marked improvement of the LIBS LODs, which
can reach a few ppm or lower depending on the element analysed and on the matrix where it
is embedded. Sturm et al. [26] found detection limits below 10 g g
-1
for C, P, S, Al, Cr, Cu,
Mn and Mo in steel samples. Piscitelli et al. [23] found an improvement of LIBS sensitivity
for Pb embedded in several metal targets of about an order of magnitude.
In a previous work [27], we calculated the limits of detection for several elements in
aluminium and steel alloys using both the single and the collinear double pulse configurations
of laser-induced breakdown spectroscopy. We used a dual-pulse Nd:YAG laser (=1064 nm,
=12 ns), where the energy per pulse was set to 30 mJ (~3 GW cm
-2
) for the ablation, and an
echelle spectrometer coupled to an intensified CCD camera (/=5000) for the spectral
acquisition. Calibration plots were constructed for Mg, Al, Si, Ti, Cr, Mn, Fe, Ni, and Cu
using a set of certified aluminium alloy samples and a set of certified steel samples. The
investigation included the optimization of the experimental conditions, where the temporal
separation between the pulses, the delay time and the gate of acquisition were varied, to
furnish the best signal-to noise ratio in both geometries.
The final LODs are reported in Table 1, evidencing that the improvement obtained in DP
configuration depends on the matrix of the target, being much higher for aluminium alloys
than for steel alloys.

Figure 2. LIBS spectra obtained from the SP ablation (black line) and the collinear DP ablation (grey
line) of a Fe-Mn alloy target. The figure has been taken from Ref.[25]
Table 1. Comparison of LIBS detection limits obtained in
SP and DP collinear geometries for aluminium and steel alloys
Element Wavelength ()
utilized
Single-pulse
LOD
Double-pulse
LOD
Aluminium alloys
Mg 2852.13 30 ppm 4 ppm
Ti 3349.41 100 ppm 10 ppm
Cr 4254.33 100 ppm 10 ppm
Mn 2949.20 0.1% 90 ppm
Fe 3719.93 400 ppm 50 ppm
Ni 3414.76 600 ppm 100 ppm
Cu 3247.54 150 ppm 80 ppm
Steel alloys
Al 3961.52 30 ppm 20 ppm
Si 2881.58 100 ppm 40 ppm
Ti 3088.02 50 ppm 25 ppm
Cr 4254.33 70 ppm 50 ppm
Mn 4823.52 300 ppm 120 ppm
Ni 3414.76 100 ppm 40 ppm
Cu 3247.54 25 ppm 5 ppm

Figure 3. ranges of enhancements R
I
1
and R
I
2
for a) ionic lines and b) neutral lines observed in the
spectral range 200900 nm at an inter-pulse delay of 1 s. R
I
1
and R
I
2
indicate the enhancement values
obtained in DP (pulse energies 60+60 mJ) with respect to the SP configuration with pulse energy of 60
mJ and of 120 mJ (corresponding to a zero interpulse delay), respectively. Taken from Ref. [28]
In a subsequent work [28], where the same apparatus described above (but an energy per
pulse of 60 mJ) was used, we studied more in detail the effect of the matrix composition on
the emission enhancement observed in DP collinear LIBS for several pure metal targets (Al,
Au, Co, Cu, Fe, Mn, Mo, Ni, Pb, Pt, Si and W).
In Figure 3 the range of enhancement of line intensities for the different targets are
reported; R
I
1
and R
I
2
indicate the enhancement values obtained in DP (pulse energies 60+60
mJ) with respect to the SP configuration with pulse energy of 60 mJ and of 120 mJ
(corresponding to a zero interpulse delay), respectively. The measurement of the emission
enhancement for neutral and ionic lines of all the samples showed a wide range of results,
going from the lowest observed for Pb, Ni and Mn to the highest values obtained for Cu, Al
and Au. It is then clear that the matrix of the target plays an important role in determining the
effects produced by DP configuration, as will be discussed successively.
A large amount of papers have been published to evidence in detail the dependence of
line intensity enhancement on many parameters e.g. the interpulse delay, the energy of the
pulses, the ionization stage of the emitting species, the energy of the upper level of the
transition, the properties of the target and of the environment gas, etc. It is clear that line
intensity enhancement is affected by two factors, which are the increase of ablated mass in the
plume related to the mechanisms of mass removal from the target, and thus to the material
and ambient gas properties and the variation of thermodynamic parameters of the plasma,
e.g. temperature and electron density, related to the ignition process of the plasma and to its
dynamical evolution. In fact, assuming the Local Thermal Equilibrium (LTE) of the plasmas,
the intensity enhancement R of a generic line in DP configuration with respect to single pulse
can be written:
))
1 1
( exp(
) (
) (
SP B DP B
k
DP
SP
SP
DP
SP
DP
T k T k
E
T Z
T Z
n
n
N
N
R = (1)
where N is the absolute total number of atoms of the chemical element considered, n is the
fraction of these atoms corresponding to the emitting species (atomic or ionic), Z is the
partition function, E
k
is the upper energy level of the transition and k
B
is the Boltzmann
constant. In turn, the ratio
SP DP
n n can be expressed in terms of the temperature and
electron density values via the Saha equation. So, the variation of experimental parameters
results in a variation of the emission enhancement via the increase of the ablated mass
(N
DP
/N
SP
) or via the enhancement of plasma temperature (terms n
DP
/n
SP
and exp(-E
k
(1/k
B
T
DP
-
1/k
B
T
SP
)) ).
A collection of the main results, dealing with the variation of experimental parameters,
which can be useful to understand the DP effects and causes, is reported in the following.
The emission enhancement depends strongly on the separation between the laser pulses,
as shown in Figure 4 for gold line intensities (=1064 nm, =12 ns), where the maximum
value is obtained for an interpulse delay going from hundreds of nanoseconds up to a few
microseconds, depending on the other experimental parameters and on the ionization state of
the emitting species. At separation delays shorter than ~100 ns a depressive effect on the
LIBS signal can be obtained, mainly due to the laser shielding of the second laser pulse by the
plasma formed by the first pulse, as clearly shown by Mao et al. [29] (Si target, = 1064 nm,
= 4 ns). The enhancement of plasma emission persists up to interpulse delays of tens of
microseconds, often being still significant at 80-100 s.
In general, the optimal interpulse delay is larger for ionic than for atomic lines, as visible
in Figure 4 where the largest enhancement for the Au I and Au II lines is obtained for
interpulse delays of 1-2 s and 4 s, respectively. Just to make some examples, in a previous
work [30] (brass target, =1064 nm =10 ns), we found an optimum interpulse delay of about
0.7 s for neutral copper lines and of approximately 2 s for ionic copper lines. In a
successive work [31], where an aluminium target was used, we found the largest
enhancement for interpulse delays in the range of 1-4 s, both from neutral and ionic lines.
St-Onge et al. [18,20], operating on an aluminium target, found that the optimum delay is less
than 1 s for Al I lines and between 2 and 5 s for Al II lines.

Figure 4. Dependence of line intensity enhancement on the separation between laser pulses for a gold
target
Gautier et al. [32] (Al target, =532 nm) found that the optimum interpulse delay
depends on the excitation energy of the transition, where for low-energy atomic lines the
highest improvement is obtained for = 0.2 s, while for ionic lines and atomic lines with
excitation energy higher than 6 eV the largest emission enhancement is obtained for higher
than 1 s.
Other works evidenced that, in most of the cases, the emission enhancement is higher for
ionic than for atomic lines, as visible in Figure 3, and for high excitation energy than for low
excitation energy lines. Such features are well evident in Figure 5, taken from Ref.[31], where
several aluminium atomic and ionic lines were observed and their enhancement was plotted
versus the energy of the transition upper level.
0 10 20 30 40 50
0
5
10
15
20
25
L
i
n
e

i
n
t
e
n
s
i
t
y

e
n
h
a
n
c
e
m
e
n
t
interpulse delay (s)
Au I 312.2
Au II 291.3
By looking at Eq.(1), it is evident that the increasing trend of emission enhancement with
the excitation energy of the upper level of the transition is due to an increase of plasma
temperature. In Ref.[31], we calculated the plasma temperature in both SP and DP-LA
plumes, finding a slight increase of the order of 10% in the latter case; it was then verified
that such increment is compatible with the slope of the points plotted in Figure 5. It was also
showed that the absolute values of emission enhancement can not be only attributable to such
slight temperature increase but must be caused by a concomitant growth of the ablated mass
by a factor of ~7, as will be discussed later.
An increase of plasma temperature was also found in other works, i.e. by Sattmann et al.
[22] (steel target, =1064 nm, = 20 ns) and De Giacomo et al. [33] (Ti target,
1
= 532 nm,
2

= 1064 nm, = 8 ns). In Ref.[28] (acquisition delay = acquisition gate= 1 s) we found an
increase of plasma temperature in DP collinear geometry with respect to SP with half-energy
for most of the targets analysed up to 1200K, where such enhancement was larger for targets
showing a higher emission enhancement; at the opposite, no evident growth of plasma
temperature with respect to SP with equivalent total energy was found. Other works
evidenced no substantial change or even a slight decrease of plasma temperature [21,29]. It is
then clear that the main contribution of the observed emission enhancement is not caused by
the higher temperature of the plasma.

Figure 5. Emission enhancement obtained in DP collinear configuration for Al I at 265.3, 305.0, 308.2
nm and Al II at 281.6, 385.6, 466.3 nm lines, for an interpulse delay time of 4 s. Taken from Ref.[31]
In Ref.[28] (acquisition delay = acquisition gate= 1 s), we calculated the plasma
electron density in DP and in SP configuration for a large quantity of metal targets, showing
in all the cases a marked decrease in DP with respect to SP configuration at equivalent total
energy; on the other hand, the electron density found in SP at half energy and DP cases are
comparable.
Colao et al. [19] (Al target, =1064 nm, = 8 ns) and St. Onge et al. [20] (Al target,
=1064 nm, = 6-12 ns) demonstrated that the electron density in plasmas induced by DP-
LA is consistently lower at early times of plasma evolution with respect to SP-LA at
equivalent total energy, but exhibits a slower decay with time, so that the values in the two
configurations approach, or electron density in DP plasma even becomes higher, at late times
(e.g. 700 ns in Ref.[20] and after 1.2 s in Ref. [19] after plasma ignition). The lower electron
density found in DP-LA at short acquisition times can explain the largest emission
enhancement observed for ionic lines with respect to neutral lines; in fact, if we assume LTE
and consider the Saha-Eggert equation, a lower electron density results in a higher ionization
degree of plasma species.
Plasma dynamics
The expansion dynamics and the consequent morphology of plasmas induced in collinear
DP configuration are noticeably different from those of plasmas produced by a single laser
pulse. In Figure 6, time-resolved images (acquisition delay = 700 ns, gate = 400 ns) of
plasmas from a brass target in air (=1064 nm, =12 ns), spectrally filtered around the Zn I @
520 nm line, induced by a single pulse, two coincident pulses, and two delayed pulses ( =
10 s) and acquired by an Intensified CCD camera, are shown. Both from the experiments
performed at atmospheric pressure and at 100 torr pressure, it is evident that the dimensions
of plasmas induced by the DP configuration are much larger than those of plasmas produced
by a single pulse and even by two coincident pulses. Moreover, the DP plasma tends to detach
from the target much more than SP plasmas, denoting a very different expansion dynamic in
the two cases.
Two sequences of frames, describing the evolution of the plasma from a brass target in
air produced by a single laser pulse and by two laser pulses delayed by 2 s, are shown in
Figure 7, taken from Ref.[34] (=1064 nm, =12 ns). The images are obtained by
shadowgraphic technique, using a white flash light to back-illuminate the region of the plume.
The exposure time of the single frame is 100 ns and the frames are separated by 500 ns. In
SP-LA, the generation, evolution and decay of the plasma at the surface of the sample,
together with the formation of a shock wave propagating in the surrounding atmosphere, are
visible. According to Figure 6, the plasma plume is near the surface of the target during all its
life. The shadowgrams of the plasma obtained in DP mode reveal that the second laser pulse,
coming 2 s after the first pulse, initiates a new plasma at the sample surface (frame 4), which
very rapidly propagates, moving away from the target and almost fills the region
encompassed by the shock wave front formed by the first pulse, resulting in a plume wider
than in SP configuration. Rapid expansion is caused by the rarefied ambient gas, formed by
the first laser pulse, where DP plasmas are generated and expand. Gas rarefaction is
evidenced also by the failure of detecting the shock wave formed by the second laser pulse,
because of the lower jump in density at the shock front [34].

Figure 6. Time-resolved images of plasmas obtained from a brass target by a single pulse (SP), two
coincident pulses (CP) and two delayed pulses (DP) obtained at atmospheric (a-c) and 100 torr (d-f)
pressure. The emission is spectrally filtered around the Zn I @ 520 nm line. Delay time of acquisition is
700 ns and gate is 400 ns

Figure 7. Shadowgrams of the laser induced plasmas in single pulse (on the left) and double pulse
configuration (on the right). In both sequences, the first photograph (left bottom) has been taken at a
delay time of ~500 ns with respect to the first laser pulse, while the temporal delay between
photographs is 500 ns. Taken from Ref.[34]
A detailed study on the different dynamics of plasmas induced in SP and DP
configuration was presented by De Giacomo et al. [33] (Ti target,
1
= 532 nm,
2
= 1064
nm). In their experimental work (sided by a LIP expansion model), it was shown that the SP
plasma expands up to ~ 1 s and then stops, due to the counterpressure of the cold
unperturbed ambient gas, at a distance of ~ 1.1 mm; differently, the DP plasma rapidly
expands in the hot rarefied gas up to ~ 400 ns and then stops at a distance of about 1.7 mm
from the target. De Giacomo et al. stress that the DP plasma expansion during the early
hundreds of nanoseconds resembles a free expansion; however, the expansion inside a hot
environment and the confinement produced by the shock wave formed after the first laser
ablation, lead also to a smaller loss of plasma energy and then to a slower decay time of
plasma temperature.
Similar results and conclusions were also presented by Noll et al.[35], using a high-speed
electro-optic camera to observe the spatial and temporal development of the plasma
morphology and a MachZehnder interferometer to detect the spatio-temporal changes of the
refractive index of the plasma. They also showed that the second laser pulse interacts
predominantly with the sample surface while the laser absorption by the residual plasma
causing its re-heating is marginal.
So, in conclusion, both the wider volume of plasma emission and the longer plasma
lifetime obtained in DP configuration produce a situation more suitable for LIBS analysis
than SP geometry.
Mass removal mechanisms, atomized ablated mass and effects of the matrix target
Many works [18,29,36-39] report that DP collinear laser ablation produces deeper craters
with respect to the SP ablation, where the ablation rate can increase from 2 to 20-fold. It was
also observed that the crater rims are lower in DP case or, however, the ratio of volumes
occupied by the rims (Volume
up
) and that of the hole (Volume
down
) is noticeably smaller than
in SP. Caneve et al. [36] (copper-based alloy target, =1064 nm, = 8 ns) found ablation
rates in the range 0.08-0.11 m/shot and 1.78-3.2 m/shot, for single and double pulse
schemes respectively; moreover, the presence of rims is well visible in the former scheme and
negligible in the latter. 3D reconstructions and 2D profiles of craters induced on an
aluminium target in both configurations (=1064 nm, =12 ns, = 4 s, pulses energy = 78
mJ), obtained by video-confocal microscopy and taken from Ref.[31], are reported in Figure
8.
In such a paper, we reported an increase of crater volume (measured as the volume of the
drilled hole) of 4-6 times in DP-LA, and a ratio Volume
up
/Volume
down
decreasing from the
range 1.8-2.5 in SP-LA to 0.8-1.1 in DP-LA. Here, it is necessary to bear in mind that values
larger than 1 of the ratio Volume
up
/Volume
down
are possible because the density of molten and
re-solidified material can be lower than that of the target. Such observations demonstrate that
DP-LA improves the laser-target coupling, reducing undesired thermal effects and
phenomena produced by plasma-target interaction, such as melt displacement and splashing
of the molten pool.

Figure 8. 3D reconstructions and profiles of craters produced in SP (on the left) and in DP configuration
(on the right). Taken from Figure [31]
The increase of mass removal is certainly one of the major contributions to the LIBS
signal emission and one of the reasons for which DP-LA is investigated for LA-ICP
application. However, the increase of the ablation rate and the reduction of thermal effects
deserved attention also in the field of micro-machining of materials [39,40]. Usually, for such
applications, thermal effects and re-deposition of debris on the surface are avoided by using
ultrashort laser pulses, which are able to produce high-quality large aspect-ratio holes;
however, fs laser pulses have several drawbacks, as the low ablation rate, the need for
reduced pressure to avoid air breakdown due to the high irradiance and the high cost of
instrumentation, which limited their commercial exploitation. Forsman et al.[40] (steel and Al
targets, =532 nm) and Wang et al. [39] (steel target, =1047 nm, = 21 ns) observed
significant enhancements of the drilling rate (3-10 times in Ref.[40] and more than one order
of magnitude in Ref.[39] depending on the experimental parameters) by using markedly
smaller energy (fractions of mJ), tighter focussing (tens of m) and smaller interpulse delays
(tens of nanoseconds) with respect to the values usually utilized in LIBS experiments. Wang
et al. showed that the drilling enhancement strongly increases with the thickness of the
sample, since SP drilling rate tends to saturate at depths larger than 400 m while DP
performance remains stable with depth.
For applications as LIBS or LA-ICP, where quantifying the enhancement of atomized
ablated mass in the plume rather than the drilling rate is important, the analysis of craters
depth and morphology is not directly informative about the effectiveness of the laser ablation
process. In fact, crater analysis does not provide the measure of the mass atomized in the
plasma because the volume of the laser induced crater is often comparable to that of the rim
around the hole, so that the calculation of the removed mass as the difference between such
volumes leads to large uncertainties. Furthermore, even a precise measure of the removed
mass would not be able to discriminate between the mass atomized in the plasma and that
ejected (and spectroscopically lost) in particles or large clusters.
A more direct measurement of the ablated mass could be obtained by weighing the target
before and after the ablation process, even if also this method does not discriminate molten
droplets and clusters; however, such approach is hindered by the low effective ablation rate,
which can be much lower than a g per pulse, so that it implies the weighing of the sample
after a large number of laser shots, as in Ref. [41].
Because of these disadvantages, in Ref.[28,31,42-44] we estimated the atomized mass in
the plasma, scaled by an arbitrary factor, directly from the analysis of emission spectra, even
if this approach is strongly affected by the uncertainties in the determination on the
thermodynamic parameters and by the geometry of signal collection in the experimental
setup. In Figure 9, where the same notation of Figure 3 is used, the enhancement of atomized
ablated mass for several metal targets is shown. By a rapid comparison with Figure 3, it is
evident that there is a strong relationship between the enhancements of LIBS signal and of
ablated mass, suggesting that the main contribution of DP-LA benefits in LIBS is produced
by the increase of mass in the plume, and, only in the second place, to the increase of plasma
temperature.
In Ref.[31], we calculated the contribution to lines intensity enhancement of both the
variations of temperature and atomized ablated mass. We showed that the calculated small
increment of temperature (~10%) resulted in a slightly higher population of higher energy
levels and a slightly higher ionization, producing a negligible variation of the intensity of the
neutral lines in the range 0.94-1.2 and an increase of the ionized lines in the range 2.3-3; the
remaining enhancement, which was by a factor of ~7, was due the increase of mass into the
plume.
By comparing the measured crater enhancement with the enhancement of the ablated
mass in the plume (measured via spectroscopic analysis or via ICP analysis), it is evident that
the latter is usually much higher; even if such comparison is incorrect, since the
measurements of crater dimensions can not be used to estimate the mass removed from the
target (see above), such observation led some authors to infer that DP-LA produces also a
higher atomization of the ablated mass and a finer aerosol. Such hypothesis seems also
confirmed by the imaging of the plume (e.g. see Ref. [45]).
Despite the evident dependence of emission and ablated mass enhancement on the matrix
of the target (see Figures 3 and 9), very few works were devoted to correlate the effects of
DP-LA with the composition and properties of the target. In a detailed work [21], Gautier
et al. analysed the effectiveness of the DP LIBS for different materials (aluminium, synthetic
glass, steel, rocks) separating the contribution of temperature and ablated mass increase. Their
results suggested that the intensity enhancement tends to be higher for the matrices
originating a cooler SP plasma.

Figure 9. Calculated enhancement of ablated atomized mass R
M
1
and R
M
2
for all the targets. The
uncertainty is ~2530%. R
M
1
and R
M
2
indicate the enhancement values obtained in DP (pulse energies
60+60 mJ) with respect to the SP configuration with pulse energy of 60 mJ and of 120 mJ
(corresponding to a zero interpulse delay), respectively. Taken from Ref. [28]

Figure 10. Ablated mass enhancement in DP LIBS (pulse energies = 60 mJ + 60 mJ) with respect to SP
configuration (energy = 60 mJ) vs. thermal diffusivity at melting point. Taken from Ref.[28]
In Ref.[28], the effect of DP-LA on several metals and semiconductors characterized by
different thermal, electronic and optical properties was studied. Other materials such as
insulators and polymers were not considered because of their different ablation mechanism
(volumetric heating) with respect to metals (surface heating). In particular, we made an
attempt to correlate the increase of ablated mass, as reported in Figure 3, with the melting
point and heat, the boiling point and heat, the reflectivity and the ionization energy of the
metal. However, no evident correlation was found. At the opposite, a correlation was
observed between the ablated atomized mass enhancement and the thermal diffusivity of the
metal, as shown in Figure 10; in order to explain such correlation, we proposed a simple
picture that will be described in the following sections.
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45
5
10
15
20
25
30
Pb Ni
Co
Fe
Mo
W
Si
Pt
Cu
Au
Al
a
b
l
a
t
e
d

m
a
s
s
e
n
h
a
n
c
e
m
e
n
t

R
1 M
thermal diffusivity at melting point (cm
2
s
-1
)
Dependence on ambient gas pressure
As final paragraph, we report some results concerning the influence of the ambient gas on
the DP-LA effects previously described, i.e. the plasma emission, the plume dynamics and the
mass removal.
Some DP-LA studies were conducted in ablation chambers and performed at ambient gas
composition different from air, such as nitrogen, argon, helium or mixtures [45-47]. Some of
such experiments were motivated by the application of DP-LA for ICP analysis [45]; some
others, where gas was flushing the interaction region, were aimed to remove the particulate
produced by precedent bursts [46]. The results obtained suggest that the gas density (at
constant gas pressure) strongly affects the drilling rate of the ablation process, both in SP and
in DP configurations, and that the magnitude of DP enhancement decreases with increasing
the density of ambient gas.
Here, however, we will focus our attention on the effects associated to the pressure of
the ambient gas, which are stronger and more significant for the modelling of DP-LA process.
In a previous paper [30], we studied the effect of DP configuration on plasma emission,
by performing laser ablation at different air pressures, ranging from 0.1 Torr to atmospheric
conditions. Two Nd:YAG laser pulses (=1064 nm, =12 ns) were separated by a time delay
ranging from 0 (coincident pulses) up to 8 s and focussed on the surface of a brass sample.
Neutral and ionized lines originated both by species deriving from the target and from the air
environment were analysed.
The results, shown in Figure 11, evidenced a different behaviour of copper species
emission versus air pressure value in single- and double-pulse- operation modes.
The line intensity measured in SP case shows a maximum emission around 100 Torr
pressure followed by a significant reduction at higher pressures. This effect can be explained,
as discussed in literature, in terms of the laser shielding of the target operated by the plasma,
which is strongly affected by the buffer gas. On the other hand, in DP scheme the emission
signal from copper species do not decrease at higher pressures, so that an enhancement with
respect to the SP case is present for pressures higher than 100 Torr. It is also noticeable the
reduction of Cu emission obtained in DP configuration at pressures lower than 100 Torr. A
similar behaviour, was also observed for other lines emitted by atoms originated from the
sample (e.g., Zn I lines).
The analysis of the O I 777.3 nm line, shown in Figure 12, reveals a completely different
behaviour with respect to that of Cu I, Zn I, and Cu II lines. The signal obtained by using a
single pulse or two coincident pulses (=0) does not reach a maximum, but, on the contrary,
shows a monotone increasing trend with increasing the air pressure in the chamber up to 300
Torr followed by a slight saturation. Such results are easily explainable by considering that
the oxygen atoms originate from the environment, so that their concentration in the plasma is
not affected by the laser shielding effect. Therefore, the increasing trend of the emission of
oxygen atoms versus pressure is due to the combined effect of the increase of their
concentration and of the raise of plasma temperature produced by the laser-shielding effect.
Similar results were obtained by Peter and Noll [47], which studied the ablation of
material and the plasma emission induced by a single pulse and two pulses ( = 1064 nm, SP
1x80 mJ, DP 2x40 mJ, = 6 s, = 20-40 ns) on iron samples at different argon pressures.
The measured ablation rate confirms the spectroscopic trends shown in Figure 11, i.e. the DP
mass removal is much more efficient than SP one at pressures higher than 100 mbar (DP
ablation rate is larger by a factor 4 at 1 bar) but the enhancement vanishes at pressures lower
than such a value.
Wang et al. [39], operating on a steel target at quite different experimental conditions
(laser energies in the order of the mJ, = 1047 nm, = 52 ns, = 21 ns), also investigated
the effectiveness of drilling in SP and DP modes at different air pressures, finding that the SP
ablation rate at the pressure of 8 mbar is close to that produced in DP configuration in the
open air.

Figure 11. On the left, Cu I 521.5 nm line intensity versus the air pressure obtained by using a single
pulse (triangles), two coincident pulses (squares), and two laser pulses separated by 700 ns (circles).
The acquisition windows are delayed by 2 s with respect to the single laser pulse and to the second
pulse. On the right, enhancement factor of Cu I 521.5 nm line expressed as the ratio of emission signal
obtained in double pulse configuration (=700 ns) over that obtained with two simultaneous pulses.
Taken from Ref.[30]

Figure 12. O I 777.3 nm line intensity versus the air pressure obtained by using a single pulse
(triangles), two coincident pulses (squares), and two laser pulses separated by 700 ns (circles). The
acquisition window is delayed by 700 ns with respect to the single pulse and to the second pulse. Taken
from Ref. [30]
Such results suggest that the effects produced by DP-LA are strongly correlated with the
environmental gas density in which the plume forms and expands. SP-LA at atmospheric
pressure is affected by a strong laser shielding, i.e. a large part of the laser energy is absorbed
before reaching the target, resulting in less ablated mass and a proportionally lower emission;
a stronger laser-target coupling in SP-LA is obtained at reduced pressure, where the optimal
situation is achieved at around 100 Torr. On the contrary, in DP case, the second laser pulse
ablation occurs in a rarefied medium, where the laser shielding is reduced and consequently
the mass removed and the plasma emission are higher. Results slightly contradicting this
interpretation were obtained by Krstulovic et al. [48,49] (Ti target, = 1064 nm, = 5 ns),
which showed a 2/3-fold enhancement of crater volume and particle number density in the
plasma in collinear DP-LA in vacuum (where evidently the rarefaction effect of the first laser
pulse is not present). Such results are observed for interpulse delays shorter than those
obtained in DP-LA at atmospheric conditions, where the optimal delay
max
for increasing
crater volume and plasma number density were 370 ns and 1 s, respectively. The authors
suggest that such effects are caused by a lowering of the target ablation threshold produced by
the heating produced first laser pulse. These results thus suggest that the pre-heating of the
target, causing a modification of its optical properties (reflectivity, absorption) and a decrease
of its ablation threshold, might have a role, though maybe not dominant, also in the DP-LA at
atmospheric pressure.
A more accurate picture of the processes occurring in the collinear configuration will be
given in next sections, since we believe the discussion will be also useful for the
understanding of the pre-ablation orthogonal DP-LA configuration.
b) Orthogonal Beams Pre-Ablation Configuration
In the orthogonal pre-ablation (or pre-spark) configuration (Figure 1b) the first laser pulse
is sent parallel to the target surface and focussed in front of it, producing a plasma, while the
second pulse passes through it and ablates the target. The plasma produced by the first pulse,
thus, is just composed by species deriving from the ambient gas and only the second pulse
removes mass from the target. In this way, the role of the first pulse is only that of preparing
the environmental conditions in which the successive ablation is more effective, because of a
stronger laser-target coupling. From a practical point of view, such configuration is probably
less viable than the collinear one because of the higher complexity of the apparatus. However,
it is more suitable for understanding the processes occurring in the DP-LA, due to the clear
separation between the roles of the two pulses. From the following discussion it will become
clear that the effects produced by this configuration are similar to the ones shown in the
previous paragraph; this suggests that the primary cause of DP-LA effects in the two cases is
the same, as will be discussed in section 3.
The pre-ablation DP scheme was proposed by the Angels group [50-53], who used two
Q-switched Nd:YAG lasers ( = 1064 nm, = 7 ns) both for producing the pre-spark (pulse
energy = 210 mJ) and the ablation (pulse energy = 100 mJ). The first pulse was focussed 1-2
mm above the target and did not produce any appreciable ablation from the surface. Such
configuration led to LIBS signal enhancement both in the case of metal target (11-fold and
33-fold for Cu and Pb, respectively [50], 16-fold for Zn [53]) and of non-conducting targets
(from 11-fold to 20-fold for Ti, Al and Fe in glass [51]). The maximum enhancement was
obtained for an interpulse delay of ~2.5 s; however, the enhancement is strong for values
up to ~100 s and persists even at ~300 s. An increase of plasma temperature up to ~5000 K
was observed as well as an increase of crater volume up to ~30 times with respect to SP-LIBS
(in this case the comparison refers to the case where only the second pulse operates). Both
these effects show a clear dependence on the interpulse delay similar to that obtained for
signal enhancement; however, the authors suggest that the primary cause of line emission
enhancement is the raise of ablated mass rather than the temperature increase [52]. The
authors also noted that the largest enhancement was observed for lines originating from
transitions departing from high energy levels; evidently, such effect is produced by the
increase of plasma temperature from SP to DP configuration.
Similar results were obtained by Gautier et al. [54] who performed DP pre-ablation LA
on an Al target, using two Q-switched Nd:YAG lasers ( = 1064 nm, = 9 ns for producing
the pre-spark and = 532 nm, = 9 ns for the ablation). The largest line enhancements were
obtained in an interpulse range going from 10 to 35 s and for lines originating from high
energy levels.
Lindner et al. [55] (Cu-Zn target, = 1064 nm, = 8 ns) measured the size distribution
and the composition of the particles generated in pre-ablation DP experiments performed in
atmospheric argon. While in SP scheme the proportion of large particles (> 0.1 m) was
predominant, ultrafine aerosols particles (< 50 nm) were generated in DP configuration
representing practically the total mass impacted. Since ultrafine particles form through
vapour-phase condensation while large clusters points to a fragmentary mass removal
mechanism, the authors conclude that the DP scheme provides a better atomization, close to
100%, of the ablated matter. According to the authors, thus, the signal emission enhancement
is produced by the increase of both the ablated mass and its atomization.
In the pre-ablation configuration, the value of the distance d of the pre-spark from the
target surface can be adjusted, which constitutes an additional experimental parameter to be
optimized, with respect to the collinear scheme. The influence of the d-value was studied by
our group in a previous paper [56], where the effect of its variation in a range between 0.1 and
4.2 mm together with that of the variation of the interpulse delay, were investigated by
spectroscopic and shadowgraphic approaches. The importance of studying the influence of
the d-value resides in the information on the DP-LA mechanisms which can be disclosed; in
particular, in the hypothesis that DP effects are produced by atmospheric effects, the effects
in the pre-ablation scheme should reduce to those obtained in the collinear case when the d-
value approaches zero.
In the work cited above, the emission spectra of the air spark could not evidence a
detectable features from target species even in the case of d = 0.1 mm, indicating that the
target ablation was negligible for all the values of the parameter d. The laser sources were two
Nd:YAG lasers, each one emitting a laser pulse in 8 ns FWHM at the wavelength of 1064 nm.
The energies of the first and second laser pulses were adjusted to 140 and 240 mJ,
respectively. A brass target with ~60% Cu, ~ 40% Zn was used.
Spectroscopic analysis of plasma emission reveals that a significant signal enhancement
for the neutral and ionic lines is observed for distances d lower than 1 mm. This behaviour is
highlighted by plotting the maximum enhancement (obtained at different interpulse delay
values) vs. distance d, as shown in Figure 13 for neutral and ionic Zn lines, where a sharp
reduction occurs around the value d = 1.0 mm.

Figure 13. Maximum signal enhancement of Zn I 472.2 nm and of Zn II 255.8 nm vs. the distance d
between the air spark and the target surface. Taken from Ref.[56].

Figure 14. Intensity enhancement of Zn II 255.8 nm line vs. the interpulse delay time obtained at
different values of the distance d. Taken from Ref.[56]
Other interesting information could be drawn from the behaviour of the signal
enhancement with the interpulse delay time. It is evident from Figure 14 that the signal
enhancement begins to increase already at a delay time of 100 ns for d=0.1 and 0.4 mm while
for increasing distances the signal enhancement occurs at progressively higher interpulse
delay times.
Moreover, for the higher values of the distance d, a reduction of the signal is visible
(DP/SP signal ~0.350.6 for the Zn I 472.2 nm line and DP/SP signal ~0.100.4 for the Zn II
255.8 nm line) at values of the interpulse delay immediately before the onset of signal
enhancement. A similar signal reduction was previously found by Stratis et al. [50] who
hypothesized a shielding of the sample from the ablation laser pulse by the air plasma.
The calculation of plasma thermodynamic parameters showed that signal enhancement is
associated to a modest increment of the temperature (generally lower than 1000 K), when
present, and to a marked decrease of the electron density. By hypothesizing Local Thermal
Equilibrium and by considering Saha equation, such features lead to a higher plasma
ionization, which is consistent with the larger enhancement observed for ionic lines with
respect to atomic lines.
In order to understand the origin of signal enhancement we estimated the increment in the
total number of emitting atoms (as an indication of the ablated mass), from the intensity of the
Zn 472.2 nm line and the calculated values of temperature and electron density. The so-
calculated ratio of mass ablated in DP over that in SP, is reported in Figure 15 for all the
combinations of the interpulse delay and the distance d used.
Again, a sharp reduction of the ablated mass enhancement for values of the distance d
larger than 1 mm is evident. A comparison of Figure 15 with Figure 14 shows clearly that the
general behaviour of the emission signal with the interpulse delay is the same of that of the
ablated mass, suggesting that the origin of the signal enhancement is mainly the higher
ablated mass in the DP configuration, as already observed in the collinear DP experiments.
For studying the dynamic evolution of the plumes obtained by using different
combinations of d- values, we acquired shadowgraphic images using a Hadland Photonics
frame camera, back-illuminating the plasma during its evolution with a white light source.
It was found that the plasma evolution is strongly dependent on the choice of the d-
values, as can be observed from Figure 16 ad.

Figure 15. Enhancement of the atomized ablated mass as a function of interpulse delay and at different
values of the distance d. Taken from Ref. [56]

Figure 16. Shadowgraphic images showing the evolution of the plume and of the first and second shock
waves produced with an interpulse delay of 2 s and a distance d of 4.2 mm (a), 2.8 mm (b) 1.9 mm (c),
and with an interpulse delay of 4 s and a distance d of 0.7 mm (d). The temporal delay between the
frames is 500 ns. Taken from Ref.[56]
The four images nearly represent all the different situations which can occur in the
orthogonal pre-ablation DP scheme. In all the cases, both the pre-spark and the ablation
plasma produced near the surface by the second laser pulse are clearly visible, as well as the
two shock waves SW1 and SW2 departing from them.
In case a) the ablation laser is fired before the shock wave SW1 generated by the air
spark arrives on the target surface. The expansion of the ablation plume and of the shock
wave SW2 shows a slow expansion in the direction perpendicular to the surface and a faster
expansion in the radial direction. SW2 slows down because it expands in a medium flowing
in the opposite direction and, at early times, with a higher gas density at SW1 front (Sedov
self-similar solution predicts that the SW radius r and the ambient gas density are related to
each other by
5 / 1
r ). It is then clear that the expansion of both the second plume and
SW2 is faster in the radial directions, where there is no density increase with respect to
atmospheric conditions. As a result the ablation plume and SW2 expand assuming a flat shape
similar to a disc and do not coalesce with the air spark.
In case b), the second pulse is fired just after the arrival on the target surface of the shock
wave SW1. As in the previous case, the ablation plume has initially a flat shape, probably due
to a slowdown caused by the interaction with the SW1 front; however, in this case, SW2 and
the ablation plume find soon the rarefied slow moving region located beyond the SW1 front
and in the middle of the air spark and accelerate their motion, assuming an elongated shape.
This results in the coalescence of the two plumes; the mixing of the two plumes leads to a
reheating of the air spark, evident by the stronger brightness of air plume in frames 5,6,7,8 of
Figure 16b with respect to Figure 16a.
In case c), the ablation laser pulse is fired well after the time taken by SW1 to reach the
target. Here, the situation is similar to case b) but the elongation is much less evident since
the rarefied region of the first plume is nearer to the target. The two plumes rapidly coalesce
and the two shock waves become almost concentric.
Finally, in case d) the ablation laser is fired well after both SW1 and also the air plasma
have reached the target. In this case, the evolution is similar to case c) but the final plume is
larger and much brighter even for larger values of the interpulse delay (frames 810 in Figure
16d).
A rough estimation of the maximum radius of the air spark from the shadowgraphic
images (the bright region coincides with the continuum emission zone) gives a value ~1 mm.
By comparing this value with the range of distances d, derived from spectroscopic analysis,
for which a large signal enhancement is obtained, it is possible to conclude that the large
signal enhancement corresponds to the case d). In other words the d- values result in a
considerable signal enhancement if the target ablation occurs inside the region of the air spark
(i.e. the air plasma has reached the surface) and not only in the region encompassed by the
shock wave SW1. Such result is significant for understanding the causes leading to the signal
and the mass removal enhancement observed in this DP scheme and, for the similarity of the
results, in the case of collinear pulses and will be discussed in section 3.
c) Orthogonal Beams Re-Heating Configuration
The orthogonal re-heating configuration (Figure 1c), strictly speaking, is not a DP-LA
technique since it does not produce a raise of the mass removed from the target. In this case,
the interaction of the second laser pulse with the plume produced by the first pulse leads to a
re-heating of the plasma and thus to an emission enhancement, that can be exploited in LIBS
measurements.
The scheme was originally introduced by Uebbing et al. [57] (Al and Mn in glass matrix;
Mg and Mn in glass, copper and aluminium matrices, = 1064 nm, E
1
= 13 mJ, E
2
= 115 mJ,
1
= 8 ns ,
2
= 5 ns), with the purpose of improving the internal standardization effectiveness
for different matrix targets. Uebbing et al., aiming at obtaining reliable quantitative analyses
by SP LIBS, noted that the usage of the same calibration curve, obtained by internal
standardization, for different matrices lead to large errors because of the different
temperatures of plasmas induced on different matrices and because of the selective
volatilization of particles and droplets of different elements in the plasma (e.g. Cu and Zn in
brass, which have very different values of vapour pressure). The second problem could be
overcome by choosing a long delay time of signal acquisition (tens of s) when the
atomization process is ended; however, the plasma emission in that temporal range is often
very low and scarcely useful for analytical measurements because of the decay of the
temperature. The authors, thus, proposed the re-heating of the atomized mass by a second
laser pulse for reducing the problems related to fractionation of materials; at the same time,
the temperature differences in plasmas induced on different matrices should also reduce
because the temperature of the second plasma is only affected by the second pulse features
(energy, duration and wavelength) and not by the properties of the target (reflectivity, thermal
conductivity, absorption, etc.). By using the re-heating DP scheme in an Ar rarefied
environment, with an interpulse time of 40 s, Uebbing et al. demonstrated the validity of
internal standard usage over three orders of magnitude of concentrations for metals embedded
in different matrices (Cu and Zn in brass; Mg and Mn in glass, copper and aluminium matrix;
Al and Mn in glass and steel).
The effectiveness of DP re-heating configuration for enhancing LIBS signal was
investigated by Gautier et al. [54,58] (Al target; ablation laser = 532 nm, = 9 ns; re-
heating laser = 1064 nm, = 9 ns), who studied the influence of the delay between the laser
pulses and of the delay time of acquisition. The authors showed that the optimal value of the
interpulse delay for enhancing ionic lines is ~200 ns, for which intensity enhancements up to
7 could be obtained. At that interpulse delay value, however, the intensity of neutral lines is
reduced, except that of lines deriving from high energy levels which slightly increases. There
is no experimental condition for which the intensity of neutral lines is significantly increased.
Such results, together with the found increasing trend of line enhancement vs. the upper level
energy, are evidently produced by the increase of plasma temperature resulting in the raise of
the ionization degree and favouring the population of high-energy atomic levels. As a
consequence, Gautier et al. show that the re-heating configuration leads to an improvement of
LODs by 2-3 times, if ionic lines are used for the analysis.
Despite the modest line enhancement, that is often lower than that obtained by other DP
schemes, such configuration can be useful in LIBS technique in cases where it is necessary to
reduce the damage on the sample or in case of re-heating of fs-plasmas, which have usually a
low temperature and decay much faster than ns-plasmas; this second case, however, will be
treated in section 4.
A slightly different re-heating approach was proposed by Cheung and coworkers [59-62],
where a second laser pulse intercepts and rekindles the ablation plume via resonant-
absorption (Resonance-Enhanced LIBS or RELIPS). The technique was probed on different
matrix targets (potassium iodate KIO
3
pellets containing traces of Na as analyte; sodium
bicarbonate NaHCO
3
pellets doped with lithium as analyte; Al alloys with Cu, Mg, Pb and Si
as analyte) where in all cases the resonant absorption was performed by tuning the
wavelength of a dye laser on a particular transition of the major component of the matrix. The
character of resonant-rekindling was evident by slightly detuning the wavelength of the dye
laser, which resulted in a sharp reduction of the RELIPS signal.
Both longitudinal and transversal interception of the second beam were probed, finding
that the latter scheme provides signal 6 to 20-times larger signals and lower background
noise. For LIBS to perform equally well, the sampling has to be ten times more destructive,
which can be undesirable for some applications. The extent of the enhancement was found to
depend on type and pressure of ambient gas, where an appropriate choice could result in the
confinement and in the thermal insulation of the plasma, leading to a maximization of signal
intensity. The sensitivity was found to depend critically also on the beam profile and on the
spatial overlap of the laser beams.
According to Cheung and coworkers, the primary mechanism of RELIPS enhancement
reside in the large volume of re-heated plasma, where, at the opposite, in a classical re-heating
DP mode (non-resonant) just the hot spots of the plasma, characterized by a large electron
density (the mechanisms is in this case the inverse Bremsstrahlung process), tend to be re-
heated. The authors argue that this feature constitutes an advantage because it allows an
uniform and stable final heating since local absorption is automatically capped whenever the
excited population of the resonant transition is saturated.
To quantify the performance, a mass LOD of about 100 amol for Mg, and a detection
sensitivity of about 0.3% of a monolayer of aluminium oxide over a 1 mm
2
probed area, were
demonstrated.
3. NANOSECOND-NANOSECOND PULSES COMBINATION:
DISCUSSION ON THE MECHANISMS
While the mechanisms leading to signal enhancement obtained in DP-reheating
configuration (either resonant or non-resonant) are clear, the mechanisms operating in
collinear and orthogonal pre-ablation DP configurations are still uncertain and need to be
discussed [33]. Although the obvious differences in the experimental setups of these last two
schemes, strong similarities in the produced effects are obtained, as listed in the previous
section, such as the similar line intensity enhancement, the large increase of crater depth and
atomized mass in the plume, the scarce increase of plasma temperature, the larger ionization
associated to a reduction of the plasma electron density, the similar expansion dynamics of
the plume (when the parameter d is lower than 1 mm). Such similarities suggest the working
hypothesis that the primary mechanism in collinear and orthogonal pre-ablation is
substantially the same, where the latter scheme approaches essentially to the former when the
distance of the pre-spark to the target surface tends to zero. As will be discussed in the
following, the lower shielding mechanism can fit well and is able to explain the gross of the
results obtained in both the configurations; on the other hand, a minor role can be played by
the pre-heating of the target in the collinear DP scheme.
In both collinear and orthogonal pre-ablation schemes, it was found that LIBS
enhancement is produced by an increase of atomized ablated mass and by a different
expansion dynamics rather than by an increase of plasma temperature. The larger ablated
atomized mass results in a larger amount of emitting atoms, which is even higher in case of
ions because of the higher ionization degree. At the same time the expansion of the plasma in
SP and DP schemes is completely different as remarked by De Giacomo et al.[33]: while a SP
plasma expands in a cold environment, exchanging energy with it, a DP plasma expands in a
rarefied hot environment composed by the same species, so that it can be considered a
closed system. In fact the limited energy loss due to dissociation of ambient gas molecules
and to excitation of ambient gas species, together to a spatial confinement of the plume at late
times by the shock wave SW1 produced by the first laser pulse, results in a slower decay of
the plasma and in a condition more favourable to LTE condition.
The reduction of plasma electron density, driving a higher ionization of the plume can be
explained by two different, probably interplaying, mechanisms. Firstly, the DP plasma
expands very rapidly during the early 300-400 ns, due to the rarefied environment
encountered, and successively stabilizes to dimensions corresponding to the region
encompassed by the shock wave SW1. The expansion results in a geometric reduction of
electron (and atom) density which drives a further ionization of the plume. Secondly, the
reduction of electron density is due to the lower contribution from the ionization of ambient
gas species due to the rarefied environment where the second plasma forms. The contribution
of electrons due to the ionization of ambient gas species is very uncertain, as well as the
amount of the ambient gas species in the plume. However, recent papers suggest that their
contribution is not negligible [63] and can be even dominant; in this case, the depletion of
ambient gas species inside the bubble formed by the first laser pulse, which can be estimated
of the order of 1/10 with respect to atmospheric conditions, results in a reduction of the
electron density and thus, considering the Saha-Eggert equation, in a larger ionization of the
plume. In both cases, the ionization is due to the fall of three-body recombination rate caused
by the drop of electrons in the plasma.
The effects produced by the different expansion dynamics of the plumes in the pre-
ablation orthogonal DP scheme, with respect to SP case, were analysed by Choi et al.[64]. In
their experiment, pre-ablation and ablation laser pulses with significantly reduced energy
were applied, so that the increase in ablated mass was negligible. In this condition, both the
larger ionization of the plume and its prolonged lifetime, where both the effects are related to
ambient gas rarefaction, were evidenced. At the same time, the results by Choi et al. suggest
that the contribution to LIBS enhancement due to dynamic effects is modest except than at
large acquisition time delays, leading to the conclusion that the primary cause of emission
enhancement in DP-LA (operated at larger laser energies) is the increase of atomized ablated
mass.
At this point, it remains to understand why the DP schemes produce an increase of crater
volume and a even higher enhancement of atomized ablated mass in the plume. Two main
hypotheses have been suggested in literature, already quoted in the early work by Maher and
Hall [4], i.e. the pre-heating of the target operated by the first laser pulse and the lower
shielding of the second laser pulse due to the environment rarefaction.
a) Target Heating Effects
This hypothesis supposes that the second laser pulse hits the target surface when it is still
hot and, for short interpulse delays, even melted, which results both in a sharp fall of target
reflectivity and in a reduction of the energy to be supplied to reach the evaporation point. In
the collinear scheme the heating of the target is evidently produced by the impact of the first
laser pulse, which obviously can not apply to the orthogonal scheme. However, it is possible
to imagine several other ways in which a LIP formation near a solid can heat the sample
surface [65]. The most direct mechanism is the absorption of the broadband emission
produced immediately after plasma formation, which can be very effective if there exists a
significant overlapping between the absorption bands of the target and the radiative emission
continuum. Other possible mechanisms are the target heating by the impact of the shock wave
and by the plasma itself, which persists above the surface for several hundreds of
microseconds.
Bogaerts et al. [66], modelled the Double Pulse Laser Ablation in case of collinear
configuration, taking into account the laser-solid interaction, the vapour plume expansion, the
plasma formation and the laser-plasma interaction. Since the model was one-dimensional, the
maximum interpulse delay considered was only 100 ns, after which the radial expansion of
the plume could not more be neglected. By comparing the DP case with the case of SP with
the same total energy (Cu target, =266 nm, = 5 ns, irradiance 0.5 GW cm
-2
per pulse),
Bogaerts et al. found that the surface temperature at the maximum is a bit lower in the DP
configuration, because of the lower irradiance of one laser pulse, but it remains high during a
longer time, because it rises again upon the second laser pulse. Also the calculated amount of
vaporized material is somewhat lower in the DP configuration, which is attributed to the
lower surface temperature. However, the only mass removal mechanism included in the
model is target vaporization, while melt splashing and phase explosion are not taken in
account. Noticing that evaporation depths are much lower than melt depths and even of
measured crater drilled depths, the authors suggest that melt effects and phase explosion can
bring a major contribution to the ablation process; such role could be enhanced in DP case
where the target remains for a longer time in the molten state.
The model of Bogaerts et al. shows also that at interpulse delay times larger than 70 ns
the target material solidifies again in between the two pulses, which suggests that the pre-
heating effects of the target become unimportant for delay times in the order of s. This
agrees with De Giacomo et al. [33], who noted that for interpulse delay times in the order of
s, the target surface has enough time to reach equilibrium.
Dissonant results were obtained by Krstulovic and Milosevic [49] which showed a 3-fold
drilling enhancement in case of ns-ns dual-pulse ablation of a titanium target in vacuum,
where the pre-heating of the target is the only hypothesis to be applicable. The maximum
enhancement was obtained for the interpulse delay of 370 ns, but a significant increase was
obtained for delay times up to 20 s.
In order to reduce the effects of target pre-heating in the DP scheme, Maher and Hall [4],
using two CO
2
lasers ( ~ 25 s) tried to misalign one of the laser beams, so that the two spots
in the surface did not overlap. When the spots on the target are tangent to one other, the
temperature increase caused by the first laser pulse in the point where the second pulse is
focussed is negligible. In fact, the thermal diffusion time is larger than the interpulse delay.
Moreover, the target heating caused by the interaction with the first plasma is strongly
reduced. At the same time, also in the case of non overlapping spots, the expansion of the pre-
ablation plume produces a depleted environment in front of the focusing spot of the second
laser pulse, so that the presumed effect due to air rarefaction, such as a decrease of laser
shielding, is still present. It means that in such geometry the pre-heating of the sample and the
environmental rarefaction effects produced by the first laser pulse are separated. The
experiment of Maher and Hall revealed that the damage on the target produced by non-
overlapping spots is similar to that produced by a collinear scheme, suggesting that the pre-
heating effect in determining DP outcomes is scarce.
In order to extend such results to the ns-ns case, we performed an experiment by using an
apparatus similar to that used by Maher et al., by using two Nd:YAG lasers in the
fundamental mode onto an Al target [67]. The energy of the first laser pulse was fixed to 90
mJ (fluence ~ 200 J cm
-2
), the interpulse delay to 1 s and the energy of the second pulse was
scanned in the range 3-125 mJ (fluence in the range 12-502 J cm
-2
). The enhancement of line
intensity, the amount of ablated atomized mass in the plume and their trend vs. laser fluence
obtained in the collinear and in the parallel non-collinear (non overlapping spots) schemes are
the same, strongly detaching from the values obtained in SP configuration. However, an
unexpected strong increase of crater drilling was found in the non-collinear configuration,
which was explained by a hydrodynamic draining out from the crater of the aerosol and of the
molten material, hindering its re-deposition (see Ref. [67]).
The above results again confirm that the effects due to the target pre-heating are scarce
unless, maybe, for short interpulse delays in the order of a few hundreds of nanoseconds.
b) Atmospheric Effects on Laser Shielding
Laser supported detonation and laser ablation
The works on the photoablation process begun in the seventies, driven by the need of
optimizing material processing techniques. According to the notation used in the literature,
laser-matter interaction is characterized by the figure of merit C
m
, defined as the ablation
pressure over the incident laser intensity or, which is the same, the momentum imparted to the
target over the total laser energy, quantifying the mechanical coupling between laser and
target [68].
During the photoablation process the momentum can be delivered to the target by the
vaporization of material, by the shock wave produced over the surface and finally by
spallation or boiling phenomena.
By the experimental measurement of C
m
parameter in vacuum, mainly by the ballistic
pendulum method, it was observed initially by Gregg and Thomas [69], that the mechanical
coupling C
m
shows a maximum in correspondence of a determined laser irradiance I
max
,
typically between 10
8
and 10
9
W cm
-2
, and then noticeably decreases at higher laser
irradiances. Such threshold is slightly higher than the laser irradiance I
p
at which plasma
ignition occurs and corresponds to the onset of a strong laser absorption in the plasma which
establishes a plasma-mediated photoablation regime.
The situation is more difficult to explain when laser ablation is performed in ambient gas
environment where, for adequate laser irradiances, the Laser Supported Detonation (LSD)
mechanism is ignited and a complex gasdynamic description must be included in the model
[70]. In this case, a hot high-pressure plasma, which is initially composed by target species, is
produced and drives a shock wave in the surrounding gas. When the laser irradiance is high
enough to ignite the LSD mechanism, the passage of the shock wave heats and ionizes a new
shell of ambient gas, allowing the laser absorption to occur in it until the plasma state is
reached. In turn, laser absorption feeds a further expansion of the shock wave, resulting in a
progressive propagation of the plasma plume in the surrounding gas [71].
A further problem arises for the description of LSD ignition in ns-regime laser pulses,
since the initiation time of the laser-supported regime is comparable with the pulse duration,
so that for a certain range of pulse durations and energies a stationary LSD regime cannot be
reached, and a transient regime should be considered. Xu et al. [72] estimated that the LSD
initiation time for a Nd:YAG 1064 nm, 10 ns laser pulse in the range of irradiance 10
8
-10
9
W
cm
-2
is of the order of 3 ns, though such value is strongly dependent on laser irradiance [73].
Although different mechanisms of laser absorption waves (i.e. blast waves) can occur at
irradiances lower than LSD threshold, it was shown by Hettche et al. [74] that the onset of
LSD wave corresponds to the beginning of a strong plasma shielding. This occurs because
most of the laser energy cannot pass through the high-absorbing region behind the SW front,
so that the shielding of the surface can be nearly complete. Therefore, the onset of LSD
corresponds to a maximum of impulse coupling C
m
parameter which tends to decrease at
large laser irradiances. The coincidence of the onset of LSD with strong plasma shielding was
observed more recently by shadowgraphy and laser drilling experiments by Gravel et al.[75],
showing that the strong laser absorption associated to LSD drastically reduces the ablation
rate. Moreover, it is expected that the variation of laser-target coupling due to the onset of
strong shielding also influences the mechanisms of mass removal and their thresholds. On
one hand, melt splashing is favoured by the formation of a hot high-pressure plasma, on the
other, phase explosion is hindered by the reduction of the effective irradiance on the target.
In a previous work [42], we studied the transitions between different mass removal
regimes varying the laser irradiance ( = 1064 nm, = 50 ns, 2.410
8
< Irradiance < 1.210
10

W cm
-2
), during the laser ablation in atmospheric air of an Al target. In a subsequent work
[43], the investigation was extended to the SP ablation in air at reduced pressures and to the
ablation in orthogonal DP pre-ablation configuration. The intensity of atomic and ionic lines
and the crater volumes were measured in the different experimental conditions; moreover, the
calculation of spatially-averaged temperature and electron density allowed also the estimation
of the atomized ablated mass in the plume (see Figure 17).

Figure 17. Drilled volume of the crater and atomized ablated mass vs. laser irradiance used. Taken from
Ref.[43]
By looking at the data obtained in SP configuration at atmospheric pressure, the trends of
line intensities (not reported here), atomized ablated mass and crater volume vs. laser
irradiance evidence a significant change of regime at ~8-910
8
W cm
-2
. In a following work
[44], where a shorter laser pulse ( = 1064 nm, = 32 ns) was focused on an Al target, the
discontinuity was found at a slightly lower irradiance value of ~710
8
W cm
-2
. At lower
irradiances, line intensities, atomized mass and crater volume increases with increasing laser
irradiance; on the contrary, above the threshold they markedly fall down, evidencing a less
efficient ablation process. The observed discontinuity indicates that a transition occurs
between a weak laser absorption in the plasma, beginning at the plasma ignition threshold,
and a strong plasma shielding, where the larger part of the pulse energy is absorbed in the
plume by inverse Bremsstrahlung processes or reflected at its surface. These latter effects
result in a significant reduction of ablated mass.
A similar discontinuity in crater drilling, although at larger irradiance values (~ 2.5 GW
cm
-2
), was found by Gravel et al. [75], (brass target, = 1064 nm, = 22 ns) who also
showed by shadowgraphic imaging that the threshold is associated to the onset of a Laser
Supported wave mechanism.
The thresholds obtained in our works [42-44] agree with the power density corresponding
to the maximum impulse-coupling coefficient found by Xu et al. [72], calculated using the
ballistic pendulum method in the ablation of an aluminium target by a 10 ns 1064 nm laser
pulse. Such threshold was again successfully modelled by considering the occurrence of LSD
wave with non-negligible initiation times.
The morphology of the craters, reported in Ref.[42], suggests that the onset of strong
shielding produces also a change in the mechanism of mass removal from the target. For
irradiance values lower than LSD threshold, melt effects on the surface were negligible and
phase explosion was the only mechanism able to justify the ablation rate (24 m per pulse)
found experimentally. This is possible because almost all the laser energy reaches the surface
and is able to heat the target surface up to the critical temperature for phase explosion onset.
Despite the extensive discussion that appeared in literature about the irradiance threshold
of phase explosion, where often much larger threshold values were proposed, striking
evidence of phase explosion occurrence in metals was found at values similar to the one
obtained here. For example, Porneala and Willis [76] (Al target, = 1064 nm, = 5 ns),
found evidence of phase explosion both by measuring a jump in the ablation rate and by
observing a violent ejection of droplets with a shadowgraphic technique, at 1 GW cm
-2
.
Differently, at laser irradiances above the LSD threshold, melt displacement and
expulsion progressively become more relevant, as testified by the increase of crater rims
formed by re-solidified material and by melt droplets splashed on the target surface around
the crater. It is likely that the motion of molten material is the effect of a lateral pressure
gradient induced by the high-pressure plasma above the target surface. Phase explosion could
be inhibited or become less efficient since, in this range, the ablation rate strongly decreases,
despite the increasing melt displacement and expulsion. It is then possible that above the LSD
threshold the main mechanisms of mass removal are the melt splashing, which however
produces mostly liquid droplets, and vaporization, which produces atomized mass in the
plasma.
Concluding the paragraph, we want to remark that the occurrence of Laser Supported
Detonation mechanism during SP laser ablation in ambient gas strongly affects the process,
reducing the mechanical coupling with the target and therefore the drilling and the LIBS
signal on one hand, and modifying the mass removal mechanism inhibiting the phase
explosion, on the other hand.
Laser supported detonation wave and ambient gas pressure
Several parameters affect the occurrence of LSD during laser ablation, mainly the target
properties and the ambient gas pressure. Maher et al. [77] noted that the laser ablation of
samples that absorb much of the incident laser energy, such as SiO
2
and Lucite, induces the
formation of blast waves instead of LSD waves, resulting in a much lower plasma absorption.
According to the authors, this occurs because of the large amount of vaporized matter that
pushes and heats the ambient air, so that the absorption blast wave moves perpendicular to the
target surface (note that, on the contrary, LSD moves toward the laser beam, an effect which
is clearly observable for non normal incidence angles).
Also the gas pressure affects both the LSD thresholds and their initiation times. Such
behaviour is comprehensible, in view of the fact that the low air pressure corresponds to low-
density gas, which makes less effective the absorption from air atoms and therefore the
feeding of LSD mechanism. Maher et al. [77] calculated the LSD threshold varying the air
pressures for different targets, showing that, for metal targets, the LSD ignition is more
difficult at pressures lower than the atmospheric, resulting in a higher ignition threshold. This
is in accordance with the trends of crater volume and atomized ablated matter obtained at
reduced air pressures plotted in Figure 17, showing that the irradiance threshold of strong
shielding, resulting in the discontinuity observed in the range 710
8
-210
9
W cm
-2
, slightly
increases when air pressure decreases. It is also evident from Figure 17 that the effectiveness
of plasma shielding similarly decreases with air pressure, where the discontinuity in the plot
is scarcely visible for pressures lower than 300 torr. As a result, the trends of crater volume,
atomized matter in the plume, and plasma line intensities (not shown here) have a monotone
increasing trend at 100 torr pressure.
These results agree with the observation that, in single pulse LIBS, the emission and the
ablation rate are maximum when the buffer gas density is lower than the atmospheric one, as
shown in Figure 11 and found experimentally by Sdorra and Niemax [78] and by Iida [79].
The same result can be obtained in Figure 17 by choosing a laser irradiance above the LSD
threshold and by progressively reducing the air pressure. The key mechanism that must be
considered is again the laser shielding operated by the plasma, since a high buffer gas density
favours the breakdown-cascade process, the formation of free electrons in the plasma and the
absorption of laser radiation.
It should also be noted that for irradiances lower than LSD threshold the values in Figure
17 are coincident in all the experimental configurations. This suggests a picture of laser
ablation in 2-steps

Step 1. From the beginning of the laser pulse to the time where the plasma electron
density reaches a critical value, a weak laser absorption occurs in the plume mainly by IB
processes. The ablation efficiency seems not to be severely affected by ambient gas density
since the ablation rate and the plasma mass are the same in SP and in DP configurations. This
agrees with the hypothesis that, at the beginning of laser-target interaction, the plume freely
expands in ambient gas without being affected by background gas properties [44,80];
however, the progressive laser absorption in the plume increases the expansion speed of the
plume and produces a pile-up of vapour atoms at the vapour-background gas interface, the so-
called snowplough effect, which forms a shock wave. The following expansion of the plume
and growing rate of electron density is progressively affected by the background density.

Step 2. During the trailing part of laser pulse the electron density reaches a critical value
producing avalanche ionization and electron cascade, driving a much stronger laser pulse
absorption and reflection, and causing a drop of the ablation efficiency. The laser absorption
feeds the shock wave expansion so that a Laser Supported wave mechanism begins.
In this picture, if laser irradiance is lower than LSD threshold, only Step 1 occurs, and
Step 2 is never reached, a condition which explains the similarities of results obtained at
different gas pressures in Figure 17.
Laser absorption in double pulse configuration
By comparing the plots in Figure 17, it is evident the strong similarity between the data
obtained in SP at 100 torr air pressures and those obtained in DP configuration, suggesting
that DP effects are mainly related to atmospheric effects. At this point, it is important to give
a picture of the environmental situation found by the second laser pulse when it reaches the
target. When the first laser pulse ends, the LSD mechanism clearly stops and a blast wave
moves in the environment, progressively dissipating its energy for the expansion and for the
heating-ionization of the ambient gas. As time elapses, the shock wave, initially in contact
with the plasma region, detaches from it and continues to expand, while the plume stops at a
radius of the order of 1 mm, depending on the experimental conditions. When all the
available energy has been dissipated in the expansion and in the excitation/ionization
processes, the pressure of the internal region equalizes with the external one and the shock
wave becomes a sonic wave. At times larger than the laser pulse width, the situation can be
well described by the point strong explosion theory, formulated by Sedov [81,82], which
describes the effect of a large amount of energy delivered in a small volume of a
homogeneous atmosphere during a short time interval. According to the theory, during the
expansion of the shock wave produced by the sudden release of laser energy, most of the
mass of the ambient gas is compressed in a thin layer near its front surface. Therefore, Sedov
theory predicts that the shock wave front is characterised by a large mass density pileup,
while beyond it the density steeply drops down to values much lower than that in the
unperturbed medium.
Unfortunately, the Sedov self-similar solution, while it can be effectively used to describe
the shock wave radius and velocity, and the profiles of temperature and gas density in the
region near the shock front, is unable to give quantitative and reliable values of such
parameters in the core of the plasma. In fact, the basic theory of strong point explosion
neglects internal heat transfer phenomena such as conduction, radiation as well as excitation
and ionization of the gas, and predicts an infinite temperature and a null density in the core of
the plume. To correct this problem, more sophisticated models [83,84] accounting for the
internal heat transport have been developed. These models predict a finite temperature in the
core of the plume. Moreover, considering the ideal gas state equation
T
P

, a non-zero gas
density is also predicted.

Figure 18. Qualitative sketch of the profiles of pressure, temperature and gas density along the pre-
ablation plume and shock wave. Taken from Ref. [56]
A qualitative sketch of the thermodynamic profiles in the air spark region is reported in
Figure 18, where the steep increase of temperature at the plume border leads to an abrupt
decrease of gas density in the core. The profiles plotted in the figure can also qualitatively
represent the situation produced by the ablation of a solid target in air, where evidently the
plasma expands from the target surface.
The density profile (accounting for both the air and plume atoms) is consistent with the
predictions and results of the numerical model by Bogaerts and Chen [85], although it is
limited only to the early hundreds of nanoseconds after the laser ablation.
The gas rarefaction in the core of the plume can be evaluated from the ideal gas relation:

plume
c atmospheri
c atmospheri
plume
c atmospheri
plume
T
T
P
P
n
n
=
(2)
According to strong explosion theory, the pressure reaches a maximum P
SW
at the SW
front and then rapidly decreases behind it toward a value P
plume
0.365 P
SW
(this value is
substantially independent on the blast wave energy down to a SW velocity around Mach 1.5).
The corrections to the Sedov model accounting for the internal heat transfer processes do not
bring significant variations in pressure profiles, showing at most a slight decrease of the value
of P
plume
; this can be also perceived from the good agreement of the measured shock wave
radius with the predicted one, since the driving force of the shock is essentially the pressure
behind it. Moreover, the SW front pressure P
SW
and the unperturbed pressure P
atmospheric
are
linked by the relation

1
) 1 2 (
2
+
+
=
M P
P
c atmospheri
SW
(3)
where M is the SW Mach number and =1.4 is the adiabatic coefficient of air [81].
Calculating the Mach number by fitting the shock radius derived from Figure 16, we obtain
M~2.2 and then P
SW
~5.5P
atmospheric
.
Finally, substituting this value in Eq. (2) and considering T
atmospheric
=300 K and
T
plume
~15,000 K (a reasonable value of the spark temperature) we obtain n
plume
/n
atomspheric
=
0.04 [56]. By considering the images in Figure 7, it is possible to make the same calculations,
as in Ref.[86], obtaining the value n
plume
/n
atomspheric
= 0.07. Such values suggest that the gas
density inside the first laser plasma is similar to the density of the gas at room temperature
and at 50 torr pressure.
At this point, it becomes immediate to observe that the occurrence of LSD mechanism
becomes more difficult and less efficient for the second laser pulse, since laser ablation
occurs in rarefied gas, resulting in a much lower plasma shielding of the target. Then, the DP-
LA process is to be compared to a SP-LA at lower air pressure, around 50-100 torr, which
explains the similarities of the trends in Figure 17 between DP and SP low pressures
configurations. In this way, the DP configuration avoids the onset or, at least, reduces the
effects of LSD wave, in particular the strong plasma shielding, resulting in a much larger
laser-target coupling and mass removal. In some sense, the first laser pulse in DP-LA has the
effect of producing a sort of low-pressure chamber, which optimizes the laser-target coupling,
but without the experimental complications inherent to the use of such apparatus.
This mechanism is effective if the interpulse delay is larger than ~200 ns [29], when the
capability of the first LIP to absorb the second laser pulse becomes unimportant and the
rarefaction effects of ambient gas become dominant. This mechanism thus agrees with the
range of interpulse delays suitable for generating DP-LA effects (see Figure 4), which are of
the order of the plasma decay time.
The mechanism proposed also allows the modelling of the influence of the distance of the
pre-spark from the target surface. If such distance is large (d>1mm in Figure 13-15), so that
only SW1 arrives on the target, this leads initially to a density growth at the surfacegas
boundary, but successively the wave reflection leads to a modest gas rarefaction, resulting in
a modest line intensity enhancement.
However, if the hot plasma region produced by the pre-ablation pulse is able to reach the
target surface (d<1 mm), the rarefaction produced at the surface boundary becomes much
stronger. In that case, the pre-ablation configuration reduces to that of collinear scheme, the
ablation process by the second pulse is very efficient and the rapid expansion of the new
resulting plume in a rarefied medium leads to a large and dense plasma region.
Finally, this mechanism agrees with the observed different expansion dynamics of DP
plasmas generating a strong ionization at early times due to fast expansion and a more steady
situation at longer times due to the confinement of SW1.
Mass removal mechanisms in DP schemes
The morphology of craters, observed and discussed in Ref.[43], suggests that the DP
scheme could also induce a change in the mass removal mechanism from the target. The
works in this field almost exclusively refer to metal targets, from which some indication on
the change of mass removal mechanisms occurring in DP scheme can be extracted. In case of
metals, the shape and dimensions of the craters indicate that the strong laser shielding at
atmospheric air pressure inhibits or makes less efficient the phase explosion mechanism in SP
case [42]. The situation can be different in DP case where phase explosion could be triggered
by the large amount of laser energy reaching the target surface. Such hypothesis agrees with
the works by Colao et al. [19] and by Mao et al. [29] who hypothesize the occurrence of
phase explosion in DP laser ablation. The change from vaporization to phase explosion by
applying SP and DP schemes could also explain the relation between DP effects and thermal
diffusivity, shown in Figure 10. In fact, supposing that in SP the pure vaporization
mechanism is predominant, being it a surface process, the metals with lower thermal
diffusivity are favoured in removing material from the target, because of the higher surface
temperature reached. Moreover, in SP (where the effective irradiance is low because of the
laser shielding) the threshold of the explosive-boiling regime can be more easily reached for
metals with lower thermal diffusivity, which dissipate less heating in the interior of the target
and for which a subsurface heating might be still possible. Both these effects concur to draw a
picture where, other material properties being neglected, in SP configuration a larger ablation
of matter is favoured for the lower thermal diffusivity metals. On the other side, in the DP
configuration, where a much larger energy reaches the target, a different situation can occur,
where all the targets probably reach the phase explosion threshold. Here, the metals with
higher thermal diffusivity are favoured in expelling material because of the larger depth of the
molten pool, in a situation opposite to that described for SP. The above considerations would
corroborate, at least qualitatively, the trend obtained in Figure 10.
The situation can be very different for non-metal targets, such as insulators or polymers,
which are characterized by very different thermal, electronic and optical properties. In this
case, the laser ablation is a volumetric heating process, where the temperature distribution in
the target is mainly determined by the laser absorption length rather than by the thermal
diffusion. This leads to significant differences in the ablation process, where other phenomena
(i.e. the spallation of the target and the absence of LSD wave) can occur and should be taken
into account for modelling purposes. Such differences results also in DP effects often
dissimilar to those obtained for metals and often in lower emission and ablation rate
enhancements (e.g. those obtained for the analysis of soils, rock and pressed pellets). It is
therefore evident that a deeper understanding of DP-LA (and even SP-LA) of such targets still
needs more and dedicated works.
To conclude, it is evident that the atmospheric effects are able to explain most of the
effects observed in ns-ns DP configurations, although the pre-heating of the target and the re-
heating of the plume can play a significant role at interpulse delays of the order of a few
hundreds of nanoseconds. A theoretical model of DP laser ablation, reliable for interpulse
delays of the order of microseconds and including the different mass removal mechanisms
(vaporization, melt displacement, melt splashing, phase explosion), although very difficult to
build, would be however very useful to confirm (or reject) the validity of the mechanisms
suggested by the experimental results, and summarized above.
4. DOUBLE PULSE WITH SHORT AND ULTRASHORT
LASER PULSES: EFFECTS AND MECHANISMS
Some authors investigated the effects induced by the use of short and ultrashort laser
pulses, separated by time delays going from hundreds of femtoseconds up to hundreds of
microseconds. Because of the different nature of laser-target interaction and for the different
mechanisms underlying the DP effects, such results will not be treated in detail in the present
chapter. However, we will try to provide a concise summary of the phenomena occurring, as
emerging from the literature, with the aim of delineating a general framework of results and
mechanisms. For a more complete list of results and related works, the reader could refer to
Ref.[1].
Two main reasons drove the studies of DP-LA with short and ultrashort pulses, i.e. the
improvement of quality and control of micromachining of materials, avoiding the saturation
of the ablation rate and the formation of recast material around the crater at the higher
fluences [87], and the enhancement of the emission of a fs-plasma to be used for LIBS
applications [12,88-92]. Besides, other possible applications emerged in literature as the
enhancement of ion yield [93], the exclusion of air breakdown [94], the enhancement of the
performance of Pulsed Laser Deposition techniques [95].
Both collinear and orthogonal beams configurations were tested, where most of the
applications, except the enhancement of LIBS emission, involve the double-ablation of the
target and then the former scheme.
Several factors make at the moment very difficult to delineate a coherent and complete
framework of the produced effects and of the underlying mechanisms associated to the
collinear configuration. First of all, the mechanisms of mass removal which occur when a
short/ultrashort laser pulse is focussed on a target surface are still unclear, where highly non-
equilibrium processes need still to be understood. Moreover, it was shown that different
ablation regimes occur depending on the laser fluence, evidently associated to different mass
removal mechanisms, so that the effects produced by the DP-LA depends on the laser
fluences used in the experiment. Finally, the still small number of publications on the subject,
where different and often not comparable experimental conditions are used, makes it very
difficult to draw an unified scheme of knowledge. Roberts et al.[96] presented a two-
temperature ablation model, predicting the time dependence of electron and lattice
temperatures in the target, and compared the outcome of the model with the ablation rates on
a silver foil obtained using single and double 130 fs laser pulses; laser fluence spanned over a
range of three orders of magnitude up to 900 J cm
-2
and pulses separation in the range from
0.1 ps up to 3.4 ns. The results allowed the authors to sketch a rough scheme of the
mechanisms occurring at different interpulse delays in collinear geometry, which agrees
with the results of other published works. In their scheme several timescales should be taken
into account for understanding DP-LA process, i.e. the electron-phonon relaxation time
ei
,
the heat diffusion time
D
and the time
T
needed for the ejecta or the plasma produced by the
first pulse to interfere with the second pulse.
For <
ei
, when the second pulse is fired the energy of the first pulse has not been still
transferred to the lattice of the target and no melting has been produced on the surface.
Therefore, two pulses behave as a single pulse of fluence corresponding to the sum of the
fluences. A rough estimate of crater depth d at different fluences F can be calculated using the
relation
) / ln(
th
F F K d =
[97], where K is a constant and F
th
is a threshold fluence; however,
since the ablation rate has a non-linear dependence on the laser fluence, due to the onset of
different mass removal mechanisms at different thresholds, the increase of crater depth can be
much larger than that estimated in such a way [96]. The value of
ei
calculated by Roberts et
al. is in the range 1-10 ps depending on the laser fluence. The results obtained by Semerok
and Dotouquet [88] (Al and Cu target, = 50 fs, 160 fs, 675 fs) agree with the previous
scheme, showing that for an interpulse delay smaller than 1 ps, the craters produced in the DP
scheme (E = 2x20 J) were almost two times deeper than those produced by a SP (E = 20 J);
the result does not depend on the duration of the laser pulse.
For >
ei
, the ablation rate of DP falls with increasing the interpulse delay. The main
reasons are the lower temperature of the target surface and the absorption/scattering of laser
radiation by ejecta or by the plasma. The onset and the relevance of such phenomena depend
on the heat diffusion time
D
and on the time
T
needed for the ejecta or the plasma induced
by the first pulse to interfere with the second pulse. Roberts et al. [96] showed that such
decrease begins at interpulse values depending on the laser fluence, in a range between 10 ps
at low fluences and 0.1 ps at large fluences. Moreover, the authors evidenced that a
completely different behaviour is obtained at fluences larger than 16 J cm
-2
, probably because
of the onset of a different mass removal mechanism. A similar decreasing trend was also
found by Semerok and Dutouquet [88] (Al and Cu target, = 50 fs, 160 fs, 675 fs), in the
range 1 < < 10 ps, and by Chowdhury et al. [98] (fused silica target, =90 fs), in the range
0.1 < < 10 ps. In all the above works the ablation rate obtained at the lowest point was
even lower than that obtained in SP scheme.
Chowdhury et al. [98] measured also the transmission of the second pulse varying .
They showed that the observed decrease of ablation rate is due to the absorption of the laser
pulse by the plasma in front of the target. A similar conclusion was reached by Semerok and
Dutouquet [88], who imaged the plasma plume produced in this temporal range with an ICCD
camera, finding a much higher intensity and a higher reproducibility of the plasma emission
in DP scheme, where the intensity rises with increasing the interpulse delay. The authors
argued that the effect was produced by the re-heating of the plume by the absorption of the
second laser pulse. Such plasma re-heating, which is optimal for ~100-200 ps according to
Ref.[88], can be fruitfully used for fs-LIBS applications which are known to suffer from a
low plasma emission.
An interesting phenomenon observed in this interpulse delay range is also the
enhancement of the low-energy ion yield, which can be fruitfully utilized for ion implantation
in microelectronics and optoelectronics. Koudoumas et al. [93] (Si target,
1
= 800 nm,
1
=
180 fs;
2
= 248 nm,
2
= 0.5 ps) showed that the utilization of two ultrashort pulses with and
an interpulse delay larger than ~1 ps results in the enhancement of the production of Si
+
ions
and in the increase of their thermal energy. The authors suggest that the effect is associated to
the creation of a melted zone exhibiting modified optical coupling properties, where the
second pulse induces a much higher temperature in a thinner surface layer.
Many papers concerning DP-approach are devoted to the enhancement of fs-LIBS
emission. The fs-LIBS has the potential advantage of reducing the matrix effect of the
technique and to assure a better stoichiometry of the ablation process. However, it often
results in a low sensitivity caused by the lower temperature of the plasma and by its faster
decay. In order to overcome these drawbacks some authors probed a double pulse approach
where a combination of ns and fs pulses are used. Scaffidi et al. [12] (Fe target, = 800 nm,
= 100 fs; = 1064 nm, = 5 ns) reported a study where a combination of fs-ns pulses in
collinear scheme was used; they found an enhancement of atomic emission at different focus
positions, suggesting that different reasons, i.e. plasma-plasma coupling and reduction of air
density during the second breakdown event, are the primary causes of such effects. Other
experiments devoted to fs-LIBS emission enhancement were performed in the orthogonal
configuration, where the processes of laser ablation and plasma re-heating are temporally well
separated. Scaffidi et al. [91] (Al and Cu target, = 800 nm, = 100 fs; = 1064 nm, = 7
ns) probed different configurations where a fs or ns pulse is used for the ablation and the
other is used for re-heating the plasma or for inducing a pre-spark in front of the target. The
combination where the fs-plasma is re-heated by a ns pulse shows the largest emission
enhancement (~30fold for the Cu I 501 nm line and ~80 for the Al I 396 nm line) at an
interpulse delay of 5 s. Significant line enhancements were obtained by Santagata et al. [92]
(Ti target,
1
= 527 nm,
1
= 250 fs;
2
= 532 nm,
2
= 7 ns) by using a similar configuration
where a fs-plasma is re-heated by a ns pulse; in this case, however, the optimal interpulse
delay, depending on the fs pulse energy, is noticeably larger than that found by Scaffidi et al.
( = 500 s for E
pulse
= 0.8 mJ and = 250 s for E
pulse
= 3 mJ).
On the other hand, the combination where the fs pulse induces a pre-spark in front of the
target and the ns pulse ablates the surface shows a modest line enhancement which appears
associated to the reduction of air density [90] and then substantially similar to the effects
already discussed in the ns-ns orthogonal scheme.
PERSPECTIVES AND FUTURE DEVELOPMENT
The large number of papers dealing with DP-LA recently appeared in literature attests the
increasing interest on the subject, motivated by its fruitful usage in many applications, among
which laser micro-sampling and laser micro-drilling.
The experimental and theoretical results reported in the present chapter allow for a quite
clear picture of the mechanisms underlying the process of ns-ns Double-Pulse laser ablation
of solid targets. However, the quantitative prediction of the enhancement in ablation rates and
optical emissions, as well as the theoretical determination of the thresholds observed in
varying the laser pulse properties and the environmental characteristics still call for a reliable
theoretical model of DP laser ablation, valid for interpulse delays of the order of
microseconds and including all the different mass removal mechanisms (vaporization, melt
displacement, melt splashing, phase explosion, spallation).
Most of the results reported in this chapter concerns the LA of metals in ambient gas, to
which prevailingly the above considerations and modelling refer to.
The utilization of the DP scheme for the ablation of solid targets immersed in liquid is
also very promising for many applications, going from analytical analyses to nanoparticles
formation; however, for the different characteristics of the LA process, the issue is not treated
here, so that we suggest the interested reader to refer to other specialized publications [14,15].
The understanding of DP-LA of non-metals targets still needs accurate and dedicated
works, because of the substantial differences of laser ablation processes, which result also in
dissimilarities in DP effects. More works are also needed in the case of DP-LA with short-
ultrashort pulses, for the still scarce knowledge on the LA process obtained with fs and ps
lasers.
ACKNOWLEDGMENTS
The authors would like to acknowledge Elsevier B.V. for the use of excerpts and figures
published in Spectrochimica Acta Part B. The authors acknowledge also IOP sciences for the
use of excerpts taken from Journal of Physics D: Applied Physics.
REFERENCES
[1] Babushok, VI; De Lucia jr, FC; Gottfried, JL; Munson, CA; Miziolek, AW.
Spectrochim. Acta Part B, 2006, 61, 999-1014.
[2] Piepmeier, EH; Malmstadt, HV. Anal. Chem., 1969, 41, 700-707.
[3] Scott, RH; Strasheim, A. Spectrochim. Acta Part B, 1970, 25, 311-332.
[4] Maher, WE; Hall, RB. J. Appl. Phys., 1976, 47, 2486-2493.
[5] Arumov, GP; Bukharov, AYu; Kamenskaya, OV; Kotyanin, SYu; Krivoshchekov, VA;
Lyash, AN; Nekhaenko, VA; Pershin, SM; Yuzgin, AV. Sov. Tech. Phys. Lett, 1987,
13, 362-363.
[6] Pershin, SM. Sov. J. Quantum Electron, 1989, 19, 1618-1619.
[7] Pershin, SM; Bukharov, AYu. Sov. J. Quantum Electron, 1992, 22, 405-407.
[8] Nyga, R; Neu, W. Optics Letters, 1993, 18, 747-749.
[9] Pichahchy, AE; Cremers, DA; Ferris, MJ. Spectrochim. Acta Part B, 1997, 52, 25-39.
[10] Burakov, VS; Tarasenko, NV; Butsen, AV; Rozantsev, VA; Nedelko, MI. Eur. Phys.
J. Appl. Phys., 2005, 30, 107-112.
[11] Kuwako, A; Uchida, Y; Maeda, K. Appl. Optics, 2003, 42, 6052-6056.
[12] Scaffidi, J; Pearman, W; Carter, JC; Angel, SM. Appl. Spectrosc, 2006, 60, 65-71.
[13] Semerok, A; Dutouquet, C. Thin Solid Films, 2004, 453-454, 501-505.
[14] Casavola, A; De Giacomo, A; Dell'Aglio, M; Taccogna, F; Colonna, G; De Pascale, O;
Longo, S. Spectrochim. Acta Part B, 2005, 60, 975-985.
[15] De Giacomo, A; Dell'Aglio, M; De Pascaleb, O; Capitelli, M. Spectrochim. Acta Part
B, 2007, 62, 721-738.
[16] Corsi, M; Cristoforetti, G; Hidalgo, M; Legnaioli, S; Palleschi, V; Salvetti, A; Tognoni,
E; Vallebona, C. Appl. Geochem, 2006, 21, 748-755.
[17] Bertolini, A; Carelli, G; Francesconi, F; Francesconi, M; Marchesini, L; Marsili, P;
Sorrentino, F; Cristoforetti, G; Legnaioli, S; Palleschi, V; Pardini, L; Salvetti, A. Anal.
Bioanal. Chem., 2006, 385, 240-247.
[18] St-Onge, L; Detalle, V; Sabsabi, M. Spectrochim. Acta Part B, 2002, 57, 121-135.
[19] Colao, F; Lazic, V; Fantoni, R; Pershin, S. Spectrochim. Acta Part B, 2002, 57, 1167-
1179.
[20] St-Onge, L; Sabsabi, M; Cielo, P. Spectrochim. Acta Part B, 1998, 53, 407-415.
[21] Gautier, C; Fichet, P; Menut, D; Dubessy, J; Spectrochim. Acta Part B, 2006, 61, 210-
219.
[22] Sattmann, R; Sturm, V; Noll, R. J. Appl. Phys. D, 1995, 28, 2181-2187.
[23] Piscitelli, V; Martinez, MA; Fernandez, C; Gonzalez, JJ; Mao, XL; Russo, RE.
[24] Cristoforetti, G; Legnaioli, S; Palleschi, V; Salvetti, A; Tognoni, E, Appl. Phys. B,
2005, 80, 559-568.
[25] Bredice, F; Borges, FO; Sobral, H; Villagran-Muniz, M; Di Rocco, HO; Cristoforetti,
G; Legnaioli, S; Palleschi, V; Pardini, L; Salvetti, A; Tognoni, E. Spectrochim. Acta
Part B, 2006, 61, 1294-1303.
[26] Sturm, V; Vrenegor, J; Noll, R; Hemmerlin, M. J. Anal. At. Spectrom, 2004, 19, 451-
456.
[27] Ismail, MA; Cristoforetti, G; Legnaioli, S; Pardini, L; Palleschi, V; Salvetti, A;
Tognoni, E; Harith, MA. Anal Bioanal Chem., 2006, 385, 316-325.
[28] Cristoforetti, G; Legnaioli, S; Palleschi, V; Salvetti, A; Tognoni, E. Spectrochim. Acta
Part B, 2008, 63, 312-323.
[29] Mao, X; Zeng, X; Wen, SB; Russo, RE. Spectrochim. Acta Part B, 2005, 60, 960-967.
[30] Cristoforetti, G; Legnaioli, S; Palleschi, V; Salvetti, A; Tognoni, E. Spectrochim. Acta
Part B, 2004, 59, 1907-1917.
[31] Benedetti, PA; Cristoforetti, G; Legnaioli, S; Palleschi, V; Pardini, L; Salvetti, A;
Tognoni, E. Spectrochim. Acta Part B, 2005, 60,1392-1401.
[32] Gautier, C; Fichet, P; Menut, D; Lacour, JL; LHermite, D; Dubessy, J; Spectrochim.
Acta Part B, 2005, 60, 792-804.
[33] De Giacomo, A; Dell'Aglio, M; Bruno, D; Gaudiuso, R; De Pascale, O. Spectrochim.
Acta Part B, 2008, 63, 805-816.
[34] Corsi, M; Cristoforetti, G; Giuffrida, M; Hidalgo, M; Legnaioli, S; Palleschi, V;
Salvetti, A; Tognoni, E; Vallebona C. Spectrochim. Acta Part B, 2004, 59, 723-735.
[35] Noll, R; Sattmann, R; Sturm, V; Winkelmann S. J. Anal. At. Spectrom, 2004, 19, 419-
428.
[36] Caneve, L; Colao, F; Fantoni, R; Spizzichino, V. Appl. Phys. A, 2006, 85, 151-157.
[37] Bergmann, HW. Appl. Surf. Sci., 1996, 96-98, 287-295.
[38] Gehlen, CD; Roth, P; Aydin, ; Wiens, E; Noll, R. Spectrochim. Acta Part B, 2008, 63,
1072-1076.
[39] Wang, XD; Michalowski, A; Walter, D; Sommer, S; Kraus, M; Liu, JS; Dausinger, F.
Optics & Laser Technology, 2009, 41, 148-153.
[40] Forsman, AC; Banks, PS; Perry, MD; Campbell, EM; Dodell, AL; Armas, MS; J. Appl.
Phys., 2005, 98, 033302.
[41] Bulgakova, NM; Bulgakov, AV. Appl. Phys., A: Solid Surf. 2001, 73, 199-208.
[42] Cristoforetti, G; Legnaioli, S; Palleschi, V; Tognoni, E; Benedetti, PA. J. Anal. At.
Spectrom, 2008, 23, 1518-1528.
[43] Cristoforetti, G. Spectrochim. Acta Part B, 2009, 64, 26-34.
[44] Cristoforetti, G; Lorenzetti, G; Benedetti, PA; Tognoni, E; Legnaioli, S; Palleschi, V. J.
Phys. D: Appl. Phys., 2009, 42, 225207.
[45] Gonzalez, J; Liu, C; Yoo, J; Mao, X; Russo, RE. Spectrochim. Acta Part B, 2005, 60,
27-31.
[46] Lbe, A; Vrenegor, J; Fleige, R; Sturm, V; Noll, R. Anal. Bioanal. Chem., 2006, 385,
326-332.
[47] Peter, L; Noll, R. Appl. Phys. B, 2007, 86, 159-167.
[48] Krstulovic, N; Cutic, N; Milosevic, S. Spectrochim. Acta Part B, 2009, 64, 271-277.
[49] Krstulovic, N; Milosevic, N. Appl. Surf. Sci., 2010, 256, 4142-4148.
[50] Stratis, DN; Eland, KL; Angel, SM. Appl. Spectrosc, 2000, 54, 1270-1274.
[51] Stratis, DN; Eland, KL; Angel, SM. Appl. Spectrosc, 2000, 54, 1719-1726.
[52] Stratis, DN; Eland, KL; Angel, SM. Appl. Spectrosc., 2001, 55, 1297-1303.
[53] Angel, SM; Stratis, DN; Eland, KL; Lai, T; Berg, MA; Gold, DM. Fresenius J. Anal.
Chem., 2001, 369, 320-327.
[54] Gautier, C; Fichet, P; Menut, D; Lacour, JL; LHermite, D; Dubessy, J. Spectrochim.
Acta Part B, 2005, 60, 265-276.
[55] Lindner, H; Koch, J; Niemax, K. Anal. Chem., 2005, 77, 7528-7533.
[56] Cristoforetti, G; Legnaioli, S; Pardini, L; Palleschi, V; Salvetti, A; Tognoni, E.
[57] Uebbing, J; Brust, J; Sdorra, W; Leis, F; Niemax, K. Appl. Spectrosc, 1991, 45, 1419-
1423.
[58] Gautier, C; Fichet, P; Menut, D; Lacour, JL; LHermite, D; Dubessy, J. Spectrochim.
Acta Part B, 2004, 59, 975-986.
[59] Chan, SY; Cheung, NH. Anal. Chem., 2000, 72, 2087-2092.
[60] Lui, SL; Cheung, NH. Appl. Phys. Lett, 2002, 81, 5114-5116.
[61] Lui, SL; Cheung, NH. Spectrochim. Acta Part B, 2003, 58, 1613-1623.
[62] Yip, WL; Cheung, NH. Spectrochim. Acta Part B, 2009, 64, 315-322.
[63] Cristoforetti, G; Lorenzetti, G; Legnaioli, S; Palleschi, V. Spectrochim. Acta Part B,
2010, 65, 787, 796.
[64] Choi, SC; Oh, MK; Lee, Y; Nam, S; Ko, DK; Lee, J. Spectrochim. Acta Part B, 2009,
64, 427-435.
[65] Scaffidi, J; Angel, SM; Cremers, DA. Anal. Chem., 2006, 78, 24-32.
[66] Bogaerts, A; Chen, Z; Autrique, D. Spectrochim. Acta Part B, 2008, 63, 746-754.
[67] Cristoforetti, G; Legnaioli, S; Palleschi, V; Tognoni, E; Benedetti, PA. Appl. Phys. A,
2010, 98, 219-225.
[68] Phipps, CR; Turner, TP; Harrison, RF; York, GW; Osborne, WZ; Anderson, GK;
Corlis, XF; Haynes, LC; Steele, HS; Spicochi, KC. J. Appl. Phys., 1988, 64, 1083-1096.
[69] Gregg, DW; Thomas, SJ. J. Appl. Phys., 1966, 37, 2787-2789.
[70] Pirri, AN. Phys. Fluids, 1973, 16, 1435-1440.
[71] Root, RG. Modeling of post-breakdown phenomena,, in: J; Radziemski, A. Cremers,
(Eds.), Laser-induced Plasmas and Applications, Marcel Dekker, New York, 1989, 69-
103.
[72] Xu, B; Wang, Q; Zhang, X; Zhao, S; Xia, Y; Mei, L; Wang, X; Wang, G. Appl. Phys.
B, 1993, 57, 277-280.
[73] Walters, CT; Barnes, RH; Beverly III, RE. J. Appl. Phys., 1978, 49, 2937-2949.
[74] Hettche, LR; Tucker, TR; Schriempf, JT; Stegman, RL; Metz, SA. J. Appl. Phys., 1976,
47, 1415-1421.
[75] Gravel, JFY; Boudreau, D. Spectrochim. Acta Part B, 2009, 64, 56-66.
[76] Porneala, C; Willis, DA. Appl. Phys. Lett, 2006, 89, 211121.
[77] Maher, WE; Hall, RB; Johnson, RR. J. Appl. Phys., 1974, 45, 2138-2145.
[78] Sdorra, W; Niemax, K. Mikrochim. Acta, 1992, 107, 319-327.
[79] Iida, Y. Spectrochim. Acta Part B, 1990, 45, 1353-1367.
[80] Wen, SB; Mao, X; Greif, R; Russo, RE. J. Appl. Phys., 2007, 101, 023115.
[81] Sedov, LI. Similarity and Dimensional Methods in Mechanics, CRC Press LCC,
Moscow, 1993.
[82] Zeldovic, YB; Raizer, YP. Physics of Shock Waves and High-Temperature
Hydrodynamic Phenomena, Academic Press, New York, 1987.
[83] Abdel-Raouf, AM; Gretler, W. Fluid Dyn. Res., 1991, 8, 273-285.
[84] Ghoniem, AF; Kamel, MM; Berger, SA; Oppenheim, AK. J. Fluid Mech., 1982, 117,
473-491.
[85] Bogaerts, A; Chen, Z. Spectrochim. Acta Part B, 2005, 60, 1280-1307.
[86] Corsi, M; Cristoforetti, G; Giuffrida, M; Hidalgo, M; Legnaioli, S; Palleschi, V;
Salvetti, A; Tognoni, E; Vallebona, C. Authors reply to Wen et al.s comment,
[87] Le Harzic, R; Breitling, D; Sommer, S; Fohl, C; Konig, K; Dausinger, F; Audouard, E.
Appl. Phys. A, 2005, 81, 1121-1125.
[88] Semerok, A; Dutouquet, C. Thin Solid Films, 2004, 453-454, 501-505.
[89] Scaffidi, J; Pearman, W; Carter, CJ; Colston Jr., BW; Angel, SM. Appl. Optics, 2004,
43, 6492-6498.
[90] Scaffidi, J; Pearman, W; Lawrence, M; Carter, CJ; Colston Jr., BW; Angel, SM. Appl.
Optics, 2004, 43, 5243-5250.
[91] Scaffidi, J; Pender, J; Pearman, W; Goode, SR; Colston Jr., BW; Carter, CJ; Angel,
SM. Appl. Optics, 2003, 42, 6099-6106.
[92] Santagata, A; Teghil, R; De Giacomo, A; DellAglio, M; Parisi, GP; De Bonis, A;
Galasso, A. Appl. Surf. Sci., 2007, 253, 7792-7797.
[93] Koudoumas, E; Spyridaki, M; Stoian, R; Rosenfeld, A; Tzanetakis, P; Hertel, IV;
Fotakis, C. Thin Solid Films, 2004, 453-454, 372-376.
[94] Mannion, PT; Magee, J; Coyne, E; OConnor, GM. Proc. SPIE, 2003, 4876, 470-478.
[95] Pronko, PP; Zhang, Z; VanRompay, PA. Appl. Surf. Sci., 2003, 208-209, 492-501.
[96] Roberts, DE; du Plessis, A; Botha, LR. Appl. Surf. Sci., 2010, 256, 1784-1792.
[97] Chichkov, BN; Momma, C; Nolte, S; von Alvensleben, F; Tunnermann, A. Appl. Phys.
A, 1996, 63, 109-115.
[98] Chowdhury, IH; Xu, X; Weiner, AM. Appl. Phys. Lett, 2005, 86, 151110.
Chapter 2
ASSESSING HUNTER-GATHERER MOBILITY
IN CIS-BAIKAL, SIBERIA USING LA-ICP-MS:
METHODOLOGICAL CORRECTION FOR LASER
INTERACTIONS WITH CALCIUM PHOSPHATE
MATRICES AND THE POTENTIAL FOR INTEGRATED
LA-ICP-MS SAMPLING OF ARCHAEOLOGICAL
SKELETAL MATERIALS
Ian Scharlotta, Andrzej Weber, S. Andy DuFane,
Olga I. Goriunova and Robert Creaser
University of Alberta, Edmonton, Alberta, Canada
ABSTRACT
Micro-sampling and analysis of tooth enamel from faunal samples in the
archaeological record has enabled research into the mobility and seasonality of animals
in prehistory. However, studies on human tooth samples have failed to yield
similar results. It is well understood that human tooth enamel does not fully mineralize in
a strictly linear fashion, but rather entails five recognizable stages of mineralization. Until
the enamel matrix fully crystallizes, the matrix remains an open chemical system, thus at
each stage of mineralization, the geochemical composition of the enamel matrix can be
altered. At present it is unclear if failure to mirror the results from faunal teeth with
human teeth is a factor of mineralization rates or simply the result of the difference in
enamel volume and formation time between human and herbivore teeth. Therefore, the
applicability of chemical analyses to human teeth is a balance between micro-sampling
analytical techniques and generating archaeologically relevant data. Yet limited case
studies have been performed to examine the scale and extent of this problem in human
teeth using laser-ablation ICP-MS. Five human molars from an Early Bronze Age
cemetery on the shores of Lake Baikal, Siberia were serially sampled and analyzed by
means of laser-ablation quadrupole and multicollector ICP-MS in order to examine the
Ian Scharlotta, Andrzej Weber, S. Andy Dufane et al. 46
nature of geochemical changes within the enamel matrix. This sampling was performed
in order to generate a statistically significant dataset to assess the effectiveness of two
approaches along with published methodologies to counter known problems with
attempts to assess Sr87. Recent research has demonstrated that among the methodological
problems, there is isobaric interference at mass 87 caused by the formation of calcium
phosphate (Ca40PO) in response to interaction between the laser and the enamel matrix.
Correction procedures using Zr91 in tandem with Ba/Sr ratios are examined.
Additionally, serial sampling of teeth from hypothesized mobile hunter-gatherers
provides useful insight into the dynamic interplay between physical sampling limitations
and the scale at which useful geochemical data can be recovered from organic minerals.
Traditional utilization of geochemical data for mobility has relied on a local/non-local
dichotomy in population level analyses; however, this approach is of limited utility with
regard to mobile populations. Our ability to effectively analyze skeletal materials at a
micro scale provides our best hope at addressing the rift between recognition of an
indirect relationship between biological intakes, mineral formation and being able to
generate relevant analytical data.
INTRODUCTION
Strontium isotope analysis has traditionally relied on thermal ionization mass
spectrometry (TIMS) due to its reliability and analytical precision. The advent of multi-
collector inductively-coupled-plasma mass-spectrometry (MC-ICP-MS) as an alternative to
TIMS coupled with either a laser microdrill or a laser ablation (LA) unit for micro-sampling
greatly expanded the possibilities for archaeometric research of Sr isotopes. Both laser
microdrills and laser ablation are far less destructive and enable higher spatial resolution for
analysis than traditional TIMS and MC-ICP-MS methodologies, however micro-sampling for
solution preparation still requires significant lab handling for sample preparation whereas
laser ablation requires virtually no special handling [1, 2]. In spite of several studies using LA
on human bone and high-Sr apatites [3, 4], analysis of phosphate minerals by LA has not
figured prominently in the scientific literature until recently [1, 5-10].
The goal of this study is to examine problems associated with the application of laser
ablation as a sample introduction method for MC-ICP-MS on human skeletal materials.
Previous research[1, 8, 10] has indicated a number of potential problems in gathering accurate
strontium isotopic data from calcium phosphate matrices using LA-MC-ICP-MS. In addition
to interference from rubidium (
87
Rb), doubly charged rare earth elements [11], and calcium
dimers [10], there is the production of a polyatomic species of CaPO that interferes with the
[87] Sr [1, 8, 9]. This polyatomic species is apparently unique to laser ablation as it is not
apparent with solution mode (SM) MC-ICP-MS. The exact source of this polyatomic species
is uncertain; however it is a relatively minor contributor of isobaric mass 87 to most
geological samples. Unfortunately, many archaeological skeletal samples have very low
concentrations of Sr and are thus susceptible to significant error terms as a result of this
polyatomic species while using LA-MC-ICP-MS.
Traditional Sr isotopic research has focused primarily on sedentary agrarian groups. With
such groups, the focus of research is on identifying the local signature so that nonlocals
(people, animals, etc.) can be recognized. Such an approach is perhaps of only limited utility
for the broader study of hunter-gatherers, as many groups utilized large ranges of territory and
Assessing Hunter-Gatherer Mobility in Cis-Baikal, Siberia Using LA-ICP-MS 47
would thus have more complex (averaged over larger areas) isotopic signatures reflecting
their lifetime mobility. Such complexity drives interest in micro sampling of skeletal
materials to access greater chronologically refined insight into mobile individuals. However,
further research is needed to fully understand the dynamic interaction between direct
chemical interaction with the biologically available strontium, the formation of skeletal
tissues, and data recovery from these tissues. This study is focused on the data recovery side
of this problem, examining the range of variability in strontium isotope ratios and trace
element composition found within human teeth.
HUNTER GATHERER MOBILITY IN CIS-BAIKAL
The Cis-Baikal region of Siberia denotes the geographic region including the western
coast of Lake Baikal, the upper sections of the Angara and Lena river drainages, and the
Tunka region adjacent to the southwestern tip of Lake Baikal (approximately between 52
and 58 N and 101 and 110 E). The topographic complexity of the rift valley that formed
Lake Baikal led to the formation of a large number of microhabitats, with a variety of
seasonally available resources [12-14]. The thermal capacity of Lake Baikal itself moderates
the local climate, resulting in generally milder temperatures during the winter and cooler
temperatures during the summer. As a result, the Angara River Valley remains relatively free
of snow during the long winter which attracts various species of ungulates looking for forage
and less restricted mobility [15]. There is a variety of large game found in the region
including moose (Alces alces), red deer (Cervus elaphus), roe deer (Capreolus capreolus
pygarus), reindeer (Rangifer tarandus), and mountain goat (Capra sibirica). Smaller species
such as hare (Lepus sp.), suslik (Spermophilus citellus), wild boar (Sus scrofa sibiricus),
marmot (Marmota sibirica), geese, and other waterfowl are also abundant in many areas
around the lake. During the summer, large runs of black grayling (Thymallus arcticus) are
found in the first section of the Angara River, and several fish species enter the tributaries of
the Angara in large numbers to spawn. The shallow coves and bays in the Little Sea region of
Lake Baikal, between Olkhon Island and the west coast of the lake, also provide excellent
opportunities for fishing and during the late winter when the lake is frozen, nerpa, the Lake
Baikal seal (Phoca sibirica) can be hunted [16-19]. Ethnographic studies of boreal forest
populations highlight the use of mushrooms, berries, and pine nuts as other non-medicinal
resources [15, 20, 21]. There is very limited evidence for plant use during the Neolithic,
however there is sufficient ethnographic evidence for the role that plants play in boreal
forager subsistence systems around the world to speculate upon their usage.
Within the Cis-Baikal region there are four main geological zones that roughly overlap
with archaeological micro-regions (Figure 1). The main zones are 1) the Baikal basin,
including the lake itself, the coastal areas as well as the Little Sea area enclosed by Olkhon
Island; 2) the drainage of the upper and middle Angara River bounded by the Eastern Sayan
Mountains to the west and the Central Siberian Plateau to the east and extending north
towards Bratsk; 3) the upper Lena river basin cutting through the Central Siberian Plateau as
it heads northwards; and 4) the Tunka region covering a sizeable valley running south of the
Eastern Sayan Mountains and broadly connecting the southwestern tip of Lake Baikal to Lake
Khovsgol in Mongolia. The upper and middle sections of the Angara River flow through
Mesozoic and Quaternary deposits, with expected
87
Sr/
86
Sr values in the range of 0.705-
0.712. The upper Lena watershed and the surrounding Central Siberian Plateau are dominated
by Cambrian and Precambrian limestones, with expected values fairly tightly clustered
around 0.709 [22, 23]. Overall values for Lake Baikal water are reported as 0.7085 [24]. The
Baikal basin includes the Primorskii and Baikalskii mountain ranges and is characterized by
relatively high
87
Sr/
86
Sr (~0.720-0.735) due to the presence of Archean and Proterozoic
granites [12]. Bedrock of similar ages occur around the southwestern shores of Lake Baikal
and drainages adjacent to the Eastern Sayan Mountains, however our preliminary data for
environmental sampling of biologically available strontium isotopes in the Cis-Baikal region
indicate that these two regions have quite different
87
Sr/
86
Sr values [25]. Both zones overlap
87
Sr/
86
Sr ranges of neighboring regions (e.g., Angara Drainage), while only the Little Sea area
exhibits values above 0.720. Further clarifications of the distinction between these two zones
of similar age will be possible upon completion of regional sampling efforts.

Figure 1. Lake Baikal, Siberia showing the location of the KN XIV cemetery, cultural micro regions,
and the age of the dominant bedrock formations
KHUZHIR-NUGE XIV CEMETERY
The KN XIV cemetery is located on the west coast of the Little Sea micro-region of the
Lake Baikal basin, near the southern end of Olkhon Island and c. 3 km southwest of the
mouth of the Sarma River (530458 N, 1064821 E). It occupies the southeast slope of a
hill rising from a shallow bay. With 79 graves and a total of 89 individuals unearthed, KN
XIV is the largest Early Bronze Age hunter-gatherer cemetery ever excavated in the entire
Cis-Baikal region (Weber et al. 2007). All the graves were only c. 30-60 cm deep sub-
rectangular pits filled with rocks and loamy sand, and covered by surface structures built of
stone slabs still visible on the surface prior to archaeological excavation. Most graves
contained single inhumations, seven were double, and two were triple interments.
The north-south orientation of Grave 7 is consistent with the Late Neolithic Serovo
culture of the Olkhon region, while all the other graves show clear similarities with the
mortuary tradition of the Early Bronze Age Glazkovo culture [22, 26, 27]. The most
diagnostic Glazkovo characteristics include the generally west-east orientation of the burials
and such grave goods as copper or bronze objects (rings, knives, needles, and bracelets),
kaolinite beads, and rings and discs made of white nephrite or calcite [28]. A recent analysis
of approximately 80
14
C dates indicates that the KN XIV cemetery was used continuously by
Glazkovo peoples for a maximum of 700 years between ~4650 and 3950 cal. BP but the
majority of the burials (70%) date to between ~4450 and 4250 cal. BP [29]. Since the analysis
did not reveal any obvious temporal trends in mortuary attributes, it seems to be justified to
treat the cemetery with the exception of the much earlier Grave 7, as one analytical unit
(McKenzie 2006; Weber et al. 2005).
In previous studies [15, 22, 26] a sample of 25 individuals from KN XIV were analyzed
for strontium isotope ratios and compared with 79 faunal samples collected throughout Lake
Baikal and the Cis-Baikal region. Of these samples, there were 20 adult individuals for which
all three molars and a femur sample were available, 5 subadult burials with only M1 and M2
crowns completed were included too. For the latter individuals (Burials 16, 35.2, 37.2, 39 and
45) the M3 was either not yet formed, or still forming. Partly developed crowns were not
examined because such crowns are incompletely mineralized and this could have affected the
isotope ratios. The five molar samples used for this research came from this pool of
previously studied materials. Teeth from Burials 7, 12, 16, 35.1, and 35.2 were used in this
study to provide continuity and comparability with previous studies on KN XIV.
This previous work has helped to expand the possible applications of strontium isotope
research and helped to identify an interesting general pattern with several mobility profiles
within KN XIV individuals. Broadly speaking, it appears that there was a significant amount
of movement of individuals during their lifetime, whereby people buried at KN XIV were
frequently not born in the Little Sea region, but only migrated there as subadults or adults [15,
22]. There was significant variability within the cemetery itself as to the origin and age of
migration to the Little Sea with indications of correlated mortuary patterning that is the
subject of ongoing research.
PRINCIPLE OF STRONTIUM CATCHMENT
Strontium ratios in herbivore bone reflect the isotopic signatures in the plants that these
animals eat and the water that they drink thus are a direct reflection of their bioavailable
geochemical environment. An herbivore foraging range will therefore roughly equate to its
Sr-catchment [30, 31]. The situation is slightly different for carnivores as their Sr-catchment
will reflect their dietary intake rather than simply their geographical territory. The territory of
a predator, human or otherwise, will intersect and contain portions of the territories of
numerous prey animals, though will likely not encompass the full procurement ranges of
these species. Therefore the strontium ratios of their prey animals may derive from geological
regions outside of the predators geographic territory. This highlights the important concept
of effective geochemistry as a step beyond bioavailable geochemical signatures. Herbivores
provide direct translations of bioavailable geochemical values in plants, thus whatever portion
of soil geochemistry can be mobilized into the food chain. Carnivores subsist largely or solely
on other animals, thus their bioavailable geochemical values will not directly translate into
either their actual movements on the landscape or their bounded procurement territory. The
only evidence to directly relate carnivores with their physical territory is the water that they
drink, any vegetal matter they may consume (e.g., berries), or small animals (e.g., rodents,
lizards, etc.) whose entire range will be limited in scale and thus contained with the
carnivores territory. Thus both human and animal predatory strontium signatures may reflect
procurement ranges both larger and different from their actual territories.
In geologically diverse regions, interpretation of bioavailable geochemistry can be
complicated by the fact that animals with small home ranges (e.g., suslik) may have adjacent
geographical territories but exist on different bedrock formations and thus have different
strontium ratios. Larger species, such as moose and red deer frequently cross geologic
boundaries during the course of an annual foraging cycle; averaging the
87
Sr/
86
Sr ratios in
their tissues. Thus interpretation of the bioavailable geochemistry can be unintentionally
biased during sampling based on sample availability.
TOOTH MINERALIZATION
Teeth are dynamic mineral structures whose complexities are still being unraveled. It has
long been recognized that the incremental striae of Retzius represented some aspect of matrix
deposition but that there is a disconnect between this matrix deposition and the final
mineralization that will finalize the mineral matrix (e.g., [32]). At the time, microsampling of
individual striae was not practical, thus the matter was largely ignored. However, there has
recently been a resurgence of interest in the formation process of the incremental growth lines
as reflections of the circadian rhythm of enamel matrix secretion with the advent of
microsampling techniques such as laser ablation and microdrilling that could theoretically
sample the enamel at such pertinent scales (e.g., [1, 4, 7, 33, 34]). Numerous hypotheses have
been forwarded regarding the pattern and progression of enamel mineralization, however the
common theme amongst all works is that the progression of mineralization of layers and/or
maturation of matrices is patchy and effectively non-linear thus making the chronological
relationship between incremental lines and geochemical signals rather tenuous [33-42]. Broad
trends whereby mineralization begins at the tooth cusp and finishes at the cingulum are still
present, though the intermediate pathways are debatable. Montgomery and Evans, [39] and
Fincham et al., [37] provide excellent discussion of the biomineralization of tooth enamel
with respect to Sr isotope analysis. The process of mineralization spans a series of five
distinct phases wherein an organic gel or protein superstructure is transformed into a mineral
matrix: 1) secretion; 2) assembly; 3) matrix formation; 4) resorption prior to maturation; and
5) maturation (see Fincham et al. [37] Figure 8; Bentley [35] Figure 18). Following assembly,
nanospheres of apatite will remain largely intact until maturation, however although these
individual crystal structures are reflexive of their formation environment, they will mingle
with other crystals to form a heterogeneous lattice of crystals in the mature matrix.
Effectively, at all stages prior to maturation, the enamel matrix remains an open chemical
system vulnerable to alteration, overprinting, or simply averaging of the matrix at the scale of
modern recovery techniques.
The practical ramifications of this open chemical system is that while the formation of
tooth crowns progresses at a well known rate and there are incremental growth lines to further
support the logical conception of enamel matrix as a progressive linear formation, all work to
date demonstrates that there is a disjunction between enamel formation and matrix
maturation. So while we know that calcification of M1 begins at birth and ends with
maturation and root formation between 3 4 years of age, we are left with nearly three years
of that molar remaining an open chemical system and a potential averaging effect [33, 43]. In
spite of this theoretical difficulty, there is still some promise to the concept of microsampling
tooth enamel. That incremental growth lines do not mineralize in a similar incremental
fashion has been well demonstrated, however we still have some broad guidelines that remain
true: 1) the crown of a tooth will fully mineralize before the root; and 2) though accomplished
in a patchy or wave-like fashion, there are still broadly linear trends in mineralization
progressing from crown to cingulum.
Ongoing research into this problem with herbivore teeth has demonstrated that there are
long-term mixing effects in action during the formation and maturation of tooth enamel [32,
42, 44-51]. Such research has highlighted a secondary problem with efforts to access the
microstructure of teeth and thus provenance their formational period, that while formation of
enamel proceeds using available mineral components within the body and that available
components come from the diet, there is a gap between intake of the raw ionic components of
the mineral structure and their incorporation into mineral tissues. Specifically this is the
problem of residence time in the body for different elements. Water has a short residence time
in the body of only 14 days; however strontium, calcium, and lead can remain in the body for
8001600 days, with 10% of traceable doses remaining active after 400 days [51-53]. Recent
works (e.g., [46, 51, 54]) have demonstrated that this residence time in the body has an
intriguing effect on isotopic signatures of a linearly-sampled herbivore tooth. Namely that an
abrupt change in geochemical geography and/or diet will not manifest as a sharp transition in
isotopic signals, but rather that there will be a gradual sloping change as contributions from
different geochemical end-members vary within the body-water average being accessed for
ionic component material in enamel formation. At face value, this combination of lag time in
mineral formation and maturation with body-water averaging of over a year should render
discussions of microsampling human teeth for interim provenance information between the
crown and cingulum, however it should be noted that there is an important difference between
herbivore and human teeth. While it is quite likely that the same mineralization primers are in
effect for both human and herbivore teeth and that the non-linear progression of mineral
maturation is effectively the same, the time spans involved are different. For example, each
bovine molar will form and fully mineralize over a span of 1218 months [51]. However,
each human molar can theoretically span a time of 2448 months between initial calcification
and final mineral maturation, though it will likely occur in less than 36 months. Thus, we
have a gap in comparative volumes and chronologies in discussing the differences between
herbivore and human teeth. While many herbivore teeth are not good candidates for
microsampling because their tooth formation rates will not outstrip uncertainties about
residence time and mineralization rates, human teeth will likely exhibit some aspects of useful
variability in isotopic signatures through formation time and thus through enamel mineral
volume/geography. We still must keep in mind that at present it is impossible to overcome
residence time for intake and maturation time for the mineral matrix, it may well be worth
pursuing microsampling of human teeth in between cusp and cingulum.
LASER ABLATION OF TEETH
The coupling of a laser ablation unit to either an ICP-MS or a MC-ICP-MS is no longer a
novel concept to the fields of analytical chemistry and archaeology, and is rapidly becoming a
mainstream tool for ongoing research and a key player in the advancement of micro-
analytical techniques (cf. [55-58]). Studies involving skeletal materials were fairly late
additions to the field, in part due to latent concerns about the materials being analyzed and
their potential for diagenetic alteration at the proposed scale of analysis. However, in the last
decade or so, ICP-MS studies on teeth and bones have picked up significantly and are now
part of a healthy academic field of research [1, 3-5, 7, 8, 51, 59-62]. Numerous studies have
demonstrated the reliability of ICP-MS and MC-ICP-MS as compared to TIMS and INAA
(cf. [57, 63-66]) using both laser ablation and solution mode sample introduction for both
elemental composition and numerous isotopic series. ICP-MS and MC-ICP-MS are generally
faster and less labor intensive than traditional analytical methods, however one of the trade-
offs is the tacit recognition of the need for corrections for a variety of interferences. The
identification of and correction for the seemingly endless string of interferences across the
mass spectrum is an extremely important part of researchers ability to use confidently ICP-
MS as an analytical tool. For single radiogenic isotopic series such as strontium, the list of
potential problems includes known isobaric interferences (
87
Rb), doubly-charge rare earth
ions [11], polyatomic species such as calcium dimers [10], calcium phosphate (CaPO) [1, 7-9,
67, 68], and other molecular species yet to be identified. While daunting and providing a
divergence from the seemingly parsimonious relationship linking artifact and data via
traditional analytical methodologies, identifying possible problems and monitoring for data
quality are important parts of any analytical process and so should not be avoided. For Sr
analysis, the largest if not most pernicious problems are isobaric interference from [87] Rb
and a recently identified polyatomic interference from calcium phosphate, though an
important distinction between the two should be made. Rubidium corrections are necessary
for all ICP-MS and MC-ICP-MS analyses as the charged [87] Rb will carry the same mass-
charge ratio as its
87
Sr counterpart, though this can be countered with accurate mass-bias
calculations. This is not a problem associated with sample introduction methodology. On the
other hand, polyatomics such as Ca dimers and calcium phosphate species are notably absent
in solution-mode analysis as sample ions are held in acid and thus prevented from
recombining as they are free to do in the carrier-gas environment of laser ablation chambers.
From the perspective of an end-user, that such interference only manifest, or are only
apparent at significant levels via laser ablation introduction both with and without aspirated
acids introduced, is both interesting and discouraging for microsampling potentials. It is
intriguing that complex molecules manifest in the highly charged plasma environment when
introduced by a carrier gas but not as an aspirated solution, as both are theoretically entering
into the plasma chamber as ionized particles.
Woodhead et al. [10], Simonetti et al. [8], Horstwood et al. [1], and Vroon et al. [9] have
all discussed the presence of significant interference on mass 87 from a previously
unidentified source, thus impinged on researchers ability to accurately assess the
87
Sr/
86
Sr
ratios of phosphate matrices with laser ablation. As all mammalian skeletal tissues are
varieties of phosphate mineral matrices, this is a major problem for efforts to access the life
signals contained therein and thus in archaeologists and paleontologists ability to accurately
interpret these signals and thus reconstruct the movement histories of these animals. It
appears that the root of the problem is the excess of Ca and P present in the charged
environment coupling with the oxide production rates within the MC-ICP-MS. In theory, Ca
and P levels should be proportional in all parts of skeletal tissues, thus mineral replacements
such as Sr, Ba, and the incorporation of other trace elements should be proportional as well,
and interferences will be related to the oxide operational conditions of the instrument itself.
This leaves us with several important points to consider: do we have reason to question any of
these starting assumptions? Can we monitor the formation of CaPO during analysis and thus
correct for it in ways other than those outlined in previous works? Can we recover useful
geochemical information from skeletal tissues using laser ablation as a microsampling
technique?
MATERIALS AND METHODS
Tooth enamel samples consist of five human molars from the KN XIV cemetery that
have previously been used for analytical work by the Baikal Archaeology Project. Samples
included 4 second molars from graves 7 (Sample #1997.211), 16 (1997.217), 35-1
(1998.355), and 35-2 (1998.359), as well as 1 third molar from grave 12 (1997.225). All
samples were previously analyzed by Haverkort et al. [22] and several were also analyzed via
TIMS by Weber et al.[26]. All samples were analyzed for elemental composition using both
SM-ICP-MS and LA-ICP-MS and likewise for
87
Sr/
86
Sr ratios using SM-MC-ICP-MS and
LA-MC-ICP-MS. All preparation and analyses were conducted at the Radiogenic Isotope
Facility of the Department of Earth and Atmospheric Sciences at the University of Alberta.
Solutions were prepared by extracting fragments of enamel (between ~0.020-0.060 g) as
close to the cingulum as possible to provide comparability between teeth with various levels
of wear. Fragments were mechanically removed using a diamond cutting disk (NTI Diamond
disc, Interflex-double sided, 8 mm diameter, 0.15 mm thickness) fitted to a Dremel tool. If
necessary, samples were abraded with the disk to remove any adhering dentine. Sample
locations were not side-specific as these teeth have been previously sampled, thus samples
were taken where adequate materials remained, though largely stemming from areas
immediately adjacent to previous sampling locations. Sample preparation occurred in a Class
100 clean room facility and followed procedures outlined in Simonetti et al. [8] and
Haverkort et al.[22]. Samples were sonicated for 15 min in milliQ (MQ) de-ionized water and
then in 5% acetic acid for 15 min. After an overnight leaching in 5% acetic acid, the acid was
removed and samples were rinsed with MQ prior to transfer to clean Teflon vial. A known
amount of
87
Rb
84
Sr spike was added, followed by 4 mL of 16 N HNO
3
and 1 mL of 12 N
HCl and capped to digest on an 80 C hotplate overnight. Digested samples were then dried
overnight on the hotplate. Dried samples were dissolved in 3 mL of 0.75 N HCl and loaded
into syringes with disposable filters. Filtered samples were loaded onto 10 cm cation
exchange columns containing 1.42 mL of 200-400 mesh AG50W-X8 resin. Columns were
rinsed with 3x1 mL of 0.75 N HCl, 3x1 mL of 2.5 N HCl and washed with 17 mL of 2.5 N
HCl. Samples of 5 mL of 2.5 N HCl containing the purified Sr were collected into clean
Teflon vials and left to dry overnight on the hotplate. Dried samples were dissolved with 1
mL of 2% HNO
3
prior to necessary dilution for MC-ICP-MS analysis. Analysis was
conducted on a Nu Plasma HR MC-ICP-MS with a DSN-100 nebulizer. Strontium isotope
data were acquired in static, multicollection mode using five Faraday collectors for a total of
400 s, consisting of 40 scans of 10 s integrations. The wash-out period following the
analysis of a sample was approximately 5 min. Prior to the aspiration of a sample, a 30 s
measurement of the gas (+acid) blank was conducted to correct for [86] Kr and [84] Kr
isobaric interferences. The isobaric interference of [87] Rb was monitored and corrected
online using the [85] Rb signal. Accuracy and reproducibility of the analytical protocol based
on long-term repeated analysis of a 100 ppb solution of the NIST SRM 987 strontium isotope
standard 0.710242 0.000041.
Elemental samples of similar size underwent similar handing, though without the [87]
Rb[84] Sr spike, and not loaded onto cation exchange columns. Digested samples were
simply dissolved in 2% HNO
3
prior to quadrupole-ICP-MS analysis. Sample solutions were
analyzed for 57 elements (Li, Be, B, Na, Mg, Al, P, Ca, Ti, V, Cr, Mn, Fe, Cu, Zn, Ga, Ge,
As, Rb, Sr, Y, [90] Zr, [91] Zr, Nb, Mo, Ru, Pd, Ag, Cd, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Pt, Au, Tl, Pb, Th, and U) using a
Perken Elmer Elan6000 quadrupole ICP-MS, and instrument operating conditions as follows:
RF power = 1200 W; dual detector mode; blank subtraction performed subsequent to internal
standard correction; unit of measurement is cps (counts per second); auto lens on; use of 4-
point calibration curves (0, 0.25, 0.50, and 1.00 ppm for Ca, Mg, and Fe; 0.005, 0.010, and
0.020 ppm for the remaining elements); sample uptake rate (using a peristaltic pump) was ~1
mL; sample analysis consisted of 35 sweeps/reading, 1 reading/replicate and 3 replicates;
dwell times were 10 ms for Al, Mn, and U, and 20 ms for the remaining elements; total
intergration times (dwell time x number of sweeps) were 350 ms for Al, Mn, and U, and 700
ms for the remaining elements (Table 1). External reproducibility, based on repeated analysis
of international whole rock standards is 5-10% (2 level) for most elements.
Laser ablation for elemental analysis of samples was conducted using the Perken Elmer
Elan6000 quadrupole ICP-MS coupled to a UP213 nm laser ablation system (New Wave
Research, USA). The instrument was optimized using the NIST SRM 612 international glass
standard reference material (RF power 1200 W, peak hopping acquisition, 50 ms dwell time).
Teeth were serially sampled (Figure 2) using LA-ICP-MS to examine the nature and extent of
useful intra-tooth geochemical variability in tandem with attempts to monitor the formation of
the CaPO polyatomic species. This sampling included 8 sampling locations or groups on each
tooth, offset but approximately equally spaced between the bottom of the crown and the
cingulum. Groups consisted of 5 lines each with a combination of laser spot size and laser
power settings were employed to assess the impact of potential laser-matrix effects. Half of
the sampling groups were conducted using 50% laser power, while the other half was run at
100% laser power. Line groups consisted of reducing laser spot sizes of 100, 80, 55, 40 and
25 m in sequence, with a repetition rate of 20Hz and an energy density of ~13 J cm
-2
.
Experiments were conducted in a mixed He/Ar atmosphere (ratio of 0.5:0.1 L min
-1
) within
the ablation cell, and mixed with Ar (1.03 L min
-1
) prior to entering the torch assembly. The
laser ablation cell was flushed with a higher flow rate of He (up to 0.9 L min
-1
) for
approximately 1 min in-between laser ablation runs to ensure adequate particle washout. The
NIST SRM 612 glass standard was used as the external calibration standard. Quantitative
results for 57 elements (Li, Be, B, Na, Al, Si, P, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Cu, Zn, Ga,
Ge, As, Rb, Sr, Y, [90] Zr, [91] Zr, Nb, Mo, Ag, Cd, In, Sn, Sb, Cs, Ba, La, Ce, Pr, Nd, Sm,
Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Au, Tl, Pb, Bi, Th, and U) were obtained
and normalized to
24
Mg, as measured by solution analysis, as the internal standard using the
GLITTER
(XP version, Macquarie University) laser ablation software (Table 2). Mg was
used instead of Ca in order to assess variability in calcium in these teeth.
Laser ablation for isotopic analysis was conducted using a UP213 nm laser system
coupled to the Nu Plasma HR MC-ICP-MS with the sample-out line from the desolvating
nebulizing introduction system (DSN-100 from Nu Instruments) to allow for simultaneous
aspiration of a 2% HNO
3
solution. At the beginning of each analytical session, parameters for
the introduction system and the ion optics were optimized by aspirating a 100 ppb solution of
the NIST SRM 987 Sr isotope standard. Based on the results of the elemental laser ablation
analysis, a full replication of the line groups was not done. Instead, overlying each full
powered elemental sampling site, three parallel lines were analyzed using 100 m laser spot
size; 100% laser power; 20 Hz repetition rate; ~15 J cm
-2
energy density (Table 3). Half
powered elemental sampling sites were not sampled for isotopic data as the elemental data
were deemed to be of poor quality. Strontium isotope data were acquired in static,
multicollection mode using five Faraday collectors for a total of 400 s, consisting of 40 scans
of 10 s integrations, for data reported. Testing for potential collector setups included attempts
at using eight collectors in order to extend the monitored mass range to include masses 90 and
91. Similar efforts were also attempted using dual-acquisition, static analysis to similar effect
following Horstwood et al.
1
. Laser data were partially monitored by repeated analysis of a
specimen of Durango Apatite with a reported value of 0.706327 0.000724 by TIMS
1
. In
one analytical session, an average value of 0.706118 0.000035 were observed, and in a
second, 0.706244 0.000028. This sample is currently being intensively sampled for its
ongoing use as a mineral standard for strontium analysis at the Radiogenic Isotopic Facility,
however at present has been analyzed fewer than fifty times and thus can only be viewed with
moderate confidence. As such, no attempts were made to standardize data for enamel samples
to apatite values. Quantification of the oxide levels during analyses using UO
+
/U
+

demonstrated levels of approximately 0.7%.

Table 1. Solution mode
87
Sr/
86
Sr ratios and elemental data for KN XIV teeth.
Local/Nonlocal determinations from Haverkort et al. 2008
Re Os Pt Au Tl Pb Th U Little Sea
Origin
0.001927 0.009514 0.001906 0.058862 0.001221 0.268555 2.340665 0.071605 Nonlocal
0.007496 0.043007 0.007412 0.298735 0.073691 0.079869 0.213768 0.015656 Local
0.005342 0.033591 0.007894 0.246172 0.04021 0.138083 0.198961 0.024269 Local
0.001878 0.028736 0.006105 0.186726 0.022941 0.054092 0.091068 0.005631 Nonlocal
0.002238 0.012796 0.002007 0.083647 0.007105 0.060767 0.030142 0.003889 Nonlocal

Figure 2. Sampling scheme used on sectioned teeth. Enlargement laser ablation scars representing one
sampling group
RESULTS AND DISCUSSION
This research included a number of different aspects, beginning with efforts to
demonstrate the value in trace element analysis of human teeth for provenance and/or
mobility purposes. The treatment of organic minerals in a similar fashion to complex
inorganic minerals for the purposes of provenance analysis is a fairly new and expanding area
of research within the realm of provenance analysis (cf. [5, 69, 70]). The underlying concept
is the same for any geochemical sourcing study, in that the range of variability must meet the
strictures of the Provenance Postulate [71]. Though this has been demonstrated for
populations on Rapa Nui [70], and in distinguishing African immigrants in a Mexican
cemetery [5, 69]; the range of useful variability in trace element composition must be
determined for each geographical region. Thus, for cemeteries in Cis-Baikal, a new database
of locally useful elemental variability must be generated. This research consisted of only 5
samples, however still presents a beginning to the formation of such a database.

Table 2. Laser ablation elemental data for KN XIV teeth
(Sample ID Laser Spot Size Sample Group)
Sample
ID_Spot
Size_Group Li Be B Na Al Si P Ca Sc Ti V Cr Mn Fe Co Cu Zn
97211_100_A 0.364 0.205 1.08 3650.44 241.22 207.24 64027.67 222294.11 0.09 4.27 2.88 1.01 35.32 112.83 0.325 0.53 111.04
97211_80_A 0.49 0.6 1.22 3547.81 43.92 117.65 63294.82 237603.84 0.163 1.69 2.99 0.72 9.61 57.92 0.082 0.34 87.43
97211_55_A 0.65 2.02 1.23 3653.11 6.41 104.64 61442.43 236211.53 0.38 4.81 3.11 1.62 4.16 42.41 0.117 0.69 78.25
97211_40_A 0.3 1.05 3.77 3716.37 47.85 146.62 64486.52 234467.86 0.44 5.07 2.47 2.11 12.8 52.47 0.124 0.93 86.53
97211_25_A 1.08 7.14 7.2 3814.94 18.7 403.09 65675.6 264530.88 1.99 21.41 3.5 9.87 9.85 44.14 0.82 4.1 82.72
97211_100_B 0.452 0.46 0.79 3657.98 21.52 104.25 58902.48 218525.92 0.083 0.85 2.6 0.88 5.81 55.75 0.072 0.243 58.72
97211_80_B 0.41 0.2 1.58 3724.74 25.71 55.41 61789.18 233481.7 0.158 1.47 2.39 1 5.95 58.15 0.065 0.25 54.58
97211_55_B 0.44 1.37 1.06 3741.95 39.4 120.28 59194.78 230185.63 0.33 4.78 2.81 1.52 9.29 50.59 0.128 0.61 45.15
97211_40_B 0.28 2.56 2.36 3569.28 75.03 83.01 59178.95 225280.58 0.45 5.9 1.69 2.12 14.62 65.95 0.155 0.91 61.21
97211_25_B 1.44 2.68 4.11 3175.41 265.42 476.86 53285.48 195903.66 1.37 15.23 1.9 7.14 31.62 128.41 0.61 3.09 63.15
97211_100_C 0.5 0.048 1.31 3649.68 14.92 101.74 55783.39 214245.89 0.076 0.66 2.25 1.05 5.91 54.41 0.035 0.205 46.04
97211_80_C 0.36 0.25 1.11 3641.77 21.53 69.43 57419.32 228728.3 0.154 1.82 2.37 1.44 7.58 53.47 0.197 0.3 50.7
97211_55_C 0.4 2.56 1.09 3607.72 35.86 135.81 55748.88 210288.25 0.257 2.65 2.11 1.18 11.68 50.49 0.107 0.41 47.52
97211_40_C 0.67 3.48 1.83 3416.2 43.02 129.46 54201.63 203894.3 0.45 4.25 2.1 2.28 16.71 59.75 0.159 0.93 56.47
97211_25_C 0.19 3.63 3.78 3474.17 94.97 287.02 55328.13 210873.78 1.48 17.57 1.53 7.03 23.61 78.31 0.33 2.68 63.14
97211_100_D 0.342 0.36 1.01 4132.01 19.07 101.29 51666.73 201905.63 0.099 0.82 2.2 0.93 10.03 51.05 0.126 0.164 31.87
97211_80_D 0.52 1.04 0.83 4204.36 37.76 95.69 58097.5 225548.22 0.193 1.53 1.94 0.75 9.76 49.51 0.116 0.25 36.83
97211_55_D 0.32 0.18 1.56 4010.44 51.79 129.55 55033.9 214956.39 0.29 2.74 1.94 1.7 15.9 65.86 0.16 0.52 48.97
97211_40_D 0.6 2.17 1.15 4146.8 62.98 156.79 56970.46 223171.36 0.43 4.14 2.28 2.25 43.31 83.66 0.332 0.93 63.01
97211_25_D 1.56 6.97 4.17 4206.67 148.6 272.57 55208.66 202296.55 1.41 17.12 2.01 6.81 214.22 161.45 2.09 2.78 88.47
97211_100_E 1.1 7.93 3.15 3894.62 10.1 154.08 48036.38 199831.05 0.88 8.08 3.12 4.24 1.51 41.3 0.39 1.39 22.07
97211_80_E 1.37 11.93 5.69 4215.7 392.19 403.74 49273.86 190208.02 1.95 15.33 1.96 8.88 26.38 122.1 0.83 2.89 25.29
97211_55_E 3.13 33.7 17.63 3801.75 1018.72 850.41 49333.76 169428.05 4.42 33.18 4.45 22.43 444.45 247.13 4.88 6.95 68.38
97211_40_E 5.44 23.82 22.8 4827.18 1198.29 1125.62 43452.75 166217.27 5.23 57.2 5.8 26.83 205.11 193.95 10.14 7.29 59.31
97211_25_E 25.95 160.17 59.52 5311.39 2085.95 4583.92 48566.3 190663.23 20.43 242.12 23.43 116.43 829.46 611.92 13.29 41.04 145.64
97211_100_F 0.35 2.8 1.2 3803.64 273.24 75.26 41278.58 155721.28 0.44 4.44 3.33 1.91 12.23 99.04 0.193 0.51 29.72
97211_80_F 1.2 2.12 3.89 3779.97 190.42 323.51 41964.24 167564.7 1.28 18.32 2.6 7.42 48.77 126.33 0.59 2.24 17.46

Table 2. (Continued)

Sample
ID_Spot
97211_55_F 1.81 0.001 9.57 3236.03 452.1 434.71 36926.37 147313.73 2.18 14.3 3.06 11.28 16.03 283.83 0.96 2.15 17.79
97211_40_F 1.78 5.31 6.65 2218.74 460.72 452.35 25898.87 100775.26 2.15 25.22 2.39 11.96 16.69 144.88 0.94 3.17 22.71
97211_25_F 4.18 17.92 12.3 1287.24 357.72 739.64 12963.16 44549.54 4.64 32.42 4.11 19.39 6.98 96.96 1.33 5.05 28.1
97211_100_G 0.51 1.31 1.58 3620.49 176.83 54.21 37092.63 147173.53 0.25 2.54 3.73 1.44 115.21 82.6 0.72 0.46 21.46
97211_80_G 0.3 0.45 1.18 2540.82 275.93 214.82 25102.88 100285.7 0.44 4.43 1.99 2.98 20.58 137.19 1.14 0.76 15.11
97211_55_G 2.77 12.88 6.89 2853.51 332 281.46 31469.35 129220.73 1.35 16.66 4.33 7.94 33.58 191.63 0.79 1.93 11.66
97211_40_G 1.84 0.001 6.83 2510.86 281.65 438.22 31199.55 117070.11 2.03 25.25 2.49 11.77 81.72 165.51 2.73 3.07 19.09
97211_25_G 0.001 19.03 6.33 2013.43 1399.86 535.55 16874.91 56437.6 2.56 30.69 2.81 14.3 238.55 309.78 4.2 4.31 19.27
97211_100_H 0.57 0.28 1.17 4636.57 262.33 84.19 46825.67 184185.75 0.39 5.41 3.66 1.95 353.34 171.42 10.1 0.57 24.26
97211_80_H 0.63 5.88 3.18 5196.43 692.49 354.25 53934.13 205958.03 1.08 9.2 2.7 5.62 314.95 193.53 7.32 1.73 28.9
97211_55_H 2.43 12.35 10.22 5194.39 833.21 450.13 54286.59 207796.53 2.14 23.24 3.04 12.6 504.33 388.33 7.08 3.39 55.69
97211_40_H 3.53 67.22 42.16 4132.36 946.69 3006.45 46711.54 206638.84 13.37 150.48 12.71 71.73 174.51 324.33 4.31 22.78 88.13
97211_25_H 21.17 92.14 72.65 3925.68 2336.83 3143.39 39578.45 170792.42 14.04 184.61 14.02 86 67.08 1350.36 8.11 24.61 106.7
97217_100_A 0.302 0.049 1.25 5322.98 4.03 87.9 73633.24 288064.91 0.097 1.05 1.29 1.17 1.19 86.75 0.522 0.443 54.82
97217_80_A 0.23 0.25 1.3 5153.04 2.83 75.32 78360.02 301801.22 0.19 1.32 1.11 0.89 1.18 81.11 0.128 0.27 60.25
97217_55_A 0.156 2.23 2.63 5177.93 0.84 188.54 76338.85 301184.59 0.39 4.09 0.83 2.03 1.37 67.95 0.158 0.62 61.75
97217_40_A 0.76 4.03 3.13 5336.97 1.83 131.66 78017.85 310309.25 0.82 5.57 0.67 3.75 0.9 77.8 0.29 1.05 52.89
97217_25_A 1.3 9.3 4.74 5415.9 4.69 445.3 79130.62 312386.91 2.45 21.26 1.88 13.64 3.08 97.92 0.8 2.14 39.46
97217_100_B 0.27 0.57 1.55 5164.93 4.97 119.17 75013.55 295278.63 0.078 0.88 0.9 1.27 2.05 74.66 0.03 0.78 80.93
97217_80_B 0.42 1.03 1.61 5245.86 5 134.56 79826.28 316606.38 0.183 1.58 1 1.63 1.26 73.82 0.051 0.32 87.49
97217_55_B 0.39 3.77 1.87 5329.83 13.07 119.79 80309.66 311098.38 0.38 2.95 0.84 2.3 2.4 58.88 0.215 0.47 109.41
97217_40_B 0.67 5.33 3.21 5352.14 8.4 122.07 81215.74 313226.5 0.59 6.23 0.6 3.35 1.22 61.34 0.4 1.09 101.06
97217_25_B 2.38 3.59 7.52 5516.12 6.8 425.48 84018.63 322509.84 2.05 13.76 2.09 11.41 2.71 108.25 0.53 2.56 124.54
97217_100_C 0.33 0.51 1.2 5361.01 7.6 101.6 72692.55 287984.03 0.096 0.69 0.98 1.31 1.48 67.52 0.054 0.142 75.36
97217_80_C 0.42 1.81 2.14 5488.83 21.42 103.23 80016.89 315531.25 0.2 1.83 1.33 2.01 2.97 72.63 0.117 0.186 128.63
97217_55_C 0.75 2.2 1.95 5538.91 27.02 160.34 79543.34 305731.81 0.4 3.86 1.25 1.94 2.79 54.57 0.114 0.49 140
97217_40_C 0.75 0.55 1.75 5787.83 42.73 177.41 84828.95 335817.41 0.63 6.61 1.4 3.62 6.08 97.04 0.228 0.67 161.98
97217_25_C 2.44 5.37 9.74 5344.36 70.34 491.56 83480.05 322326.03 1.82 24.66 1.82 11.19 12.04 64.64 0.74 2.35 225.47


Sample
ID_Spot
97217_100_D 0.253 0.15 1.16 5927.98 17.49 147.25 77479.99 304195.91 0.1 0.94 1.47 1.31 2.15 62.82 0.054 0.166 89.66
97217_80_D 0.29 1.12 0.83 6053.21 17.32 121.23 82094.33 330688.81 0.176 1.46 1.51 1.76 2.16 67.75 0.088 0.32 133.34
97217_55_D 0.45 2.44 3.84 6359.43 49.05 153.02 84394.7 331941.84 0.41 4.45 1.85 2.5 4.04 97.87 0.134 0.48 161.51
97217_40_D 0.73 3.93 1.3 6338.53 43.1 176.99 83431.14 331381.16 0.58 8.74 1.78 3.22 4.55 93.64 0.215 2.99 171.33
97217_25_D 2.22 7.97 8.81 5876.09 25.42 554.23 80796.29 310824.81 1.88 15.15 1.55 9.78 4.27 55.41 0.31 1.91 213.6
97217_100_E 1.35 0.73 3.36 4874.99 1.95 157.63 74659.08 288323.47 0.85 7.2 0.84 4.14 0.98 64.49 0.39 1.05 18.04
97217_80_E 3.37 12.55 8.4 4940.43 4.08 385.68 66046.16 272802.16 1.79 15.89 1.75 11.14 2.54 79.98 0.83 2.72 15.44
97217_55_E 5.58 29.31 13.91 4384.32 8.34 716.33 62152.77 253801.8 3.52 22.6 3.24 19.99 4.58 102.32 1.12 5.22 31.78
97217_40_E 12.48 46.07 38 5117.52 18.48 1674.86 72106.77 255346.58 8.62 76.39 7.03 44.99 11.92 233.36 3.91 11.55 44.87
97217_25_E 29.37 340.96 89.22 6593.72 46.4 5197.13 73007.28 252952.38 29.53 268.9 24.41 141.67 29.96 750.51 7.09 45.08 157.48
97217_100_F 0.51 5.72 3.36 5447.38 1.32 131.51 61558.16 238079.16 0.76 7.09 0.89 3.55 0.88 23.24 0.215 0.9 29.97
97217_80_F 0.34 11.48 9.56 4986.99 8.92 344.7 56684.51 229622.8 1.68 17.35 1.59 9.32 2.18 51.4 0.61 1.92 39.49
97217_55_F 3.48 25.14 13.56 6080.22 96.24 594.78 62864.18 221898.14 3.43 21.84 2.4 22.42 3.83 100.09 1.33 8.17 30.27
97217_40_F 7.5 38.1 15.21 5933.6 15.44 1192.35 59769.67 229634.73 6.21 65.84 6.56 34.57 6.24 219.56 3.17 9.38 63.28
97217_25_F 25.38 90.59 53.91 6416.94 30.51 2850.36 54528.75 229070.47 15.06 145.7 12.4 76.63 17.4 403.72 5.81 22.22 77.88
97217_100_G 0.67 4.74 1.63 5204.55 1.22 112.05 61292.16 230307.47 0.7 2.87 0.62 3.12 0.65 21.43 0.197 0.87 27.64
97217_80_G 1.2 20.96 10.35 5310.13 5.06 430.95 63336.43 257116.75 1.91 30.52 1.87 11.28 2.32 72.1 0.77 3.09 16.15
97217_55_G 6.13 9.41 12.93 5367.78 7.75 701.58 63516.46 232396.8 3.02 31.54 2.97 19.41 4.13 98.5 2.23 5.71 22.12
97217_40_G 15.07 60.66 25.88 4478.11 19.24 1402.86 55760.45 209294.88 6.99 57.12 5.88 37.26 9.29 189.85 1.56 10.36 41.25
97217_25_G 11.67 185.76 112.51 5050.97 65.11 6014.97 71602.13 211325.31 27.45 291.19 18.66 167 34.55 847.78 9.54 48.97 146.95
97217_100_H 1.45 5.01 2.94 5566.45 1.24 145.54 62848.21 245832.11 0.76 6.6 1.14 4.02 0.9 39.04 0.256 1.2 25.61
97217_80_H 4.18 28.56 15.91 4952.52 8.03 654.89 64016.12 269740.88 3.04 33.5 2.67 17.63 3.94 82.8 1.03 5.71 20.12
97217_55_H 3.73 23.31 11.66 4308.03 6.13 752.29 56822.76 217050.23 3.64 33.31 3.2 20.4 4.49 99 1.67 7.16 24.28
97217_40_H 15.94 43.94 27.01 6457.71 16.53 1401.29 63017.98 239038.19 6.55 57.01 5.23 37.44 8.11 211.21 2.33 10.75 39.32
97217_25_H 15.77 49.86 73.04 5397.13 54.8 4588.98 56168.67 254952.69 19.83 203.67 16.15 128.87 25.43 710.13 7.25 42.1 127.89
97225_100_A 0.138 0.21 2.15 7009.91 11.65 236.14 118420.75 547999.25 0.197 2.5 2.63 2.29 22.63 164.72 0.267 0.54 233.38
97225_80_A 0.36 0.81 2.79 6991.29 5.8 203.36 117615.88 533000.56 0.33 3.72 1.9 1.42 19.45 92.34 0.203 0.41 197.71
97225_55_A 1.27 0.88 2.69 7209.43 11.45 115.56 115827.97 534019.63 0.64 8.39 1.45 2.84 30.69 79.29 0.29 0.74 180.02


Sample
ID_Spot
97225_40_A 1.3 8.14 5.23 7091.02 22.99 406.28 116400.12 528096.56 1.06 15.75 2.51 5.28 51.46 105.56 0.34 1.62 148.62
97225_25_A 2.1 32.21 12.01 7298.59 30.42 969.63 115523.09 538233.38 3.77 49.6 3.75 19.59 70.57 115.7 0.91 6.09 160.13
97225_100_B 0.26 1.4 1.7 7110.85 11.32 188.03 105481.35 486559.34 0.231 3.32 1.52 2.09 72.05 89.8 0.361 0.4 110.46
97225_80_B 0.39 1.66 2.26 7101.9 27.67 173.43 107869.02 500983.44 0.46 4.6 1.73 1.84 116.74 101.37 0.57 0.67 133.36
97225_55_B 0.53 4.56 2.74 7213.48 2.87 221.78 103344.02 493218.41 0.61 6.87 1.37 3.04 41.39 72.48 0.24 0.72 136.73
97225_40_B 0.35 0.001 4.4 7262.51 50.78 334.47 102750.77 452287.69 0.89 22.02 1.63 4.32 139.16 129.37 0.36 1.29 137.3
97225_25_B 6.26 4.97 10 6867.13 144.9 1187.44 99076.79 433927.63 2.96 32.24 2.44 15.95 191.49 255.37 1.72 14.63 121.88
97225_100_C 0.21 0.76 2.66 6903.09 29.25 245.45 94364.73 429419.22 0.23 1.82 1.91 2.16 90.3 108.12 0.94 0.59 63.11
97225_80_C 0.14 2.5 3.65 6900.58 62.83 240.13 96928.23 447873.19 0.27 4.24 2.29 1.63 114.56 195.85 0.62 1.16 83.93
97225_55_C 0.82 3.33 2.59 7091.58 40.18 166.9 102025.57 446393.53 0.58 5.72 2.15 2.63 117.72 124.74 0.34 0.7 100.05
97225_40_C 0.94 5.58 3.44 6971.92 90.88 330.92 98884.62 439993.31 0.85 9.97 1.55 4.42 133.45 246.59 0.61 1.16 127.31
97225_25_C 5.34 21.27 14.47 6917.97 312.97 1007.41 110471.86 451093.31 3.48 40.78 3.03 17.02 165.93 284.82 1.11 3.99 159.73
97225_100_D 0.34 0.78 2.64 7044.42 45.77 252.37 87573.85 407170.88 0.278 2.47 1.75 2.08 66.22 154.96 1.71 0.56 50.85
97225_80_D 0.12 1.76 3.04 7369.27 61.45 193.14 95663.72 454880.19 0.31 2.81 1.48 1.38 71.25 104.73 0.43 0.53 82.18
97225_55_D 1.63 0.001 2.82 7249.75 97.82 324.94 95804.03 437473.03 0.56 5.18 1.56 2.79 96.46 162.87 0.82 0.63 109.97
97225_40_D 1.23 6.65 6.96 6012.49 1168.06 2203.63 81548.66 354900.31 0.65 199.39 3.84 3.44 198.46 1195.9 1.45 2.29 147.13
97225_25_D 1.83 14.99 13.52 6205.92 1193.8 1523.9 81772.52 382409.78 2.3 41.36 3 12.07 317.94 1467.85 4.88 4.52 209.36
97225_100_E 2.38 5.64 7.22 7142.03 153.98 717.12 86554 394904.47 1.44 67.73 2.46 6.6 25.13 183.52 0.69 24.17 44.22
97225_80_E 6.32 23.43 21.38 6578.72 124.8 729.19 80613.89 377897.91 3.66 32.64 3.34 17.86 55.97 122.69 2.54 12.67 43.21
97225_55_E 0.001 108.18 25.63 6918.53 315.61 1919.67 78710.49 390870.03 7.92 129.8 6.66 48.22 417.99 525.76 10.67 28.57 46.12
97225_40_E 54.37 241.3 81.33 7743.79 621.28 4511.08 102583.11 454514.84 20.08 287.86 17.18 112.72 47.27 554.84 7.48 49.34 191.91
97225_25_E 65.04 232.96 216.3 7593.37 1749.5 7438.72 84279.17 319535.22 35.12 436.9 26.82 185.53 252.2 1294.26 14.38 166.2 175.58
97225_100_F 2.36 8.36 10.21 6720.33 112.88 329.52 78545.98 347284.44 1.24 11.31 2.58 6.04 215.38 147.61 2.67 5.66 32.93
97225_80_F 5.63 19.7 14.88 8880.7 485.34 631.81 73909.46 324531.34 2.91 31.28 2.7 14.9 324.34 479.44 3.26 22.62 38.32
97225_55_F 13.96 48.22 35.32 7745.32 780.71 1511.97 85002.02 358737.06 7.42 134.15 5.78 36.92 5553.71 1667.19 111.06 34.72 45.03
97225_40_F 20.93 11.64 75.92 7110.64 855.26 2208.14 76997.26 312071.31 11.41 308.31 7.37 55.22 983.29 465.53 18.13 23.08 58.93
97225_25_F 41.89 0.001 104.35 13476.81 1660.19 7062.54 73522.03 303866.94 38.06 324.19 28.36 181.28 4583.88 3465.42 94.51 63.43 166.3
97225_100_G 2.66 1.36 24.07 6693.77 449.02 196.77 64489.92 288153.59 0.72 30.89 4.19 3.44 995.24 661.69 10.7 7.49 49.91


Sample
ID_Spot
97225_80_G 6.55 21.49 18.48 6380.51 1021.31 1335.82 67508.48 292432.97 2.07 61.34 4.61 11.34 1122.96 1626.33 28.25 9.74 52.58
97225_55_G 22.54 51.58 27.72 6193.42 859.05 1466.06 70270.96 350032.38 8.38 77 5.45 35.98 146.26 811.2 3.06 7.5 48.88
97225_40_G 22.79 51.42 58.92 5364.01 1316.62 1545.29 53421.58 238860.69 7.78 75.24 5.16 39.87 587.92 1544.88 22.83 10.52 33.97
97225_25_G 97.52 306.78 192.06 7696.5 2135.23 6449.39 58507.17 299051.5 29.7 357.12 23.14 157.61 76.04 1325.45 11.05 31.23 128.11
97225_100_H 3.32 14.55 9.17 6893.58 1161.7 905.22 80838.57 352329.72 1.44 51.19 2.65 6.74 714.47 1753.68 15.33 5.73 112.81
97225_80_H 7.57 3.35 27.47 6836.5 1539.04 1612.08 87671.91 401446.84 3.35 61.56 4.48 17.02 2161.51 2538.6 76.2 8.44 174.01
97225_55_H 13.67 28.11 50.85 8864.9 1908.91 2008.06 96971.75 391857.13 5.97 110.92 16.21 29.96 7760.16 4277.3 141.86 11.78 386.13
97225_40_H 13.86 41.03 26.43 5652.05 3108.64 3307.72 65682.73 304642.97 5.25 211.5 18.87 32.3 11867.08 5616.39 249.35 26.78 181.63
97225_25_H 13.25 88.78 70.58 5005.34 5094.67 9918.99 75493.9 264445.81 10.08 224.26 10.29 61.11 4544.06 8637.84 238.78 16.51 194.79
98355_100_A 0.54 1.24 5.76 5715.82 47.49 160.44 76667.38 416772.53 0.221 1.21 8.08 2.16 30.84 96.47 0.34 0.727 112.49
98355_80_A 1.01 1.92 5.56 5622.5 73.4 147.51 78834.41 431454.03 0.236 2.12 7.73 1.35 27.08 65.61 0.148 0.38 85.24
98355_55_A 2.44 4.42 4.37 5663.76 32.12 171.84 77084.85 409923.94 0.51 3.64 7.25 2.52 20.22 74.58 0.178 0.81 67.55
98355_40_A 2.97 2.14 5.01 5670.43 26.4 237.2 80196.4 426649.38 0.84 6.64 7.12 4.53 15.82 48.68 0.184 0.96 56.57
98355_25_A 14.16 3.61 15.13 4686.16 28.89 588.75 75901.7 387291.19 2.92 29.52 5.07 15.51 13.3 85.65 0.88 3.7 45.46
98355_100_B 1.19 0.91 3.2 5657.17 3.01 148 68496.59 364693.19 0.107 0.94 5.11 1.96 10.49 48.69 0.116 0.495 32.04
98355_80_B 0.98 1.25 3.23 5615.04 0.49 126.5 68328.76 369036.72 0.222 1.51 4.19 1.97 5.33 34.46 0.084 0.25 25.22
98355_55_B 1.47 5.58 2.88 5372.02 1.08 191.85 65910.07 343270.53 0.44 4.07 3.48 2.24 3.39 45.33 0.09 0.45 22.53
98355_40_B 3.55 6.75 5.29 5249.11 1.6 142.09 68869.52 350840.31 0.68 6.01 3.06 3.78 4.13 43.18 0.31 0.68 22.76
98355_25_B 1.27 25.41 10.19 6173.66 7.56 527.63 72705.4 368005.75 2.38 22.59 4.81 14 4.17 64.66 0.58 3.2 19.42
98355_100_C 0.6 1.03 2.48 5582.27 1.09 105.88 62837.27 323981.69 0.111 0.91 2.82 1.58 2.88 58.47 0.064 0.206 30.29
98355_80_C 0.9 1.71 2.96 5446.07 0.45 57.24 64233.39 333070.44 0.158 0.81 2.62 1.57 3.19 30.25 0.103 0.159 35.1
98355_55_C 1.93 6.37 3.75 5575.09 1.44 191.56 63542.27 319095 0.35 1.88 2.2 1.99 2.66 39.47 0.132 0.34 48.45
98355_40_C 2.61 6.53 2.63 5514.95 3.48 132.94 65848.53 335529.44 0.61 6.21 3.02 3.56 3.05 36.14 0.3 0.55 72.28
98355_25_C 2.72 0.001 10.44 5778.55 7.16 483.09 71633.34 355946.41 2.04 16 3.83 13.25 4.09 67.77 1.51 2.37 78.21
98355_100_D 0.95 0.98 1.91 6429.01 237.45 1193.9 59013.73 323913.41 0.085 10.85 4.06 3.3 28.16 245.76 0.456 10.24 35.88
98355_80_D 1.58 0.75 2.22 6421.12 323.44 1267.38 60990.56 341151.97 0.143 16.11 3.78 4.59 54.91 369.97 0.716 11.73 49.34
98355_55_D 1.29 1.07 2.31 6820.49 273.27 1211.85 62857.28 344753.59 0.3 8.05 4.16 3.56 30.31 306.27 0.193 12.21 58.79
98355_40_D 3.25 12.4 3.08 7765.45 729.25 943.44 70267 347507.31 0.77 23.78 3.95 5.72 23.01 456.15 0.39 1.86 74.3


Sample
ID_Spot
98355_25_D 7.48 28.57 10.06 7226.71 816.36 1445.24 60617.42 327554.84 2.04 34.46 3.85 11.1 15.73 523.33 0.78 1.78 82.64
98355_100_E 2.65 7.15 7.09 7003.48 451.6 304.93 73559.76 387677.06 0.65 7.17 7.29 3.96 281.81 159.94 3.34 1.23 35.97
98355_80_E 8.41 12.24 9.7 6643.06 164.06 450.82 72134.31 389539.25 1.99 22.75 6.89 11.84 187.55 70.34 1.95 2.24 30.44
98355_55_E 5.53 7.48 27.77 6571.61 110.82 1095.75 77795.85 403901.31 5.13 39.24 8.59 29.63 783.73 138.07 13.7 4.13 26.03
98355_40_E 45.64 123.51 43.72 6222 51.48 1935.38 73093.86 390653.22 7.73 81.43 9.83 52.67 376.86 244.42 5.11 6.48 50.53
98355_25_E 135.38 518.4 106.08 7630.24 80.32 7652.89 67619.34 390669.75 32.84 223.27 25.21 204.87 328.08 907.71 8.08 33.26 124.6
98355_100_F 2.76 2.74 4.8 6357.18 17.83 183.21 65250.62 346684.97 0.6 4.91 4.88 3.35 20.55 39.85 0.48 0.52 19.58
98355_80_F 0.001 34.52 10.28 6530.7 31.94 369.99 69647.97 371498.56 1.82 8.55 4.9 9.88 3.77 56.89 0.85 1.8 19.08
98355_55_F 14.86 57 26.19 6482.76 29.75 899.09 75102.91 386510.13 4.56 44.54 4.45 24.29 5.97 111.98 2.16 3.64 23.78
98355_40_F 35.13 67.4 43.86 5455.34 49.25 1417.57 57715.38 302612.47 5.73 52.55 5.27 37.58 9.16 217.75 2.08 6.08 36.41
98355_25_F 116.58 206.26 159.77 10722.04 100.66 6978.81 79516.3 406200.09 37.13 220.29 16.19 181.6 44.79 844.32 11.95 30.78 159.19
98355_100_G 0.32 1.72 4.2 6637.35 9.56 145.86 62604.81 323535.66 0.7 3.14 3.57 3.23 1.99 32.76 0.139 0.52 25.05
98355_80_G 8.75 16.82 9.83 6358.15 14.6 327.27 62025.96 320332.09 1.38 13.03 3.9 8.88 2.86 46.4 0.36 1.07 28.27
98355_55_G 17.38 33.42 21.87 6488.91 12.41 688.09 59559.25 312780.53 3.14 30.57 3.25 18.31 5.73 81.55 1.77 3.46 21.33
98355_40_G 14.44 55.57 23.03 6861.44 16.2 852.42 67326.55 279488.56 3.21 30.32 3.39 22.44 5.09 129.05 1.47 3.21 21.62
98355_25_G 68.33 0.001 44.58 6309.71 74.92 2313.8 61648.47 272751.09 9.56 110.94 8.52 60.58 15.53 283.86 3.27 10.36 58.73
98355_100_H 2.35 6.39 3.47 6866.28 233.88 124.11 60993.12 314303.63 0.54 6.67 2.68 3.34 8.33 188.03 0.34 0.7 28.24
98355_80_H 2.86 27.29 8.03 6626.17 472.36 370.88 61651.24 316833.75 1.46 13.23 2.72 9.55 47.32 383.12 0.92 1.33 40.54
98355_55_H 4.17 23.26 18.14 6971.95 577.83 1629.38 56879.88 281299.06 2.29 27.08 2.87 13.16 642.65 736.87 18.4 2.57 33.35
98355_40_H 12.33 21.93 8.09 5529.31 2086.6 2253.96 48220.17 201172.02 3.38 79.21 5.01 19.37 35.12 1438.3 1.24 2.73 29.19
98355_25_H 13.1 0.001 90.89 5899.21 9426.62 16379.57 28831.54 120600.91 9.06 438.55 20.38 63.91 3839.48 7596.34 127.47 12.61 63.06
98359_100_A 0.89 0.28 1.97 5155.86 83.85 295.08 71507.77 375569.22 0.105 1.96 3.85 2.3 7.37 87.05 0.16 0.389 99.1
98359_80_A 0.64 3.05 2.62 5219.42 41.29 134.21 73027.66 389421.38 0.199 2.63 3.5 1.7 8.23 53.1 0.16 2.34 64.81
98359_55_A 2.01 6.43 2.34 5111.96 1.61 152.6 69484.04 366452.78 0.45 4.35 3.32 2.34 2.86 27.35 0.235 1.96 50.85
98359_40_A 5.07 5.39 5.68 5250.39 1.49 148.71 70842.09 372658.91 0.62 6.05 2.29 3.91 1.4 26.45 0.136 3.33 41.51
98359_25_A 14.36 7.48 18.51 4523.82 5.66 532.77 69690.9 341599.88 2.7 20.95 3.02 13.66 3.32 69.27 0.58 8.1 29.85
98359_100_B 0.87 0.28 1.78 4936.14 23.98 152.36 61188.7 321109.91 0.103 2.07 3.65 1.8 1.81 73.71 0.044 0.207 54.9
98359_80_B 0.74 2.87 1.58 5005.04 2.6 97.72 64117.52 331139.34 0.328 1.52 3.04 1.19 1.03 28.83 0.06 0.38 42.41


Sample
ID_Spot
98359_55_B 0.85 6.15 1.84 4997.4 0.9 193.66 62665.92 320117.16 0.4 3.85 2.83 2.3 1.14 20.95 0.157 0.52 37.53
98359_40_B 2.72 1 2.62 5108.13 1.48 138.25 65434.02 336027.06 0.7 6.11 2.6 3.71 1.08 41.69 0.126 0.65 38.11
98359_25_B 9.34 36.26 17.2 4932.36 4.83 536.52 65240.82 323575.19 1.89 19.11 3.12 12.41 3.04 57.78 0.75 2.23 32.91
98359_100_C 0.35 0.97 1.7 4903.19 1.42 131.86 57371.66 297024.63 0.084 9.34 2.68 1.44 5.56 25.07 0.034 0.144 32.56
98359_80_C 0.28 0.76 1.93 4943.03 0.4 75.48 59334.29 307361.75 0.205 1.4 2.65 0.96 0.66 28.16 0.078 0.28 30.94
98359_55_C 2.13 4.14 2.5 4978.02 0.78 174.13 60393.65 307603.44 0.35 1.94 2.83 2.03 0.92 27.2 0.046 0.6 33.48
98359_40_C 2.44 9.48 4.4 4939.95 1.26 160.23 60888.34 308996.72 0.49 5.86 2.47 3.95 0.9 27.81 0.074 1.06 34.83
98359_25_C 8.56 40.81 7.12 4685.97 4.62 424.1 60645.27 302050.69 1.9 15.54 2.84 12.05 2.59 48.3 0.68 2.76 46.73
98359_100_D 0.85 0.87 1.82 5348.59 0.371 108.87 56437.51 289109.75 0.069 0.4 2.44 1.68 0.541 26.33 0.035 0.153 39.78
98359_80_D 0.96 2.6 2.04 5498.72 0.41 74.36 59835.91 313633.91 0.141 1.35 2.76 2.29 0.66 25.96 0.038 0.204 54.79
98359_55_D 1.37 3.78 2.29 5397.37 0.83 138.84 57691.97 298639.34 0.32 2.48 2.76 2.41 0.74 16.67 0.114 0.35 68.81
98359_40_D 1.94 6.63 3.11 5637.41 2.74 119.24 62415.65 315019.06 0.48 3.42 2.13 3.43 1.6 18 0.27 0.62 95.38
98359_25_D 1.06 5.84 13.21 5009.01 8.41 385.34 60288.12 296060.66 1.41 10 3.11 11.95 2.57 51.89 0.62 2.15 143.8
98359_100_E 2.28 6.7 4.99 5693.73 1.73 120.81 61014.26 294051.94 0.6 5.77 0.87 3.19 0.77 22.66 0.235 0.97 18.37
98359_80_E 2.68 25.98 7.94 5703.57 3.71 359.4 59933.54 293452.13 1.48 8.44 1.07 8.7 2.03 37.9 0.64 2.48 23.36
98359_55_E 27.73 44.3 19.64 6335.57 8.38 845.04 65396.54 319323.88 2.87 24.87 2.47 22.56 4.73 85.3 2.19 4.88 28.19
98359_40_E 4.03 91.09 34.21 5890.06 12.74 1292.55 58709.2 274251.97 5.54 46.59 3.59 35.73 8.45 184.32 1.29 5.93 24.78
98359_25_E 88.56 0.001 199.35 6135.47 52.47 4619.15 51783.14 220297.39 19.94 209.49 12.45 125.24 28.88 612.7 6.96 26.93 78.4
98359_100_F 0.34 6.06 11.18 5376.1 2.45 117.25 54854.95 270489.22 0.56 3.38 1.33 4.39 0.71 22.55 0.171 0.56 23.29
98359_80_F 10.43 20.45 10.92 5545.46 4.28 369.16 56081.06 283891.38 1.75 11.38 1.43 9.97 2.15 49.12 0.41 1.87 16.37
98359_55_F 12.91 4.96 16.16 5018.12 7.04 777.74 56912.63 285265.88 2.89 25.69 2.92 19 4.46 74.04 1.43 4.11 35.53
98359_40_F 36.32 71.31 38.18 5154.94 18.9 1514.04 61955.3 298124.88 7.33 39.52 4.4 41.9 9.36 169.8 2.83 8.52 35.4
98359_25_F 132.88 261.06 213.89 4990.08 54.35 5214.77 88965.34 299012.84 20.08 128.23 24.21 140.9 34.68 693.69 10.34 24.89 110.36
98359_100_G 0.99 1.84 7.84 6065.3 1.48 122.57 58369.95 283876.56 0.62 5.77 2.29 3.19 0.88 35.08 0.109 0.67 24.71
98359_80_G 5.82 22.91 7.43 6486.02 3.49 306.39 61152.07 304762.22 1.24 11.51 2.48 8.59 1.73 59.96 0.105 5.64 25.48
98359_55_G 16.32 8.32 21.05 6366.62 8.73 607.2 64143.27 284995.59 2.74 22.78 3.24 16.17 3.46 69.29 0.25 4.12 26.7
98359_40_G 12.99 36.17 25.21 7365.09 11.35 721.1 68626 258389.66 2.63 32.38 3.48 19.71 4.13 99.63 1 5.21 36.11
98359_25_G 26.59 20.52 23.14 6516.75 14.08 1466.4 54682.33 183066.75 6.14 46.8 3.69 39.59 9.15 167 2.9 9.47 62.63


Sample
ID_Spot
98359_100_H 3.75 2.99 4.01 6224.87 12.51 207.87 58702.38 285996.91 0.6 6.59 2.59 3.5 1.68 45.43 0.204 3 60.05
98359_80_H 2.82 0.001 9.87 6294.9 7.55 238.55 61310.42 263535.66 0.98 9 1.89 6.58 1.44 32.42 0.5 1.61 104.34
98359_55_H 6.31 38.17 16.94 6217.4 47.8 711.08 59534.62 281567.31 3.06 58.95 2.67 18.7 4.28 83.31 1.28 5.5 133.56
98359_40_H 22.02 43.49 20.41 12534.47 79.04 857.8 71561.28 280557.31 3.93 27.23 5.46 86.26 5.75 109.72 1.69 17.16 239.34
98359_25_H 0.001 74.28 23.4 7188.94 52.02 1536.63 42252.8 179132.05 6.78 51.88 4.79 41.22 10.26 199.94 3.52 10.06 117.26

Ga Ge As Rb Sr Y Zr90 Zr91 Nb Mo Ag Cd In Sn Sb Cs Ba La Ce Pr
0.289 0.059 0.26 0.113 97.83 0.637 0.118 0.195 0.0091 0.132 0.046 0.119 0.0095 0.174 0.025 0.01 31.86 2.48 2.59 0.386
0.28 0.115 0.59 0.101 99.13 0.202 0.027 0.027 0.0101 0.187 0.026 0.118 0.0181 0.134 0.028 0.0226 27.73 1.112 0.471 0.126
0.205 0.35 1.08 0.264 99.69 0.03 0.064 0.77 0.088 0.31 0.035 0.35 0.0248 0.164 0.1 0.039 26.19 0.08 0.064 0.024
0.23 0.43 1.33 0.29 99.84 0.249 0.095 0.53 0.047 0.47 0.146 0.65 0.058 0.32 0.106 0.048 29.06 1.06 0.454 0.189
1.4 2.42 8.53 1.53 113.04 0.206 0.45 3.81 0.31 2.68 0.69 0.76 0.32 1.14 0.98 0.26 28.33 0.47 0.187 0.145
0.164 0.06 0.25 0.048 98.87 0.095 0.0166 0.092 0.014 0.129 0.026 0.046 0.0091 0.099 0.032 0.0078 26.24 0.376 0.295 0.0577
0.201 0.178 0.51 0.119 99.7 0.093 0.058 0.206 0.04 0.156 0.033 0.143 0.0175 0.226 0.04 0.0261 25.92 0.453 0.322 0.086
0.227 0.36 1.21 0.226 99.58 0.136 0.024 0.22 0.058 0.27 0.131 0.23 0.024 0.223 0.131 0.0259 27.05 0.778 0.4 0.123
0.356 0.37 1.29 0.32 98.14 0.473 0.136 0.36 0.025 0.42 0.107 0.43 0.03 0.29 0.27 0.055 28.35 1.9 1.36 0.277
0.99 1.82 4.97 1.1 90.62 1.46 0.4 2.61 0.28 2.98 0.51 2.47 0.06 0.95 0.76 0.16 32.27 6.98 3.72 1.45
0.173 0.066 0.3 0.048 94.49 0.0663 0.0216 0.08 0.0155 0.115 0.027 0.096 0.0084 0.113 0.0157 0.0093 23.09 0.478 0.301 0.0706
0.159 0.112 0.54 0.093 93.42 0.115 0.0181 0.114 0.03 0.136 0.055 0.096 0.0216 0.123 0.054 0.0124 23.17 0.568 0.297 0.078
0.227 0.31 1.02 0.163 89.69 0.272 0.045 0.35 0.031 0.35 0.057 0.38 0.03 0.158 0.105 0.0222 25.15 1.1 0.514 0.108
0.25 0.5 1.46 0.28 88.4 0.564 0.037 0.44 0.059 0.3 0.108 0.65 0.066 0.25 0.225 0.042 25.52 1.96 0.952 0.353
0.67 1.15 5.52 0.95 91.61 1.29 0.54 1.63 0.26 2.09 0.34 1.78 0.256 0.92 0.58 0.149 28.06 3.11 1.41 0.491
0.179 0.057 0.227 0.043 94.98 0.146 0.031 0.099 0.0123 0.111 0.028 0.026 0.0098 0.162 0.0282 0.0099 23.15 0.762 0.379 0.1098
0.146 0.158 0.69 0.089 98.26 0.098 0.031 0.34 0.0092 0.107 0.039 0.202 0.0119 0.184 0.046 0.0132 23.85 0.389 0.186 0.061
0.33 0.235 1.07 0.194 94.41 0.302 0.11 0.5 0.036 0.191 0.038 0.36 0.06 0.193 0.083 0.043 25.99 1.44 0.722 0.198
0.26 0.51 1.42 0.31 100.4 0.365 0.085 0.41 0.062 0.59 0.162 0.76 0.078 0.32 0.135 0.038 29.78 2.28 1.02 0.513
0.86 1.58 4.82 0.85 98.18 1.08 0.29 1.85 0.143 1 0.64 1.88 0.25 0.98 0.19 0.235 33.55 6.87 6.91 0.96
0.44 0.69 2.2 0.5 115.82 0.106 0.162 1.47 0.112 1.26 0.29 1.22 0.089 0.66 0.34 0.144 27.56 0.273 0.139 0.06


1.32 2.24 6.29 1.14 114.88 1.93 0.34 1.56 0.47 1.2 0.76 2.23 0.267 0.97 1.02 0.239 35.36 5.16 2.97 1.26
2.29 5.01 13.02 2.81 108.6 3.74 1.76 5.07 0.77 3.88 1.01 2.96 0.43 2.11 2.34 0.51 49.17 9.96 6.19 1.51
2.61 5.47 19.01 3.94 102.1 4.43 2.36 7.56 0.94 4.73 2.77 6.23 0.83 3.45 1.09 0.82 46.24 9.84 8.43 2.6
10.95 25.87 93.03 15.15 124.85 7.55 10.16 20.66 5.44 22.39 10.16 24.01 2.5 13.34 11.62 3.15 81.83 18.26 23.55 2.48
0.448 0.42 0.86 0.266 98.78 1.072 0.177 0.72 0.022 0.55 0.145 0.66 0.0166 0.28 0.078 0.051 33.08 3.9 1.91 0.805
0.74 0.93 4.22 0.81 110.75 2.2 0.29 2.98 0.5 1.03 0.76 1.54 0.255 1.24 0.43 0.258 38.03 6.8 3.12 1.22
0.84 2.42 5.82 1.5 111.94 3.57 0.44 1.99 0.43 0.47 0.57 3.26 0.42 1.48 0.91 0.34 39.03 12.31 4.9 2.28
1.49 2.28 6.6 1.54 87.97 2.89 0.77 2.75 0.3 1.94 0.55 2.24 0.235 1.98 1.4 0.31 36.26 13.53 4.43 1.98
2.29 4 13.63 2.81 65.19 1.75 0.52 4.32 0.84 4.07 2.24 2.6 0.39 2.14 1.45 0.42 38.63 16.01 4.56 2.37
0.27 0.26 1.37 0.164 103.57 1.18 0.104 0.23 0.086 0.31 0.078 0.188 0.032 0.202 0.074 0.026 32.91 5.22 1.48 0.693
0.34 0.42 2.25 0.32 83.64 1.93 0.107 0.83 0.073 0.64 0.137 0.55 0.108 0.38 0.051 0.062 32.04 9.71 2.42 1.52
0.98 1.58 4.6 0.96 108.29 3.67 0.42 1.3 0.34 1.74 0.53 1.41 0.194 1.26 0.42 0.121 40.59 13.1 4.24 2.35
1.45 2.56 6.75 1.38 102.31 1.6 0.31 3.33 0.41 1.64 0.78 4.02 0.33 1.39 1.06 0.23 34.87 10.14 3.46 1.81
1.3 2.43 9.05 1.86 92.34 3.72 1.11 3.31 0.3 1.8 0.67 1.89 0.35 2.22 1.05 0.33 52.26 17.38 6.8 2.94
0.35 0.41 1.45 0.246 101.59 1.25 0.112 0.51 0.077 0.55 0.146 0.41 0.061 0.33 0.107 0.051 34.27 3.87 2.89 0.549
0.77 1.19 3.52 0.7 108.49 2.75 0.22 1.75 0.34 1.56 0.41 0.52 0.15 0.88 0.55 0.124 42.02 5.68 2.8 1.36
1.13 2.39 5.99 1.56 108.61 3.88 1.23 2.76 0.32 4.31 1.06 1.7 0.105 2.5 0.94 0.25 53.94 10.85 8.85 1.86
7.62 15.65 43.8 8.79 131.1 5.01 2.52 11.45 1.74 8.83 4.69 15.91 1.39 7.67 3.61 1.49 54.43 17.58 13.22 5.65
9.57 14.68 65.94 9.98 199.86 23.33 4.61 14.81 2.25 19.79 6.99 11.86 2.54 11.67 4.65 2.36 178.6 64.67 31.76 14.75
0.621 0.081 0.222 0.114 113.4 0.0071 0.0415 0.112 0.0098 0.099 0.034 0.072 0.0096 0.231 0.04 0.0059 85.83 0.0104 0.0439 0.0063
0.471 0.179 0.7 0.096 113.59 0.0161 0.0188 0.224 0.034 0.238 0.025 0.127 0.0236 0.142 0.07 0.0222 78.45 0.0129 0.0161 0.0126
0.43 0.37 1.27 0.28 113.71 0.1 0.082 0.64 0.098 0.29 0.188 0.51 0.037 0.33 0.285 0.052 71.86 0.03 0.027 0.036
0.38 0.79 2.15 0.4 113.51 0.027 0.147 1.16 0.144 0.73 0.34 1.19 0.115 0.57 0.42 0.087 73.39 0.054 0.048 0.053
1.34 2.38 6.35 1.73 110.88 0.232 0.71 3.23 0.49 1.9 1.17 3.63 0.196 1.75 0.38 0.36 64.21 0.186 0.088 0.181
0.547 0.072 0.25 0.081 120.11 0.0202 0.026 0.116 0.0144 0.09 0.028 0.052 0.0115 0.216 0.029 0.01 87.27 0.0284 0.0251 0.0063
0.68 0.191 0.43 0.105 123.23 0.0208 0.053 0.319 0.045 0.106 0.02 0.134 0.0117 0.144 0.074 0.02 94.47 0.034 0.0321 0.0164
0.84 0.35 0.89 0.217 122.05 0.062 0.111 0.5 0.133 0.33 0.119 0.071 0.043 0.255 0.155 0.062 101.74 0.029 0.044 0.028
0.51 0.77 2.05 0.37 124.06 0.062 0.135 0.86 0.186 0.49 0.254 0.96 0.074 0.42 0.266 0.091 104.38 0.049 0.062 0.034
1.31 2.43 6.35 1.49 121.92 0.117 0.47 3.04 0.33 1.66 1.1 1.37 0.185 1.49 1.14 0.28 99.09 0.117 0.103 0.207
0.73 0.069 0.36 0.052 126.72 0.0145 0.0182 0.165 0.0085 0.066 0.034 0.067 0.0071 0.189 0.025 0.0137 102.59 0.0178 0.0299 0.0065

Table 2. (Continued

0.78 0.148 0.38 0.108 129 0.0205 0.052 0.288 0.0273 0.122 0.049 0.185 0.0039 0.211 0.051 0.034 123.08 0.07 0.064 0.0131
0.97 0.33 1.26 0.212 128.36 0.048 0.109 0.33 0.053 0.27 0.146 0.27 0.032 0.225 0.151 0.045 137.93 0.075 0.057 0.028
1.38 0.61 1.89 0.43 138.29 0.114 0.019 0.65 0.066 0.5 0.33 0.61 0.096 0.61 0.279 0.048 177.35 0.159 0.065 0.051
1.27 2.18 5.65 1.14 124.89 0.143 0.25 3.62 0.71 1.62 0.88 2.31 0.36 1.64 0.43 0.31 160.01 0.168 0.26 0.164
1.24 0.097 0.33 0.103 142.7 0.0087 0.0254 0.086 0.0035 0.131 0.036 0.067 0.0104 0.225 0.052 0.0126 154.58 0.0097 0.0212 0.0038
1.12 0.198 0.43 0.117 147.03 0.0209 0.067 0.175 0.0267 0.192 0.074 0.236 0.037 0.215 0.106 0.0158 160.86 0.025 0.0183 0.0039
1.21 0.46 1.43 0.222 150.12 0.0155 0.144 0.102 0.016 0.41 0.195 0.34 0.056 0.27 0.162 0.059 179.69 0.053 0.038 0.036
1.51 0.5 1.35 0.35 148.55 0.025 0.072 0.86 0.025 0.47 0.25 1.05 0.052 0.39 0.258 0.063 184.3 0.081 0.043 0.036
1.11 1.98 5.93 1 141.15 0.261 0.108 3.15 0.28 2 0.54 2.82 0.31 1.11 0.55 0.3 191.44 0.145 0.128 0.068
0.54 1.03 1.87 0.46 107.97 0.111 0.17 0.77 0.034 0.6 0.33 1.04 0.066 0.47 0.232 0.133 93.47 0.027 0.077 0.06
1.13 2.54 5.05 1.02 99.03 0.123 0.42 1.45 0.5 2.96 0.57 2.08 0.43 1.22 0.36 0.242 82.7 0.215 0.134 0.04
1.99 3.68 14.72 2.1 94.71 0.147 1.17 3.37 0.48 3.44 0.94 6.83 0.6 2.45 1.01 0.59 86.54 0.25 0.22 0.244
4.95 11.7 22.35 4.47 84.06 1.22 1.53 6.92 0.77 10.78 3.6 9.24 1.46 7.33 4.14 1.08 90.61 1.23 0.97 0.38
15.88 29.5 84.77 15.29 133.39 3.27 5.03 32.21 6.03 17.75 16.76 24.8 1.96 19.28 9.62 3.12 126.97 2.56 2.26 1.77
0.77 0.8 2.13 0.32 121.7 0.086 0.22 0.6 0.159 0.46 0.181 0.65 0.104 0.48 0.36 0.088 140.69 0.048 0.021 0.033
1.08 1.92 2.56 1.1 106.33 0.42 0.53 4.16 0.52 2.96 0.31 1.84 0.253 1.25 0.71 0.152 143.84 0.135 0.037 0.09
2.71 3.94 8.82 1.64 109.06 0.53 5.2 6.15 0.69 4.56 0.76 2.83 0.39 3.5 0.97 0.36 376.5 0.21 0.254 0.35
4.11 6.78 16.77 2.79 121.88 0.001 1.59 9.65 1.7 12.3 3.77 7.39 0.48 3.56 2.34 0.71 193.63 0.44 0.55 0.31
8.42 18.06 44.23 8.29 131.03 1.34 1.59 13.18 0.83 17.83 3.27 10.07 1.61 10.88 1.6 1.8 195.51 1.04 2.99 1.02
1.11 0.82 1.45 0.28 108.09 0.131 0.019 0.97 0.148 0.76 0.208 0.64 0.072 0.36 0.143 0.05 119.4 0.066 0.034 0.032
1.36 2.12 4.51 0.98 127.42 0.38 0.47 2.13 0.46 1.67 0.65 2.82 0.184 1.62 0.63 0.38 152.91 0.169 0.258 0.165
2.16 3.75 7.95 1.96 117.05 0.63 1.36 3.08 0.47 4.17 0.82 4.06 0.59 2.34 1.81 0.45 141.88 0.49 0.3 0.098
3.5 7.68 20.3 3.52 103 0.4 2.7 10.58 1.32 6.76 3.22 9.28 0.91 5.16 1.79 0.77 124.83 0.48 0.43 0.58
11.52 37.92 103.24 17.55 131.44 3.79 5.82 45.6 4.03 15.84 11.34 19.97 1.4 18.79 10.92 4.49 165.22 3.59 1.83 1.44
1.35 0.67 2.45 0.35 118.94 0.144 0.31 1.41 0.029 0.55 0.215 0.76 0.149 0.39 0.29 0.072 157.4 0.079 0.049 0.067
1.82 3.45 9.34 1.65 114.98 0.133 0.89 4 0.067 4.43 1.22 4.28 0.35 2.02 1.43 0.38 115.34 0.223 0.197 0.31
1.87 3.82 7.56 2.13 95.27 0.47 1.61 4.6 0.99 4.41 1.72 3.47 0.4 2.39 2.12 0.41 104.97 0.36 0.035 0.218
3.91 8.13 20.01 3.55 91.21 0.3 1.78 6.09 1.87 6.75 1.22 6.5 1.05 4.89 3.07 0.83 113.29 0.31 0.6 0.33
12.77 22.53 74.21 12.26 100.22 0.7 4.39 39.75 2.63 15.57 8.62 12.95 2.98 12.67 10 3.05 88.85 2.43 1.38 2.16
1.81 0.216 0.45 0.232 206.73 0.318 0.055 0.177 0.0157 0.292 0.063 0.431 0.0153 0.352 0.059 0.0156 163.9 0.447 0.363 0.0649


1.53 0.27 0.76 0.34 196.19 0.139 0.139 0.34 0.03 0.52 0.76 0.26 0.0069 0.333 0.139 0.036 148.62 0.267 0.177 0.0459
1.55 0.62 2.12 0.7 205.11 0.201 0.136 1.05 0.053 0.39 0.229 0.53 0.064 0.32 0.122 0.084 171.93 0.459 0.353 0.094
1.63 1 2.64 1.15 198.42 0.605 0.37 0.2 0.163 0.84 0.23 1.31 0.159 0.59 0.3 0.148 164.96 0.705 0.501 0.131
3.32 4.37 8.97 4.4 194.21 1.29 1.13 5.12 0.64 3.29 0.87 7.81 0.44 2.24 2.39 0.45 182.34 1 1.25 0.252
1.4 0.132 0.3 0.161 193.9 0.176 0.04 0.234 0.0227 0.388 0.056 0.248 0.0091 0.32 0.042 0.121 142.54 0.281 0.342 0.0523
1.59 0.29 0.83 0.29 194.45 0.324 0.094 0.3 0.0157 0.31 0.094 0.158 0.025 0.296 0.121 0.042 158.96 0.544 0.419 0.101
1.09 0.6 1.36 0.55 189.39 0.059 0.181 0.58 0.14 0.53 0.181 0.74 0.071 0.46 0.145 0.051 136.55 0.085 0.172 0.024
1.66 1.02 1.95 0.83 178.93 0.68 0.34 0.97 0.149 0.22 0.37 0.41 0.119 0.44 0.276 0.06 156.83 1.15 1.05 0.074
2.33 2.53 5.66 2.98 161.1 1.67 1.15 4.01 0.5 1.83 1.78 1.15 0.45 1.7 0.65 0.234 160.34 2.37 2.81 0.41
1.44 0.119 0.35 0.139 186.09 0.527 0.047 0.095 0.0145 0.241 0.042 0.65 0.0183 0.262 0.038 0.0143 163.42 0.83 0.93 0.165
1.45 0.207 0.62 0.226 184.64 1.09 0.147 0.219 0.048 0.319 0.069 0.161 0.023 0.308 0.087 0.0221 174.71 1.94 1.4 0.395
1.76 0.58 1.47 0.43 180.38 0.571 0.091 0.41 0.025 0.61 0.017 0.43 0.071 0.27 0.231 0.055 166.84 0.98 1.03 0.232
1.93 0.99 1.92 0.76 181.43 0.83 0.215 1.19 0.149 0.77 0.204 0.87 0.103 0.55 0.38 0.134 180.55 1.63 1.49 0.301
2.5 3.47 9.58 2.67 180.83 1.82 1 5.19 0.4 2.9 0.82 1.9 0.32 2.07 1.45 0.37 179.16 3.14 2.86 0.71
1.09 0.13 0.34 0.85 177.93 0.635 0.033 0.095 0.0145 0.219 0.055 0.069 0.0164 0.379 0.026 0.0126 123.46 0.782 1.74 0.18
1.06 0.275 0.47 0.222 186.82 0.73 0.105 0.212 0.033 0.168 0.134 0.27 0.037 0.437 0.102 0.0238 125.96 1.03 0.702 0.174
1.47 0.48 1.13 0.44 185.44 0.602 0.193 0.76 0.054 0.32 0.138 0.45 0.1 0.32 0.211 0.062 131.01 0.722 0.97 0.201
2.1 0.61 1.98 0.83 159.81 1.9 0.214 0.79 0.172 1.17 0.252 0.86 0.084 0.47 0.221 0.069 159.81 4.38 3.84 0.781
3.04 2.31 6.26 1.72 160.61 6.99 0.88 1.78 0.27 1.73 0.98 1.83 0.22 1.26 0.7 0.27 264.05 12.94 13.27 2.72
1.41 1.14 2.89 0.94 162.01 1.08 1.8 2.1 0.163 0.83 1.27 1.79 0.129 1.91 0.111 0.158 190.43 1.4 1.23 0.195
2.54 3.87 9.25 2.57 153.97 2.06 1.4 1.59 0.31 3.07 0.87 10.95 0.24 2.01 1.52 0.51 192.38 2.4 2.2 0.62
6.74 9.46 19.98 6.25 167.69 6.31 3.23 7.28 1.58 8.15 3.28 9.13 1.41 5.16 2.01 0.89 217.35 6.41 5.17 1.57
12.2 22.17 49.42 15.86 193.57 9.23 5.85 27.95 1.72 18.08 4.46 23.34 2.43 14.76 7.72 2.28 268.64 9.73 9.64 2
25.27 43.11 97.02 24.64 199.85 15.14 23.78 46.47 3.81 21.26 14.85 33.56 5.21 23.53 10.46 1.89 375.55 18.25 16.68 4.18
2.36 1.09 2.77 0.85 151.26 2.82 0.37 0.96 0.208 0.76 0.33 0.98 0.144 0.71 0.263 0.151 177.84 2.25 2.75 0.713
2.66 3.31 6.48 1.89 157.07 9.13 1.22 3.17 0.49 1.78 1.02 0.84 0.44 1.42 0.87 0.223 227.77 6.31 9.1 2.13
12.23 7.5 15.72 4.86 173.82 12.57 2.6 10.91 1.45 6.12 3.03 6.8 1.06 4.46 2.99 0.81 737.75 9.57 56.14 2.05
7.62 10.44 28.82 6.98 155.48 12.15 2.52 9.16 2.47 6.38 2.99 8.67 1.4 6.23 3.81 1.44 276.48 7.38 14.34 2.86
20.67 35.41 68.97 24.42 152.54 15.98 6.04 54.48 8.38 30.58 15.18 33.86 2.75 18.62 7.45 3.03 742.59 13.73 104.21 6.49
2.93 0.58 1.56 0.57 155.8 10.67 0.82 0.7 0.169 0.42 0.32 0.76 0.096 0.48 0.134 0.073 307.13 10.27 10.94 2.51


2.72 2.42 4.8 1.45 156.39 10.98 1.16 2.91 0.27 2.31 1.08 2.94 0.146 1.35 0.125 0.22 354.16 13.44 25.84 3.47
4.08 6.68 20.86 4.56 181.93 15.09 1.78 6.1 1.23 4.5 3.66 4.05 1.1 4.39 1.54 0.6 250.35 12.07 5.77 2.63
4.71 7.5 14.09 4.63 132.64 14.19 2.63 9.72 1.49 4.46 2.56 8.01 1.2 4.69 1.53 0.96 256.57 15.86 10.76 3.54
14.98 32.33 80.38 19.07 148.55 21.68 9.03 23.52 6.27 18.71 6.59 16.78 4.1 17.17 7.74 4.04 274.65 14.36 16.65 5.86
3.09 1.56 2.57 0.85 186.2 12.91 0.95 1.11 0.24 1.53 0.95 1.12 0.216 0.7 0.3 0.134 249.58 18.37 18.96 3.55
6.39 3.66 8.1 1.88 201.28 21.79 0.95 3.5 0.38 1.97 1.39 3.05 0.37 2.26 1.5 0.25 437.42 26.89 52.44 6.68
12.6 5.16 14.87 3.39 208.04 18.21 1.92 6.19 1.73 3.48 2.01 5.39 0.38 3.19 1.67 0.43 1199.26 26.84 163.57 6.77
18.47 4.94 10.8 3.5 208.2 44.51 5.02 7.52 0.76 3.46 2 3.08 0.93 3.07 1.17 0.71 1671.06 58 186.59 12.35
11.85 9.31 19.6 6.67 222.18 55.27 5.62 10.81 1.66 7.44 3.04 6.62 1.41 7.8 5.63 1.13 1419.87 72.04 301.29 17.47
2.32 0.105 0.25 0.09 164.29 0.0442 0.036 0.143 0.0216 0.152 0.04 0.252 0.0059 0.252 0.035 0.0097 250.44 0.425 0.212 0.0386
2.47 0.209 0.59 0.182 168.34 0.041 0.095 0.255 0.047 0.186 0.088 0.203 0.0214 0.158 0.044 0.0229 262.66 0.524 0.105 0.0209
2.78 0.51 0.98 0.38 168.1 0.072 0.127 0.41 0.089 0.128 0.166 0.174 0.066 0.29 0.175 0.066 252.21 0.105 0.027 0.03
1.71 0.89 1.88 0.59 170.07 0.075 0.228 1.29 0.225 0.31 0.211 0.8 0.119 0.4 0.123 0.095 245.61 0.136 0.048 0.038
1.46 3.1 5.17 2.26 155.8 0.135 0.54 3.54 0.53 0.78 1 2.21 0.201 1.64 0.87 0.32 223.98 0.257 0.162 0.179
2.03 0.089 0.238 0.071 167.05 0.0088 0.053 0.19 0.0128 0.097 0.013 0.075 0.0136 0.157 0.036 0.0071 238.67 0.0503 0.427 0.0202
1.99 0.206 0.41 0.163 160.26 0.0162 0.083 0.34 0.0175 0.191 0.085 0.152 0.04 0.131 0.06 0.0185 230.61 0.0176 0.0111 0.0219
2.11 0.47 1.24 0.26 152.23 0.052 0.079 0.36 0.078 0.56 0.18 0.32 0.034 0.3 0.127 0.0206 216.93 0.026 0.024 0.0261
1.6 0.75 1.76 0.52 151.87 0.088 0.134 0.62 0.038 0.48 0.143 0.39 0.071 0.32 0.153 0.081 214.98 0.064 0.04 0.063
2.01 3.59 4.46 2.1 160.76 0.234 1.13 2.33 0.61 1.8 0.67 1.46 0.202 1.54 0.81 0.36 221.25 0.169 0.262 0.118
1.69 0.067 0.198 0.052 146.77 0.0095 0.0144 0.149 0.0143 0.089 0.027 0.059 0.0026 0.238 0.033 0.0093 202.42 0.0368 0.196 0.0089
1.8 0.217 0.4 0.108 145.79 0.0169 0.059 0.35 0.0237 0.121 0.089 0.138 0.0085 0.145 0.077 0.02 199.97 0.029 0.0273 0.0079
1.6 0.25 0.76 0.258 137.35 0.048 0.102 0.88 0.0068 0.26 0.135 0.3 0.027 0.235 0.033 0.054 183.53 0.045 0.031 0.0169
1.83 0.67 1.53 0.7 137.33 0.084 0.128 0.4 0.09 0.92 0.169 0.64 0.117 0.43 0.147 0.081 192.41 0.064 0.038 0.03
2.53 2.52 3.9 1.44 139.54 0.29 0.44 2.85 0.31 0.26 0.82 2.19 0.28 1.37 0.87 0.32 199.11 0.207 0.198 0.102
1.843 0.073 0.203 0.615 210.62 0.452 0.29 0.198 0.0184 0.084 0.0362 0.1 0.0142 0.167 0.031 0.0287 197.17 0.663 0.599 0.14
1.75 0.161 0.32 1.5 221.73 0.43 0.395 0.281 0.081 0.156 0.047 0.103 0.0209 0.323 0.076 0.0423 199.39 1.024 1.148 0.191
1.55 0.36 0.77 0.69 217.34 0.435 0.479 0.48 0.047 0.26 0.156 0.34 0.056 0.2 0.135 0.034 182.75 0.771 0.789 0.141
1.43 0.89 1.18 0.42 165.43 0.769 0.366 0.78 0.145 0.75 0.225 0.78 0.077 0.37 0.111 0.08 211.52 1.55 1.48 0.413
1.84 3 4.17 1.12 145.39 0.75 0.39 2.06 0.39 1.4 0.9 1.6 0.251 1.44 0.63 0.28 198.71 1.76 1.98 0.389
2.73 0.72 1.93 0.43 192.06 1.05 0.238 1.27 0.039 0.4 0.259 0.8 0.089 0.45 0.159 0.069 369.39 6.69 1.81 0.453
2.44 1.62 6.13 1.18 194.28 0.202 0.45 0.27 0.164 1.57 0.82 0.34 0.28 1.42 0.41 0.218 348.85 0.206 0.184 0.041


3.09 6.52 9.67 3.32 214.18 0.49 2.37 6.91 1.05 3.82 2.83 4.35 0.69 3.13 1.74 0.82 399.64 0.62 0.45 0.133
5.39 11 29.6 5.97 195.33 0.77 4.07 10.83 1.65 6 0.72 10.79 0.88 6.57 2.2 1.24 358.22 0.56 1 0.77
16.58 43.92 90.07 25.02 186.24 3.23 12.05 32.04 0.71 10.91 22.76 20.2 2.6 21.29 8.07 3.12 328.93 2.33 2.08 3.24
2.3 0.57 1.48 0.38 183.41 0.08 0.108 0.46 0.036 0.89 0.189 0.41 0.065 0.37 0.232 0.055 275.99 0.047 0.03 0.023
3.29 2.01 4.83 1.16 201.3 0.151 0.16 1.5 0.228 1.18 0.97 1.34 0.243 1.12 0.38 0.273 296.07 0.154 0.016 0.131
2.46 4.15 10.83 2.7 206.12 0.5 1.52 6.04 0.75 2.74 1.44 4.41 0.49 3.23 1.25 0.48 325.8 0.156 0.39 0.25
4.01 6.7 13.82 3.98 161.84 0.15 3.1 8.22 1.25 4.15 2.4 2.86 0.82 4.36 1.47 0.7 250.62 0.42 0.69 0.29
21.01 38.44 73.54 23.54 257.53 3.88 10.26 47.15 5.87 21.45 7.94 24.33 3.6 20.77 11.96 3.52 302.23 2.8 0.58 1.38
2.01 0.74 1.98 0.42 192.01 0.055 0.119 0.29 0.118 0.43 0.16 0.49 0.063 0.34 0.278 0.097 279.18 0.056 0.05 0.028
2.13 1.26 2.66 0.85 199.72 0.251 0.31 1.44 0.028 1.14 0.94 0.91 0.165 0.93 0.37 0.172 291.95 0.105 0.162 0.073
2.48 3.84 10 1.83 172.15 0.166 0.62 4.03 0.38 3.18 1.18 2.55 0.33 2.19 1.03 0.37 273.52 0.207 0.186 0.204
2.37 3.58 8.03 2.23 173.45 0.48 1.45 8.17 0.078 0.41 0.98 3.66 0.54 2.48 1.2 0.46 267.88 0.224 0.234 0.239
5.64 10.9 26.22 6.47 170.76 1.3 3.96 12.85 1.96 10.18 4.61 9.98 1.28 7.01 4.64 1.41 299 2.16 1.06 0.22
2.15 0.58 1.56 0.35 147.27 0.887 0.117 0.76 0.044 0.43 0.224 0.59 0.062 0.34 0.195 0.079 217.4 1.268 0.949 0.372
2.78 2.08 2.58 1.13 153.53 1.85 0.61 1.62 0.35 1.82 0.95 2.06 0.264 1.28 0.112 0.211 244.32 2.3 1.75 0.549
3.18 2.9 5.67 1.4 138.43 0.97 0.74 1.95 0.194 2.19 0.37 2.47 0.225 1.59 0.87 0.29 323 2.29 6.69 0.53
2.05 4.79 8.97 2.43 110.57 2.69 1.3 4.58 0.35 0.73 1.43 1.78 0.46 2.12 1.25 0.44 289.22 3.85 3.44 0.95
12.52 7.97 19.99 7.77 116.7 4.21 4.87 9.68 0.46 15.4 2.85 8.69 0.79 7.67 4.31 1.17 941.25 10.73 57.26 2.63
1.397 0.081 0.253 0.087 110.03 0.344 0.038 0.086 0.0089 0.119 0.036 0.079 0.0122 0.193 0.031 0.0177 149.34 1.344 0.95 0.236
1.48 0.193 0.49 0.114 113.44 0.141 0.039 0.178 0.039 0.172 0.053 0.16 0.0291 0.222 0.046 0.0277 157.5 0.733 0.287 0.063
1.06 0.44 0.92 0.273 110.51 0.054 0.164 0.53 0.057 0.42 0.248 0.193 0.053 0.31 0.097 0.049 157.73 0.039 0.04 0.001
0.9 1.01 1.5 0.4 111.12 0.067 0.144 1.14 0.101 0.74 0.195 0.84 0.076 0.5 0.241 0.079 160.42 0.039 0.061 0.033
1.56 1.89 3.69 1.57 103.01 0.062 0.067 1.84 1.55 1.82 0.95 2.9 0.186 1.53 0.59 0.225 140.3 0.37 0.149 0.199
1.178 0.124 0.21 0.099 100.03 0.0223 0.038 0.122 0.0264 0.13 0.026 0.055 0.0122 0.229 0.012 0.0095 136.64 0.0099 0.0369 0.0044
1.095 0.243 0.41 0.101 99.25 0.029 0.036 0.233 0.0205 0.132 0.049 0.105 0.0135 0.137 0.043 0.0141 134.46 0.0065 0.0108 0.0083
0.94 0.4 1.15 0.228 99.12 0.051 0.031 0.095 0.077 0.4 0.127 0.23 0.0195 0.25 0.159 0.039 139.1 0.045 0.0124 0.0252
1.22 0.8 0.99 0.34 104.09 0.061 0.089 0.85 0.131 0.84 0.048 0.54 0.06 0.53 0.272 0.099 142.2 0.044 0.039 0.031
1.45 1.95 5.88 1.49 95.76 0.209 0.45 3.58 0.214 1.66 1.38 1.32 0.34 1.44 0.54 0.29 137.8 0.151 0.018 0.104
1.044 0.107 0.223 0.156 99.42 0.0112 0.0296 0.078 0.012 0.089 0.0233 0.086 0.0128 0.181 0.029 0.0109 131.46 0.0169 0.037 0.0043


1.072 0.165 0.35 0.084 98.43 0.0041 0.033 0.214 0.0031 0.122 0.064 0.078 0.0215 0.235 0.056 0.0198 131.73 0.0191 0.0171 0.0108
1.22 0.33 0.89 0.171 100.79 0.032 0.145 0.33 0.051 0.38 0.171 0.085 0.027 0.251 0.087 0.052 140.09 0.059 0.001 0.0167
1.03 0.63 1.02 0.33 98.44 0.054 0.165 0.53 0.055 0.35 0.225 0.28 0.062 0.48 0.075 0.032 132.39 0.055 0.024 0.038
1.95 2.21 3.11 1.23 95.29 0.189 0.66 1.87 0.29 1.22 0.79 1.2 0.46 1.22 0.98 0.29 127.06 0.136 0.122 0.094
0.909 0.061 0.194 0.04 97.5 0.0028 0.015 0.068 0.0043 0.096 0.041 0.088 0.0113 0.222 0.036 0.0113 108.44 0.0087 0.0045 0.0049
0.83 0.152 0.42 0.097 97.72 0.0147 0.032 0.145 0.0223 0.117 0.043 0.093 0.0238 0.123 0.054 0.0125 105.28 0.0085 0.0134 0.0127
0.722 0.43 0.95 0.161 91.98 0.03 0.065 0.42 0.079 0.42 0.154 0.19 0.024 0.249 0.078 0.039 101.3 0.025 0.001 0.015
0.99 0.7 1.59 0.34 95.94 0.075 0.114 1.47 0.032 0.17 0.221 0.47 0.043 0.27 0.137 0.068 106.17 0.054 0.077 0.0212
1.16 1.86 4.03 0.91 87.44 0.208 0.37 0.91 0.26 1.94 0.137 1.02 0.139 1.32 0.77 0.223 95.92 0.123 0.111 0.148
1.26 0.55 1.97 0.31 114.69 0.021 0.077 0.74 0.114 0.6 0.222 0.47 0.061 0.31 0.037 0.058 168.93 0.026 0.034 0.046
1.97 1.43 3.11 0.97 114.12 0.25 0.31 2.47 0.237 1.16 0.43 0.91 0.166 0.97 0.53 0.131 186.32 0.147 0.025 0.144
2.12 4.5 7.5 2.29 123.07 0.3 1.06 4.84 0.75 2.79 2.06 4.4 0.63 2.16 0.91 0.54 189.52 0.5 0.033 0.3
2.95 6.9 17.56 2.91 109.47 0.26 2.18 9.93 0.77 4.04 1.5 3.19 0.71 3.48 2.28 0.36 174.35 0.72 0.056 0.217
11.22 24.79 41.45 11.19 102.25 3.83 5.85 32.64 5.77 21.71 9.85 17.14 2.2 16.52 7.08 2.11 135.46 1.38 2.14 1.9
1.33 0.59 1.12 0.32 113.21 0.082 0.078 0.46 0.072 0.93 0.198 0.092 0.077 0.35 0.214 0.04 177.44 0.021 0.061 0.033
0.97 1.65 4.63 0.88 120.06 0.085 0.185 2.7 0.241 1.27 0.67 1.42 0.258 1.02 0.59 0.207 177.52 0.228 0.069 0.079
2.32 4.86 5.4 2.1 126.26 0.55 1.2 2.73 0.42 4.45 1.43 3.04 0.5 1.97 1.26 0.27 209.42 0.282 0.099 0.195
3.56 7.75 14.22 3.57 130.86 0.53 1.68 12.09 0.84 7.66 3.66 4.93 0.45 3.8 1.11 0.94 189.63 0.56 0.71 0.61
13 26.08 39.31 13.17 102 2.01 4.34 19.73 3.05 16.15 8.47 9.78 3.26 18.68 6.5 3.83 190.86 1.33 1.3 1.41
1.43 0.6 1.15 0.35 111.29 0.0071 0.122 0.73 0.043 0.6 0.222 0.33 0.074 0.38 0.093 0.052 147.23 0.03 0.034 0.037
0.83 1.83 3.65 0.86 112.48 0.02 0.46 1.22 0.33 1 0.37 1.36 0.3 0.91 0.46 0.106 155.12 0.044 0.113 0.087
1.49 2.68 4.83 1.51 103.07 0.35 0.34 1.87 0.37 2.79 1.03 2.2 0.206 1.85 0.65 0.34 143.27 0.249 0.224 0.172
1.52 3.79 10.52 1.75 101.63 0.48 0.84 4.67 0.72 0.92 1.84 1.21 0.39 1.65 1.03 0.38 144.46 0.34 0.178 0.193
3.65 9.72 20.04 3.66 63.2 1.12 2.1 5.51 1.48 9.06 2.38 7.12 1.02 4.23 2.57 0.78 109.49 0.4 0.63 0.39
0.76 0.59 1.57 0.25 91.15 0.079 0.28 0.86 0.147 0.36 0.167 0.5 0.045 0.41 0.153 0.083 94.55 0.097 0.206 0.029
1.15 1.33 1.92 0.64 84.59 0.096 0.83 1.02 0.15 0.24 0.29 0.61 0.085 0.62 0.44 0.126 93.22 0.266 0.086 0.068
1.87 3.52 7.56 1.85 88.8 0.57 4.86 4.87 0.067 3.28 1.49 2.57 0.23 2.11 0.76 0.37 81.3 0.158 0.185 0.142
1.99 4 9.2 1.97 83.46 0.135 8.82 6.39 0.99 4.56 2.19 0.57 0.46 5.73 0.86 0.53 86.45 0.097 0.3 0.228
3.5 9.31 11.1 3.98 65.71 0.78 70.15 10.87 0.52 4.49 2.88 6.1 0.64 5.17 2.55 0.78 50.98 0.56 0.62 0.48


Nd Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Hf Ta W Re Au Tl Pb Bi Th U
1.35 0.183 0.0481 0.127 0.0211 0.108 0.0202 0.0345 0.0046 0.0449 0.0056 0.0164 0.0076 0.029 0.0162 0.029 0.0197 0.335 0.009 0.0106 0.0345
0.541 0.092 0.0174 0.058 0.0075 0.045 0.0122 0.024 0.005 0.052 0.0082 0.0321 0.0192 0.083 0.045 0.116 0.061 0.122 0.0231 0.0142 0.0112
0.099 0.282 0.044 0.084 0.0249 0.15 0.053 0.111 0.0258 0.019 0.0168 0.034 0.045 0.098 0.039 0.3 0.103 0.086 0.041 0.047 0.0052
0.38 0.33 0.046 0.129 0.03 0.189 0.047 0.083 0.038 0.091 0.058 0.149 0.062 0.179 0.117 0.45 0.164 0.105 0.068 0.025 0.056
0.67 1.39 0.37 0.41 0.213 0.23 0.13 0.27 0.156 0.86 0.234 0.7 0.18 0.84 0.39 1.32 0.77 0.67 0.38 0.115 0.206
0.129 0.065 0.0098 0.022 0.0046 0.027 0.0084 0.0102 0.0058 0.0159 0.0061 0.0201 0.0127 0.04 0.017 0.034 0.0242 0.072 0.0053 0.0104 0.0095
0.23 0.153 0.028 0.048 0.0071 0.068 0.0132 0.023 0.0105 0.029 0.0136 0.036 0.0106 0.039 0.047 0.108 0.051 0.049 0.0235 0.0077 0.0129
0.39 0.117 0.029 0.073 0.0284 0.099 0.025 0.073 0.017 0.081 0.0255 0.102 0.055 0.049 0.109 0.302 0.106 0.079 0.057 0.0058 0.0335
1.1 0.31 0.07 0.266 0.0215 0.169 0.039 0.118 0.0274 0.106 0.024 0.134 0.05 0.17 0.105 0.56 0.138 0.12 0.06 0.028 0.027
4.66 1.25 0.25 0.55 0.111 0.58 0.083 0.42 0.033 0.39 0.149 0.28 0.165 0.62 0.44 1.66 0.5 0.35 0.222 0.103 0.327
0.154 0.053 0.017 0.0228 0.0034 0.033 0.0059 0.0159 0.0058 0.0168 0.0053 0.0174 0.0051 0.0269 0.0118 0.036 0.0226 0.062 0.0125 0.0077 0.006
0.362 0.119 0.0187 0.056 0.0118 0.058 0.0177 0.047 0.0071 0.067 0.0106 0.035 0.0144 0.093 0.033 0.088 0.046 0.068 0.0193 0.0126 0.0147
0.451 0.174 0.03 0.082 0.0225 0.088 0.0224 0.036 0.0253 0.104 0.0186 0.041 0.031 0.068 0.069 0.127 0.1 0.086 0.035 0.0158 0.0214
0.63 0.51 0.041 0.156 0.04 0.199 0.055 0.104 0.034 0.199 0.044 0.119 0.069 0.13 0.081 0.34 0.181 0.208 0.047 0.043 0.035
1.62 1.29 0.224 0.78 0.164 0.31 0.191 0.232 0.132 0.51 0.114 0.26 0.021 0.41 0.42 0.41 0.51 0.48 0.255 0.134 0.064
0.404 0.106 0.0127 0.0277 0.0049 0.03 0.0089 0.0161 0.005 0.0206 0.0053 0.0276 0.0072 0.027 0.0069 0.056 0.0233 0.102 0.0112 0.0062 0.0102
0.21 0.119 0.0255 0.04 0.0118 0.051 0.0154 0.0287 0.0087 0.041 0.013 0.03 0.0215 0.02 0.044 0.086 0.049 0.037 0.0236 0.0152 0.0047
0.77 0.262 0.042 0.083 0.015 0.091 0.0159 0.047 0.022 0.04 0.0286 0.108 0.039 0.118 0.052 0.154 0.104 0.066 0.049 0.027 0.0225
1.42 0.39 0.043 0.124 0.046 0.148 0.058 0.134 0.0254 0.121 0.027 0.088 0.073 0.305 0.069 0.25 0.178 0.126 0.084 0.044 0.037
3.91 1.25 0.194 0.58 0.135 0.192 0.144 0.177 0.023 0.22 0.122 0.49 0.033 0.44 0.31 0.8 0.47 0.4 0.18 0.115 0.095
0.36 0.48 0.109 0.46 0.062 0.33 0.124 0.197 0.102 0.31 0.097 0.275 0.093 0.35 0.216 0.63 0.29 0.192 0.057 0.04 0.027
4.82 1.88 0.166 0.76 0.093 0.8 0.129 0.42 0.168 0.2 0.178 0.34 0.31 0.74 0.53 0.94 0.58 0.57 0.28 0.167 0.124
5.06 4.03 0.75 1.42 0.37 2.24 0.68 0.68 0.39 0.49 0.53 1.54 0.39 1.19 0.85 1.52 1.59 1.25 0.85 0.38 0.32
10.96 4.54 0.79 1.73 0.37 1.93 0.64 0.82 0.54 2.58 0.41 1.44 0.67 0.22 1.47 1.85 2.35 1.13 1.03 0.33 0.24
24.06 16.18 1.52 5.8 1.23 6.48 2.27 1.37 1.81 6.1 2.35 11.74 4.48 13.74 4.26 15.1 9.89 5.04 2.82 3.1 0.74
2.7 0.57 0.13 0.254 0.061 0.199 0.046 0.089 0.039 0.143 0.058 0.109 0.034 0.064 0.086 0.34 0.11 0.167 0.069 0.027 0.038
4.08 1.54 0.197 0.59 0.112 0.48 0.084 0.5 0.024 0.39 0.124 0.29 0.236 0.25 0.27 0.97 0.44 0.6 0.272 0.1 0.067
7.68 1.69 0.42 1.03 0.2 1.71 0.25 0.52 0.214 1.17 0.23 1.05 0.25 0.66 0.53 0.83 0.75 0.73 0.208 0.148 0.169
8.7 2.32 0.37 0.44 0.163 1.1 0.3 0.48 0.208 0.28 0.125 0.42 0.3 0.91 0.52 0.81 0.82 0.77 0.37 0.144 0.168
9.83 2.7 0.33 1.26 0.27 1.62 0.57 0.6 0.28 1.04 0.36 1.18 0.4 1.06 0.93 3.97 1.4 0.97 0.57 0.24 0.159
2.82 0.31 0.08 0.434 0.031 0.282 0.05 0.097 0.029 0.118 0.036 0.121 0.046 0.077 0.048 0.166 0.099 0.053 0.052 0.024 0.043


6.63 0.67 0.199 0.64 0.075 0.24 0.06 0.179 0.045 0.31 0.041 0.144 0.014 0.224 0.098 0.39 0.163 0.154 0.065 0.05 0.075
9.97 1.23 0.49 1.01 0.203 0.47 0.184 0.52 0.14 0.25 0.148 0.28 0.23 0.28 0.51 0.93 0.45 0.39 0.153 0.096 0.151
4.67 2.69 0.28 0.93 0.114 0.85 0.157 0.36 0.066 0.98 0.07 0.58 0.29 0.64 0.88 1.11 0.91 0.62 0.43 0.052 0.088
11.23 2.78 0.37 1.3 0.223 0.84 0.3 0.47 0.144 0.44 0.39 0.71 0.088 1.73 0.83 2.75 0.83 0.95 0.31 0.24 0.115
2.39 0.34 0.085 0.224 0.047 0.203 0.054 0.135 0.0222 0.128 0.041 0.077 0.077 0.119 0.095 0.206 0.108 0.158 0.064 0.027 0.058
5.26 1.2 0.3 0.52 0.147 0.51 0.143 0.241 0.125 0.3 0.132 0.31 0.199 0.58 0.208 0.92 0.41 0.26 0.166 0.073 0.192
5.2 1.26 0.31 1.01 0.145 1.07 0.133 0.4 0.187 0.99 0.276 0.78 0.26 1.21 0.43 1.21 0.74 0.65 0.32 0.216 0.328
12.41 11.78 1.18 1.96 0.96 4.1 0.89 3.04 1.22 2.07 1.5 4.23 1.42 2.33 4.06 7.97 4.53 4.3 1.53 0.83 0.79
55.41 13.9 2.16 8.21 1.51 4.61 1.62 5.55 0.91 2.29 2.37 4.46 1.84 8.46 4.29 5.93 4.25 3.75 3.57 0.75 1.76
0.043 0.054 0.0076 0.0253 0.0066 0.033 0.0041 0.0092 0.008 0.019 0.006 0.0195 0.008 0.0135 0.0076 0.0258 0.0203 0.036 0.0097 0.0065 0.002
0.092 0.188 0.0164 0.024 0.001 0.069 0.01 0.03 0.0013 0.047 0.0103 0.034 0.0197 0.052 0.045 0.109 0.056 0.044 0.0237 0.0113 0.0076
0.124 0.27 0.094 0.014 0.049 0.266 0.052 0.121 0.023 0.109 0.0243 0.21 0.057 0.017 0.076 0.33 0.122 0.094 0.055 0.0143 0.0179
0.32 0.93 0.069 0.32 0.039 0.169 0.073 0.125 0.041 0.34 0.044 0.247 0.083 0.38 0.158 0.59 0.264 0.184 0.077 0.048 0.056
1.08 2.53 0.33 0.89 0.269 1 0.287 0.6 0.282 1.77 0.211 0.84 0.53 0.41 0.6 1.56 0.68 0.57 0.37 0.162 0.074
0.022 0.079 0.0119 0.0037 0.0079 0.024 0.0054 0.025 0.0058 0.0196 0.0062 0.0246 0.0102 0.031 0.0209 0.045 0.027 0.073 0.0096 0.0082 0.0064
0.08 0.162 0.03 0.047 0.0141 0.113 0.0213 0.045 0.0208 0.07 0.0191 0.062 0.006 0.056 0.0188 0.066 0.043 0.027 0.028 0.0169 0.0161
0.118 0.39 0.052 0.074 0.0053 0.179 0.039 0.034 0.0218 0.18 0.04 0.13 0.069 0.117 0.093 0.196 0.128 0.119 0.033 0.0127 0.0238
0.35 0.67 0.034 0.168 0.036 0.222 0.066 0.046 0.0051 0.253 0.069 0.07 0.014 0.108 0.144 0.53 0.205 0.136 0.099 0.074 0.029
0.096 1.79 0.44 1.32 0.102 1.33 0.3 0.57 0.053 0.25 0.242 0.64 0.33 1 0.67 1.18 0.8 0.59 0.167 0.061 0.027
0.044 0.091 0.0085 0.045 0.0048 0.029 0.0073 0.0267 0.0051 0.0242 0.0076 0.0303 0.0072 0.0271 0.0238 0.0129 0.027 0.062 0.0122 0.0047 0.0055
0.055 0.17 0.0069 0.043 0.0079 0.094 0.0181 0.044 0.0145 0.069 0.0108 0.035 0.0145 0.055 0.048 0.091 0.054 0.063 0.019 0.0031 0.0078
0.116 0.25 0.029 0.096 0.0205 0.153 0.054 0.113 0.0215 0.145 0.046 0.09 0.043 0.281 0.058 0.134 0.095 0.067 0.033 0.0243 0.0164
0.214 0.47 0.094 0.251 0.0102 0.33 0.041 0.114 0.04 0.189 0.073 0.194 0.046 0.212 0.132 0.5 0.192 0.215 0.113 0.063 0.0163
0.98 1.23 0.144 0.81 0.123 0.55 0.262 0.39 0.128 1.37 0.272 0.44 0.37 0.68 0.65 1.79 0.56 0.57 0.36 0.205 0.138
0.04 0.079 0.0123 0.033 0.0034 0.048 0.0076 0.032 0.0091 0.0202 0.0056 0.026 0.0129 0.0188 0.032 0.033 0.028 0.029 0.0138 0.004 0.004
0.039 0.205 0.012 0.068 0.0229 0.044 0.0109 0.033 0.0107 0.041 0.0161 0.064 0.0264 0.081 0.041 0.094 0.052 0.047 0.03 0.012 0.014
0.176 0.47 0.054 0.103 0.044 0.164 0.053 0.07 0.023 0.156 0.0245 0.159 0.074 0.123 0.077 0.247 0.121 0.093 0.065 0.0174 0.0247
0.2 0.35 0.107 0.067 0.035 0.3 0.066 0.113 0.052 0.177 0.088 0.181 0.074 0.28 0.142 0.276 0.215 0.115 0.027 0.059 0.039
0.6 1.5 0.185 0.27 0.057 0.64 0.3 0.091 0.03 1.18 0.016 0.21 0.158 0.84 0.37 1.93 0.67 0.45 0.31 0.124 0.204
0.25 1.01 0.111 0.03 0.078 0.43 0.118 0.249 0.047 0.225 0.087 0.33 0.067 0.36 0.181 0.41 0.28 0.24 0.071 0.091 0.079
0.63 2.08 0.098 0.73 0.111 0.83 0.119 0.179 0.117 0.56 0.174 0.4 0.29 0.88 0.5 0.71 0.53 0.55 0.3 0.129 0.087


1.78 2.58 0.64 1.7 0.26 2.35 0.52 0.82 0.192 0.91 0.203 0.66 0.209 1.02 0.63 2.33 1.14 1.08 0.68 0.3 0.247
2.27 8.57 0.99 1.88 0.4 4.59 0.61 2.57 0.6 1.09 0.45 2.06 0.85 2.04 1.62 5.75 2.6 2.51 1.01 0.81 0.45
12.95 29.72 2.31 6.2 2.3 8.07 2.84 4.23 1.39 9.38 1.47 9.59 1.98 7.42 4.61 11.94 9.24 7.05 4.44 1.54 1.79
0.097 0.61 0.086 0.163 0.078 0.37 0.053 0.223 0.064 0.247 0.067 0.126 0.104 0.32 0.107 0.38 0.185 0.197 0.039 0.04 0.047
0.56 1.56 0.026 0.071 0.171 0.74 0.259 0.45 0.104 0.076 0.19 0.62 0.147 0.78 0.34 1.4 0.56 0.28 0.33 0.11 0.171
1.21 2.64 0.37 0.29 0.126 1.13 0.23 0.134 0.226 1.32 0.45 1.1 0.28 0.85 1.01 1.66 0.92 0.81 0.38 0.248 0.118
3.16 5.13 0.22 2.62 0.32 3.12 0.6 1.46 0.34 0.84 0.88 2.03 0.44 1.81 1.45 1.32 2.03 1.56 0.88 0.37 0.35
1.77 10.84 1.33 5.05 0.31 3.49 0.98 3.45 1.61 2.62 1.7 4.8 2.8 1.76 3.44 4.82 4.19 3.51 2.69 0.88 0.59
0.27 0.6 0.098 0.131 0.04 0.32 0.03 0.22 0.03 0.244 0.031 0.144 0.045 0.223 0.126 0.35 0.186 0.105 0.094 0.032 0.0217
0.28 1.24 0.3 1 0.067 0.79 0.33 0.4 0.184 0.25 0.195 0.63 0.41 0.65 0.43 0.78 0.73 0.46 0.28 0.142 0.095
1.42 2.53 0.31 1.44 0.253 1.33 0.192 1.14 0.188 1.79 0.34 1.29 0.38 2.24 0.67 1.93 0.98 1 0.49 0.35 0.194
2.82 3.55 0.3 1.65 0.35 3.05 0.66 2.26 0.53 1.78 0.39 3.39 0.53 2.8 1.01 2.21 2.34 1.14 1.11 0.7 0.38
12.12 30.53 0.82 10.05 2.64 9.29 3.66 10.89 2.78 7.65 2.4 7.8 3.22 8.54 7.51 13.42 9.52 9.85 4.48 3.48 1.17
0.32 0.71 0.071 0.269 0.041 0.3 0.075 0.185 0.023 0.35 0.064 0.256 0.0082 0.32 0.217 0.36 0.262 0.089 0.079 0.081 0.0084
0.71 3.48 0.49 1.32 0.164 1.41 0.47 0.74 0.299 0.38 0.36 0.59 0.35 1.83 0.57 1.76 1.02 0.61 0.28 0.263 0.125
1.06 3.52 0.65 0.88 0.27 1.4 0.45 0.85 0.2 0.94 0.51 0.96 0.4 1.05 0.53 1.64 1.06 0.86 0.36 0.21 0.143
0.32 2.49 1.06 2.32 0.35 3.04 0.54 1.13 0.53 1.77 0.55 2.21 0.74 2.57 1 4.35 2.13 1.6 0.87 0.13 0.46
12.89 16.09 2 5.35 1.19 8.57 2.14 3.67 2.71 9.98 1.81 8.31 2.97 9.09 3.6 7.07 6.01 3.69 3.11 0.22 1.74
0.393 0.107 0.0148 0.047 0.0069 0.044 0.0155 0.038 0.0062 0.042 0.0066 0.037 0.0088 0.033 0.031 0.088 0.033 0.094 0.0226 0.0114 0.0161
0.181 0.214 0.0199 0.043 0.0198 0.07 0.027 0.037 0.0121 0.081 0.018 0.083 0.03 0.095 0.061 0.155 0.062 0.06 0.031 0.0069 0.0121
0.44 0.43 0.074 0.114 0.025 0.237 0.026 0.176 0.037 0.133 0.047 0.199 0.082 0.138 0.121 0.148 0.138 0.147 0.086 0.039 0.0222
0.54 0.62 0.078 0.21 0.045 0.46 0.104 0.196 0.065 0.058 0.068 0.271 0.112 0.242 0.275 0.45 0.243 0.225 0.135 0.071 0.046
0.95 3.18 0.199 0.85 0.17 1.04 0.32 1.09 0.254 1.71 0.077 0.87 0.44 0.38 0.45 2.29 1.14 0.77 0.46 0.189 0.127
0.191 0.127 0.0181 0.04 0.0104 0.052 0.007 0.0181 0.0026 0.03 0.0134 0.038 0.0127 0.034 0.03 0.081 0.027 0.054 0.0148 0.0067 0.0094
0.475 0.229 0.021 0.082 0.0123 0.106 0.0264 0.088 0.013 0.062 0.0193 0.077 0.037 0.097 0.065 0.127 0.069 0.065 0.036 0.0192 0.0128
0.228 0.44 0.091 0.17 0.024 0.3 0.057 0.13 0.025 0.205 0.0045 0.121 0.078 0.228 0.134 0.243 0.15 0.106 0.063 0.037 0.025
0.74 0.67 0.119 0.32 0.056 0.3 0.095 0.219 0.059 0.187 0.062 0.202 0.102 0.221 0.159 0.33 0.157 0.218 0.061 0.062 0.041
1.67 1.62 0.33 0.87 0.133 0.93 0.25 0.43 0.243 0.67 0.21 0.48 0.44 1.05 0.53 0.79 0.75 1.17 0.58 0.253 0.169
0.648 0.142 0.0188 0.09 0.011 0.057 0.0164 0.06 0.0054 0.058 0.0079 0.028 0.0081 0.031 0.03 0.045 0.028 0.125 0.0133 0.0056 0.0305
1.36 0.287 0.038 0.255 0.0178 0.202 0.0298 0.084 0.0175 0.109 0.0183 0.064 0.037 0.07 0.044 0.024 0.05 0.14 0.0197 0.0134 0.065


0.6 0.47 0.071 0.132 0.033 0.176 0.072 0.13 0.05 0.118 0.045 0.12 0.078 0.263 0.067 0.241 0.112 0.105 0.063 0.031 0.03
1.12 0.55 0.118 0.26 0.096 0.45 0.073 0.31 0.042 0.027 0.044 0.246 0.101 0.118 0.193 0.61 0.212 1.13 0.096 0.061 0.051
2.79 3.14 0.257 0.69 0.21 0.91 0.23 0.32 0.222 0.75 0.235 0.76 0.54 0.83 0.42 0.82 0.63 0.77 0.51 0.229 0.156
0.642 0.129 0.0316 0.099 0.0129 0.077 0.0148 0.041 0.0081 0.044 0.0049 0.0053 0.0081 0.043 0.0218 0.039 0.03 0.12 0.0132 0.0059 0.0282
0.71 0.255 0.042 0.113 0.021 0.082 0.039 0.061 0.0128 0.061 0.0135 0.088 0.036 0.096 0.0164 0.124 0.057 0.063 0.026 0.0132 0.035
0.43 0.46 0.056 0.115 0.034 0.241 0.027 0.113 0.026 0.126 0.056 0.128 0.064 0.14 0.071 0.29 0.124 0.102 0.047 0.061 0.026
3.3 0.64 0.096 0.52 0.045 0.34 0.069 0.145 0.034 0.228 0.051 0.116 0.107 0.179 0.204 0.26 0.219 0.202 0.092 0.119 0.08
10.01 1.76 0.32 1.01 0.265 1.08 0.303 0.75 0.152 0.87 0.196 0.64 0.214 1.14 0.61 0.59 0.48 0.54 0.29 0.101 0.373
1.3 0.84 0.179 0.28 0.104 0.37 0.091 0.271 0.063 0.3 0.095 0.31 0.126 0.127 0.295 0.26 0.31 1.79 0.092 0.129 0.061
1.74 2.47 0.47 1.03 0.068 1.35 0.38 0.87 0.072 0.79 0.175 1.13 0.33 0.88 0.45 1.29 0.88 0.7 0.34 0.169 0.178
5.9 5.85 0.72 3.33 0.72 1.79 1 2.66 0.76 2.09 0.8 0.001 0.88 3.29 1.87 3.13 2.15 1.49 0.83 0.32 0.63
11.72 19.43 1.59 3.68 1.84 5.81 1.72 4.17 1.38 10.37 1.45 4.71 1.94 7.28 4.14 13.03 6.29 5.01 2.24 0.99 0.92
19.63 26.36 1.22 7.07 2.16 11.43 4.66 4.52 2.29 7.71 3.42 13.56 2.46 8.56 8.14 17.65 10.45 10.01 6.14 1.64 2.2
2.39 0.87 0.152 0.53 0.077 0.48 0.118 0.32 0.116 0.3 0.086 0.197 0.115 0.123 0.22 0.212 0.28 0.312 0.117 0.024 0.129
7.6 2.2 0.57 1.7 0.258 1.46 0.34 0.58 0.135 1.33 0.32 0.58 0.269 1.24 0.51 2.2 0.66 1.24 0.37 0.237 0.52
5.05 7.57 0.54 2.48 0.31 3.28 0.67 2.3 0.47 1.45 0.6 1.12 0.93 1.74 1.25 4.72 2.02 1.38 0.67 0.47 1.09
6.3 8.51 0.64 4.72 1.21 4.84 0.85 2.93 1.08 4.61 0.33 1.65 1.36 2.56 2.6 3.7 2.64 2.19 1.65 0.49 0.96
14.91 24.65 3.79 10.12 1.34 13.38 2.89 8.6 1.64 1.13 2.45 9.72 3.27 12.26 6.97 19.82 9.51 7.93 2.38 1.65 1.56
10.59 1.21 0.52 1.61 0.228 1.1 0.306 0.84 0.105 0.54 0.101 0.175 0.059 0.169 0.178 0.226 0.212 0.335 0.053 0.041 0.57
9.99 3.6 0.39 1.81 0.254 1.07 0.4 0.73 0.149 0.77 0.151 0.35 0.142 0.75 0.38 0.54 0.31 0.84 0.231 0.135 0.72
12.64 4.52 0.79 2.1 0.64 2.35 0.75 1.43 0.32 2.3 0.62 2.02 0.48 2.55 1.45 1.41 1.79 1.7 0.7 0.34 0.67
17.06 5.48 1.35 2.08 0.42 3.37 0.77 1 0.76 3.67 0.5 1.15 1.06 3.09 1.43 1.81 1.77 1.72 0.69 0.48 0.99
20.52 22.98 4.61 6.16 1.33 9.99 2.49 3.71 1.42 11.67 1.49 11.84 3.45 12.94 5.37 18.55 5.95 8.68 4.09 1.41 0.98
13.94 3.01 0.58 1.84 0.355 1.62 0.257 1.07 0.114 0.76 0.122 0.32 0.163 0.28 0.25 0.5 0.43 0.79 0.118 0.134 0.76
21.2 2.97 0.88 3.83 0.31 2.48 0.72 2.74 0.3 1.64 0.27 0.51 0.36 0.79 0.89 1.78 0.72 1.1 0.5 0.258 1.08
25.07 6.02 1.41 2.23 0.52 2.4 0.61 1.38 0.36 1.37 0.28 0.9 0.35 2.41 1.32 3.13 1.38 3.57 0.38 0.37 0.89
42.94 9.13 1.33 9.46 0.89 6.25 0.68 2.99 0.39 2.88 0.48 1.78 0.52 2.75 0.86 3.67 1.5 1.43 0.53 0.59 2.24
57.18 9.83 3.7 9.75 0.91 5.92 2.11 4.15 0.65 3.78 0.86 1.94 1.12 0.86 1.51 6.65 2.48 3.15 1.4 0.95 3.39
0.13 0.101 0.0136 0.0215 0.008 0.027 0.0071 0.0152 0.0099 0.0183 0.0075 0.052 0.0158 0.027 0.0249 0.026 0.0217 0.063 0.0059 0.0025 0.0032
0.133 0.12 0.0243 0.066 0.0143 0.107 0.0246 0.033 0.0108 0.074 0.0231 0.054 0.0145 0.055 0.036 0.056 0.04 0.041 0.0184 0.0106 0.0158


0.177 0.36 0.056 0.087 0.0232 0.142 0.036 0.108 0.0249 0.016 0.037 0.088 0.061 0.134 0.116 0.13 0.097 0.104 0.055 0.042 0.0162
0.32 0.76 0.123 0.078 0.042 0.256 0.12 0.237 0.045 0.088 0.048 0.223 0.127 0.032 0.269 0.252 0.195 0.202 0.164 0.0118 0.077
1.51 2.38 0.41 1.13 0.094 0.86 0.43 0.65 0.213 0.73 0.226 0.75 0.37 0.001 0.4 1.57 0.78 0.77 0.33 0.147 0.098
0.041 0.093 0.014 0.0148 0.0082 0.041 0.0073 0.0156 0.0072 0.0033 0.0077 0.031 0.0145 0.026 0.0194 0.046 0.033 0.114 0.0132 0.0053 0.0033
0.052 0.115 0.0163 0.063 0.0052 0.083 0.0148 0.032 0.0103 0.05 0.0155 0.073 0.0254 0.079 0.028 0.094 0.04 0.05 0.0202 0.0054 0.0045
0.11 0.35 0.023 0.19 0.041 0.089 0.029 0.067 0.0219 0.106 0.023 0.109 0.031 0.118 0.045 0.163 0.132 0.092 0.037 0.0115 0.0077
0.188 0.59 0.084 0.32 0.049 0.261 0.066 0.161 0.053 0.181 0.04 0.227 0.075 0.109 0.142 0.278 0.163 0.143 0.073 0.073 0.035
1 2.02 0.31 0.61 0.226 0.8 0.201 0.29 0.038 0.46 0.02 0.49 0.28 0.76 0.42 1.28 0.72 0.72 0.18 0.136 0.092
0.02 0.063 0.0089 0.0028 0.0037 0.028 0.0041 0.008 0.0057 0.0273 0.0074 0.0199 0.0057 0.031 0.0108 0.037 0.0206 0.0366 0.0079 0.00128 0.0037
0.067 0.16 0.0149 0.041 0.0175 0.066 0.0213 0.05 0.0188 0.064 0.0141 0.033 0.0231 0.051 0.04 0.122 0.041 0.036 0.0131 0.0129 0.0123
0.143 0.259 0.045 0.123 0.0187 0.141 0.0204 0.137 0.035 0.097 0.0213 0.1 0.049 0.109 0.077 0.107 0.096 0.091 0.044 0.0105 0.0132
0.25 0.4 0.056 0.154 0.033 0.38 0.072 0.109 0.05 0.069 0.065 0.125 0.071 0.33 0.096 0.152 0.11 0.122 0.049 0.069 0.04
1.05 1.56 0.283 0.086 0.195 1.47 0.173 0.83 0.121 0.58 0.182 0.6 0.297 0.66 0.39 0.11 0.5 0.65 0.4 0.203 0.052
0.528 0.112 0.0344 0.056 0.0078 0.063 0.0113 0.0258 0.0053 0.043 0.0056 0.0132 0.0075 0.029 0.0144 0.035 0.022 0.298 0.0083 0.027 0.0143
0.653 0.11 0.0235 0.077 0.0112 0.06 0.0152 0.043 0.012 0.067 0.0128 0.0247 0.0099 0.065 0.0231 0.037 0.038 0.235 0.0164 0.032 0.0197
0.73 0.36 0.042 0.115 0.0247 0.107 0.032 0.081 0.0087 0.056 0.034 0.061 0.027 0.1 0.088 0.031 0.093 0.213 0.037 0.0168 0.0247
1.13 0.44 0.053 0.194 0.031 0.253 0.082 0.123 0.047 0.194 0.035 0.116 0.094 0.255 0.143 0.178 0.178 0.167 0.05 0.056 0.029
2.1 1.39 0.3 0.47 0.142 0.62 0.109 0.47 0.108 0.3 0.162 0.38 0.265 0.59 0.35 0.82 0.58 0.37 0.185 0.104 0.1
1.54 0.55 0.085 0.311 0.0191 0.38 0.062 0.172 0.026 0.184 0.057 0.231 0.054 0.207 0.18 0.35 0.139 0.17 0.084 0.052 0.0236
0.082 2.05 0.43 0.52 0.112 0.84 0.173 0.64 0.12 0.16 0.256 0.42 0.34 0.66 0.46 1.12 0.58 0.62 0.27 0.117 0.079
0.2 4.23 0.46 0.17 0.037 2.91 0.52 0.48 0.29 0.19 0.29 2.06 0.93 0.65 0.8 0.64 1.57 1.33 0.77 0.115 0.27
2.32 5.13 0.73 1.3 0.43 3.72 0.54 3.44 1.13 0.72 1.2 2.1 0.65 2.51 1.78 2.88 2.46 1.77 0.91 0.45 0.049
4.21 32.8 5.28 2.42 2.53 15.58 4.78 3.4 1.92 4.03 2.04 11.68 2.73 10.66 5.39 20.84 9.6 8.75 4.27 0.54 1.8
0.241 0.56 0.076 0.208 0.026 0.224 0.079 0.189 0.0277 0.189 0.029 0.137 0.039 0.151 0.142 0.212 0.143 0.134 0.073 0.027 0.0258
0.91 1.3 0.202 0.68 0.069 0.73 0.258 0.55 0.09 0.43 0.096 0.32 0.221 0.73 0.58 0.98 0.47 0.35 0.179 0.087 0.059
1.06 3.02 0.33 0.91 0.48 0.85 0.43 0.64 0.161 0.62 0.222 1.27 0.3 1.15 0.81 2.28 0.77 1.08 0.29 0.203 0.138
0.46 3.9 1.11 2.62 0.29 2.45 0.87 1.07 0.35 1.68 0.52 1.11 0.86 3.32 1.35 4.26 1.87 1.34 0.49 0.89 0.231
11.65 21.06 3.66 7.09 2.63 17.52 3.32 7.05 2.31 6.42 2.26 0.93 5.18 8.97 4.13 17.86 10.37 6.29 3.25 1.58 2.42
0.234 0.56 0.021 0.143 0.053 0.27 0.033 0.1 0.047 0.043 0.06 0.163 0.019 0.255 0.064 0.31 0.151 0.16 0.073 0.045 0.0218
0.44 0.96 0.137 0.53 0.08 0.177 0.152 0.263 0.086 0.32 0.13 0.23 0.031 0.18 0.29 0.82 0.32 0.3 0.149 0.032 0.014


0.86 2.91 0.47 1.48 0.159 1.39 0.49 0.74 0.099 1.43 0.026 1.04 0.34 0.94 0.66 1.33 0.89 0.59 0.45 0.165 0.049
0.93 2.88 0.55 1.23 0.32 1.99 0.2 0.56 0.4 1.93 0.3 1.57 0.28 1.69 0.87 1.1 1.39 0.98 0.56 0.193 0.061
3.89 8.61 1.22 3.35 1.13 2.56 0.96 2.88 1.09 2.14 1.16 1.87 1.09 5.2 2.38 2.94 2.39 1.63 1.63 0.91 0.51
1.61 0.63 0.041 0.24 0.052 0.29 0.066 0.14 0.046 0.168 0.0139 0.16 0.065 0.25 0.109 0.179 0.09 0.112 0.085 0.025 0.066
1.3 1.4 0.218 0.44 0.085 0.79 0.14 0.42 0.097 0.47 0.103 0.68 0.239 0.14 0.38 0.76 0.41 0.34 0.217 0.188 0.091
1.95 2.38 0.41 0.72 0.188 0.95 0.196 0.62 0.287 0.37 0.124 0.82 0.166 1.12 0.45 0.86 0.49 0.53 0.39 0.129 0.191
5.68 3.26 0.31 1.04 0.22 1.37 0.3 0.51 0.24 1.15 0.179 0.59 0.48 0.93 0.74 1.87 0.74 0.71 0.34 0.23 0.13
10.82 9.16 1.42 5.64 0.54 3.26 1.18 1.77 1.01 1.29 0.62 2.03 1.17 4.54 1.61 2.98 2.91 3.01 1.42 0.77 0.59
1.018 0.155 0.0218 0.096 0.0097 0.063 0.0091 0.045 0.0096 0.0269 0.0072 0.0257 0.0079 0.041 0.0096 0.0117 0.031 0.142 0.0241 0.0034 0.0056
0.31 0.119 0.0169 0.046 0.0141 0.087 0.0243 0.046 0.0151 0.073 0.0092 0.065 0.0143 0.016 0.042 0.032 0.051 0.049 0.0185 0.0103 0.0142
0.161 0.205 0.0144 0.196 0.036 0.129 0.032 0.097 0.001 0.029 0.041 0.136 0.032 0.249 0.117 0.36 0.099 0.103 0.039 0.0087 0.015
0.28 0.72 0.108 0.172 0.037 0.278 0.08 0.17 0.056 0.051 0.042 0.276 0.079 0.029 0.155 0.31 0.198 0.153 0.131 0.038 0.026
0.46 1.52 0.31 0.59 0.127 1.11 0.196 0.42 0.137 0.66 0.145 0.39 0.052 0.76 0.66 1.33 0.83 0.58 0.194 0.018 0.025
0.0175 0.047 0.0077 0.0225 0.0068 0.036 0.0105 0.0222 0.0052 0.0248 0.0123 0.0255 0.0127 0.027 0.0144 0.029 0.0238 0.049 0.0073 0.0027 0.0049
0.05 0.18 0.0222 0.043 0.0092 0.09 0.0225 0.06 0.014 0.019 0.0257 0.035 0.0199 0.078 0.034 0.079 0.048 0.042 0.0244 0.0095 0.0036
0.072 0.36 0.034 0.092 0.034 0.149 0.0215 0.064 0.0029 0.102 0.0225 0.181 0.001 0.118 0.102 0.207 0.083 0.052 0.052 0.035 0.0057
0.183 0.23 0.015 0.021 0.034 0.255 0.064 0.045 0.0097 0.246 0.054 0.179 0.073 0.201 0.124 0.24 0.133 0.089 0.063 0.049 0.024
0.89 1.38 0.106 0.29 0.163 0.5 0.102 0.53 0.175 0.08 0.186 0.43 0.176 1.19 0.49 0.7 0.55 0.43 0.33 0.016 0.219
0.033 0.052 0.0149 0.0204 0.0044 0.0026 0.0082 0.0143 0.0047 0.0091 0.0067 0.0164 0.0094 0.052 0.0185 0.059 0.0195 0.0215 0.0082 0.0064 0.0034
0.018 0.165 0.0116 0.0106 0.0045 0.0149 0.013 0.0186 0.0091 0.044 0.0104 0.071 0.0257 0.027 0.031 0.051 0.045 0.047 0.0224 0.0059 0.0105
0.001 0.223 0.0085 0.086 0.0099 0.114 0.029 0.085 0.034 0.064 0.017 0.139 0.028 0.156 0.067 0.159 0.073 0.109 0.045 0.0269 0.0133
0.087 0.68 0.0137 0.019 0.03 0.184 0.046 0.097 0.0172 0.154 0.027 0.112 0.045 0.36 0.141 0.182 0.154 0.056 0.072 0.031 0.03
0.98 1.25 0.36 0.49 0.147 0.46 0.114 0.48 0.112 0.001 0.266 0.68 0.159 0.51 0.31 1.11 0.54 0.55 0.277 0.108 0.051
0.036 0.046 0.0065 0.0179 0.0038 0.0236 0.0059 0.0034 0.0058 0.0197 0.0062 0.0143 0.0058 0.0154 0.0081 0.033 0.019 0.0431 0.0083 0.0039 0.0028
0.044 0.177 0.0195 0.025 0.0022 0.05 0.0153 0.053 0.0012 0.042 0.0092 0.052 0.0123 0.049 0.03 0.07 0.044 0.03 0.0124 0.0118 0.0039
0.09 0.227 0.04 0.11 0.0234 0.072 0.036 0.022 0.0178 0.035 0.0189 0.088 0.0102 0.199 0.05 0.177 0.07 0.062 0.031 0.0241 0.012
0.064 0.35 0.0067 0.192 0.05 0.31 0.084 0.095 0.0042 0.212 0.057 0.109 0.063 0.07 0.062 0.253 0.123 0.14 0.063 0.042 0.0141
0.51 1.46 0.108 0.88 0.133 0.92 0.206 0.31 0.102 0.2 0.152 0.61 0.249 0.57 0.35 1.01 0.45 0.25 0.145 0.097 0.037
0.223 0.35 0.033 0.193 0.0117 0.18 0.032 0.095 0.031 0.15 0.074 0.109 0.052 0.303 0.124 0.31 0.131 0.133 0.078 0.004 0.021
0.43 0.78 0.36 0.53 0.112 0.6 0.15 0.37 0.148 0.71 0.091 0.42 0.21 0.83 0.42 0.7 0.45 0.211 0.193 0.116 0.081


0.15 4.18 0.24 0.13 0.191 0.85 0.209 0.27 0.06 2.2 0.22 0.1 0.41 0.17 0.41 1.68 0.81 0.51 0.29 0.278 0.196
1.5 6.35 0.67 1.83 0.39 0.63 0.74 1.28 0.155 2.86 0.45 1.8 0.42 1.67 0.84 2.44 1.55 1.16 0.43 0.28 0.35
9.89 10.28 1.79 4.92 1.05 7.96 1.15 3.44 0.62 2.22 2.4 6.83 3.21 6.35 6.76 16.04 3.86 3.41 3.24 1.87 1.32
0.141 0.4 0.044 0.242 0.037 0.196 0.049 0.12 0.039 0.133 0.042 0.119 0.056 0.221 0.136 0.32 0.11 0.119 0.08 0.0164 0.042
0.47 1.2 0.257 0.71 0.151 0.154 0.051 0.49 0.162 0.45 0.14 0.33 0.107 0.14 0.37 0.77 0.37 0.33 0.213 0.127 0.063
1.17 2.97 0.37 0.71 0.34 0.67 0.33 0.5 0.164 1.57 0.3 0.81 0.33 0.92 0.57 1.65 0.91 0.81 0.33 0.156 0.156
2.84 5.11 0.3 2 0.6 3.23 0.74 2.2 0.46 2.69 0.69 3.2 1.3 3.16 1.3 2.69 1.57 1.7 0.49 0.3 0.38
3.68 18.64 1.88 5.16 1.1 4.82 1.3 9.51 2.37 8.02 1.77 10.1 1.03 6.67 4.1 11.98 5.72 5.06 3.8 1.96 1.38
0.156 0.28 0.069 0.135 0.029 0.218 0.03 0.094 0.0042 0.21 0.057 0.152 0.024 0.3 0.088 0.188 0.122 0.108 0.104 0.004 0.0209
0.64 1.24 0.232 0.001 0.068 0.51 0.061 0.31 0.012 0.115 0.077 0.25 0.103 0.41 0.29 0.74 0.27 0.31 0.149 0.139 0.07
0.73 2.27 0.46 1.09 0.035 0.59 0.29 0.88 0.144 0.98 0.191 0.87 0.35 0.32 0.71 0.85 0.83 0.71 0.36 0.138 0.138
0.82 1.8 0.57 1 0.261 1.47 0.37 0.98 0.162 1.1 0.172 0.98 0.4 1.29 0.56 1.9 0.7 0.85 0.23 0.309 0.11
1.67 2.13 0.52 1.44 0.43 1.9 0.48 1.74 0.66 1.58 0.5 1.99 0.47 1.87 1.48 3.37 2.06 1.21 0.83 0.32 0.39
0.134 0.52 0.104 0.143 0.0165 0.189 0.033 0.04 0.0177 0.157 0.0188 0.162 0.025 0.186 0.132 0.194 0.129 0.404 0.075 0.044 0.024
0.29 0.89 0.09 0.076 0.118 0.231 0.1 0.172 0.0087 0.38 0.12 0.28 0.114 0.148 0.161 0.75 0.31 0.3 0.1 0.05 0.054
1.21 3.07 0.041 1.04 0.41 0.97 0.172 0.72 0.169 0.25 0.36 1.02 0.26 0.59 0.59 1 0.53 1.77 0.34 0.099 0.198
0.13 2.46 0.3 1.18 0.178 1.56 0.39 0.16 0.159 1.83 0.203 0.94 0.77 1.08 0.86 1.61 0.75 2.3 0.44 0.182 0.13
0.34 4.19 0.52 2.46 0.61 1.88 0.37 1.71 0.46 2.7 0.85 1.6 0.8 1.85 1.97 3.87 1.88 2.64 0.74 0.54 0.22

Ian Scharlotta, Andrzej Weber, S. Andy DuFrane et al. 78
Table 3. Laser ablation
87
Sr/
86
Sr ratio data for KN XIV teeth
(Sample ID_Sample Group)
Sample ID total Sr (V) 88Sr (V) 85Rb (V) 87Sr/86Sr 2 error 84Sr/86Sr 2 error
97.211_A1 0.5155146 0.45866608 2.89E-04 0.7123743 0.0001806 0.05591817 0.000181
97.211_A2 0.5160899 0.453345569 2.41E-04 0.7125077 0.0001684 0.05651735 0.000202
97.211_A3 0.4953065 0.428867147 2.70E-04 0.7125393 0.000204 0.05614837 0.000192
97.211_B1 0.5237191 0.436220764 2.80E-04 0.7122774 0.000198 0.05598387 0.000182
97.211_B2 0.5002587 0.4155926 1.92E-04 0.7120285 0.0001622 0.05664957 0.000115
97.211_B3 0.4872413 0.4048075 2.08E-04 0.71261 0.0001414 0.05541669 0.000272
97.211_C1 0.5060082 0.420384 1.77E-04 0.7116353 0.0001572 0.05709169 0.000112
97.211_C2 0.4307859 0.3578929 1.41E-04 0.7115308 0.000202 0.05717407 0.000116
97.211_C3 0.5063735 0.4208142 1.77E-04 0.7117711 0.000164 0.05517618 0.000191
97.211_D1 0.4994893 0.4150779 2.26E-04 0.712428 0.0001718 0.05474164 0.000404
97.211_D2 0.46193 0.3837917 1.12E-04 0.7119169 0.0001888 0.05678069 0.000109
97.211_D3 0.540535 0.4492097 1.67E-04 0.7114825 0.000214 0.0562032 0.000262
97.217_A1 0.4115777 0.3417825 3.00E-04 0.7158983 0.0001974 0.05696245 0.000175
97.217_A2 0.4041834 0.3355515 3.99E-04 0.7170207 0.000274 0.05821956 0.000114
97.217_A3 0.4004222 0.3324746 4.29E-04 0.7172126 0.0002 0.05708164 0.000112
97.217_B1 0.3322841 0.2759177 2.38E-04 0.7163448 0.00032 0.05776875 0.000196
97.217_B2 0.3403646 0.2825703 2.91E-04 0.7168815 0.0001302 0.05858407 0.000147
97.217_B3 0.3680073 0.3055199 3.38E-04 0.7174497 0.000204 0.05726491 0.000129
97.217_C1 0.2988586 0.2481763 2.15E-04 0.7153606 0.000214 0.0579626 0.000155
97.217_C2 0.4335352 0.359995 2.94E-04 0.7158572 0.00024 0.05737652 0.000145
97.217_C3 0.4269052 0.3544793 2.86E-04 0.7151173 0.000204 0.05757585 0.000102
97.217_D1 0.3627065 0.3011957 1.91E-04 0.7151284 0.000234 0.05827334 0.000167
97.217_D2 0.3776331 0.3135448 2.07E-04 0.715732 0.000195 0.05776602 0.000131
97.217_D3 0.379205 0.3147506 2.35E-04 0.7160216 0.000236 0.05894893 0.00015
97.225_A1 0.2559062 0.212446 3.16E-04 0.7144163 0.000294 0.05954526 0.000222
97.225_A2 0.2326417 0.1931096 2.65E-04 0.7161518 0.000312 0.05905727 0.00019
97.225_A3 0.2678432 0.2222689 3.13E-04 0.7163261 0.000208 0.05987656 0.000232
97.225_B1 0.2201758 0.182762 3.03E-04 0.7155843 0.000296 0.05914619 0.000166
97.225_B2 0.2348739 0.194932 3.21E-04 0.716525 0.000252 0.05998222 0.000208
97.225_B3 0.2483402 0.206077 3.51E-04 0.7161068 0.0003 0.05992156 0.000216
97.225_C1 0.2104877 0.1746781 3.30E-04 0.715738 0.0003 0.06010092 0.000246
97.225_C2 0.2590772 0.2149743 3.62E-04 0.7153563 0.000252 0.06026456 0.000159
97.225_C3 0.2533799 0.2102729 3.90E-04 0.7159872 0.00028 0.05949909 0.000169
97.225_D1 0.1873117 0.1554626 2.53E-04 0.7150012 0.00032 0.06019127 0.00026
97.225_D2 0.2179966 0.1808601 3.44E-04 0.7166502 0.000348 0.06077109 0.00023
97.225_D3 0.1321271 0.1097235 1.64E-04 0.7152321 0.000672 0.05440657 0.000842
98.355_A1 0.2093049 0.174305 5.31E-05 0.7132161 0.000366 0.03778981 0.001754
98.355_A2 0.1914608 0.1597384 5.37E-05 0.7152994 0.00042 0.02281661 0.001328
98.355_B1 0.17089 0.1419118 5.08E-05 0.7126116 0.00045 0.06041714 0.00036
98.355_B2 0.195499 0.1623537 5.24E-05 0.7120714 0.000302 0.05998997 0.000192
98.355_B3 0.2208219 0.1833904 6.25E-05 0.7119601 0.000278 0.05933711 0.00024
98.355_C1 0.170033 0.1412572 4.84E-05 0.7116431 0.000414 0.05909435 0.00024
98.355_C2 0.1643442 0.1365448 6.00E-05 0.7121804 0.000448 0.05917739 0.000226


Sample ID total Sr (V) 88Sr (V) 85Rb (V) 87Sr/86Sr 2 error 84Sr/86Sr 2 error
98.355_C3 0.1749326 0.1453045 6.72E-05 0.7126502 0.000346 0.05839649 0.000288
98.355_D1 0.1417553 0.1177061 5.70E-05 0.713514 0.000632 0.05987801 0.000342
98.355_D2 0.1710117 0.1420012 1.05E-04 0.7136801 0.00039 0.05868803 0.000278
98.355_D3 0.154442 0.1282176 6.71E-05 0.7146961 0.000464 0.05890335 0.00024
98.359_A1 0.08855514 0.07353076 3.41E-05 0.7117397 0.00069 0.06180479 0.00049
98.359_A2 0.09535257 0.07918973 3.17E-05 0.7127162 0.00066 0.05925366 0.00047
98.359_A3 0.09603494 0.07977681 3.54E-05 0.7118754 0.000672 0.05880733 0.000402
98.359_B1 0.07893794 0.06555476 2.82E-05 0.7117544 0.00071 0.06094116 0.000444
98.359_B2 0.0850022 0.07058874 2.74E-05 0.7129407 0.000916 0.06024675 0.000504
98.359_B3 0.09881024 0.08204339 2.92E-05 0.7129047 0.000712 0.06003406 0.00044
98.359_C1 0.07774534 0.06454512 2.07E-05 0.7141845 0.001052 0.05964469 0.000504
98.359_C2 0.09139404 0.07587025 1.97E-05 0.7134008 0.00068 0.05944841 0.000456
98.359_C3 0.0969025 0.08046143 2.68E-05 0.7137356 0.00061 0.05919033 0.000352
98.359_D1 0.0784394 0.0651374 1.65E-05 0.7133296 0.00086 0.06141835 0.000484
98.359_D2 0.08522065 0.07078526 2.26E-05 0.7123873 0.00088 0.06142619 0.000472
98.359_D3 0.08934028 0.0742008 3.15E-05 0.7126201 0.0008 0.06015517 0.000414

We must first establish the veracity of hypothesized expectations for Cis-Baikal
inhabitants. Within each sampling group, five lines of different sizes: 100, 80, 55, 40, and 25
m, were drawn to demonstrate the impact that sample size has within a microsampling
environmental. Figures 3 and 4 show the results of different laser spot sizes being used on
strontium and rubidium at full laser power; rubidium being representative of elements of low
concentration (below 20 ppm) and strontium of elements of higher concentration. The results
are not surprising as the direct relationship between the physical amounts of sample
introduced into the ICP-MS is integral to the functioning of the equipment; however it does
provide a reminder that mass ranges with low concentrations are subject to significantly
larger error terms as beam size is reduced. As such, the use of low concentration mass ranges
(i.e., rubidium or zirconiuim) for correction factors must be taken carefully as the sampling
methodology can have a major impact on the effectiveness of such a correction factor. The
difference in variability is strictly the results of resultant signal strength, which can be equally
altered by changes in the spot size and the laser power. This variability viewed as confidence
ellipses on bivariate plots will yield relatively larger or smaller ellipses. Figure 5
demonstrates this as a compounded effect of both laser power and spot size as each ellipse
represents one group of five laser lines of different size. The extent of variability related to
laser effects was somewhat surprising, not in that the concentrations were more variable, but
rather that these data formed significantly different shapes in statistical space. This could be
interpreted as reflecting significant internal variability within a single tooth, greater than may
actually be present, simply as an effect of the laser power. As these data came from
prehistoric hunter-gatherer teeth, it is possible that such variability is reflective of provenance
shifts during the life of the individual, however with the neat divide between groups measured
with 50% and 100% laser power, it is reasonable to assume that the ranges seen are in fact the
result of the laser settings and not fully reflective of internal variability within the enamel
matrix.

Figure 3. Rubidium values by spot size

Figure 4. Strontium values by spot size

Figure 5. Impact of laser effects shown by groups variability clustering by laser power rather than by
internal variability

Figure 6. Strontium and zinc bivariate plot, suggests a transitional period during the early period of
molar formation followed by a period of relative stability in geography and diet and the beginning of
another transition towards the end of molar formation

Figure 7. Barium and manganese bivariate plot shows an intriguing separation between paired groups
A-B and C-D demonstrating a clear shift in geography or diet between the first and second half of the
molar growth period
The next question is whether there is adequate variability reflected in the geochemical
data from serial sampling of a tooth to potentially address the underlying concern of the
disjunction between enamel matrix formation and the supposed dietary source of these
signals. Figures 6 and 7 demonstrate that there is significant variability within the span of a
single tooth. As noted by Britton et al. [46] and Montgomery et al.[51], the incorporation of a
sudden change in geochemical input signal will lead to a moderately sloped interchange
reflecting both the old and new end-members of the geochemical signal, so any significant
change in the elemental data is likely outstripping the visibility of this effect, or showing
snapshots along the transition slope still reflecting different values and statistical morphology.
This is highly suggestive of the presence of useful variability in trace element composition in
the hunter-gatherer population of Cis-Baikal comparable to effects noted in agrarian groups
by Cucina et al. [5, 69] and Dudgeon [70].
However, one interest aspect of the range of variability within a single tooth raises some
concerns about the extent of the validity of the assumption that the hydroxyapatite matrix
contains relatively stable quantities of Ca and P. Figures 8 and 9, show calcium and
phosphorous projected against strontium, two elements that are supposed to be present in a
fairly constant ratio throughout the tooth, should show similar patterning. The predictable
nature of calcium phosphate matrices is the primary feature that enables geochemical research
to be conducted on skeletal tissues. The range of variability visible in this one sample is still
within the ranges to be expected for normal Ca:P ratios of teeth not significantly altered by
diagenetic processes, however the distribution and differences in statistical morphology is
intriguing.

Figure 8. Strontium and calcium are strongly correlated as expected as interchangeable mineral
components

Figure 9. Surprising variability in the phosphorus values both in extent and direction with correlation
not following suit of Sr/Ca ratios as is generally hypothesized
After establishing that trace element analysis is a useful tool for analyzing hunter-
gatherers from Cis-Baikal, we must identify elements that may mirror or enhance provenance
information acquired from
87
Sr/
86
Sr ratios. Strontium isotope ratio is a well developed
analytical approach for provenancing skeletal tissues, however it has one major caveat in its
ability to elucidate either origins or mobility of an individual; that it can only operate on the
scale of the dominant bedrock formation and/or geologic zone. In some areas of the world,
this is more than adequate to answer all of the current research questions relating to available
cemetery populations. This is particularly true for agrarian groups, where questions are
dominated by a local/nonlocal dichotomy where the primary goal is to establish the local
signal and thus identify immigrants in a population, with the provenancing of the immigrants
falling to secondary level of investigation. Geologically complex areas such as Cis-Baikal are
broadly speaking, quite amenable to such a research approach as there are geologic
formations spanning three major epochs in fairly well defined and non-overlapping
geography, however we encounter several problems in this situation. Previous studies in Cis-
Baikal have demonstrated that the
87
Sr/
86
Sr technique works in the region, but also that there
are two situations that cannot be clarified without further research: that there are some
individuals who, though likely mobile, stayed within a single geological zone; and that there
are two major zones of similar age and thus theoretically indistinguishable, leaving a rather
difficult scenario where hypotheses regarding regional population exchange will inevitably be
hampered by an inability to separate out individuals from these two regions. Two potential
solutions to this problem are intensive environmental sampling in order to improve the
comparison map available for samples, and the addition of another elemental and/or isotopic
series to provide statistical depth to the data and enable multivariate analyses. Within Cis-
Baikal, four elements appeared to meet the criteria for their ability to enhance the
87
Sr/
86
Sr
data: rubidium (Figure 10), cesium (Figure 11), barium (Figure 12), and rhenium (Figure 13).
That Rb concentrations can mimic
87
Sr/
86
Sr ratios is not too surprising as most radiogenic
formations also contain higher levels of Rb and Sr, however this does not inhibit its value as
an elemental signal in helping to elucidate further provenancing of samples within a
radiogenic zone as there is still considerable variability in the raw concentrations of the
element encountered in the environment. Rhenium functions in a similar fashion. Barium and
cesium do not replicate
87
Sr/
86
Sr data as effectively, demonstrating instead their usefulness in
discriminating between groups within a single zone (Cs) or between individuals who all come
from an area with similar
87
Sr/
86
Sr values, but markedly different Ba concentrations, and thus
likely from different areas within another zone. Examined more closely, rhenium and zinc
values, for example, show a fair amount of variability throughout the geography of a single
tooth (Figure 14), illustrating this individuals continual presence within a single geologic
zone, in this case the Little Sea, however also showing that they had notable variability in
their interaction with rhenium through their environment via either dietary or mobility
changes.
Discussions over methodological approaches to obtaining accurate
87
Sr/
86
Sr data using
laser ablation frequently include debates over diagenetic alterations and the presence of
various interferences. Doubly-charged rare earth elements frequently fall within the mass
ranges monitored for
87
Sr/
86
Sr analysis, thus their presence is of great concern. Theoretically,
the presence of elements unable to make direct replacements in the mineral matrix strongly
supports proponents of the view that all rare earth elements are diagenetic in origin and thus
represent both contaminated samples and a dead end avenue for geochemical research.
However, there are very often anomalies within any mineral matrix, especially so in organic
matrices such as calcium hydroxyapatite, and these areas of imperfect mineral matrix are
effectively traps for other mineral constituents, including trace elements in general.
Furthermore, studies demonstrating the utility of trace elemental analysis on human teeth tend
to overshadow concerns of diagenetic overprinting or alteration of samples preventing the
recovery of useful compositional data from teeth. Following in light of this debate, we
attempted to see if there were significant correlations between the strontium and barium
values. Sr
2+
replaces calcium within enamel at a rate not exceeding 1 in 10 ions, and so has a
limited capability for accumulation within skeletal tissues even if abundant in the body water
supply at the time of enamel formation. Similarly, Ba
2+
sometimes substitutes strontium in the
same position, again at a fraction of the potentially available positions in the matrix. So,
significant shifts in the Sr:Ba ratios should hypothetically be a signal that there is diagenetic
alterations that could render normal interference calculations for rare earth elements or other
interferences inaccurate. However, in the teeth analyzed for this research, no significant
correlations could be found linking Sr:Ba ratios with other forms of interference in
87
Sr/
86
Sr
analyses.

Figure 10. Rubidium replicates Sr isotope groupings

Figure 11. Cesium values largely replicate Sr isotope groupings, however suggest greater internal
variability for local groupings than is suggested by isotopic analysis
The last major goal of this research was to generate adequate data to test the potential for
an online or in situ measurement of interference on mass 87 from the polyatomic molecule
[40] Ca [31] P[16]O. Previous research has demonstrated that the formation of this
polyatomic species is the source of significant interference for laser ablation analyses of
strontium isotopes at such a scale that interpretations can be biased through methodological
fault. As the [40] Ca [31] P [16] O is the result of interactions between the enamel surface, the
laser and the charged oxidation environment of the plasma, however it remains unclear which
element in the system is primarily responsible for this interference, or if it is truly an
unavoidable consequence of having excess amounts of Ca, P and O in a charged environment.
There are several uncertain variables in this equations, thus the easiest way to measure [40]
Ca [31] P [16] O production during analysis would be to measure the related species [44] Ca
[31] P [16] O that will skew values of mass 91 in relative proportion to the level of
interference on mass 87. In order to measure the interference at mass 91, we need to compare
the mass peaks of zirconium 90 and 91. A comparison of [90] Zr and [91] Zr between
solution mode and laser ablation quadrupole-ICP-MS clearly shows the presence of the
hypothesized offset between the two masses of Zr (Figure 15). The LA values include the
data from small laser spot sizes as well as larger ones, so there is significantly more
variability in the laser data than the solution data, though there is still a readily apparent offset
and linear trend in the offset that can be used for a correction. Such a correction follows the
logic that the visible offset in Zr values will correlate with the
87
Sr/
86
Sr differences between
laser and solution data.

Figure 12. Barium values suggest greater variability in nonlocal interpretation than is indicated by Sr
isotope values.
As a test of this concept, we first utilized the published dataset from Simonetti et al.
8
to
see if using reported Sr concentrations we could correct the LA data and get results within
the original error terms of the analysis. The published data contained Sr concentrations, but
no information on Zr, so an added step was needed in this experiment. A linear relationship
between the concentrations of Sr and Zr were drawn from the KN XIV analyses and applied
to the reported Sr values in order to generate the expected offset of [91] Zr. This offset was
then compared to the differences in
87
Sr/
86
Sr data to gain a second linear relationship for the
expected error from [40] Ca [31] P [16] O based on the levels of Sr and Zr (Figure 16). The
dataset lacked information on specific corrections used, however the laboratory protocols
from the time did not incorporate REE or Ca-dimer corrections, so additional blanket
correction values were included in the process, however the correction procedure largely
followed that outlined by Horstwood et al.
1
. Due to the number of variables missing, there is
a fair amount of uncertainty in the accuracy of the final corrected data, yet the new LA data
largely fall on or near the SM data reported. Several of the values did not end within the
original error terms, showing the difficulties in applying corrections to data with significant
amounts of uncertainty attached and compounding concerns over the comparability of
microsampling locations with the masses of enamel homogenized for solutions. The fact that
the majority of samples fell surprisingly close to the SM values strongly supports the
potential for this avenue of online correction. The difficulty with this situation is that these
data were drawn from quadrupole-ICP-MS analysis that is equipped with different electron-
multipliers and will have different operating oxide conditions than both another quadrupole-
ICP-MS and a MC-ICP-MS. This problem could theoretically be overcome if the quadrupole-
ICP-MS and the MC-ICP-MS were connected to the same ablation chamber and online
correlations could be drawn between
87
Sr/
86
Sr values and Zr concentrations, however the RIF
laboratory is not set up in such a fashion.

Figure 13. Grouping via rheniuim replicates Sr isotope groupings

Figure 14. Rhenium values for a single local individual illustrate their continued residence within a
geologic region, though with some smaller scale mobility

Figure 15. Comparison between
90
Zr/
91
Zr between solution mode and laser ablation ICP-MS for KN
XIV teeth

Figure 16. Zirconium difference extrapolated from strontium concentrations and compared with
observed laser ablation and solution modeMC-ICP-MS differences for Simonetti et al.2008 data
Table 4. Laser ablation
87
Sr/
86
Sr ratio data for
KN XIV teeth with correction results
Sample ID 87Sr/86Sr Zr Corrected #1 Zr Corrected #2 Sr Corrected 2 error
97.211_A1 0.7123743 0.708214083 0.711088326 0.710569148 0.0001806
97.211_A2 0.7125077 0.708232427 0.7112217 0.710718353 0.0001684
97.211_A3 0.7125393 0.708248213 0.711406978 0.710756634 0.000204
97.211_B1 0.7122774 0.708167282 0.711007949 0.710484925 0.000198
97.211_B2 0.7120285 0.708107142 0.710774713 0.710245952 0.0001622
97.211_B3 0.71261 0.708259837 0.711366711 0.710826027 0.0001414
97.211_C1 0.7116353 0.707992527 0.710362712 0.709787549 0.0001572
97.211_C2 0.7115308 0.707963213 0.710267076 0.709668758 0.000202
97.211_C3 0.7117711 0.708035033 0.710558893 0.709856572 0.000164
97.211_D1 0.712428 0.708211639 0.711157536 0.710586686 0.0001718
97.211_D2 0.7119169 0.708071365 0.71069914 0.710117022 0.0001888
97.211_D3 0.7114825 0.707968825 0.710286141 0.709633692 0.000214
Standard Deviation 0.000113406 0.000415611 0.00044487
97.217_A1 0.7158983 0.709163308 0.714625791 0.714258617 0.0001974
97.217_A2 0.7170207 0.709466918 0.715773901 0.715382757 0.000274
97.217_A3 0.7172126 0.709530354 0.716033087 0.715575752 0.0002
97.217_B1 0.7163448 0.709282721 0.71507506 0.7147632 0.00032
97.217_B2 0.7168815 0.709433961 0.715642341 0.715324752 0.0001302
97.217_B3 0.7174497 0.709599039 0.716232863 0.715883702 0.000204
97.217_C1 0.7153606 0.709011616 0.714099739 0.713830202 0.000214
97.217_C2 0.7158572 0.709152765 0.714610899 0.714343247 0.00024
97.217_C3 0.7151173 0.70895875 0.713868661 0.71359879 0.000204
97.217_D1 0.7151284 0.708948668 0.713851615 0.713702191 0.000234
97.217_D2 0.715732 0.709119498 0.71446194 0.714330123 0.000195
97.217_D3 0.7160216 0.709208743 0.714729529 0.714636228 0.000236
97.225_A1 0.7144163 0.708755271 0.713143106 0.713245991 0.000294
97.225_A2 0.7161518 0.709239481 0.714888032 0.714950852 0.000312
97.225_A3 0.7163261 0.709286307 0.715136798 0.715151286 0.000208
97.225_B1 0.7155843 0.709074139 0.714320011 0.714376255 0.000296
97.225_B2 0.716525 0.709337331 0.715261989 0.715318674 0.000252
97.225_B3 0.7161068 0.709231976 0.714866517 0.714884275 0.0003
97.225_C1 0.715738 0.709117164 0.714457597 0.714504436 0.0003
97.225_C2 0.7153563 0.709023225 0.714078762 0.71411776 0.000252
97.225_C3 0.7159872 0.709190372 0.714739576 0.71473358 0.00028
97.225_D1 0.7150012 0.708913961 0.713722761 0.71373858 0.00032
97.225_D2 0.7166502 0.709373185 0.715376629 0.715419111 0.000348
97.225_D3 0.7152321 0.708993929 0.71401245 0.713996315 0.000672
98.355_A1 0.7132161 0.708425491 0.711944233 0.711898467 0.000366
98.355_A2 0.7152994 0.709003086 0.714034025 0.713999032 0.00042
98.355_B1 0.7126116 0.708261768 0.711343396 0.711305823 0.00045
98.355_B2 0.7120714 0.708117652 0.710820199 0.71073572 0.000302


Sample ID 87Sr/86Sr Zr Corrected #1 Zr Corrected #2 Sr Corrected 2 error
98.355_B3 0.7119601 0.708087172 0.710714156 0.710585614 0.000278
98.355_C1 0.7116431 0.707992121 0.710377001 0.710239802 0.000414
98.355_C2 0.7121804 0.708145311 0.710937714 0.710771703 0.000448
98.355_C3 0.7126502 0.708280574 0.711487117 0.711191809 0.000346
98.355_D1 0.713514 0.708529766 0.712218521 0.712354224 0.000632
98.355_D2 0.7136801 0.708583201 0.712382943 0.712548372 0.00039
98.355_D3 0.7146961 0.70886989 0.7134102 0.713553632 0.000464
98.359_A1 0.7117397 0.70802341 0.710463167 0.710068174 0.00069
98.359_A2 0.7127162 0.708290944 0.711456789 0.711076884 0.00066
98.359_A3 0.7118754 0.70808271 0.710661269 0.710208528 0.000672
98.359_B1 0.7117544 0.708028108 0.710486623 0.709975754 0.00071
98.359_B2 0.7129407 0.708352823 0.711697772 0.711152791 0.000916
98.359_B3 0.7129047 0.708341993 0.711632711 0.711115233 0.000712
98.359_C1 0.7141845 0.708692376 0.712909064 0.712398622 0.001052
98.359_C2 0.7134008 0.708478361 0.712154703 0.711602994 0.00068
98.359_C3 0.7137356 0.708591637 0.71248943 0.711965841 0.00061
98.359_D1 0.7133296 0.708455316 0.712055396 0.711520369 0.00086
98.359_D2 0.7123873 0.708200505 0.711126393 0.710580792 0.00088
98.359_D3 0.7126201 0.708271653 0.711417852 0.7107383 0.0008

Figure 17.
87
Sr/
86
Sr ratios by sample for SM, LA, and LA corrected for REE, calcium dimer and CaPO
In order to enable in situ correction of mass 87 using mass 91 for
87
Sr/
86
Sr analysis, the
same machine must monitor both masses simultaneously. Unfortunately, the MC-ICP-MS
used for this research was not sensitive enough to measure peaks at masses 90 or 91 without
special tuning. It remains theoretically possible that this machine could be effectively used for
LA
87
Sr/
86
Sr analysis using a Zr offset correction; however the special tuning would render
the procedure impractical and likely interfere with regular operations of the instrument. Thus
at present, efforts to correct
87
Sr/
86
Sr data for [40] Ca [31] P [16] O interference remain most
ably demonstrated with the procedures used by Horstwood et al.
1
. Without the same depth of
suitable reference materials and sample runs, we can still examine new data, but must
approach it with some measure of caution. Taking the LA data for the Cis-Baikal samples and
applying several different approaches to correction, we find a significant amount of
variability. Applying the correction equation used for the Simonetti et al. [8] directly, but
with measured Zr concentrations, we clearly have an overcorrection (Table 4). There is likely
to be a significant divergence of the laser data from the single solution datum as we realize
the disconnect between internal variability of a tooths formation and the homogenizing
effects of solution preparation, however are overcorrected by a
87
Sr/
86
Sr ratio of
approximately 0.002. A second attempt at using zirconium differences as a correction yield
better results, which are well within the realm of uncertainty regarding internal variability
relative to the solution data available. We find similar results from a correction drawn directly
from strontium concentrations and bypassing zirconium offsets altogether. These later two
corrections are difficult to assess without a coupled set of microsampled set of solutions.
Given the added uncertainty of drawing these data from a different instrument, we were
inclined to have greater faith in the strontium corrected laser data in this case. The strontium
data are likely to be more similar between the two instruments and thus less prone to
measurement errors within the scope of this experiment. These data also highlight a fair
amount of internal variability regardless of which correction is used. Of the five teeth
sampled, there is an average deviation of 0.000773 for
87
Sr/
86
Sr ratios, with some individuals
exhibiting significantly more variability than others. This is strongly suggestive of
87
Sr/
86
Sr
ratios indicative of mobility across geologic zones and/or changes in dietary geochemical
interactions of these individuals.
CONCLUSION
Microsampling of complex minerals is a delicate balance between microsampling
methodology, analytical precision and the formation events responsible for the initial
complexity. This will be true whether the mineral matrix is organic or inorganic. For skeletal
materials, there is greater uncertainty attached to the formation process and the contributing
ionic pool of resources used to form the final matrix. Dietary intakes will be averaged within
the body, for over a year for elements such as strontium, and the forming mineral structure
remains an open chemical system for weeks or months after the formation of the structures
visible as Retzius lines. This makes progress difficult to impossible for efforts to generate
useful provenance and/or dietary data for individuals at a temporal scale smaller than a tooth
as a whole. Evidence from herbivore teeth strongly suggest that lag times can outstrip
effective mineralization rates, making intensive microsampling an unnecessary effort as the
same trend lines can be generated with a fraction of the total analyses involved in intensive
microsampling. The same may or may not be true for human teeth as they take longer to form
and in a smaller volume than herbivore teeth, thus potentially incorporating geochemical
information at a temporal scale either within the body residence time of heavy elements or
sufficiently long that changes in body averages can become visible using mixing models to
interpret such data effectively. The data generated for this research strongly support two
conclusions: 1) that trace element analysis can provide a useful contribution to understanding
provenance/mobility data for skeletal tissues; and 2) that microsampling of human teeth is a
worthwhile effort, with laser ablation being a reasonable option with appropriate corrections
applied.
REFERENCES
[1] Horstwood, MSA; Evans, JA; Montgomery, J. Determination of Sr isotopes in calcium
phosphates using laser ablation inductively coupled plasma mass spectrometry and their
application to archaeological tooth enamel. Geochimica et Cosmochimica Acta, 2008,
72(23), 5659-5674.
[2] Nowell, GM; Horstwood, MSA. Comments on Richards et al. Journal of
Archaeological Science, 35, 2008. Strontium isotope evidence of Neanderthal mobility
at the site of Lakonis, Greece using laser-ablation PIMMS. Journal of Archaeological
Science, 2009, 36, 1334-1341.
[3] Bizarro, M; Simonetti, A; Stevenson, RK; Kurszlaukis, S. In situ 87Sr/86Sr
investigations of igneous apatites and carbonates using laser-ablation MC-ICP-mS.
Geochimica et Cosmochimica Acta, 2003, 67(2), 289-302.
[4] Prohaska, T; Latkoczy, C; Schultheis, G; Teschler-Nicola, M; Stingeder, G.
Investigation of Sr isotope ratios in prehistoric human bones and teeth using laser
ablation ICP-MS and ICP-MS after Rb/Sr separation. Journal of Analytical Atomic
Spectrometry, 2002, 17, 887-891.
[5] Cucina, A; Dudgeon, J; Neff, H. Methodological strategy for the analysis of human
dental enamel by LA-ICP-MS. Journal of Archaeological Science, 2007, 34(11), 1884-
1888.
[6] Horstwood, MSA; Parrish, RR; Condon, DJ; Pashley, V. Laser ablation acquisition
protocols and non-matrix matched standardisation of U-Pb data. Geochimica et
Cosmochimica Acta, 2006, 70(18, Supplement 1), A264-A264.
[7] Richards, MP; Harvati, K; Grimes, V; Smith, C; Smith, T; Hublin, JJ. Strontium isotope
evidence of Neanderthal mobility at the site of Lakonis, Greece using laser-ablation
PIMMS. Journal of Archaeological Science, 2008, 35(5), 1251-1256.
[8] Simonetti, A; Buzon, MR; Creaser, RA. In-situ elemental and Sr isotope investigation
of human tooth enamel by laser-ablation-(MC)-ICP-MS: successes and pitfalls.
Archaeometry, 2008, 50(2), 371-385.
[9] Vroon, PZ; van der Wagt, B; Koornneef, JM. Problems in obtaining precise and
accurate Sr isotope analysis from geological materials using laser ablation MC-ICPMS.
Analytical and Bioanalytical Chemistry, 2008, 390(465-476).
[10] Woodhead, JD; Swearer, S; Hergt, J; Maas, R. In situ Sr-isotope analysis of carbonates
by LA-MC-ICP-MS: interference corrections, high spatial resolution and an example
from otolith studies. Journal of Analytical Atomic Spectrometry, 2005, 20, 22-27.
[11] Paton, C; Woodhead, JD; Hergt, J; Phillips, D; Shee, S. Sr-isotope analysis of
kimberlitic groundmass perovskite via LA-MC-ICP-MS. Geostandard Geoanalytical
Research, 2007, 31(4), 321-330.
[12] Galazii, GI. Baikal Atlas. Russian Academy of Sciences, Moscow, 1993.
[13] Weber, AW; Link, DW; Katzenberg, MA. Hunter-Gatherer Culture Change and
Continuity in the Middle Holocene of the Cis-Baikal, Siberia. Journal of
Anthropological Archaeology, 2002, 21(2), 230-299.
[14] Weber, AW. Biogeographic profile of the Lake Baikal region, Siberia. In Prehistoric
Foragers of the Cis-Baikal, Siberia, Proceedings of the First Conference of the Baikal
Archaeology Project, AW; Weber, H. McKenzie, Eds. Canadian Circumpolar Institute
Press: Edmonton, 2003, 51-66.
[15] Haverkort, CM; Bazaliiski, VI; Savelev, NA. Identifying hunter-gatherer mobility
patterns using strontium isotopes. In Prehistoric Hunter-Gatherers of the Baikal
Region, Siberia: Bioarchaeological Studies of Past Lifeways., AW; Weber, MA;
Katzenberg, TG. Schurr, Eds. University of Pennsylvania Museum of Archaeology and
Anthropology: Philadelphia, 2010, 217-239.
[16] Levin, MG; Potapov, LP. The Peoples of Siberia. University of Chicago Press:
Chicago, 1964.
[17] Losey, RJ; Nomokonova, T; Goriunova, OI. Fishing ancient Lake Baikal, Siberia:
inferences from the reconstruction of harvested perch (Perca fluviatilis) size. Journal of
Archaeological Science, 2008, 35(3), 577-590.
[18] Weber, AW. The neolithic and early bronze age of the Lake Baikal Region: A review of
recent research. Journal of World Prehistory, 1995, 9(1), 99-165.
[19] Weber, AW; Link, DW; Goriunova, OI; Konopatskii, AK. Patterns of Prehistoric
Procurement of Seal at Lake Baikal: A Zooarchaeological Contribution to the Study of
Past Foraging Economies in Siberia. Journal of Archaeological Science, 1998, 25(3),
215-227.
[20] Katzenberg, MA; Weber, AW. Stable Isotope Ecology and Palaeodiet in the Lake
Baikal Region of Siberia. Journal of Archaeological Science, 1999, 26(6), 651-659.
[21] Lam, YM. Isotopic evidence for change in dietary patterns during the Baikal Neolithic.
Current Anthropology, 1994, 35, 185-190.
[22] Haverkort, CM; Weber, AW; Katzenberg, MA; Goriunova, OI; Simonetti, A; Creaser,
RA. Hunter-gatherer mobility strategies and resource use based on strontium isotope
(87Sr/86Sr) analysis: a case study from Middle Holocene Lake Baikal, Siberia. Journal
of Archaeological Science, 2008, 35, 1265-1280.
[23] Huh, Y; Coleman, D; Edmond, J. 87Sr/86Sr in Siberian Rivers, EOS. Transactions of
the American Geophysical Union, 1994, 75(16), 142.
[24] Kenison Falkner, K; Lebaron, G; Thouron, D; Jeandel, C; Minster, JF. Cr, V and Sr in
Lake Baikal, EOS. Transactions of the American Geophysical Union, 1992, 73(14),
140.
[25] Scharlotta, I. In Spatial variability of biologically available
87
Sr/
86
Sr, rare earth and
trace elements in the Cis Baikal region, Siberia: Evidence from environmental samples
and small cemeteries, 38th International Symposium on Archaeometry, Tampa, Florida,
May 10th-14th, 2010, Tampa, Florida, 2010.
[26] Weber, AW; Creaser, RA; Goriunova, OI; Haverkort, CM. Strontium isotope tracers in
enamel of permanent Human molars provide new insights into prehistoric hunter-
gatherer procurement and mobility patterns: a pilot study of a Middle Holocene group
from Cis-Baikal. In Prehistoric Foragers of the Cis-Baikal, Siberia, Proceedings of the
First Conference of the Baikal Archaeology Project, AW; Weber, H. McKenzie, Eds.
Canadian Circumpolar Institute Press: Edmonton, 2003, 133-153.
[27] Weber, AW; Katzenberg, MA; Goriunova, OI. KHUZHIR-NUGE XIV, a Middle
Holocene Hunter-Gatherer Cemetery on Lake Baikal, Siberia: Osteological Materials.
CCI Press and the Baikal Archaeology Project: Edmonton, 2007.
[28] Weber, AW; Goriunova, OI; McKenzie, H. KHUZHIR-NUGE XIV, a Middle Holocene
Hunter-Gatherer Cemetery on Lake Baikal: Archaeological Materials. CCI Press and
the Baikal Archaeology Project: Edmonton, 2008.
[29] Weber, A; McKenzie, HG; Beukens, R; Goriunova, OI. Evaluation of radiocarbon dates
from the Middle Holocene hunter-gatherer cemetery Khuzhir-Nuge XIV, Lake Baikal,
Siberia. Journal of Archaeological Science, 2005, 32(10), 1481-1500.
[30] Bentley, RA; Knipper, C. Geographical patterns in biologically available strontium,
carbon and oxygen isotope signatures in prehistoric SW Germany. Archaeometry, 2005,
47, 629-644.
[31] Price, TD; Burton, JH; Bentley, RA. The characterization of biologically available
strontium isotope ratios for the study of prehistoric migration. Archaeometry, 2002, 44,
117-135.
[32] Brown, WAB; Christoffersen, PV; Massler, M; Weiss, MB. Postnatal tooth
development in cattle. American Journal of Veternary Research, 1960, XXI, 7-34.
[33] Hillson, S. Dental Anthropology. 2nd ed; Cambridge University Press: Cambridge,
2002.
[34] Kang, D; Amarasiriwardena, D; Goodman, AH. Application of laser ablation
inductively coupled plasma-mass spectrometry (LAICPMS) to investigate trace
metal spatial distributions in human tooth enamel and dentine growth layers and pulp.
Analytical and Bioanalytical Chemistry, 2004, 378(6), 1608-1615.
[35] Bentley, RA. Strontium Isotopes from the Earth to the Archaeological Skeleton: A
Review. Journal of Archaeological Method and Theory, 2006, 13(3), 135-187.
[36] Dolphin, AE; Kang, D; Goodman, AH; Amarasiriwardena, D. Microspatial analyses of
intra- and intertooth variations in the distribution of trace elements. American Journal
of Physical Anthropology, 2003, Supplement 36, 90.
[37] Fincham, AG; Moradian-Oldak, J; Simmer, JP. The Structural Biology of the
Developing Dental Enamel Matrix. Journal of Structural Biology, 1999, 126(3), 270-
299.
[38] Hillson, S. Teeth. 2nd ed; Cambridge University Press: Cambridge, 2005.
[39] Montgomery, J; Evans, JA. Immigrants on the Isle of Lewis - combining traditional
funerary and modern isotope evidence to investigate social differentiation, migration
and dietary change in the Outer Hebrides of Scotland. In The Social Archaeology of
Funerary Remains, R; Gowland, C. Knsel, Eds. Oxbow: Oxford, 2006, 122-142.
[40] Suga, S. Progressive mineralization pattern of developing enamel during the maturation
stage. Journal of Dental Research, 1982, 61, 1532-1542.
[41] Suga, S. Enamel hypomineralization viewed from the pattern of progressive
mineralization of human and moneky developing enamel. Advances in Dental
Research, 1989, 3, 188-98.
[42] Tafforeau, P; Bentaleb, I; Jaeger, JJ; Martin, C. Nature of laminations and
mineralization in rhinoceros enamel using histology and X-ray synchrotron
microtomography: Potential implications for palaeoenvironmental isotopic studies.
Palaeogeography, Palaeoclimatology, Palaeoecology, 2007, 246(2-4), 206-227.
[43] Avery, JK. Essentials of Oral Histology and Embryology - A Clinical Approach.
Mosby-Year Book, Inc.: St. Louis, 1992.
[44] Balasse, M. Potential biases in sampling design and interpretation of intra-tooth isotope
analysis. International Journal of Osteoarchaeology, 2003, 13, 3-10.
[45] Balasse, M; Ambrose, SH; Smith, AB; Price, TD. The seasonal mobility model for
prehistoric herders in the south-western Cape of South Africa assessed by isotopic
analysis of sheep tooth enamel. Journal of Archaeological Science, 2002, 29, 917-932.
[46] Britton, K; Grimes, V; Dau, J; Richards, MP. Reconstructing faunal migrations using
intra-tooth sampling and strontium and oxygen isotope analyses: a case study of
modern caribou (Rangifer tarandus granti). Journal of Archaeological Science, 2009, 36
(5), 1163-1172.
[47] Hoppe, KA; Koch, PL; Carlson, RW; Webb, DS. Tracking mammoths and mastodons:
Reconstruction of migratory behavior using strontium isotope ratios. Geology, 1999,
27, 439-442.
[48] Hoppe, KA; Koch, PL; Furutani, TT. Assessing the preservation of biogenic strontium
in fossil bones and tooth enamel. International Journal of Osteoarchaeology, 2003, 13,
20-28.
[49] Hoppe, KA; Stover, SM; Pascoe, JR; Amundson, R. Tooth enamel biomineralization in
extant horses: implications for isotopic microsampling. Palaeogeography,
Palaeoclimatology, Palaeoecology, 2004, 206 (3-4), 355-365.
[50] Koch, PL; Heisinger, J; Moss, C; Carlson, RW; Fogel, ML; Behrensmeyer, AK.
Isotopic tracking of change in diet and habitat use in African elephants. Science, 1995,
267, 1340-1343.
[51] Montgomery, J; Evans, JA; Horstwood, MSA. Evidence for long-term averaging of
strontium in bovine enamel using TIMS and LA-MC-ICP-MS strontium isotope intra-
molar profiles. Environmental Archaeology, 2010, 15(1), 32-42.
[52] Dahl, SG; Allain, P; Marie, PJ; Mauras, Y; Boivin, G; Ammann, P; Tsouderos, Y;
Delmas, PD; Christiansen, C. Incorporation and distribution of strontium in bone. Bone,
2001, 28(4), 446-453.
[53] Bowen, HJM. Evnironmental Chemistry of the Elements. Academic Press: London,
1979.
[54] Montgomery, J; Evans, JA; Cooper, RE. Resolving archaeological populations with Sr-
isotope mixing models. Applied Geochemistry, 2007, 22(7), 1502-1514.
[55] Gratuze, B. Obsidian Characterization by Laser Ablation ICP-MS and Its Application to
Prehistoric Trade in the Mediterranean and the Near East: Sources and Distribution of
Obsidian within the Aegean and Anatolia. Journal of Archaeological Science, 1999, 26,
869-881.
[56] Russo, RE; Mao, X; Liu, H; Gonzalez, J; Mao, SS. Laser ablation in analytical
chemistry - a review. Talanta, 2002, 57(3), 425-451.
[57] Speakman, RJ; Neff, H. Laser ablation-ICP-MS in archaeology research. University of
New Mexico Press: Santa Fe, 2005.
[58] Tykot, RH; Young, SMM. Archaeological Applications of Inductively Coupled Plasma
- Mass Spectrometry. In Archaeological Chemistry, AM; Pollard, C. Heron, Eds. Royal
Society of Chemistry: Cambridge, 1996, 116-130.
[59] Budd, P; Montgomery, J; Cox, A; Krause, P; Barreiro, B; Thomas, RG. The distribution
of lead within ancient and modern human teeth: implications for long-term and
historical exposure monitoring. The Science of the Total Environment, 1998, 220, 121-
36.
[60] Copeland, SR; Sponheimer, M; le Roux, PJ; Grimes, V; Lee-Thorp, JA; de Ruiter, DJ;
Richards, MP. Strontium isotope ratios (87Sr/86Sr) of tooth enamel: a comparison of
solution and laser ablation multicollector inductively coupled plasma mass
spectrometry methods. Rapid Communications in Mass Spectrometry, 2008, 22(20),
3187-3194.
[61] Copeland, SR; Sponheimer, M; Lee-Thorp, JA; Le Roux, PJ; De Ruiter, DJ; Richards,
MP. Strontium isotope ratios in fossil teeth from South Africa: assessing laser ablation
MC-ICP-MS analysis and the extent of diagenesis. Journal of Archaeological Science,
2010, 37(7), 1437-1446.
[62] Trotter, JA; Eggins, SM. Chemical systematics of conodont apatite determined by laser
ablation ICP-MS. Chemical Geology 2006, 233, 196-216.
[63] Christensen, JN; Halliday, AN; Lee, DC; Hall, CM. In situ Sr isotopic analysis by laser
ablation. Earth and Planetary Science Letters, 1995, 136, 79-85.
[64] Kin, FD; Prudncio, MI; Gouveia, M; Magnusson, E. Determination of Rare Earth
Elements in Geological Reference Materials: A Comparative Study by INAA and ICP-
MS. Geostandards and Geoanalytical Research, 1999, 23(1), 47-58.
[65] James, WD; Dahlin, ES; Carlson, DL. Chemical compositional studies of
archaeological artifacts: Comparison of LA-ICP-MS to INAA measurements. Journal
of Radioanalytical and Nuclear Chemistry, 2005, 263(3), 697-702.
[66] Revel, G; Ayrault, S. Comparative use of INAA and ICP-MS for Environmental
Studies. Journal of Radioanalytical and Nuclear Chemistry, 2000, 244(1), 73-80.
[67] Horstwood, MSA; Evans, JA. Complications of LA-MC-ICP-MS Sr isotope analysis of
phosphate matrices. In Eighth International Conference on Plasma Source Mass
Spectrometry, University of Durham, UK, 2002.
[68] Horstwood, MSA; Nowell, GM. Multi-collector devices. In ICP-MS Handbook, Nelms,
S., Ed. Blackwell Scientific Publications: Oxford, 2005, 54-68.
[69] Cucina, A; Neff, H; Tiesler, V. Provenance of African-born individuals from the
colonial cemetery of Campeche (Mexico) by means of trace element analysis. Dental
Anthropology, 2005, 17, 65-69.
[70] Dudgeon, J. The genetic architecture of the late prehistoric and protohistoric Rapa Nui.
Doctoral Dissertation, University of Hawai'i, Manoa, 2008.
[71] Weigand, PC; Harbottle, G; Sayre, EV. Turquoise Sources and Source Analysis:
Mesoamerica and the Southwestern U.S.A. In Exchange Systems in Prehistory, TK;
Earle, JE. Ericson, Eds. Academic Press: New York, 1977, 15-34.
Chapter 3
MODELING OF LASER ABLATION INDUCED BY
NANOSECOND AND FEMTOSECOND LASER PULSES
Tatiana E. Itina
1*
, Mikhail E. Povarnitsyn
2

and Konstantin V. Khishchenko
2

1
Hubert Curiens Laboratory, CNRS 55216, 18 rue de Professeur Benot Lauras,
Bat. F, 42000, Saint-Etienne, France
2
Joint Institute for High Temperatures RAS, 13 Bd. 2, Izhorskaya street,
Moscow, Russia
ABSTRACT
The chapter considers the problem of numerical modeling of laser-matter
interactions. The main objective is to clarify the mechanisms of this extremely complex
process.
Comparison of femtosecond and nanosecond laser ablation is first presented.
Thermal model is used for nanosecond ablation. The physical phenomena involved into
the interaction of a laser-generated plasma plume with a background environment are
furthermore studied. A three-dimensional combined model is developed to describe the
plasma plume formation and its expansion in vacuum or into a background gas. The
proposed approach takes advantages of both continuous and microscopic descriptions.
The simulation technique is suitable for the simulation of high-rate laser ablation for a
wide range of the background pressure. The model takes into account the mass diffusion
and the energy exchange between the ablated and background species, as well as the
collective motion of the ablated species and the background gas particles. The developed
approach is used to investigate the ablation of aluminum in the presence of a background
gas. The influence of the background gas on the expansion dynamics of the laser-
generated plume is examined. Experimental density distributions are explained based on
the simulation results.
A detailed analysis of material decomposition in femtosecond regime is then
performed by using a hydrodynamic model with a thermodynamically complete equation

*
Corresponding author: Email: tatiana.itina@univ-st-etienne.fr.

and Konstantin V. Khishchenko 100
of state. As a result, several ablation mechanisms are observed. A major fraction of the
ablated material is found to originate from the metastable liquid region, which is
decomposed either thermally in the vicinity of the critical point into a liquid-gas-mixture
or mechanically at high strain rate and negative pressure into liquid droplets and chunks.
The calculation results agree with the results of previous molecular dynamics simulations
and explain recent experimental findings. In addition, effects of the ultra-short laser
excitations of wide band gap materials need a particular attention. In this case, material
ionization through multi-photon excitation and electron-impact ionization should be
considered. Laser interactions are simulated with a particular focus on the control over
laser plume expansion process. The properties of the laser-generated plasma plume are
shown to be strongly affected by the laser-mater interaction mechanism
1. INTRODUCTION
Shortly after the demonstration of the first laser, the most intensely studied theoretical
topics dealt with laser-matter interactions. Many experiments were undertaken to clarify the
mechanisms of this extremely complex process. At the same time, numerous models, both
analytical and numerical, were proposed to describe these interactions. In these models,
different experimental conditions were considered, and several terms were proposed to denote
the processes occurring during laser action on different materials. Thus, "laser ablation",
"evaporation", "desorption" or "sputtering" all these terms are relevant to the interaction of
a laser beam with a solid (or a liquid) surface that results into transition of the surface
particles into a gas phase. For simplicity, here we will use only the term "laser ablation".
Laser ablation has found a number of industrial applications, such as laser cleaning,
micromachining, molecular mass spectrometry, plasma technology, laser surgery, etc. One of
the main advantages of this technique is the simplicity of the experimental set-up. The other
advantage is the possibility of adjusting the experimental conditions in order to obtain the
desirable treatment quality. Among the important experimental parameters one should
mention the followings

laser pulse parameters (fluence, beam dimensions, duration, time-shape)
target material
target-substrate distance
ambient gas (pressure, atomic mass, temperature)
substrate characteristics

Recently, a particular attention has been attracted to various surface-treatment
applications, such as laser micromachining, marking, modification of the surface properties,
etc. One of the major problems that arise in the development of these applications is
connected with prevention of collateral thermal damage of the treated material. One way of
the minimization of the undesired thermal effects is the decrease of laser pulse duration. That
is why starting from the beginning of 80
th
, the interest of researches turned to lasers with
nanosecond pulse duration. After recent commercialization of laser systems with short
(picosecond) and ultra-short (femtosecond) laser pulse duration, the attention of researches
has been naturally focused on the advantages of these systems [1-7]. The rapid evolution in
laser system development has opened new horizons for laser applications. Laser wavelength
Modeling of Laser Ablation Induced by Nanosecond and Femtosecond 101
now varies from infrared to ultra-violet and starts to penetrate into X-ray. Laser power has
grown considerably, so that smaller focusing is required. Among other important adjustable
parameters, one can note laser pulse shape, polarization and beam quality. Therefore, lasers
are currently used not only for surface treatment, cleaning, micro and nano-machining,
structuring, but also for nanoparticle formation, surface analysis, optics and photonics, micro-
electronics, nanoplasmonics, nano-bio-technology, atomic physics, chemistry, medical
applications, etc. In particular, femtosecond laser pulses provide unique opportunities for such
applications as laser spectroscopy (LIBS), nanoparticle synthesis both in vacuum, in gas, and
in liquid, laser surgery, nano-fabrication, etc. [8,9,10]. One one hand, cluster formation by
laser ablation provides an attractive avenue for fabrication of nanostructured materials and for
medicine [15,11,12,13,14]. The applications based on cluster deposition include fabrication of
nano-crystalline or cluster-assembled films and coatings, deposition of metal particles for
catalysis, or composite compound semiconductors for electro-optical applications. On the
other hand, the presence of clusters or particulates in the ablation plume can be harmful for
the quality of thin films grown in pulsed laser deposition (PLD) [15]. In addition, the
formation of debris and re-deposition of ejected particulates can cause problems in
manufacturing of surface microstructures. Clusters in the expanding plume can scatter the
incident laser light and lead to a shielding of the target surface in the case of long laser pulses
or in the multi-pulse irradiation regime. For all these reasons, it is crucial to be able to predict
and control the parameters of clusters formed in laser ablation, such as particle size
distributions, velocities, and temperature at the time of deposition.
Despite rapid development in laser physics, one of the fundamental questions still
concerns the definition of proper ablation mechanisms. Apparently, the progress in laser
systems implies several important changes in these mechanisms, which depend on both laser
parameters and material properties. Among the more studied ablation mechanisms there are
thermal, photochemical and photomechanical ablation processes [11]. Frequently, however,
the mechanisms are mixed, so that the existing analytical equations are hardly applicable. In
this case, numerical simulation is needed to better understand and to optimize the ablation
process [16,17,18].
So far, thermal models are commonly used to describe nanosecond (and longer) laser
ablation [19, 20]. In these models, the laser-irradiated material experiences heating, melting,
boiling and evaporation. Thermal effect plays therefore a major role, particularly in the case
of metals with high thermal conductivity. In this case, the ablation flux can be described by a
Hertz-Knudsen equation. The interaction of femtosecond pulses even with metals implies,
however, a change in the ablation mechanism due to not only the absence of equilibrium
between electrons and lattice-ions during the pulse, but also because the heating is too fast.
The Hertz-Knudsen equation is inapplicable in this case and a numerical study is for the
careful optimization of the laser processing of metals.
Recently, many experimental and theoretical investigations of the mechanism of
femtosecond (< 100 fs) ablation have been performed [21,22,23,24]. Evidently, the interest in
femtosecond lasers was caused by numerous exciting laser applications listed above. Among
the main advantages of these short pulses is the possibility of laser treatment of any materials,
even these that were considered to be transparent, in a possibility of control over electronic
excitations, and in the minimization of non-desirable thermal effects. However, the
mechanisms of these interactions are often rather different from that of longer pulses, and
many difficulties first arouse in the corresponding numerical modeling. The main point that

makes ultra-short interactions difficult to model, is that the pulse duration is shorter than the
electron-phonon/ion relaxation time t
ei
~1-10 ps. As a result of strong difference between the
electron and ion mass, the mean electron energy rises much faster and higher that that of ion
subsystem. The terms electron and ion temperatures, however, require equilibrium in each
sub-system that also may take longer time to establish. If these terms can be applied, electron
temperature is much larger that ion temperature during the interaction. The knowledge about
the required equation of state (EOS) is also very limited. In addition, metastable matter states,
such as superheated liquid one, seem to play a role. All these points limit the information
about model parameters and make computer simulation rather difficult.
In studies of femtosecond interactions with metals, new ablation mechanisms have been
proposed both for metals and semiconductor materials [21,22,23,25-34]. In particular, for
semiconductor and/or dielectric materials, such processes as multi-photon/tunneling
ionization, electron-impact, or avalanche ionization, charge separation, optical breakdown,
material damage and ablation have been investigated [35]. Previous theoretical studies used
either the detailed Boltzmanns equation [35,36] or simplified rate equations to describe laser
excitation kinetics [37-41]. For metals, two-temperature model [42,43] has yielded
information about electron and lattice temperature evolution. However, the validity of the
classical TTM model is limited due to the conditions of equilibrium to be established in each
of two sub-systems and because of the heat diffusion equations that do not describe the heat
front. As a result, the general conclusion was that the conventional TTM can be used for a
bulk metal target at relatively high intensities. At smaller laser intensities, there is no
equilibrium in the electron sub-system. In addition, for metal films, the ballistic electron
transport should be considered [44]. In general, even in the case of a bulk target, the heat
diffusion equation disregards the finite time of the heat propagation. In addition, the
calculation of model parameters represents a challenge because of the lack of knowledge of
electron distribution and temperature-dependency of such parameters as heat capacity,
thermal conductivity, electron-phonon coupling, etc in the absence of both thermal and
electron-ion equilibrium. Only recently, ab-initio calculations were performed [45] to account
for the excitation of d-band electrons [46] in some metals, such as gold, silver, nickel.
However, these first results need more analysis and verification
To calculate material motion (and not only its temperatures), three numerical approaches
were used, such as

Atomistic approach, based on such methods as molecular dynamics (MD)
[25,47,48,49] and Direct Monte Carlo Simulation (DSMC) [50,51,52].Typical
calculation results provide detailed information about atomic positions, velocities,
kinetic and potential energy;
Macroscopic approach based hydrodynamic models [18,53,54] This model allows
the investigations of the role of the laser-induced pressure gradient, which is
particularly important for ultra-short laser pulses. The models are based on a one
fluid two-temperature approximation and a set of additional models (equation of
state) that determines thermal properties of the target. Recently electron-phonon
coupling parameter was calculated as a function of electron temperature by using ab-
initio quantum mechanical methods [45];
Multi-scale approach based on the combination of two approaches cited above was
developed by several groups and was shown to be particularly suitable for laser
applications.

The ejection of liquid and/or solid particulates has been studied for metals [55,56,57,58],
semiconductors [59,60,61,62], dielectrics [63,64], and organic materials [11,65]. The
parameters of the ejected particles are found to have a strong dependence on the laser
irradiation conditions and the background gas pressure. A number of scenarios of cluster
formation in laser ablation have been discussed in the literature. In many cases, observation of
small clusters is attributed to the collision-induced condensation in the dense regions of the
ejected plume [62,64,66,67]. Some evidences of the direct ejection of nanoparticles by ultra-
short laser pulses were also obtained.
Before considering the modeling details, we would like to emphasize that the laser-target
interaction is an extremely complex process involving more than one physical phenomenon.
These phenomena include the absorption of laser radiation, the creation of a high pressure and
temperature region in the solid, the propagation of the compression and thermal waves, phase
transitions, material decomposition and ionization, the ejection of electrons, ions and/or
neutrals, laser plume expansion, the interaction of the ablated species with background gas,
chemical reactions, cluster formation, etc That is why it is difficult to formulate a complete
and self-consistent model to interpret all observations. In general, laser ablation models can
be subdivided into two categories

modeling of the interaction of the laser beam with a surface, where attention is
focused on the primary mechanisms of the material ejection;
modeling of the formation of a laser plume (secondary mechanisms) and its
expansion in vacuum or in a background gas.

These categories are closely connected, since the first one provides initial conditions for
the second one. Models that describe all the ablation process self-consistently and combine
both calculations are exceptional. Some models are based on approaches with considerable
mathematical complexity, some rely on simple physical descriptions, and others are
phenomenological. Most of the theoretical studies do not provide insights directly applicable
to improve the experimental conditions. In addition, the calculations contain many
parameters, some of which are unknown and most of them are temperature dependent.
Nevertheless, as far as several particular characteristics of the process are concerned, the
quantitative comparison with experimental data turns out to be possible. The latter is valid
especially for the experiments with either very small or very large laser fluence. This former
case is of a particular interest because of a number of technical and scientific applications.
Herein, we examine the different approaches used in the modeling of laser ablation and
the most interesting results that were obtained in this field.

2. MODELING OF NANOSECOND LASER ABLATION
In this section we consider the modeling of laser ablation induced by nanosecond laser
pulses. The description consists of two parts that correspond to the two categories of the
ablation models.
2.1. Primary Mechanisms of the Material Ejection under Nanosecond Laser
Action
As we have noted in the Introduction, the most common and simplest model that
describes the laser-solid interaction under low power density is based on a thermal effect.
The problem of the evaporation of a metal surface heated up to a certain temperature T
0
was
considered by a number of authors, for example, by Anisimov et al [68], and by Ready. A
simplified one-dimensional model which neglected the presence of a liquid phase was used in
the first papers. Later, more realistic models of target heating and evaporation were
developed, where moving boundary conditions were used. One can note, for example, the
model of Luikov et al [69]. More recently, temperature, pressure and density discontinuity
across Knudsen layer were considered by Anisimov [70].
To describe the heat transport one can use the heat flow equation that can be written in
one-dimensional form as follows [71]:
( ) ( ) t z I
z
T
T z K
z t
T
T T c , , ) ( ) ( +
, (1)
where I is the absorbed laser radiation given by (1.1).
For simplicity, the quantities c, and K are frequently assumed to be temperature and
space independent. If one neglects, furthermore, surface melting and the movement of the
evaporation front, the boundary conditions for a surface laser source and a semi-infinite solid
target can be written as follows:

0
) 1 ( 0 I R I z = = , (2)

0
0 , 0 T T t z = = = ,
and the solution of Eq. (1.6) obtained analytically using Green function technique is
( )
0
0
2
0
4
exp
) ( 1
, T d
z t I
c
t z T
t
+

(3)
Then, the time-evolution of the surface temperature is given by the equation:
( )

+
=
t
T d
t I
c
A
t z T
0
0
) (
,

(4)
where A=1-R is the absorption coefficient. This equation allows the calculation of the surface
temperature for a given time-evolution of the laser intensity. Using the solution obtained one
can estimate the minimum (threshold) laser intensity I
th
for evaporation by using the equation
T
max
= T
Vap
, where T
max
is the maximum surface temperature obtained from Eq. (1.9), and T
Vap

is the material vaporization temperature. For example, for a top-hat laser pulse it gives:
) (
2
0
T T
A
c
I
Vap th
=

. (5)
If thermal desorption mechanism is assumed, the initial velocity distribution is half-
Maxwelian with the surface temperature T(t). Since the desorbed current is cosine distributed,
the ablated flow velocity U
0
(t)=V
T
(t)/2, where
m t kT t V
T
/ ) ( 8 ) ( =
, k is a Boltzmanns
constant and m is the particle mass. The desorption flux
) ( ) ( ) (
0 0
t U t n t =
, where n
0
(t) is the
density of the desorbed material immediately in front of the surface.
If surface melting takes place, phase transition must be considered. To consider solid-
liquid or liquid-solid transitions, two boundary conditions are required at the interface where
the phase transition occurs. First of these is an energy balance:

int int
int
) (
+
=
z
liq
z
sol tr m
z
T
K
z
T
K T H (6)
where T
tr
is the temperature at which the transition takes place, K
sol
and K
liq
are thermal
conductivities of solid and liquid phase respectively, H
m
is the heat of melting at T= T
tr
, and
int
is the solid-liquid interface velocity. Moreover, the thermodynamics of crystallization
(Pererlongo et al., Ref.71) requires that
int
should be a function of the supercooling T
tr
- T
m
,
) (
int m tr
T T f = . (7)
During the vaporization the surface recedes with velocity
r
. It is, however, still
possible to label its position with z=0 in the reference frame moving with a receding surface.
Then, neglecting mass accumulation and temperature dependence, Eq. (1) becomes
( ) t z I
z
T
c
z
T
K
t
T
c
r
,
2
2
+
(8)

A simple way to compute
r
is to consider that liquid is in thermal equilibrium with its
saturated pressure. In this case the number N
V
of particles vaporizing per unit time and area is

( )
S V
C
kTm
p
N
2 / 1
2
= , (9)
where p is the gas pressure, and C
S
is the sticking coefficient. If one assumes that this
equation also holds in a nonequilibrium situation as when particles are emitted into vacuum,
then the velocity

( )
S r
C
m kT
p
2 / 1
/ 2
= (10)
The relation between the equilibrium vapor pressure and the temperature may be obtained
from the Clausius-Clapeyron equation in the limit V
liq
<<V
gas
, V
liq
and V
gas
being molar
volume of liquid and gas, respectively. Assuming the inequality T<T
tc
, where T
tc
is the
thermodynamic critical temperature, one can write

=
T T k
m T H
p p
b
b
b
1 1 ) (
exp

, (11)
where p
b
=1atm, ) (T H
is the heat of vaporization that can be assumed approximately

equal to the value at the boiling temperature T
b
at 1atm.
During last decade, new mechanisms of the material ejection stage were investigated. For
instance, Ostland and Orlander [72] considered nonequilibrium surface processes. A so-called
phase explosion mechanism was proposed by Martynyuk [73]. Then, Kelly et al. [74]
proposed the mechanism of thermal-shock-induced exfoliation. Lukyanchuk et al. [75]
studied photophysical ablation of organic polymer materials.
2.2. Secondary Mechanisms: Plasma Plume Expansion after Nanosecond
Laser Pulse
If the ablation flux is large enough, the emitted particles tend to move according to the
laws of gas-dynamics. The application of the gas-dynamical equations requires the presence
of a thermodynamical equillibrium in the considered region of the flow. Since, the outer part
of the plume always goes to free-molecular flight, these methods can not describe all the
flow. Although, if the density of the evaporated material is sufficiently large, the hypothesis
of the thermodynamical equilibrium is justified for a major part of the flow until a certain
time. Several analytical models of plume expansion were proposed. First analytical models
based on a system of gas-dynamical equations were developed by Dawson [76] and by Singh
and Narayan [77]. Later, a more accurate self-similar adiabatic expansion model was
proposed by Anisimov et al. [78] to adequately describe plume evolution in vacuum. A
number of numerical solutions of the system of gas-dynamical equations were furthermore
proposed. One can note the modeling of the plume dynamics performed by Peterlongo et al.
[79], Bulgakov and Bulgakova [80], and Le et al. [81]. These studies demonstrated numerous
gas-dynamic effects taking place during the plume expansion both in vacuum and in the
presence of a background gas.
An alternative approach, particularly suitable to study of the effects of gas-phase
collisions, based on the Direct Simulation Monte Carlo method (DSMC) [82] was used in a
few papers. In this method, the time evolution of the gas cloud is obtained by following
simultaneously a number of representative flow particles (10
3
to 10
6
) which undergo
collisions (and chemical reactions). The method turns out to be very effective for describing
non-equilibrium flows with high density-gradients and strong time-variations of the
parameters. In addition, chemical reactions, internal mode excitation and exchange can be
directly included in the simulation procedure. That is why, recently it was successfully used
to study pulsed laser desorption for low and moderate evaporation fluxes. For example,
NoorBatcha et al. [83], with the aid of the one-dimensional DSMC algorithm, considered the
characteristics of the desorption flow containing atoms and molecules with internal degrees of
freedom. Furthermore, Urbassek and Sibold [84] investigated the one-dimensional pulsed
laser desorption problem with recondensation. As a result, the numerical solution was
obtained for a first time to this problem for a wide range of Knudsen number. Later, this
solution was compared with analytical results obtained by Kelly [85] and with analytical
solution proposed by Sibold and Urbassek [86]. A three-dimensional Monte Carlo simulation
of the desorption from a finite-sized laser spot was carried out by Sibold and Urbassek [87]
for a top-hat thermal desorption flux. The effects of the jet formation and of the segregation
of heavy and light components were shown to result from the collisions in the laser plume.
Later, by the author with the co-workers the DSMC method was used to show the effects of
recombination-dissociation in the plume on the angular distribution of the ablated particles
[52]. In addition, combined DSMC-Random Trajectories method was developed to calculate
the stoichiometry distribution of thin films deposited by laser ablation of binary targets [50].
The Monte Carlo methods also were used to analyze the results of time-of-flight (TOF)
experiments [88]. The microscopic methods have thus yielded a wealth of information about
the ablated plume. The main limitation of these methods is, however, connected with the
density and size of the plume, since the calculation resources needed for the DSMC method
are proportional to Kn
-n
, where Kn=l/L is the Knudsen number; l is the mean free path of the
species; L is the characteristic size of the plume; and n is the dimensionality of the problem.
To effectively study plume expansion into a background gas, a novel hybrid method has
been recently developed [51]. This method combines both continuous and microscopic
descriptions of laser-induced plasma expansion and is applicable for different background
pressures, starting from the plume expansion into vacuum and up to the regime of strong
shock waves. The method is particularly useful to study the transitional background pressure
regime. It takes advantages both of the gas dynamical description of the plume at the early
stage, and of the DSMC simulation at the late stage of the plume expansion, avoiding the
above-described challenging issues of these techniques. As a result, the expansion of a high-
density plume in the presence of a background gas can be tackled during a time as long as 5-
10 microsecond, at ambient gas pressures from zero to hundreds Pa. The developed model is
three-dimensional and uses axial symmetry. We assume that a laser beam with radius R
0
and

pulse duration interacts with a plane target (z 0). The half-space z > 0 is filled by a
background gas (pressure P
b
, density
b
). Under laser irradiation, the target absorbs a part of
the laser energy; the target material is heated and ablated forming a laser plume near the
target surface.
2.2.1. Combined LP -DSMC method
At the first stage, we consider the plasma plume as a non-viscose and non-heat-
conductive vapor containing atoms, ions and electrons. In the plume, the temperatures of
electrons, T
e
, deviates from the one of ions and neutrals, T
a
, because of the slow rate of
energy transfer between electrons and heavy particles. Based on these considerations, we
adopt an approach of one-fluid two-temperature gas-dynamics to describe the movement of
the laser plume. In this case, the system of gas-dynamical equations can be written in the
divergent form as follows (the plume expands along the Z axis):
( ) 0 = +
W
r
div
t
, (12)
( ) 0 =
+ +
z
P
U div
t
U
W
r
, (13)
( ) 0 =
+ +
r
P
V div
t
V
W
r
, (14)
( ) ( )
ea ei a a
a
Q Q P div E div
t
E
+ = + +
W W
r r
, (15)
( ) ( ) F P div E div
t
E
= + +
W W
r r
, (16)
2 /
2
W
r
+ + =
e a
E , 2 /
2
W
r
+ =
a a
E , (17)

e a
P P P + = , ( )
a a
P 1 = , ( )
e e e
P 1 = (18)
where is the density, U and V are Z and R components of the velocity vector W
r
; is the
specific heat ratio;
a
is the thermal energy of ions and neutrals;
e
is the thermal energy of
electron gas; P
a
and P
e
are the partial pressures of the heavy (ions and neutrals) and light
(electrons) gases. In Eq.(15), Q
ei
and Q
ea
describe the energy exchange between the electron
gas and the gas composed of ions and neutrals, and F is the energy lost by electrons for
ionization. In Eq. (12-18), a local thermodynamic equilibrium is assumed, and ideal-gas
equations of state are used.
To solve numerically the system (17)-(23) we use the method of large particles (LP)
adapted to the case of laser-solid interaction [89]. The advantages of this method are the
uncoupling of physical processes and the combination of the Euler and Lagrange approaches,
which gives the possibility of following initial plume expansion into a background gas in an
affordable computer time. The heat obtained by ions and atoms in elastic collisions with
electrons is
( ) ( )
ea ei e a e
e
ea ei
v v n T T k
m
m
Q Q + = +
2
3 2
, (19)
where
ei
v and
ea
v are the mean frequencies of electron-ion (e-i) and electron-atom (e-a)
collisions respectively. The collision frequencies are

( )
2 / 3 2 / 1
4
2 / 1
) ( 3
2 4
e e
C i
ei
kT m
e n
v

=

, (20)

2
e a
ea
n n c
v

= , (21)
where
C
is the Coulomb logarithm, and c is the average relative velocity, and is the
electron-atom collision cross-section. The energy lost by electrons for ionization

3
2
ei i a e
k n n
F

= , (22)
where

( )
=
e
i
rec
e
e e
ei
T
k
n h
kT m
k

exp
2
2
3
2 / 3
(23)
is the e-impact ionization rate constant, and is the three-body recombination constant.

( )
( )
e
e e
rec
n
kT m
e
k
2 / 9
2 / 1
10
2 / 1
9
2 4
= (24)
Initial boundary conditions at the surface z 0 = are calculated as a heat source resulting
from the absorption of the laser radiation corresponding to a laser pulse with gaussian
temporal shape and the pulse duration . The thermal evaporation model is used, so that the
vapor pressure at the surface is obtained from the Klasius - Clapeyron equation. The

temperature distribution along the laser-irradiated area is assumed to be uniform. Electron gas
temperature at the beginning is set to be higher than the one of heavy atoms, because
electrons absorb laser radiation. The initial flow parameters at 0 = z and
0
R r <

are
calculated using the jump conditions at the Knudsen layer boundary [90,91]. The flow
velocity at the Knudsen layer boundary U
K
is assumed to be equal to the velocity of sound a
K
,
so that the Mach number 1 = M at z 0 = [91]. For one-atomic vapor ( = 5/3), the Knudsen
layer parameters are T
K
= 0.65 T
S
, n
K
= 0.62 n
S
, U
K
= 1.31 T
S
, where index S refers to the
parameters at the surface, and K to the border of the Knudsen layer.
The large particle calculations are performed until a certain time t
0
, and then, the motion
of the ablated and background species is followed by using a microscopic Monte Carlo
method. On one hand, the switch time t
0
should be long enough for the plume density to
diminish by several orders of magnitude with respect to the initial values. As a result of the
plume expansion, the characteristic Knudsen number drops down to the values required for
the effective application of the DSMC method. Moreover, the t
0
should be long enough to
account for the ionization-recombination processes in the plasma plume. On the other hand,
the switch time should be short enough, such that the mass diffusion and the heat exchange
between the plume and the background gas are insignificant during the t
0
. For t > t
0
, the
ablated plume expansion into a background gas is calculated using the Direct Simulation
Monte Carlo (DSMC) method. In this method, gas flows are modeled by a representative
ensemble of atoms or molecules (typically from 10
3
to 10
6
). The DSMC procedure uses the
uncoupling of the molecular motion and the intermolecular collisions. The method has the
same limitations as kinetic theory of gases, which includes Boltzmann equation. The principal
limitations are the assumption of molecular chaos and requirement of a dilute gas. The details
of the method can be find in Ref.82.
2.2.2. Results of the combined LP -DSMC calculations
The developed model has been used for a series of calculations of laser plume expansion
in the presence of a background gas. Hereafter, we present the simulation results obtained for
laser ablation of solid targets (Al) in the presence of several background gases.
At small background pressure, initial plume expansion is slightly affected by the gas, and
then the ablated material transport becomes diffusion-driven. Starting from a certain pressure,
which can be determined from our simulation, a snowplow effect can be observed in the two-
dimensional contour maps of the plume and gas densities (Figure 1). This effect implies the
compression of the background gas in front of the expanding plume. In addition, a
compression of the plume front also takes place. If laser fluence is such that plume expansion
is under-sonic, the compression does not imply shock-wave formation, and diffusion is
strong. Monte Carlo simulation, which easily treats diffusion, is well suitable for these cases.
If, furthermore, laser fluence several times exceeds the ablation threshold, laser plume
expansion is super-sonic, and two shock waves are formed. One of them (external) propagates
in the background gas, whereas the other (internal) moves backward inside the plume
[92,93,94,]. Gas-dynamic description including a turbulent stage of Rayleigh Taylor
instability [95] become relevant when the sizes of all shock waves are much larger than
corresponding local mean free paths.

Figure 1. Calculated contours of number density. (above) plume species; (below) gas species. The
numbers are in m
-3
. Results are obtained for Al target in the presence of oxygen with laser spot radius of
1 mm, laser energy of 15 mJ, at background gas pressure of 70 Pa, and at t = 2.6 s after the beginning
of the laser pulse
Simulation results show, furthermore, that the dimensions of the laser spot affect the
expansion process (Figure 2). For instance, at the same laser fluence, the larger is the laser
spot, the higher is the density in the compressed plume front. At larger spot, the plume
expansion in radial direction is weaker; the thermal energy of the plume is transferred into the
kinetic energy of the outward motion, so that the flow velocity is larger.

Figure 2. Maximum plume front density as a function of background pressure. The calculations are
performed for Al in O
2
at two different radius of the laser spot and same laser fluence of 20 J/cm
2
. The
calculation results are obtained at t = 2.6 s after the beginning of the laser pulse


(a)

(b)
Figure 3. (a) Calculated spatial distribution of the product of the number densities of Al and O
2
,
( )
2
O Al
n n Z r, np =
. (b) Experimentally measured contour maps proportional to the AlO ground-state
population density. The results are obtained at t = 3 s after the beginning of the laser pulse, at laser
spot radius of 0.15 mm, laser fluence F~20 Jcm
-2
, and background pressure of 13 Pa
If, furthermore, ambient pressure is small, the plume-gas mixing is stronger than in the
snowplow mode. The plume expansion mode with an enhanced plume-gas mixing is
preferable for the reactive laser ablation. Typical background pressures used to produce
molecules by laser ablation depend on the molecular weight of the background gas. For
aluminum ablation in oxygen, these pressures range from 10 to 30 Pa. This regime, which
was particularly difficult for previous gas-dynamic simulations, is considered below.
To determine the flow regions with potentially maximum
0
AlO
n production rate, we
consider the calculated distribution of the product of the number densities of Al and O
2
,
( )
2
O Al p
n n Z r, n =
, (Figure 3). The n
p
distribution reveals a surprising similarity with the
experiments, in spite of the fact that n
p
represents only one of the factors determining the
production of AlO. Most remarkably a spatial distribution with similar two maxima at the
plume periphery can be observed at t = 6.3 s. These maxima can be explained if we compare
the calculated n
p
with the velocity flow-field. The comparison indicates that one of the
maxima, which is closer to the target, results from the backward particle fluxes. In fact, the
backward fluxes, which are composed of both ablated atoms and gas molecules, have been
observed in our calculations. The maximum of these backward flows is at the position of the
first n
p
maximum. The second maximum results from the dynamics of the plume expansion
and mixing with the gas. The ablated particles flying near the plume axis are stronger
decelerated by the gas than the ones flying at oblique directions because of the preferential

plume expansion in the direction of the outward target normal. At a certain time, the plume
starts preferentially expanding in radial (oblique) directions. As a result, the plume-gas
mixing is more intense at the plume periphery than near the plume axis.
3. MODELING OF SHORT AND ULTRA-SHORT
(FEMTOSECOND) LASER ABLATION
In this part we consider the aspects of modeling of laser ablation under action of
femtosecond laser pulses. For simplicity, we consider only metals. The description contains
the same parts corresponding to the two main categories of the ablation models.
3.1. Primary Mechanisms of the Material Ejection under Femtosecond Laser
Action
3.1.1. Metallic targets
In the case of femtosecond laser, the heating is so fast that the material temperature can
approach and even overcome the critical temperature of the material. In this case, no well-
defined interfaces between different phases (melting and evaporation fronts) exist. These
boundaries are well defined only at relatively small energy absorbed, when material
temperature is much smaller than the critical temperature. Because thermal processes, such as
thermal evaporation, are rather slow and take at least several nanoseconds, a different
mechanism should be considered in the case of femtosecond laser interaction with metals.
To bring more light on the mechanisms of material decomposition in the femtosecond
laser ablation of metals, we performed a detailed hydrodynamic modelling [53,54]. Remind,
that compared to atomistic techniques, hydrodynamic models allow calculations for much
larger systems and take much shorter computer time. Our numerical model is based on the
solution of a system of Eulerian hydrodynamic equations by a high-order multi-material
Godunovs method [96]. The equations were extended to the case of two-temperature
hydrodynamics with laser energy absorption source, electron heat conductivity and electron-
phonon energy exchange terms [54]. A Gaussian temporal profile is used to simulate the laser
energy deposition. The electron-phonon/ions energy exchange term, the reflectivity
coefficient and the optical penetration depth are derived from the wide-range frequency of
electron-phonon collisions [18]. For the completeness of our model, we use a semi-empirical
thermodynamically complete EOS for aluminum with separated components of electrons and
lattice (heavy particles). The EOS meets the following requirements: (i) to describe
experimental results on compression and expansion for a wide range of densities and
temperatures including data on critical and triple points; (ii) to contain separate information
about electron and ion/lattice sub-systems; (iii) to represent changes of thermodynamic
parameters during phase transitions. In addition, we switched between two different
modifications of the EOS: (i) with metastable states; and (ii) without metastable states. To
account for kinetic processes, an estimation of the realistic lifetime of metastable liquid state
was introduced as we describe in what follows.

In our model, when the binodal line is crossed, we include a particular treatment for each
of the following two competitive effects: (i) for the spinodal decomposition, a criterion of the
metastable liquid lifetime, based on the theory of homogeneous nucleation [97] is used; (ii)
for the fragmentation, a mechanical failure algorithm of Grady [20] is applied. In the first
case, we estimate the metastable liquid lifetime as ( ) T k W CnV
B
exp ) (
1
= , where C = 10
10
s
-
1
is the kinetic coefficient, n is the concentration, V is the volume,
2 3
3 16 P W = is the
work needed to cause the phase transition, P is the difference between saturated vapor
pressure at the same temperature and the pressure of substance, k
B
is the Boltzmann constant
and T is the temperature of the sub-system of heavy particles. The temperature dependence of
the surface tension is described as
( )
25 . 1
0
1
c
T T =
, where T
c
is the temperature in critical
point (CP),
0
the surface tension at normal conditions. In this case, as soon as the lifetime
in the volume V is expired, the phase state in this point is no more metastable. The EOS with
metastable phase states is therefore no more relevant in this volume, so that we continue to
calculate the thermodynamic properties by using the stable EOS. To account for the second
effect, a fragmentation criterion is used for the liquid phase with the spall strength
( )
3 / 1
3 2
6 & c P
s
=
and the time to fracture
( )
3 / 1
2
6
1
&
c
t
s
=
, where is target density; & is
the strain rate and c is the sound speed. When this criterion is satisfied we introduce vacuum
into the cell and relax the pressure to zero. Both of these criteria are used simultaneously and
each of them can prevail in a given computational cell depending on the substance location on
the phase diagram.

Figure 4. Phase diagram of aluminum with stable and metastable (in parenthesis) phase states and
trajectories of different target layers. The phase trajectories 1 7 correspond to the depth of 5, 15, 20,
30, 50, 80, 130 nm from the free surface of the target, respectively. Here, the laser pulse parameters are
L
= 100 fs, = 800 nm, and F = 5.0 J/cm
2

For the analysis of the target material evolution after the laser irradiation, it is convenient
to use a phase diagram in the temperature-density plane (T, ) given by the EOS (Figure 1).
The binodal line corresponds to the gas-liquid equilibrium (saturated vapor curve). The
spinodal line (dashed) gives a limit of thermodynamic stability of the matter. The regions
between the binodal and the spinodal lines show the metastable states of matter: the
superheated liquid (SHL) and the supercooled vapor (SCV) state. Initially, the ablated target
of aluminum is in a solid state and is subjected to a laser pulse with F = 5 J/cm
2
,
L
= 100 fs
pulse width, = 800 nm wavelength. The matter absorbs laser energy in a very thin region
(skin-depth, on the order of 10 30 nm, trajectories 1 4 in Figure 4). Then, a heat wave
propagates into the bulk, which is followed by a shock wave (SW). This moment corresponds
to the right-hand deviation of the trajectories 4 7 in Figure 1. The SW goes into the target
and it is followed by a rarefaction wave (RW). The RW leads to the material expansion
(decreasing of the density along trajectories, Figure 1). The initial temperature in the vicinity
of the target surface (depth < 15 nm) is high enough (up to T ~ 30 kK), so that the phase
trajectories from this layer go above the CP and the target material is directly transformed
into the gas phase (trajectories 1 2 in Figure 1). Then, these trajectories penetrate into the
SCV region, where condensation begins leading to the appearance of a liquid-gas mixture.
Note, however, that this layer represents a very small fraction of the ablated material, so that
the condensation degree is insignificant. Next layer in the target (depth from 20 to 30 nm) is
first transformed into a metastable liquid state. The upper part of this layer is heated to a high
temperature (~ 25 kK), so that the corresponding phase trajectories cross the binodal line in
the vicinity of the CP and enter the metastable region (SHL). Under these conditions, the
target material is thermodynamically unstable. The lifetime of this state is estimated as
described above. Thermodynamic instabilities are known to occur near the CP (particularly, at
0.9 T
c
< T < T
c
, where T
c
= 6595 K for Al) leading to a rapid decomposion (several
picoseconds) of the matter into a liquid-gas mixture. This process is similar to the phase
explosion [25,26,47], though occurs during simultaneous material expansion and cooling. It
better corresponds to the critical point decomposition or spinodal decomposition outlined in
[22]. This mechanism, however, concerns only quite a thin slice of the ablated target
( 10 nm). In fact, the melted layer is much thicker than the one, which trajectories enter the
SHL region near the critical point. The rest of the trajectories (trajectories 5 7 in Figure 4),
which originate from the deeper lying melted layers, also enter the metastable SHL region,
but their temperatures are much smaller than the critical one. In this case, the matter can stay
in the metastable state much longer. As a result, mechanical decomposition occurring under
the action of a tensile stress (negative pressure) starts to dominate over thermal effects (time
to fracture is shorter than the metastable liquid lifetime). As soon as the time to fracture is
exceeded, the material is decomposed into clusters and chunks (metastable liquid decay). The
mechanism is similar to the dynamic fragmentation due to the mechanical origin of the
decomposition. This mechanism concerns the major part of the ablated material at the
considered laser fluence.
The dynamics of the target decomposition is presented in Figure 5. Initially the free
surface of the target is located at x = 0 nm. Upon electron energy relaxation, a SW propagates
into the target (pressure peak in Figure 2), leading the material expansion in the opposite
direction through a RW, where pressure decays and can drop below zero. At a delay t = 10 ps
after the beginning of the laser pulse, the density profile is still continuous [Figure 5(a)]. At

t = 20 ps, the trajectories originated from the skin-layer (thickness 30 nm) reach the binodal
line and penetrate into the metastable liquid region, where thermal material decomposition
sets in [Figure 2(b)]. This process is completed by t~ 40 ps. Then, only mechanical
mechanisms are involved into the material decomposition process. By t ~ 80 ps [Figure 5(d)],
the mechanical decay of the liquid phase is completed. This result corresponds to the final
vibrations of the trajectories 5 7 in Figure 1 that take place in the neighborhood of the
binodal curve, where pressure is zero.
The fractions of the target material ablated due to the described mechanisms depend both
on the material properties and on laser parameters. We present here the analysis of these
fractions as a function of laser fluence (F). At very small fluences (F < 0.25 J/cm
2
for
aluminum) only melting occurs. When laser fluence is slightly above this value, material
spallation takes place, in agreement with the previous MD simulations.. When laser fluence is
further increased, both metastable liquid decay and spallation mechanisms play a role. At
larger F, all three mechanisms (i) direct atomization; (ii) thermal decomposition (critical
point or spinodal decomposition); and (iii) mechanical decomposition (metastable liquid
decay and spallation) occur in different regions of the target. The third mechanism, however,
is found to be dominant (up to 80% of ablated mass) at all considered laser fluences (from 0.1
to 5 J/cm
2
).

Figure 5. Contour plots of density (solid) and pressure (dashed) for different time moments after
irradiation: (a) 10 ps, (b) 20 ps, (c) 30 ps and (d) 80 ps. Here, 1 is thermal (spinodal)
decomposition zone, 2 is mechanical decomposition zone. The laser pulse parameters are the same as
in Figure

Figure 6. Melted (open triangles, solid line) and ablated (black triangles) depths as a function of laser
fluence for aluminum. Experimental data are taken from [98] (black stars) and [100] (open stars).
Results of the simulation [17] are also shown (squares)
Finally, we propose several predictions from our simulations and compare our results
with the available experimental findings [98,99,100]. It turns out, that the consideration of
only critical point or spinodal decomposition results in a significant underestimation of the
ablation depth (several times) with respect to the experimental values. This underestimation
can be explained by the fact that only 10-20% of the target material is ablated due to these
critical effects, whereas most of the ablated material is ejected due to the mechanical
decomposition of the liquid phase. These results confirm that the decomposed melted zone
contributes strongly into the estimation of the ablated zone (Figure 6).
3.1.2. Dielectric targets
The density of the conduction band electrons is typically too small in wide band gap
materials for the efficient laser energy absorption. Nevertheless, focused ultra-short laser
pulses can induce electronic excitations and ionize these materials. Therefore, to model the
ultra-short laser interactions with dielectric materials, we consider the laser excitation
processes that provide conduction band electrons. In addition, laser energy absorption and
propagation are calculated. The present study is focused only on the case of moderate laser
intensities typically used in industrial applications. Therefore, a system of simplified rate
equations can be used instead of the detailed Boltzmann equation. The corresponding system
of one-dimensional differential equations accounts for the multi-photon ionization process
(MPI), for the electron tunneling effect, the electron-impact (or, avalanche) ionization, as well
as for the formation of self-trapped excitons (STEs), and plasma relaxation
processes[30,101,102,103]

e
e m
S m e i
v
e V e
t
n
I n I n a
n
n n
t
n
+ +
) (
, (25)


S
e m
S m
S
t
n
I n
t
n
+ =
, (26)
I
n
n n
k
z
I
a
v
e V

) (
h , (27)
where z is the depth below the laser-irrdiated surface; t is time; n
e
(t,z) is the number density of
conduction band electrons; is the laser frequency; I(t,z) is the laser intensity; n
v
is the
number density of valence band electrons in the non-excited dielectric; (t,z) accounts for the
laser field ionization (MPI/tunneling) processes; a
i
is the electron avalanche parameter
obtained as in Ref.36; n
S
is the number density of STEs; m is the number of photons needed
for STE excitation (m=5);
m
is the multi-photon cross sections for STEs; t
e
is the electron
plasma life-time due to recombination and trapping (between 100 fs and several ps, here 1ps);
t
s
is the characteristic trapping time; and h is Planks constant. For STE excitation,
5
is set
to be 10
-93
m
10
s
5
/J
5
. The field ionization term (t,z) is calculated as a function of laser field
intensity I(t,z) by using a well-known Keldysh equation.[102] According to the Keldyshs
formalism,[102] the transition from the multi-photon to the tunneling ionization process
occurs when the parameter
L
g
eE
E m
*
=
drops well below unity, where e is the electron
charge; m
*
is the reduced electron mass
* * *
/ 1 / 1 / 1
h e
m m m + =
, index e corresponds to
electrons and h to holes (we assume m
*
=0.5 m
e
,); is laser frequency; E
L
(t)=
0
/ 2 c I n
r
is
electric laser field; n
r
is the refractive index;
0
is vacuum permittivity; c is the speed of light;
and E
g
is the bandgap. The system is solved by using the fourth-order Rounge-Kutta method.
In the present work, the calculations are carried out for fused silica since this material was
widely used in previous studies. For simplicity, the plasma relaxation time, t
e
, is assumed to
be equal to t
s
. As a result of a parametric study, this parameter was set to be 1 ps because this
value gives a reasonable agreement with the experimental results that we used. More precise
value can be obtained only based on additional experimental results. The laser wavelength is
800 nm in all the calculations.
For wide band gap materials, the complex dielectric function contains contributions from
the unexcited solid and the response of the laser-induced free-electron gas
( ) ( )
( )
1
*
1
1
1 1 1

+
+
c
c
e
V
e
g e
i
n
n
n
n
n
, (28)
where
2
r g
n = is the dielectric function of non-excited material; n
r
is the refractive index;
c

is the characteristic collision time;
2
0
2
/ e m n
e c
= is the critical plasma density; and
0
is
the vacuum permittivity. The collision time
imp eph ee c
+ + =
1
, where
ee
is the
electron-electron collision frequency;
eph
=310
14
s
-1
is the frequency of the electron-phonon
collisions; and
imp
is the frequency of electron collisions with the impurities. In the present
calculations, we neglect
ee
and
imp
. Both reflectivity R and the absorption coefficient
a

are calculated by using the Fresnels equations as follows (normal incidence)

( ) [ ] ( )
( ) [ ] ( ) z t k z t k
z t k z t k
R
, 1 ,
, 1 ,
2
2 1
2
2 1
+ +
+
= , (29)

( )
c
z t k
a
, 2
2
= , (30)
where k
1
and k
2
are real and imaginary parts of the complex refraction index that are
calculated using Eq. (4), so that
2 / ) (
2
2
2
1 1 1
+ + = k
, and
2 / ) (
2
2
2
1 1 2
+ + = k
,
where
1
and
2
are the real and imaginary parts of the complex dielectric function,
respectively.
We present the calculation results obtained for single-shot excitations. These calculation
results can be used as a reference for the analysis of more complex laser excitations. First, we
consider fused silica and determine the optical breakdown threshold (I
th
, or OBT) based on
the maximum number density of conduction band electrons, N
e
, reached in the calculations
[104]. The optical breakdown is supposed to occur when N
e
reaches the critical density, or
2
0
2
/ e m n
e c
=
. For fused silica at 800 nm, n
c
=1.7410
21
cm
-3
.
Figure 7 shows the calculated N
e
as a function of the incident laser intensity I
0
(peak
value). A very sharp growth can be observed in the dependency at I
0
>I
th
. At this intensity
(here, ~5 10
13
W/cm
2
), N
e
overcomes the plasma critical density n
c
. Interestingly, the
experimentally measured plasma radiation from the breakdown region was shown to increase
similarly with laser intensity. These results confirm the validity of our model.

Figure 7. Maximum density of the conduction band electrons as a function of the peak laser intensity.
Here, calculations are performed for 50 fs laser pulse at 800 nm

The calculated optical breakdown threshold as a function of the laser pulse width is
shown in Figure 8. One can see that the threshold intensity rises for laser pulses shorter than
100 fs. This result is in good qualitative agreement with recent experimental observations,
where similar pulse width dependency and intensities values were observed [105]. Larger
threshold values that obtained in the experiments for ultra-short pulses (<100 fs) can be
attributed to the fact that that in this regime ionization takes place during shorter time, so that
larger intensities are needed to reach the critical electron density. Furthermore, because free
electrons oscillate in the electric laser field, the effective ionization potential
2 *
2 2
*
4 m
E e
E E
L
g g
+ =
increases with laser intensity [35], where E
g
is the band-gap, and E
L
the
frequency and amplitude of electric laser field, respectively, and m* is the reduced effective
mass. The calculated values are slightly smaller because we consider only surface damage
(electron density is maximum just below the surface), whereas the pulses were focused 150
m inside the fused silica sample in Ref. 29. In the latter case, the laser beam propagation can
be strongly affected by material ionization, beam dispersion and other effects resulting in a
higher threshold. When laser fluence is used to determine the OBT, the threshold fluence
decreases with pulse shortening below 100 fs. As we have indicated in the description of our
model, the Keldysh parameter varies as a function of laser intensity during the pulse.
Considering the peak laser intensity, one can calculate the corresponding and estimate
which process, multi-photon ionization or tunneling effect, is expected to prevail if one
neglects the avalanche ionization process (Figure 8). The results of this estimation show that
an intermediate regime is realized at the considered peak intensities. Typically, multi-photon
ionization is considered to be a dominant process in this case, resulting in a small
overestimation of the ionization probability. In a multi-pulse regime, the STE excitations also
provide seed electrons. The contribution of the electron impact (or avalanche) ionization
process rises with the temporal pulse width, and, is dominant for high peak intensities, in
agreement with Ref. [106].

Figure 8. Threshold laser intensity (peak value for Gaussian pulse) as a function of temporal pulse
width (circles). The Keldysh parameter values corresponding to the peak threshold intensity are shown
by triangles
3.2. Secondary Mechanisms: Plasma Plume Expansion after Femtosecond
Laser Pulse
The initial axial density distribution in the gas phase is thus given by the dynamics of the
shock wave propagation and the rarefaction wave formation driving the femtosecond laser
ablation
The calculations of the two-dimensional plasma expansion in vacuum [107] with the
initial conditions obtained from the 1D model of femtosecond interaction show that the
plasma is much more forward directed (Figure 9). This result agrees with the experimental
observations. In addition, the plume density distribution is more extended (prolonged) here
compared with that created by nanosecond pulses.
These results can be attributed to the different initial conditions caused by the
femtosecond interaction mechanism. At the same laser fluence, both temperature and pressure
gradients are much larger in the femtosecond ablation. Because of the propagation of pressure
wave and fast cooling due to the electron heat conduction, the species ejected earlier travel
longer distances than the ones that are ejected later. As a result, the density distribution is
prolonged. Furthermore, ablation induced by a femtosecond pulse continues for several
r
,
which is still much shorter than the ablation time under nanosecond pulse. The ablation depth
is, however, comparable in both cases. As a result, the initial plume density and the axial
density gradient are much larger than these after the femtosecond pulse.

Figure 9. Two-dimensional density profile obtained in the calculations of the laser plume expansion at
t=1 s after a femtosecond laser pulse.

CONCLUSION
To summarize, several physical phenomena that take place during pulsed laser ablation
are modeled by different numerical methods. Each of these methods has its advantages and
limitations. Therefore, only combinations of different methods may describe the ablation
process for a wide range of the experimental conditions.
To study femtosecond laser ablation of metal targets hydrodynamic simulations is shown
to be promising. The obtained results show that when laser fluence is sufficiently high, three
following mechanism can play a role: (i) direct atomization; (ii) thermal decomposition (near
critical point); (iii) mechanical decomposition. Relative importance of these processes varies
as a function of depth. In addition, we have recently used this model with calculation of
absorption in the expanding plasma to explain an interesting effect of the decay in the
ablation depth observed in double-pulse experiments. For transparent materials, we have
started developing a model to describe non-linear electronic excitations, ionization, nd
absorption. For this excitation part we have used the Boltzmann-equation, the system of
rate equations.
The properties of the laser-generated plasma plume are shown to be strongly affected by
the laser-mater interaction mechanism. Experimental diagnostics of the expanding plasma
may help to better understand these mechanisms. The calculations demonstrate furthermore
the crucial role of strong pressure gradients induced in the metals during femtosecond laser
ablation. This study can be useful for different applications dealing with both laser treatments
of surfaces and laser plasma technologies.
Despite considerable efforts focused on the understanding of femtosecond interactions
and mechanisms involved in laser nano-cluster formation and nanostructuring, many points
need further much more detailed investigations. The definition of electron-phonon
interactions and electron conductivity are still puzzling. New models with wider limits of
applicability should be developed and used in future multi-scale simulation.
REFERENCES
[1] Nolte, S; Momma, C; Jacobs, H; Tnnermann, A; Chichkov, BN; Wellegehausen, B;
Welling, H. JOSA B, 1997, vol. 14, Issue 10, 2716-2722.
[2] Kper, S; Stuke, M. Appl. Phys. B, 1987, vol. 44, 199.
[3] Pronko, P; Dutta, S; Squier, J; Optics Commun, 1995, vol. 114, 106.
[4] Banks, PS; Feit, MD; Rubenchik, AM; Stuart, BC; Perry, MD. Appl. Phys. A, 1999, vol.
69, S377.
[5] Chichkov, BN; Momma, C; Nolte, S; von Alvensleben, F; Tnnermann, A. Appl. Phys.,
A, 1996, vol. 63, 109.
[6] Kautek, W; Krer, J. Proc. SPIE, 1994, vol. 2207, 600.
[7] Teghil, R; D'Alessio, L; Santagata, A; Zaccagnino, M; Ferro, D; Sordelet, DJ. Appl.
Surf. Sci., 2003, vol. 3-4, 307.
[8] Short Pulse Laser Interactions with Matter: An Introduction, P. Gibbon, Imperial
College Press, London, 2005.
[9] Femtosecond Laser Spectroscopy, Peter Hannaford, Springer, 2004.
[10] Femtosecond Technology for Technical and Medical Applications, F. Dausinger, F.
Lichtner, H. Lubatschowski, Springer, 2004.
[11] Laser Processing and Chemistry, D. Buerle, Springer-Verlag, Berlin Heidelberg,
2000.
[12] Heitz, J; Dickenson, JT. Appl. Phys. A, 1999, vol. 68, 515-523.
[13] Ayyub, P; Chandra, R; Taneja, P; Sharma, AK; Pinto, R. Appl. Phys. A, 2001, vol. 73,
67-73.
[14] Borsella, E; Botti, S; Giorgi, R; Martelli, S; Turt, S; Zappa, G. Appl. Phys. Lett, 1993,
vol. 63, 1345-1347.
[15] Pulsed Laser Deposition of Thin Films, Chrisey, DB; Hubler, GK. Wiley-Interscience,
New York, 1994.
[16] Tsui, YY; Santiago, J; Li, YM; Fedosejevs, R. Opt. Commun., 1994, vol. 111, 360.
[17] Komashko, AM; Feit, MD; Rubenchik, AM; Perry, MD; Banks, PS. Appl. Phys. A,
1999, vol. 69, s95.
[18] Eidmann, K; Meyer-ter-Vehn, J; Schlegel T; Hller, S. Phys. Rev. E, 2000, vol. 62(1),
1202.
[19] Anisimov, SI; Bonch-Bruevich, AM; Elyashevich, MA; Imas, Ya. A; Pavlenko, NA;
Romanov, GS. Sov. Phys.-Tech. Phys., 1967, vol. 11, 945.
[20] Anisimov, SI; Luk'yanchuk, BS. Uspehi Fiz. Nauk., 2002, 172(3), 301.
[21] Rethfeld, B; Sokolowski-Tinten, K; von der Linde, D; Anisimov, SI. Phys. Rev. B,
2002, vol. 65, 092103.
[22] Vidal, F; Johnston, TW; Laville, S; Barthlemy, O; Chaker, M; Le Drogoff, B; Margot,
J; Sabasi, M. Phys. Rev. Lett, 2001, vol. 86, 2573.
[23] Bulgakova, NM. Phys. Rev. E, 1999, vol. 60, R3498.
[24] Gamaly, E; Rode, A; Luther-Davies, B; Tikhonchuk, V; Phys. Plasm., 2002, vol. 9(3),
949.
[25] Zhigilei, LV; Garrison, BJ. Appl. Phys. Lett, 1999, vol. 74, 1341.
[26] Garrison, BJ; Itina, TE; Zhigilei, LV; Phys. Rev. E, 2003, vol. 68, 041501.
[27] Du, D; Liu, X; Korn, G; Squier, J; Mourou, G. Appl. Phys. Lett, 1994, vol. 64, 3071.
[28] Lenzner, M; Krger, J; Sartania, S; Cheng, Z; Spielmann, C; Mourou, G; Kautek, W;
Krausz, F. Phys. Rev. Lett, 1998, vol. 80 , 4076.
[29] Stuart, BC; Feit, MD; Herman, S; Rubenchik, AM; Shore, BW. Pery, M. D. Phys. Rev.
B, 1996, vol. 53, 1749.
[30] Mao, SS; Qr, F; Guizard, S; Mao, X; Russo, RE; Petite, G; Martin, P. Appl. Phys. A,
2004, vol. 79, 1695.
[31] Mero, M; Sabbah, AJ; Zeller, J; Rudolph, W. Appl. Phys. A, 2005, vol. 81, 317.
[32] Jasapara, J; Mero, M; Rudolph, W. Appl. Phys. Lett, 2002, vol. 80(15), 2637.
[33] Jia, TQ; Chen, HX; Huang, M; Zhao, FL. Phys. Rev. B, 2006, vol. 73, 054105.
[34] Sanner, N; Utza, O; Bussiere, B; Coustillier, G; Leray, A; Itina, T; Sentis, M. Appl.
Phys. A, 2009, vol. 94, 889.
[35] Kaiser, A; Rethfeld, B; Vicanek, M; Simon, G. Phys. Rev. B, 2000, vol. 61, 11437.
[36] Rethfeld, B. Phys. Rev. Lett, 2004, vol. 92(18), 187401.
[37] Schaffer, CB; Jamison, AO; Mazur, E. Appl. Phys. Lett, 2004, vol. 84, 1441.
[38] Li, M; Menon, S; Nibarger, JP; Gibson, GN. Phys. Rev. Lett, 1999, vol. 82(11), 2394.
[39] Itina, TE; Mamatkulov, M; Sentis, M. Optical Engineering, 2005, vol. 44(5), 051109.
[40] Jiang, L; Tsai, HL. J. Appl. Phys., 2008, vol. 104, 093101.

[41] Chowdhury, IH; Wu, AQ; Xu, X; Weiner, AM. Appl. Phys. A, 2005, vol. 81, 1627.
[42] Kaganov, M; et al. Zh. Eksp. Teor. Fiz., 1956, vol. 31, 232.
[43] Anisimov, SI; et al. Zh. Eksp. Teor. Fiz., 1974, vol. 66, 776.
[44] Carpene, E; Phys. Rev. B, 2006, vol. 74, 024301.
[45] Lin, Z; Zhigilei, LV; Celli, V. Phys. Rev. B, 2008, vol. 77, 075133.
[46] Inogamov, N; et al. Appl, Surf Sience, 2009, vol. 255, 9712.
[47] Perez, D; Lewis, LJ. Phys. Rev. B, 2003, vol. 67, 184102.
[48] Itina, TE; Zhigilei, LV; Garrison, BJ. J. Phys. Chem. B, 2002, vol. 106, 303-310.
[49] Itina, TE; Zhigilei, LV; Garrison, BJ. Nuclear Instr. & Methods in Phys. Res. B , Beam
Interaction with Materials and Atoms, 2001, vol. 180, 238-244.
[50] Itina, TE; Marine, W; Autric, M. J. Appl. Phys., 1997, vol. 82(7), 3536.
[51] Itina, TE; Hermann, J; Delaporte, P; Sentis, M. Phys. Rev. E, 2002, vol. 66, 066406.
[52] Itina, TE; Tokarev, VN; Marine, W; Autric, M. J. Chem. Phys.,1997, vol. 106(21),
8905.
[53] Povarnitsyn, ME; Itina, TE; Sentis, M; Khishenko, KV; Levashov, PR. Phys. Rev. B,
2007, vol. 75, 235414.
[54] Povarnitsyn, ME; Itina, TE; Khishchenko, KV; Levashov, PR. Phys. Rev. Lett, 2009,
vol. 103, 195002.
[55] Song, KH; Xu, X. Appl. Surf. Sci., 1998, vol. 127-129, 111-116.
[56] Bennett, TD; Grigoropoulos, CP; Krajnovich, DJ. J. Appl. Phys., 1995, vol. 77, 849-
864.
[57] Zhang, X; Chu, SS; Ho, JR; Grigoropoulos, CP. Appl. Phys. A, 1997, vol. 64, 545-552.
[58] Serna, R; Dreyfus, RW; Solis, J; Afonso, CN; Allwood, DA; Dyer, PE; Petford-Long
AK. Appl. Surf. Sci., 1998, vol. 127-129, 383-387.
[59] Yoo, JH; Jeong, SH; Mao, XL; Greif, R; Russo, RE. Appl. Phys. Lett, 2000, vol. 76,
783-785.
[60] Yoo, JH; Jeong, SH; Greif, R; Russo, RE. J. Appl. Phys., 2000, vol. 88, 1638-1649.
[61] Okano, A; Takayanagi, K. Appl. Surf. Sci., 1998, vol. 127-129, 362-367.
[62] Marine, W; Patrone, L; Lukyanchuk, B; Sentis, M; Appl. Surf. Sci., 2000, vol. 154-
155, 345-352.
[63] Webb, RL; Dickinson, JT; Exarhos, GJ. Appl. Spectrosc, 1997, vol. 51, 707-717.
[64] Kozlov, BN; Mamyrin, BA. Tech. Phys., 1999, vol. 44, 1073-1076.
[65] Hankin, SM; John, P. J. Phys. Chem. B, 1999, vol. 103, 4566-4569.
[66] Callies, G; Schittenhelm, H; Berger, P; Hgel, H. Appl. Surf. Sci., 1998, vol. 127-129,
134-141.
[67] Mizuseki, H; Jin, Y; Kawazoe, Y; Wille, LT. Appl. Phys. A, 2001, vol. 73, 731.
[68] Anisimov, SI; Bonch-Brouevich, AM; Elyashevich, MA; Imas, Ya. A; Pavlenko, NA;
Romanov, GS. Sov. J. Tech. Phys., 1966, vol. 36, 1273.
[69] Luikov, AV; Perelman, TL; Anisimov, SI. Int. J. Heat Mass Transfer, 1971, vol. 14,
177.
[70] Anisimov, SI. Sov. Phys. JETP, 1968, vol. 27(1), 182.
[71] Peterlongo, A; Miotello, A; Kelly, R. Phys. Rev. E, 1994, vol. 50(6), 4716.
[72] Ostland, RA; Orlander, ER. J. Appl. Phys., 1975, vol. 46,1499.
[73] Martynyuk, MM. Russ. J. Phys. Chem., 1983, vol. 57, 494.
[74] Kelly, R; Cuomo, JJ; Braren, BE; Aliotta, CF; Rothenberg, JE; Leary, PA. Nucl. Instr.
Methods Phys. Res. B, 1985, vol. 9, 329.
[75] Lukyanchuk, B; Bityrin, N; Anisimov, S; Malyshev, A; Arnold, N; Bauerle, B. Appl.
Surf. Science, 1996, vol. 106, 120.
[76] Dawson, M. Physics of Fluids, 1964, vol. 7, 981.
[77] Singh, RK; Narayan, J. Phys. Rev. B, 1990, vol. 41(13), 8843.
[78] Anisimov, SI; Buerle, D; Lukyanchuk, BS. Phys. Rev. B, 1993, vol. 48, 12076.
[79] Peterlongo, A; Miotello, A; Kelly, R. Phys. Rev. E, 1994, vol. 50(6), 4716.
[80] Bulgakov, AV; Bulgakova, NM. J. Phys. D: Appl. Phys., 1998, vol. 31, 693.
[81] Le, HC; Vuillon, J; Zeitoun, D; Marine, W; Sentis, M; Dreyfus, RW. Appl. Surf. Sci.,
1996, vol. 96-98 76.
[82] Molecular Gas Dynamics and the Direct Simulation of gas flows, G.A.Bird, Clarendon,
Oxford, 1994.
[83] NoorBatcha, I; Lucchese, RR; Zeiri, Y. J. Chem. Phys., 1987, vol. 86, 5816.
[84] Sibold, D; Urbassek, HM. Phys. Rev. A, 1991, vol. 43, 6722.
[85] Kelly, R. Chem. Phys., 1990, vol. 92(8), 5047.
[86] Sibold, D; Urbassek, HM. Phys. Fluids A, 1992, vol. 4(1), 165.
[87] Urbassek, HM; Sibold, D, Phys. Rev. Lett, 1993, vol. 70, 1886.
[88] Itina, TE; Patrone, L; Marine, W; Autric, M. Appl. Phys. A, 1999, vol. 69, s59-s65.
[89] Belotserkovskii, OM. J. Comput. Phys., 1970, vol. 5, 587.
[90] Knight, CJ. AIAA Journal, 1979, vol. 17(5), 519.
[91] Anisimov, SI. Sov. Phys. JETP, 1968, vol. 27(1), 182.
[92] Brode, HL. Phys. Fluids, 1959, v. 2, 217.
[93] Unsteady Motion of Continuous Media, Stanyukovich, K. P., Pergamon, London, 1960.
[94] Arnold, N; Gruber, J; Heitz, J. Appl. Phys. A, 1999, vol. 69(7), s87.
[95] Anisimov, SI; Zeldovich, Ya. B. Sov. Phys. Lett.,1977, vol. 3(10), 445.
[96] Miller, GH; Puckett, EG. J. Comput. Phys., 1996, vol. 128, 134.
[97] Kinetic Theory of Liquids ; . Frenkel, J; Clarendon Press, Oxford, 1946.
[98] Amoruso, S; Bruzzese, S; Vitiello, M; Nediakov, NN; Atanasov, PA. Appl. Phys., 2005,
vol. 98, 044907.
[99] Plech, A; Kotaidis, V; Lorenc, M; Boneberg, J. Nature Physics, 2006, vol. 2, 44.
[100] Colombier, JP; Combis, P; Bonneau, F; Le Harzic, R; Audouard, E. Phys. Rev. B, 2005,
vol. 71, 165406.
[101] Qur, F; Guizard, S; Martin, P. Europhysics Letters, 2001, vol. 56,138-144.
[102] Keldysh, LV. Soviet Physics JETP, 1965, vol. 20, 1018 .
[103] TE; Itina, N. Shcheblanov, Appl. Phys. A: Materials Science and Processing, 2010, vol.
98(4), 769-775.
[104] Olivi, G; Gigure, D; Vidal, F; Ozaki, T; Kieffer, JC; Nada, O; Brunette, I. Optics
Express, 2008, vol. 16,(6), 4121.
[105] Rajeev, PP; Gertsvolf, M; Corkum, PB; Rayner, DM; Phys Rev Lett, 2009, vol. 102(8)
083001.
[106] Rethfeld, B. Phys. Rev. B, 2006, vol. 73, 035101.
[107] Itina, TE; Vidal, F; Delaporte, Ph; Sentis, M. Appl. Phys. A, 2004, vol. 79 , 1089-1092.
Chapter 4
FABRICATION OF SILICON NANOCRYSTAL
BASED STRUCTURES WITH NANOSECOND LASER
ABLATION PROCESSINGS IN LIQUID MEDIA
V. vrek
*

Research Center for Photovoltaics, National Institute of Advanced
Industrial Science and Technology (AIST), Tsukuba, Japan
ABSTRACT
In this chapter a nanosecond (ns) laser ablation and fragmentation processing in
water, pure and doped spin on glass (SOG) polymer-based solutions are discussed. The
confinement of laser-generated plasma in liquids allows the silicon nanocrystals (Si-ncs)
formation with a quantum confinement size effects. We demonstrate that ns laser
processes in liquid can be efficiently applied for the fabrication and tuning the
optoelectronic properties of Si-ncs based nanostructures. The laser fragmentation in water
induces the self-assembly and allows formation of closely-packed stable luminescent Si-
ncs over ~ 200 m. Contrary to the water, the laser ablation and fragmentation in pure
and doped SOG solutions inhibit aglomeration and enhance the Si-ncs luminescence
properties. Finnally, we disccuss physics and dynamics of Si-ncs formation through the
serial growth processes that occurred in liquid media confined ns laser generated plasma.

Keywords: silicon nanocrystals, ns laser ablation and fragmentation in liquid,
photoluminescence, quantum confinement.
1. INTRODUCTION
Since pulsed laser ablation of solid materials is easily carried out as a result ablation
almost any kinds of solid materials has been widely investigated and developed [1, 2].

*
Corresponding author: Tel: +81-29-861-5429 Fax: +81-29-861-3367. Email: vladimir.svrcek@aist.go.jp,
V. vrek 128
However, most researchers have focused on pulsed laser ablation of solid targets in vacuum
and in a diluted gaseous ambient [3-6]. In such a way pulsed laser ablation has been
successfully employed to fabricate novel microstructures, wide band gap semiconductors,
nanocrystals, clean and elaborate surface of many types of materials [7-10]. Between the
nanostructures nanoparticles with quantum confinement effects increased interest many
scientific communities [7]. It has to be noted that nanoparticles synthesized in gas phase are
very often agglomerated due to unstable surface properties [5, 6].
Last decade laser ablation conducted directly in liquid media has shown to be a peculiar
technique to generate the nanoparticles [11,12]. This approach offer strong advantages
comparison to the ablation in vacuum or gas atmosphere. Generated nanoparticles are
obviously charged possessing a high zeta potential (>30 mV), which avoids agglomeration
and results in high nanoparticles stability. Even more nanoparticles directly produced and
dispersed in liquid media are not inhalable and thus leads to facilitating of the process safety
requirements. Moreover, the chemical precursors are not necessary therefore compared to
laser ablation in gas atmosphere enhanced purity of colloidal particles is widely reported [13,
14]. It has to be stress that nowadays besides element metal, alloying, and oxide nanocrystals
also organic fullerene-like nanostructures have been produced by laser ablation in liquids [15,
16].
Silicon nanocrystals (Si-ncs), since the discovery of visible room-temperature
photoluminescence (PL) from anodized porous silicon, have attracted much attention due to
their potential application in many fields (i.e. optoelectronics, photovoltaics, biology). Laser
ablation in liquid can be employed in producing of highly luminescent Si-ncs with strong
quantum confinement effects [17-19]. As Si-based technology will keep playing an crucial
role for device fabrication, also silicon dioxide (SiO
2
) will remain a fundamental interface
material. Direct processing in water or oxide based liquid media might allow engineer Si-
dioxide interface at Si-ncs at superior quality by cost effective way. Thus might consent to
control and even enhance overall Si-ncs properties. Environmental and human body
compatible procedure based on laser processing in water can be another factor for producing
non-toxic, room temperature luminescent Si-ncs, which might at the same time provide a
further foundation for applications in biology or medicine.
In this chapter cheap and scalable nanosecond-laser ablation and fragmentation
processing in liquids is applied for the fabrication of Si-ncs based nanostructures. The
confinement of laser-generated plasma in liquids allows the Si-ncs formation with quantum
confinement size effects. Particularly, we discuss aspects of the Si-ncs preparations in water
and liquid transparent polymers i.e. pure and doped spin on glass (SOG). We demonstrate that
compared to the water the SiO
2
-based SOG inhibits aggregation and enhance the
photoluminescence properties of Si-ncs. In order to enhance the Si-ncs rate formation, an
effective way to prepare luminescent Si-ncs by pulsed laser-induced fragmentation of Si
micrograins prepared by electrochemical etching in water and SOG is outlined. We
demonstrate that nanosecond-pulsed laser fragmentation in water can be efficiently used to
induce the self-assembly of closely-packed and stable luminescent nanocrystals. Finnaly, the
mathematical description of dynamical Si-ncs formation within laser plasma confined by
liquids is applied to describe obtained results.
Fabrication of Silicon Nanocrystal Based Structures with Nanosecond 129
2. EXPERIMENTAL DETAILS
2.1. Laser Ablation
Our experimental set-up for the synthesis of Si-ncs with strong quantum confinement
effect is based on a recently developed nanosecond laser ablation technique described
elsewhere [17,19]. In this approach the laser-produced plasma with high pressure (~GPa) is
confined in liquid media [17,18]. Figure 1 represents schematic sketch of our experimental
set-up. The Si-ncs are fabricated by using a single-crystal silicon wafer fixed in glass ware
filled with liquid medium. Both types of (n-type, p-type, <100>, resistivity 0.1 cm, thickness
0.525 mm) as a target could be used. To induce laser ablation and the Si-ncs formation a
third-harmonic of Nd:YAG laser (Spectra Physics LAB-150-30, 355 nm, 30 Hz, = 8 ns) or
KrF excimer laser ((KrF, 245 nm, 20 Hz, 10 ns).) are used to irradiate onto the target
immersed in liquid media (water, SOG solution) at room temperature.
It has to be noted that the SOG polymers solutions are commercially available (Si-59000
Tokyo Ohka Kogyo Co., Ltd.). The laser beam is focused on the target by a lens (f = 250 nm)
[17, 18]. Relatively low laser fluences are used to obtain a spherical shape of the plume, to
limit excessive bubble formation, and to avoid generation of strong shock waves in liquid [19,
20]. During the ablation process the container with liquid and immersed Si target was rotated.
To observe visible PL the aging processes of Si-ncs in water was assured by keping them in
aqeuos solution at ambient temperature [17, 18]. The colloidal suspension prepared by laser
ablation in SOG was sonicated for 10 min and solidified in air atmosphere at 323 K for 24 h,
resulting in the formation of self-supporting samples [21, 22].

Figure 1. Schematic sketch of the experimental set-up used for fabrication of silicon nanocrystals (Si-
ncs) by laser ablation of crystalline silicon target in liquid media. In this work two types of ns lasers
have been applied independently (Nd:Yag and excimer KrF laser)
V. vrek 130

Figure 2. Sketch of the experimental set-up used for preparation of Si-ncs by ns laser fragmentation of
silicon micrograins prepared by electrochemical etching
2.2. Laser Fragmentation
Figure 2 shows sketch of experimental set-up used for preparation of Si-ncs by ns laser
fragmentation method of Si-ncs micrograins prepared by electrochemical etching. The
technique involves the etching of a silicon wafer (p-type boron doped, h1 0 0i, 0.1 X cm,
thickness 0.525 mm) for 1 h at 1.6 mA/cm
2
constant current in HF:ethanol electrolyte (1:4).
After the etching process, the resulting porous silicon wafer has been subsequently
mechanically pulverized [21]. After mechanical pulverization of several porous silicon wafers
the powder with Si-ncs micrograins is collected. The fragmentation of Si-ncs micrograins
have been proceed in water, pure and phosphorus doped SOG (Liquid pure and doped SOG
are commercially available from Tokyo Ohka Kogyo Co., Ltd.)) [23-25]. Colloidal solutions
were placed into a glass ware, and irradiated by ns pulsed lasers (Nd:YAG, or KrF)
independantly at room temperature. The laser beam in both cases was focused on the liquid
surface. During irradiation, the glass container with colloidal solutions was closed and
rotated.
Fragmentation by ns pulsed laser requires a homogenous dispersion of the Si-ncs
micrograins [25], therefore in the case that the Si-ncs micrograins were observed to disperse
poorly in water, a small amount of ethanol (20 drops) was used to wet the micrograins surface
prior to the introduction of water. The color of homogenously dispersed aqueous and SOG Si
micrograins solution is yellow. When the nanosecond pulsed laser irradiation is applied,
fragmentation of the micrograins occurs and at prolonged laser irradiation, the solutions
become almost transparent [25]. After fragmentation, the transparent colloidal dispersions
were used to prepare two types of samples. Upon preparation in water the Si-ncs have shown
to self-assemble in specific structures when let it dry on glass substrate. In the case of SOG
after irradiation, the colloidal suspensions was dried for solidification [23] in air at 323 K for
24 h to obtain self-supporting SOG films.

Figure 3. Photos of blue luminescent Si-ncs prepared by excimer KrF laser in water and aged in water
for 7 months. Image (a) represents Si-ncs prepared from p-type and photo (b) from n-type doped
crystalline silicon wafer
3. SI-NCS AND SI-NCS BASED COMPOSITES PRODUCED
BY LASER ABLATION IN LIQUID MEDIA
Si-based technology keeps and most likely will keep playing a key role for electronics
and photovoltaic industry. Due to the compatibility, non toxicity and most importantly purity
of the nanoparticles surface highly luminescent Si-ncs with quantum confinement effects
prepared by laser ablation in water with Si-dioxide surface termination might play an
important role for development novel types of devices [17, 19, 20]. Surface passivation
achieved by laser ablation in water leads to stable PL properties [19], that can facilitate the
integration within existing Si based technologies. The employment of doped Si-ncs prepared
by laser ablation can expand the possibilities of utilization of Si-ncs. Figure 3 represents
photographs of room temperature luminescent Si-ncs prepared by excimer KrF laser in water
and aged in water for 7 months. Image (a) represents Si-ncs prepared from p-type and photo
(b) from n-type doped crystalline silicon wafer. Visible blue-room temperature PL is
observed from both colloids under He:Cd laser excitation at 325 nm. At ambient conditions
Si-ncs in colloidal solution show a stable blue-bands with maxima centered at ~420 nm.
Compared to the Si-ncs made from p-type doped wafer, the PL band for n-type doped is
stronger more than 2 times. Since for n-type doped silicon a smaller surface recombination
velocity has been reported compared to p-type Si wafers [26], similar effects could be
expected for Si-ncs and different surface termination due to the dopant most likely influences
the PL intensity.
In order to overcome aging process and allow to appear the PL ns laser ablation in SiO
2

based polymer solution semms to be an effective way [18]. Our results showed that we can
successfully prepare Si-ncs directly in SiO
2
based polymers, which decreased the aging time
from months to several hours [18]. The Figure 4 (a) shows the chemical formula of the
polymer solution. The polymer consists of the mixture of thylpolysillicate
(C
2
H
5
O(SiO)C
2
H
5
O)
2
n(C
2
H
5
), ethanol, and ethylacetate. The contents of these chemicals in
SOG are 9%, 71%, and 20%, respectively. Such transparent solution has refractive index of
1.44, which allows ablation process directly in solution without considerable deterioration of
polymer quality. The fabrication of Si-ncs directly in polymer solutions opens also flexibility
V. vrek 132
for variety of sample structures. From Si-ncs/polymer colloidal solutions we can prepare thin
films at low-cost (Figure 4 (b), either by spin coating or printing technique, in principle, on
any type of the substrate. On the other hand, by simple solidification of the Si-ncs/polymer
colloidal solution we can form self-supporting samples (Figure 4.c) with high concentrations
of Si-ncs and different architectures. It has to be noted that this SOG polymers can be doped
and doping level might help easy to control the PL properties of embedded Si-ncs [27].
It is observed that at low ablation intensities [28] irregular Si-nc fragments obtained by
laser ablation in water are stabilized into regular-spherical particles. Figure 5 shows typical
SEM images of Si-ncs prepared by laser ablation in water (a) by Nd:Yag and (b) by KrF
excimer laser, respectively. In both cases SEM images shows that Si-ncs aggregates just after
the preparation. As depicted, spherical aggregates reaching size distributions ranging from 2
to 100 nm, which is rather similar for both lasers. It was clearly observed that the smaller
irregular aggregates of Si-ncs were obtained at higher laser fluences [28]. At higher fluences
the formation of spheres is inhibited mostly because of enhanced fragmentation processes.
Such fragmentation is induced by the increased density and intensity of shock waves that
propagate through the liquid at higher laser fluence. Detailed structural analysis revealed that
agglomerates contain Si-ncs with irregular shape smaller than the strong quantum
confinement limit for silicon (<5 nm) [17]. Namely that both electrons and holes are spatially
confined in such a small Si-ncs.

Figure 4. (a) Chemical formula of the spin on glass (SOG) polymer. (b) Schematic representation of
using the colloidal solution for the thin film formation and (c) self-supporting samples based on Si-ncs
directly produced in SOG by laser ablation

Figure 5. Typical SEM images of Si-ncs prepared by ns laser ablation in water (a) by Nd:Yag and (b)
by KrF laser, respectively
In the case of the polymer the Si-ncs do not agglomerate and remain separated and
homogenously dispersed within the polymer matrix. Compare to the water produced Si-ncs,
visualization of single Si-ncs by HRTEM is more difficult due to the presence of SOG
polymers. Surrounding amorphous SOG did not permit a clear visualization of single Si-ncs,
and we could not directly identify the crystalline lattice interplanar distance. However, dark
separated areas of < 5 nm were clearly observed from HRTEM images [18]. The excess of
silicon content by elemental analysis indicated increased Si content within SOG matrix.
Independently to that, the electron diffraction pattern and XRD confirmed the presence of Si-
ncs with single diamond like crystalline fraction.
It has to be noted that in such composites we have also observed four additional strong
peaks be possibly assigned to a silicon oxide that surrounds the silicon nanocrystals [18].
Those peaks were assigned to be silicon mono-oxide. It must also be noted that no diffraction
spots were recorded from solidified SOG without Si-ncs after laser irradiation and subsequent
drying; and that only the halo pattern of the amorphous phase was exhibited. It is supposed
that as the SOG matrix allows proper Si-ncs dispersion during the laser ablation process. As a
results dispersed Si-ncs are well exposed to SOG polymer and might enhance the formation
of the silicon oxide in crystalline phase. However, at this stage of the research the mechanism
of the formation the silicon oxide in crystalline phase is not clear yet, and further
investigations are underway.
The most important feature of Si-ncs prepared either in water or polymer based solution
is their visible blue PL. Figure 6 compares typical PL spectra from Si-ncs in solidified SOG
polymer and in water after aging. Blue triangles represent the PL spectrum of a self-
supporting sample prepared by laser ablation of the silicon crystalline target in SOG solution
(Nd:Yag @ 0.76 J.cm
2
) and subsequent solidification. Red open circles denote PL that from
a Si-ncs solution prepared by laser ablation of the Si target in water under the same laser
irradiation conditions and subsequent aging in water (6 months). The PL peaks are
normalized to the PL maxima intensity. In both solution the PL from Si-ncs is centered at
around 2.9 eV at room temperature. The PL spectrum in SOG was red-shifted by 0.2 eV and
broadened by 250 meV compared to that in water. It has to be noted that contribution from
SOG matrix to overall PL properties is negligible. Black symbols indicate PL signal of
solidified SOG treated by ablation process. No PL in this spectral region was recorded. It is
believed that the Si-ncs prepared in SOG contain most likely more defects and larger size
distribution of formed Si-ncs that broader the PL spectrum.
Indeed, the luminescence dynamics can give important inside and help in identifying the
nature of an emission from the Si-ncs [20]. Our results showed that the PL decay clearly
indicates the contribution of a very fast decay component induced by light scattering [20].
This effect disappeared for emission at lower energies (<2.5 eV). By using conventional
analysis software (DAS 6), we were been able to remove the contribution of the scattering
effect and estimate the PL decay time of Si-ncs [20]. The correct value of the PL decay time
lies between around ~6 ns, that strongly support the quantum confinement phenomenon
indicated from structural analysis and temperature depended PL spectroscopy [19].
V. vrek 134

Figure 6. Blue symbols represent the PL spectrum of a self-supporting sample prepared by laser
ablation of the silicon crystalline target in SOG solution. Red circles denote PL spectrum from a Si-ncs
water solution prepared by laser ablation of the Si target in water and subsequently aged in water for six
months. Black symbols indicate PL signal from a self-supporting SOG only treated by ablation process
and is shown for comparison
4. INDUCED SELF-ASSEMBY & TUNING OF SI-NCS OPTICAL
PROPERTIES BY NS LASER FRAGMENTATION IN LIQUID MEDIA
As we discussed above a termination of Si-ncs surface by silicon oxide is favorable for
stabilizing PL properties of Si-ncs. One of the choice that can enhances the Si-ncs rate
production is exploration of fragmentation of Si-ncs micrograins prepared by independent
technique with higher production rates e.g. electrochemical etching. In order to achieve Sincs
passivation by silicon oxide (mono-, di-oxide) formation ns laser fragmentation is conducted
in SiO
2
dioxide polymer or water is applied [23]. Laser fragmentation processing in SOG
polymer improves the PL properties and allows tuning of the PL spectra position as a function
of ns laser fluence. The polymer doping with silicon compatible dopands (i.e phosphorus,
boron) can considerably influence the optical properties of the Si-ncs [27]. Figure 7
summaries the PL intensity as a function of the wavelength for Si-ncs embedded in pure (blue
symbols) and phosphorous-doped SOG polymer (black symbols) after laser fragmentation
and solidification. The PL spectrum of Si-ncs micrograins in solid SOG before irradiation is
shown for comparison (red symbols). With laser fluence increases, an enhancement in blue
shift of PL peak accompanied with PL intensity increase (more than 10 times) is recorded. It
is assumed that the blue shift (from 1.7 eV to 2.8 eV) and the PL intensity enhancement are
due to the formation of higher concentration of Si-ncs with quantum confinement effect.
Small sizes Si-ncs contributed to increase both the surface states and the efficiency of
radiative recombination. It also been observed that in the case of doped SOG the PL intensity
is weaker more then 6 times compared to the pure SOG polymer. The origin of this decrease
could be related to phosphorous that might acts as a nonradiative recombination center or
prevent proper Si-ncs oxide surface passivation [24]. Similar to the Si-ncs prepared by laser
ablation (Figure 6) observed bright PL of Si-ncs obtained by fragmentation is mainly due to
the simultaneous effects of surface states and quantum confinement. This is also supported by
performed extensive structural analysis [23] i.e. XRD, HRTEM. Elemental and structural
analysis revealed that fabricated Si-ncs embedded in both polymers posses a silicon crystal
structure in cubic phase. One can argue that increased concentrations of smaller Si-ncs
increases specific surface area of Si/SiO
x
, that can also be efficient source of blue PL [29]. Of
course thus contribute to the PL intensity enhancement however the contribution compared to
the quantum confinement effects from Si-ncs is minor [18]. We also verified that laser
irradiation and solidification of only polymers their self in liquid phase are not responsible for
observed blue PL.
As mention above, laser processing in water is environmental and human body
compatible therefore, the Si-ncs laser fragmentation directly in water can be beneficial for
many biological and medical applications. Figure 8(a) is a photo of aqueous colloidal solution
with Si-ncs before fragmentation process. When the colloidal solutions is excited by He:Cd
laser a strong orange PL can be observed from Si-ncs attached on the micrograins or freely
dispersed in solution. Basically the colloidal solution is yellowish and not transparent. The
beam of the excitation laser cannot penetrate into solution and remain to excite only at the
beginning of the ware. The color of the colloidal solution varies during the fragmentation
process. Color of solution, initially yellowish, changes into more transparent during ns laser
irradiation. As the micrograins got fragmented and colloidal solution become more
transparent,CdHe laser beam penetrate mor into the solution and overal PL emission of the
solution is improved (Figure 8b). It has to be noted that prolonged fragmentation time and
increased laser fluence can lead to the quenching of the PL emission. Similar to laser ablation
in water followed by aging in water is observed. After several weeks the blue PL emission
from colloidal solution produced by fragmentation of Si-ncs micrograins can be seen (Figure
8(c)). However in this case the PL intensity is rather weak.

Figure 7. The photoluminescence (PL) intensity as a function of wavelength for Si-ncs embedded in
pure solid SOG (blue symbols) and phosphorous-doped SOG matrices (black symbols) after laser
fragmentation in polymer solution (Nd:Yag @ 5.9 mJ/pulse for 2 hours). The PL spectrum of Si-ncs
micrograins in SOG before fragmentation is shown for comparison (red symbols)

Figure 8. Photos represent aqeuous colloidal solutions with silicon nanocrystals (Si-ncs) micrograins (a)
before and (b) after ns laser fragmentation processing in in water. (c) Photo of Si-ncs/water colloidal
solution after increased laser fragmentation fluence and aging in water for several months is shown. In
all cases the colloidal solutions are excited by He:Cd laser at wavelength 325 nm
V. vrek 136

Figure 9. (a) Typical SEM image of Si-ncs based self-assemblies induced after ns laser fragmentation in
water. (b) Corresponding Micro-Raman spectra of the self-organized structures (blue symbol line).
Black line represents the reference from crystalline silicon
Other important feature that we could observe is that the drop of fragmented-aqueous
luminescent colloidal solution on not pattern substrate results self-assembly formation. Figure
9 (a) shows SEM image of Si-ncs prepared by ns laser fragmentation of Si-ncs micrograins in
water. Since in ethanol or SOG well done separation of Si-ncs is achieved [30], the self-
assembled structures are only observed when the ns processing is conducted in water. It has to
be noted that extended interconnected structures exceeded several hundred micrometers in
length. Furthermore, micro-Raman was employed to verify the presence of Si-ncs in the
networks. Micro-Raman investigations revealed that the self-assembled patterns contain Si-
ncs with quantum confinement features. Compared to crystalline silicon (black line in Figure
9b), the spectrum of the self-assembled structure exhibits a shift in the maximum of the peak
and broadening of the spectrum (Figure 9(b), symbol line). The peak width is related to the
Sinc mean size and was evaluated to be around ~ 4 nm in diameter [31]. However, detailed
micro-Raman investigation revealed as well as that some parts of the self-assembled branches
consisted of larger silicon particles (>10 nm) and amorphous silicon tissue produced during
laser fragmentation process [30].
On the other hand, those self-assembled structures showed to possess a good mechanical
stability when exposed to a low-temperature and low-pressure plasma [30]. The self-
assembled networks do not possess any organic surfactant layer that could hinder subsequent
surface functionalization. A clean surface can then enhance the interaction between the laser
elaborated nanoparticles. Self-assembly in our case is most likely induced by multiple
mechanisms that act at the same time. The most significant process that promotes self-
assembly is a dewetting process [32]. It has been shown that the interactions between
hydrophobic particles and water can be affected during water evaporation [30]. On the other
hand, the spontaneous self-assembly of isometric nanoparticles 1D-arrays can be produced
with intrinsic magnetic [33] or electric dipoles [34]. However, contrary to metallic
nanostructures, the semiconductor nanoparticles exhibit intrinsic electric dipole. The link
between dipole interactions and self-assembly mechanisms remains uncertain and is still
under debate [35]. Anyway it is believed that electric dipoles produced in the surface charge
during laser fragmentation of the Si-ncs micrograins in water play a crucial role for self-
assembly. In ethanol SOG polymer, the formation of electric dipoles is reduced due to the
immediate stabilization of the Si-ncs micrograin surfaces by the organic layer that leads to
increase in zeta potential. Contrary to that our studies shown an where zeta potential decrease
after processing in water [28]. Low zeta potential helps to aggregation of the laser-elaborated
particles as the oxygen based vacancies are formed [28]. The fragmentation process in water
induces the ineffective screening of the Si-ncs micrograin dipoles and increases inter-particle
electric dipoledipole interactions. Due to the non-uniform dipole distribution [30] random
self-assembly can be achieved.
5. PHYSICS OF THE NANOSECOND-LASER
PROCESSINGS IN LIQUID MEDIA
Though, the formation mechanism of Si-ncs is not completely understand yet, the laser
ablation process in water and/or liquid SOG solutions can be schematically describe by
following way. Figure 10 represents sketch of a ns laser ablation mechanism and formation of
Si-ncs in a liquid medium (i.e. water). The absorption of ns pulses in a Si wafer immersed in
liquid led to rapid heat generation. As a result a dense cloud of Si atoms spread over the
plume is formed on the Si surface. Embryotic particles are produced in such a cloud as well.
The initial rapid attachment of silicon atoms to ejected embryotic particle continued until all
silicon atoms in the confined plum area are completely consumed. When particles escape
from the plume into the water or SOG polymer solution, the nanocrystal growth is
suppressed. The reasons for suppression are multiple but most important suppression in our
opinion is due to the SiO
x
. Those molecules are widely presented in both solutions and
immediately stack on the Si-nc surface. As a result Si-ncs with size of few nanometers with
strong quantum confinement effects are formed.
The dissipated kinetic energy of the material ejected by pulsed laser ablation is
proportional to the Gibbs energy of as-formed nanocrystallites [36]. Then ablation rate R for
particle formation can be written through the Gibbs energy (G) and can be written as follow

=
a
E
G
const R exp . (1)
where E
a
is the activation energy [37]. The kinetic energy differences between the embryotic
particle initially ejected and that ejected at the end of the flight when the Si-nc enters into
liquid media is proportional to the G. Then the Gibbs energy of as-formed spherically
condensed Si-ncs with diameter d is linearly proportional to the initially ejected velocity (v
0
)
and to the pressure (P) induced in the plume. As reported elsewhere [18], after performing
some simple algebraic operations, the G can be expressed by

0
. . v d G (2)
The slowing coefficient is proportional to the particle geometrical cross section and Si
atom density within the plume. The mathematical description of dynamical formation
V. vrek 138
processes indicating that the initial size of the embryotic particle ejected by nanosecond
pulsed laser irradiation is the determinant for the final Si-nc size [18].

Figure 10. Schematic representation of the laser ablation process and dynamical Si-ncs formation in
liquid media (i.e.water)
In the case of ns laser induced fragmentation of Si-ncs micrograins in liquid media
similar processes likely happen when the laser beam directly interact with micrograns. In that
case of an instantaneous point interaction results laser ablation and plum generation in liquid.
Additionally, we consider that thermal heating alone could not be responsible for Si
fragmentation. Rapid heating and expansion of the plasma generate high-pressure shock
waves. Shock waves that propagate from the laser spot [23, 38] through the liquid medium
cause the mechanical deformations at regions relatively far from the irradiation spot [23]. The
shock waves can develop after propagation over a characteristic distance (L)

P
c
L
. . 2
. .

(3)
where is the medium density, the duration of a transient stress wave inversely proportional
to laser pulse frequency, c the speed of sound (c = 1.5 km/s), the permeability of liquid
media, and P the pressure. We believe that such shock waves are at least responsible for the
dissociation of fine Si-ncs that are weakly attached on Si micrograins. When the shock wave
moves a sufficiently large distance away from the point of explosion, the fragmented particles
continue to expand in liquid media. Furthermore, L linearly depends on the density of the
liquid medium that is higher for SOG polymeric solution than for water. As a result the shock
waves in SOG can propagate farther from the point of explosion and leads to more efficient
fragmentation [23].
CONCLUSION
In symmary, the fabrication and stabilization of blue photoluminescent silicon
nanocrystals (Si-ncs) by nanosecond (ns) Nd:YaG and excimer KrF laser processing has been
disccussed. In both cases the ns laser induced ablation in liquid media offers fabrication
conditions with unique surface chemistry that allowed formation of luminiscent Si-ncs with
quantum confinrment effects. We have shown that the self-limiting oxidation in water and
doped spin on glass (SOG) polymer solutions provide oxide shell for stable surface resulting
in room temperature blue PL. Particularly electron-hole recombination in the Si-ncs with high
quality surface passivation in water promotes carriers trapping in oxygen-related localized
states. Produced Si-ncs in water and SOG based solutions exhibited room-temperature PL
peaked at around ~400 nm with a lifetime of about 6 ns, which could be attributed to the
quantum confinement effect of Si-ncs embedded in oxide-based surroundings. The processing
in SOG polymers can successfully prepare thin films and self-supporting samples containing
blue luminescent Si-ncs at high concentrations. Importantly, through the processing in SOG
based polymers the aging time to obtain blue photoluminescence from Si-ncs is significantly
shortened.
Furthermore, we showed that luminescent Si-ncs can be efficiently produced by ns pulsed
laser fragmentation of electrochemically etched Si micrograins. We succeeded in preparing
and tuning the luminescent Si-ncs properties by both lasers (Nd:YaG and excimer KrF laser)
in water, pure and doped SOG polymers. Interestingly, we could produce self-assembled
networks of the Si-ncs on no-patterned substrate after fragmentation in water. We
demonstrated that even fragmentation process in SOG (ethanol) is more efficient, however,
only the fragmentation in water leads to such self-assembled nanoarchitectures.
A Si-nc formation scheme, which describes serial processes of rapid formation and
growth of embryotic Si particles, consecutive oxidation in water or SOG and growth
termination by quenching was applied to interpret obtained results. Laser plasma confined by
liquid media significantly increases the Gibbs free energy of as-formed silicon nancrystallites
and the Si-nc producing rate. We discussed a dynamical formation processes pointed out that
the initial size of the embryotic particle ejected by ns pulsed laser irradiation is the
determinant for the final Si-nc size. In the case of the laser fragmentation laser irradiation
energy over the band gap of silicon provokes an optical absorption and resulting plasma
superheat, together with strong shock waves, induce Si micrograins fragmentation.
One can expect that this relatively simple and affordable ns laser fabrication of Si-ncs
with strong quantum confinement could be useful procedure in a wide variety of applications.
For instance direct preparation of fine blue luminescent Si-ncs in silicon technology
compatible doped SOG polymers might help the formation of films with high Si-ncs
concentrations and enhance the stimulated emission processes (i.e. optical gain). On the other
hand, using of the Si-ncs self-assembled architectures prepared by laser fragmentation in
water can be very useful for biological and photovoltaic applications.
ACKNOWLEDGMENTS
We are deeply indebted to all colleagues who contributed to this work over the past years.
Especially we wish to mention the members of groups in Japan (Nanoarchitectonics Research
Center, Photovoltaics Research Center, National Institute of Advanced Industrial Science and
Technology (AIST), Tsukuba) and Prof. D. Mariotti at University of Ulster, U.K. This work
was also partially supported by a JSPS fellowship and NEDO project
V. vrek 140
REFERENCES
[1] Root, RG. Laser-induced plasma and applications, Marcel Dekker, New York, 1989.
[2] Bauerle, D. Laser processing and chemistry (3rd ed.), Springer-Verlag, Berlin, 2000.
[3] Geohegan, DB; Puretzky, AA; Duscher, G; Pennycook, SJ. Appl Phys Lett, 1998, 73,
438.
[4] Lowndes, DH; Rouleau, CM; Thundat, TG; Duscher, G; Kenik, EA; Pennycook, SJ. J
Mater Res, 1999, 14, 359.
[5] Wu, KT; Yao, YD; Wang, CRC; Chen, PF; Yeh, ET. J Appl Phys., 1999, 85, 5959.
[6] Link, S; El-Sayed, MA. Int Rev Phys Chem., 2000, 19, 409.
[7] Fogarassy, E; Lazare, S. Laser ablation of electronic materialsbasic mechanisms and
applications, Elsevier, Amsterdam, 1992.
[8] Chrisey, DB; Hubler, GK. Pulsed laser deposition of thin solid films, Wiley-
Interscience, New York, 1994.
[9] Lu, F; Song, WD; Ang, BW; Chan, DSH; Low, TS. Appl Phys A, 1997, 65, 9.
[10] Tornan, V; Zafiropulos, V; Vainos, NA; Fotakis, C. Optics Laser Eng., 2000, 34, 309.
[11] Fojtik, A; Henglein, A. Ber. Bunsen-Ges. Phys. Chem., 1993, 97, 252.
[12] Mafun, F; Kohno, J; Takeda, Y; Kondow, T; Sawabe, H. J. Phys. Chem. B, 2000, 104,
8333.
[13] Mafun, F; Kohno, J; Takeda, Y; Kondow, T; Sawabe, H. J. Phys. Chem. B, 2000, 104,
9111.
[14] Kabashin, AV; Meunier, M. J Appl Phys., 2003, 94, 7941.
[15] Izgaliev, AT; Simakin, AV; Shafeev, GA. Quantum Electron, 2004, 34, 47.
[16] Barcikowski, S; Hahn, A; Kabashin, AV; Chicjkov, BN. Appl. Phys. A, 2007, 87, 47.
[17] vrek, V; Sasaki, T; Shimizu, T; Koshizaki, N. Appl. Phys. Lett, 89 (2006) 213113.
[18] vrcek, V; Sasaki, T; Shimizu, Y; Koshizaki, N. J. Appl. Phys., 2008, 103, 023101.
[19] vrek, V; Mariotti, D; Kondo, M. Optics Express, 2009, 17 , 520.
[20] vrcek, V; Sasaki, T; Katoh, R; Shimizu, T; Koshizaki, N. Appl. Phys., B, 2009, 94,
133.
[21] vrcek, V; Slaoui, and A; Muller, JC. J. Appl. Phys., 2004, 95, 3158.
[22] vrcek, V; Slaoui, A; Muller, JC; Rehspringer, JL; Hnerlage, B; Tomasiunas, R;
Pelant, I. Physica E, 2003, 16, 420.
[23] vrcek, V; Sasaki, T; Shimizu, Y; Koshizaki, N. Chem. Phys. Lett, 2006, 429, 483.
[24] vrcek, V; T. Sasaki, Y. Shimizu and N. Koshizaki, Physica E, 40. (2007) 293.
[25] vrek, V. Pure and Applied Chemistry, 2008, 80, 2513.
[26] Yablonovitch, E; Allara, DL; C> Chang, C; Gmit-ter, T; Bright, TB. Phys. Rev. Lett,
1986, 57, 249.
[27] vrcek, V; Slaoui, A; Rehspringer, JL; Muller, JC. J. of Lumin, 2003, 101, 269.
[28] vrcek, V; Sasaki, T; Shimizu, Y; Koshizaki, N. Journal of Laser
Micro/Nanoengineering, 2007, 2, 15.
[29] Fauchet, PM. J. of Lumin., 1996, 70, 294.
[30] vrek, V; Mariotti, D; Kalia, K; Kondo, M. Chem. Phys. Lett, 2009, 478, 224.
[31] Kanemitsu, Y; Uto, H; Masumoto, Y; Matsumoto, T; Futagi, T; Mimura, H. Phys. Rev.
B, 1993, 48, 2827.
[32] Deegan, RD; Bakajin, O; Dupont, TF; Huber, G; Nagel, SR; Witten, TA. Nature, 1997,
389, 827.
[33] Tlusty, T; Safran, SA. Science, 2000, 290, 1328.
[34] Tang, ZY; Kotov, NA; Giersig, M. Science, 2002, 297, 237.
[35] Jackson, AM; Myerson, JW; Stellacci, F. Nat. Mater, 2004, 3, 330.
[36] Oraevsky, AA; Letoshkov, VS; Esenafiev, RO. Pulsed LaserAblation of Biotissue:
Review of Ablation Mechanisms, Springer, Berlin, 1991.
[37] Geohegan, DB. Appl. Phys. Lett, 1992, 60, 2732 .
[38] Zeldovich, YB; Raizer, YP. Physics of Shock Waves and High- Temperature
Hydrodynamic Phenomena, Dover Publications, Inc, New York, 2001.
Chapter 5
HO:YAG LASER LITHOTRIPSY
Jinze Qiu
1
, Thomas E. Milner
1

and Joel M. H. Teichman
2

1
Dept. of Biomedical Engineering, The Univ. of Texas at Austin,
107 W Dean Keeton, Austin TX, USA 78712
2
Dept. of Urologic Sciences, University of British Columbia,
and St. Paul's Hospital, 1081 Burrard St., Burrard Bldg.
C307, Vancouver BC, Canada V6Z 1Y6
ABSTRACT
The long-pulse Ho:YAG laser has been used for intracorporeal laser lithotripsy of
urinary calculi since the mid-1990s and is considered the gold standard modality for
endoscopic laser lithotripsy. We present an overview of Ho:YAG laser lithotripsy. We
begin with an introduction of the ablative mechanism of Ho:YAG laser lithotripsy, and
compare to short-pulse (< 10 usec) laser lithotripsy. Ablative properties of Ho:YAG laser
lithotripsy are reviewed and we summarize several practical problems and safety issues
of existing optical fibers for Ho:YAG lithotripsy.
INTRODUCTION
Clinical application of intracorporeal laser lithotripsy to human urinary calculi began in
the mid 1980s[1-3]. The surgical technique of visualizing a calculus in the urinary tract by
inserting a ureteroscope and fragmenting the stone by fiber delivered laser energy has
undergone significant advances over the past twenty years[4]. The principle advantage of
intracorporeal laser lithotripsy over previous surgical techniques is the use of small diameter
flexible optical fibers (<400 um) that can be passed through the working channel of a small
caliber ureteroscope (typically less than 3 mm diameter) for pulsed laser energy delivery to
achieve stone fragmentation. The laser lithotripsy procedure is considered to be minimally
invasive and provides access to both ureteral and renal calculi.[2] A variety of lasers were
Jinze Qiu, Thomas E. Milner and Joel M. H. Teichman 144
introduced and applied clinically before the advent of the Ho:YAG laser: these included 1)
the Q-switched Nd:YAG laser (wavelength: 1064 nm; pulse duration: tens of nanoseconds);
2) the Q-switched alexandrite laser (wavelength: 755 nm; pulse duration: hundreds of
nanoseconds); and 3) the flashlamp pumped pulsed dye laser (FPDL, wavelength: around
540nm; pulse duration: several microseconds).[1, 3] These three short-pulse lasers, with their
pulse durations ranging from several nanoseconds to several micro-seconds, fragment stones
using a photomechanical mechanism.[5] Application of these lasers for lithotripsy produce
large sized fragments (fragments larger than 4mm in diameter were found) and fragmentation
of hard urinary calculi, such as calcium oxalate monohydrate and cystine stones, is poor[6, 7].
The Ho:YAG laser has been used for laser lithotripsy since the mid 1990s. For laser
lithotripsy, pulse duration of the Ho:YAG laser is set at several hundred micro-seconds and
fragmentation of stones uses a photothermal mechanism. Unlike the short-pulsed lasers
mentioned above, the Ho:YAG laser fragments all stone compositions and produces smaller
sized fragments. In recognition of the superior ablation characteristics, the Ho:YAG laser is
widely recognized by urologists as the gold standard for intracorporeal laser lithotripsy of
urinary calculi.[7-18]
MECHANISM OF HO:YAG LASER LITHOTRIPSY
Short-pulse lasers fragment urinary calculi using a photomechanical mechanism.[1, 5, 19,
20] In short-pulse laser lithotripsy, plasmas are generated on the targeted area immediately
following onset of the laser pulse. The plasmas expand to a hemispherical bubble and
collapse or implode within a few hundred microseconds. In nanosecond Q-switched Nd:YAG
or Q-switched alexandrite laser lithotripsy, both plasma expansion and bubble collapse
generate shock waves. The resulting shock waves, with pressures that exceed 100 bars in
magnitude, fragment stones as they traverse stone surfaces. In microsecond pulsed dye laser
lithotripsy, fragmentation only occurs upon the shock wave produced by cavitation bubble
collapse. Pressures produced from the shock wave resulting from plasma expansion are too
weak to generate fragmentation.
Existing Ho:YAG lasers for laser lithotripsy operate with pulse durations of 250 to 700 us
with most in the range of 250-350 us. Optical intensity profiles of two typical Ho:YAG pulses
are displayed in Figure 1. The fragmentation process of long-pulse Ho:YAG lithotripsy is
governed by a photothermal ablative mechanism instead of photomechanical or photoacoustic
mechanisms.[21] Laser energy is absorbed first by water between fiber tip and stone surface
to form a vapor bubble, a phenomenon called the Moses effect. The remaining laser energy
is transmitted through the vapor channel and absorbed by the stone. The short duration of the
laser pulse ensures heat confinement within the irradiation area and causes melting and
ejection of debris. Within a few hundred microseconds, the vapor bubble expands and
collapses asymmetrically to multiple loci, producing weak pressure transients, typically 8 bars
or less. Magnitude of these pressure waves are substantially weaker than those produced by
short-pulse lasers.[22, 23]
Ho:YAG Laser Lithotripsy 145

Figure 1. Optical intensity profiles of Ho:YAG laser pulses measured by a photodetector(EG&G J12-
18C-R250U).[24]
Various studies have confirmed a photothermal mechanism and the paucity of
photomechanical effects for long-pulse Ho:YAG laser lithotripsy. In experiments reported by
Chan et al. [21], direct irradiation of stone surface was shown as the ablative mechanism
rather than shockwave induced ablation. Ablation was more efficient for dehydrated stones in
air than for hydrated stones in air or in water. High-speed imaging showed that ablation
occurred only after the laser beam was transmitted through the vapor bubble to the stone
surface, an evidence of the Moses effect. The most efficient lithotripsy was achieved by
minimizing the separation distance between the fiber tip and the stone surface, while a small
separation between the fiber tip and the stone surface (~1 mm) was required to maximize
ablation efficiency for the short-pulse lithotripsy.[21, 25] Moreover, for the long-pulse
Ho:YAG laser, no lithotripsy effect was attributed to pressure waves. Pressure transient
measured by a hydrophone was less than a few bars and about 1% of that from short-pulse
induced shock wave lithotripsy, corroborating reports from other groups.[23, 26] No
fragmentation occurred when the fiber was oriented parallel to the stone surface, but in this
configuration, maximal bubble expansion occurred and the pressure transient corresponding
to the bubble collapse was about 20 bars, larger than that produced by orientating fiber
perpendicular to the stone surface. Thus, a larger vapor bubble did not increase Ho:YAG
stone fragmentation. In contrast, short-pulse lasers can fragment stones with the delivery fiber
oriented parallel to the stone surface since shock waves propagate spherically outward in all
directions.[13, 22] Post-lithotripsy products were found to have components resulting from
thermal decomposition, a result that was also confirmed by Dushinski et al.[14] and Schafer
et al.[27]. Cystine stones were discovered to produce free sulfur and cysteine after lithotripsy
and Uric acid stones were discovered to produce cyanide. Teichman et al. reported that
application of the Ho:YAG laser yields smaller fragments and symmetric ablation craters
whereas short-pulse lasers produce asymmetric ablation craters, indicating the ablation
mechanism of the two types of lithotripsy lasers is different.[7, 15]
PROPERTIES OF HO:YAG LASER LITHOTRIPSY
Compared to short-pulse shock wave induced lithotripsy, Ho:YAG laser lithotripsy has at
least four characteristic properties, making it more suitable for intracorporeal lithotripsy.
First, the Ho:YAG laser can fragment all stone compositions.[7] Second, debris produced
with the Ho:YAG laser are smaller than those produced by photomechanical lithotripsy
devices. Third, Ho:YAG lithotripsy is clinically safe because of high absorption of Ho:YAG
light by water, reducing damage by stray radiation. Fourth, Ho:YAG lithotripters cause
minimal stone retropulsion compared to short-pulsed laser devices. [28, 29]
The main limitation of Ho:YAG lithotripsy is a reduced speed compared to short-pulse
shock wave induced lithotripsy. A less significant limitation is stone retropulsion. Debris
ejected during the course of Ho:YAG laser lithotripsy travel along the normal to the stone
surface. The stone being targeted thus moves in the opposite direction due to conservation of
momentum and results in stone retropulsion.[30, 31] Increased operating time is needed for
urologists to move the ureteroscope and fiber to the more proximal stone position. Lee et al.
showed that retropulsion was greater for larger diameter fibers at a given energy or for larger
energies for a given fiber diameter.[31, 32] Based on vector analysis, the geometry of the
crater explains why larger diameter fibers cause increased retropulsion. A large diameter fiber
produces a wide and shallow crater. Since fragments eject along the normal, a wide and
shallow crater ejects fragments in a more uniform direction off the stone surface, producing
greater momentum to the stone in the opposite direction. Similar results were reported by
White et al.[30] Finley et al. reported dependence of stone retropulsion on Ho:YAG pulse
duration in vitro[33]. Similar results were reported by Kang et al by a detailed measurement
of laser pulse duration.[24] Longer pulses (FWHM: 280us) produce less stone retropulsion
than shorter pulses (FWHM: 150us) regardless of pulse energy when a single laser pulse is
applied. One possible reason is the occurrence of recoil pressure during debris ejection.[34]
Debris ejection is associated with high temperature and pressure gradients of the ablated area
caused by intensive laser irradiation. Based on conservation of momentum, debris ejection
produces a so-called recoil pressure on the stone sample. The recoil pressure is proportional
to radiant power[35] and therefore inversely proportional to pulse duration for a fixed pulse
energy.
FIBERS FOR HO:YAG LASER LITHOTRIPSY
Optical fibers, because of their flexibility and high efficiency in transmitting laser
radiation, are widely used in biomedical applications. Ho:YAG laser radiation, highly
absorbed by hydroxyl groups, is delivered by low OH silica fiber to the stone surface in
intracorporeal laser lithotripsy.[36] Potential problems when using these fibers were
investigated by several groups in order to mitigate potential damage to fibers and injury to
patients.[37-40] This section reviews several important factors of optical fibers for the safe
delivery of laser radiation, including laser-to-fiber coupling, fiber damage at extreme bending
conditions and fiber tip degradation during lithotripsy.
Diameter of the fiber core used for lithotripsy is variable from 150 um to 940 um,
normally much smaller than diameter of the collimated laser beam. NA of Ho:YAG fiber
cores is approximately 0.2 to 0.22[37]. Fluorine doped silica, good at Ho:YAG light
transmission, is the main choice of cladding materials.[36]
The beam is focused through a convex lens and launched into the fiber core. Two
parameters, diameter and numerical aperture (NA), are critical to obtain high efficiency laser-
to-fiber coupling.[36, 41] Diameter of the beam at the fiber surface is fairly large but smaller
than the core-diameter to prevent direct fiber damage by high fluence or an overfilled fiber
core.[37] NA of a fiber determines maximal divergence angle a beam can have before
entering the fiber[36]. Optical fiber transmits radiation using total internal reflection at the
core-cladding interface. Excessive divergence of the incident beam causes some light to
penetrate the fiber cladding and possibly damage the fiber or be lost as a radiation mode.
The proximal end of the fiber is directly attaches to the clinical Ho:YAG laser. A
standard connector, termed subminiature version A (SMA), is used to protect the proximal
end so that fibers with different diameters can easily connect to the same laser. An SMA
connector is designed with an air filled cavity surrounding the proximal end of the fiber to
protect from leakage-related damage, a simple and low cost method called an air-well
approach. A more detailed description of the air-well approach are documented by Nazif et
al.[36]
Small diameter fibers (core diameter less than 300 um) are normally used for upper
urinary-tract lithotripsy where more flexibility is required to allow the fiber to access the
ureter and kidney through a small caliber ureteroscope (less than 3 mm diameter). The beam
diameter of most clinical Ho:YAG lasers are 100-300 microns at the exit aperture. For
example, the beam diameter of the Lumenis Ho:YAG laser is approximately 160um, as
reported by the manufacturer. To prevent fiber damage from energy leakage or overfill, the
proximal end is designed with a core-diameter larger than fiber diameter to form a large-to-
smaller taper.[37] Unfortunately, fiber damage due to low laser-to-fiber coupling is not
uncommon in the case of small core diameter fibers (less than 300 um). Two reasons
commonly contribute to damage of the proximal fiber end. First is the misalignment between
the laser beam and fiber. A small misalignment may be acceptable for larger core-diameter
fibers as long as the focused beam is within the fiber core, but can result in overlap between
the laser beam and cladding of small core-diameter fibers and damage. A second source of
fiber damage at the proximal end is beam leakage through the taper cladding. Significant
leakage of laser radiation into the cladding can cause fiber damage if the fiber is
misaligned[37].
When Ho:YAG laser radiation enters the proximal end of a fiber without damage, the
beam propagates through the fiber and is transmitted onto the stone surface from the distal
end of the fiber. When treating upper urinary-tract calculi, small core diameter fibers (less
than 300um) are needed to pass through the working channel of small caliber ureteroscopes.
Typically the ureteroscope is less than 3 mm diameter, and the working channel is often on
the order of 1 mm diameter. Further, these small caliber fibers may be bent extremely if the
ureteroscope itself is bent extremely, as required for retrograde ureteroscopic management of
lower pole stones. At extreme bending condition, risk of radiation leakage into the cladding
increases and can result in fiber damage, so-called thermal breakdown.[36, 38] In a series of
in vitro experiments, fibers from several different manufacturers were compared with respect
to thermal breakdown.[38] Threshold pulse energy for thermal breakdown was documented at
a bending diameter of 1 to 3 cm. Large core diameter fibers were reported to have lowest
damage thresholds. Small diameter fibers from different manufacturers performed differently
even at the same bending diameter. Fiber failure always occurs at the point of maximal
bending condition and only during laser transmission and never from mechanical fatigue
alone. The results of studies investigating fiber damage at different bend diameters are critical
for urologists to select correct fibers for different surgical procedures.
When the Ho:YAG beam transmits through the fiber without fiber damage, the beam can
be targeted to the stone surface for lithotripsy. No optical elements are positioned between the
distal fiber tip and the stone. During lithotripsy, fiber tip degradation can occur at high pulse
energy output.[15, 40] Fiber tip degradation may cause decrease of beam transmission
through the fiber, decrease ablation efficiency and require intraoperative replacement of the
fiber. Fiber replacement lengthens operating time, results in a resource loss, and compromises
process efficacy. A recent study compared fiber degradation among different
manufacturers.[40] Fiber tip degradation was an energy density related phenomenon and was
significant for small core diameter fibers (200-273um) and at pulse energies larger than
1.0J(pulse energy at fiber input). Fibers with high output energies tended to have high fiber
degradation. Fiber tip degradation might result in a less collimated output beam and an
irregular tip surface.
SAFETY ASPECT OF HO:YAG LASER LITHOTRIPSY
Ho:YAG laser lithotripsy has a good clinical safety profile. Sofer et al. reported a high
stone-free rate of 97% in Ho:YAG lithotripsy for 598 patients with upper urinary-tract
calculi.[42] Only 4% of patients had complications. Intraoperatively, 13 patients had
complications, including laser related ureteral perforation in 1 patient and laser fiber breakage
within the ureteroscope in 3 patients. Thus, 4 of 598 (0.7%) patients experienced laser related
complications. Watterson et al. showed a similar stone-free rate in their procedures and
reported that 29 out of 30 procedures were completed with no significant complication.[43]
Most large series studies of Ho:YAG laser lithotripsy for ureteral calculi show similar stone-
free outcomes (typically greater than 90% are stone-free) with minimal complications.
Ureteral perforation caused by direct irradiation is a serious potential complication during
Ho:YAG lithotripsy. An ex vivo comparison of four commonly used lithotripters showed that
a Ho:YAG laser beam could easily perforate the ureter wall, but the experiment was
completed under the extreme conditions of direction absorption, and the fiber tip was
normally oriented to the ureteral mucosal surface. Perforation did not occur when the fiber tip
was maintained at least 2mm away from the ureteral mucosal surface and separated by water
because the Ho:YAG wavelength (2.1 um) is well absorbed by water.[44] In clinical
circumstances, the optical fiber is usually oriented tangential to the ureteral mucosal surface
(low fluence to the wall), and working under visual guidance allows urologists to maintain the
fiber tip in contact with the stone surface and not the ureteral mucosa. In the authors
experience (Teichman), laser related perforation of the ureteral wall is an uncommon
complication. In the kidney, direct absorption of laser energy to the kidney epithelium is
usually of little clinical concern as the depth of penetration is minimal (<0.4 mm).
Another potential concern is the potential risk of chemical byproducts of photothermal
ablation. Photothermal ablation of uric acid calculi can produce cyanide, a deadly poison if
produced in sufficient concentrations but has never been observed clinically.[45-47] No
evidence of cyanide toxicity was found in reports by multiple groups.
CONCLUSIONS
The free-running Ho:YAG laser is currently considered the gold standard by urologists
for intracorporeal laser lithotripsy. In this article we have summarized several important
aspects of clincial Ho:YAG laser lithotripsy. Ablation mechanism and ablation properties of
Ho:YAG laser lithotripsy were reviewed. Documentation of fiber-related problems and safety
issues provide important practical knowledge for administering successful clinical
procedures.
REFERENCES
[1] Rink, K; Delacretaz, G; Salathe, RP. "Fragmentation process of current laser
lithotriptors," Lasers in Surgery and Medicine, 1995, 16(2), 134-146.
[2] Chan, KF; Choi, B; Vargas, G; Hammer DX; Sorg, B; Pfefer, TJ; Teichman, JMH;
Welch, AJ; Jansen, ED. "Free electron laser ablation of urinary calculi: an experimental
study," IEEE Journal on Selected Topics in Quantum Electronics, 2001, 7(6), 1022-
1033.
[3] Marks, AJ; Teichman, JMH. "Lasers in clinical urology: state of the art and new
horizons," World Journal of Urology, 2007, 25(227-233)
[4] Teichmann, H; Herrmann, TR; Bach, T. "Technical aspects of lasers in urology," World
Journal of Urology, 2007, 25(221-225.
[5] Rink, K; Delacretaz, G; Salathe, RP. "Fragmentation process induced by nanosecond
laser pulses," Applied Physics Letters, 1992, 61(22), 2644-2646.
[6] Qiu, JZ; Teichman, JMH; Kuranov, RV; Mcelroy, AB; Wang, T; Paranjape, AS;
Milner, TE."Near infrared femtosecond laser ablation of urinary calculi in water," in
Photonics West 2009, SPIE, San Jose, CA.
[7] Teichman, JM; Vassar, GJ; Bishoff, JT; Bellman, GC. "Holmium:YAG lithotripsy
yields smaller fragments than lithoclast, pulsed dye laser or electrohydraulic
lithotripsy," Journal of Urology, 1998, 159(1), 17-23.
[8] Liu, MK; Liu, PL; Yiu, TF; Chan, AYT. "Clinical experience with holium:YAG laser
lithotripsy of ureteral calculi," Lasers in Surgery and Medicine, 1996, 19(103-106.
[9] Razvi, HA; Denstedt, JD; Chun, SS; Sales, JL. "Introcorporeal lithotripsy with the
holium:YAG laser," Journal of Urology, 1996, 156(3), 912-914.
[10] Das, A; Erhard, MJ; Bagley, DH. "Intrarenal Use of the Holmium Laser," The Journal
of Urology, 1998, 160(2), 630-631.
[11] Adams, DH. "Holmium:YAG laser and pulsed dye laser: A cost comparison," Lasers in
Surgery and Medicine, 1997, 21(1), 29-31.
[12] Teichman, JMH; Rao, RD; Rogenes, VJ; Harris, MJ. "Ureteroscopic Management of
Ureteral Calculi: Electrohydraulic versus Holmium:YAG Lithotripsy," The Journal of
Urology, 1997, 158(4), 1357-1361.
[13] Teichman, JMH; Rao, RD; Glickman, RD; Harris, JM. "Holmium: YAG Percutaneous
Nephrolithotomy: The Laser Incident Angle Matters," The Journal of Urology, 1998,
159(3), 690-694.
[14] Dushinski, JW; Lingeman, JE. "High-Speed Photographic Evaluation of Holmium
Laser," Journal of Endourology, 1998, 12(2), 177-181.
[15] Vassar, GJ; Teichman, JMH; Glickman, RD. "Holmium:YAG lithotripsy efficiency
varies with energy density," Journal of Urology, 1998, 160(2), 471-476.
[16] Teichman, JM; Vassar, GJ; Glickman, RD. "Holmium:yttrium-aluminum-garnet
lithotripsy efficiency varies with stone composition," Urology, 1998, 52(3), 392-397.
[17] Teichman, JMH; Rogenes, VD; McIver, BJ; Harris, JM. "Holmium:YAG laser
cystolithotripsy of large bladder calculi," Journal of Urology, 1997, 50(1), 44-48.
[18] Teichman, JMH; Vassar, GJ; Glickman, RD; Beserra, CM; Cina, SJ; Thompson, IM.
"Holmium:YAG lithotripsy: photothermal mechanism converts uric acid calculi to
cyanide," The Journal of Urology, 1998, 160(2), 320-324.
[19] Rink, K; Delacretaz, G; Salathe, RP. "Influence of the pulse duration on laser induced
mechanical effects," in SPIE, 1994, 181-194, San Jonse.
[20] Rink, K; Delacretaz, G; Salathe, RP. "Fragmentation process induced by microsecond
laesr pulses during lithotripsy," Applied Physics Letters, 1992, 61(3), 258-260.
[21] Chan, KF; Vassar, GJ; Pfefer, TJ; Teichman, JMH; Glickman, RD; Weintraub, ST;
Welch, AJ. "Holmium:YAG laser lithotripsy: A dominant photothermal ablative
mechanism with chemical decomposition of urinary calculi," Lasers in surgery and
medicine, 1999, 25(1), 22-37.
[22] Jansen, ED; Asshauer, T; Frenz, M; Motamedi, M; Delacretaz, G; Welch, AJ. "Effect of
pulse duration on bubble formation and laser-induced pressure waves during holmium
laser ablation," Lasers in Surgery and Medicine, 1996, 18(3), 278-293.
[23] Schafer, SA; Durville, FM; Jassemnejad, B; Bartels, KE; Powell, RC. "Mechanisms of
biliary stone fragmentation using the Ho:YAG laser," Biomedical Engineering, IEEE
Transactions on, 1994, 41(3), 276-283.
[24] Kang, HW; Lee, H; Teichman, JMH; Oh, JO; Kim, J; Welch, AJ. "Dependence of
calculus retropulsion on pulse duration during Ho:YAG laser Lithotripsy," Lasers in
Surgery and Medicine, 2006, 38(8), 762-772.
[25] Zhong, P; Tong, HL; Malenbaum, J; Cocks, FH; Preminger, GM. "Transient cavitation
and acoustic emission produced by different laser lithotripters," Journal of
Endourology, 1998, 12(4), 371-378.
[26] Beghuin, D; Delacretaz, G; Schmidlin, F; Rink, K. "Fragmentation process during
Ho:YAG laser lithotripsy revealed by time-resolved imaging," in SPIE, 220-224, San
Jose, 1998.
[27] Schafer, SA; Durville, FM; Jassemnejad, B; Bartels, KE; RC. Powell, "Mechanisms of
biliary stone fragmentation using the Ho:YAG laser," IEEE Trans On Biomedical
Engineering 41(3), 276-283 (1994)
[28] Charles G, M; Jeff C, S; Patrick, SW; James O, L; Songlin, Z; Pei, Z; David, A; M;
Glenn M, P. "In vitro comparison of stone retropulsion and fragmentation of the
frequency doubled, double pulse Nd:YAG laser and the holmium:YAG laser," The
Journal of Urology, 2005, 173(5), 1797-1800.
[29] Spindel, ML; Moslem, A; Bhatia, KS; Jassemnejad, B; Bartels, KE; Powell, RC;
O'Hare, CM; Tytle, T. "Comparison of holmium and flashlamp pumped dye lasers for
use in lithotripsy of biliary calculi," lasers in Surgery and Medicine, 1992, 12(482-489.
[30] White, MD; Moran, ME; Calvano, CJ; Borhan-Manesh, A; Mehlhaff, BA. "Evaluation
of retropulsion caused by holmium:YAG laser with various power settings and fibers,"
Journal of Endourology, 1998, 12(2), 183-186.
[31] Lee, HO; Ryan, RT; Teichman, JMH; Kim, J; Choi, B; Arakeri, NV; Welch, AJ. "Stone
Retropulsion During Holmium:Yag Lithotripsy," The Journal of Urology, 2003, 169(3),
881-885.
[32] Lee, H; Ryan, RT; Kim, J; Choi, B; Arakeri, NV; Teichman, JMH; Welch, AJ.
"Dependence of Calculus Retropulsion Dynamics on Fiber Size and Radiant Exposure
During Ho:YAG Lithotripsy," Journal of Biomechanical Engineering, 2004, 126(4),
506-515.
[33] Finley, DS; Petersen, J; Abdelshehid, C; Ahlering, M; Chou, D; Borin, J; Eichel, L;
McDougall, E; Clayman, R. "Effect of holmium:YAG laser pulse width on
lithotripsy retropulsion in vitro," Journal of Endourology, 2005, 19(8), 1041-1044
[34] Bauerle, D. Laser processing and chemistry, Springer-Verlag Berlin, 2000.
[35] Dieter Bauerle, Laser Processing and Chemistry, Springer, Berlin (2000).
[36] Nazif, OA; Teichman, JMH; Glickman, RD; Welch, AJ. "Review of laser fibers: a
practical guide for urologists," Journal of Endourology, 2004, 18(9), 818-829.
[37] Marks, AJ; Mues, AC; Knudsen, BE; Teichman, JMH. "Holmium:Yttrium-Aluminum-
Garnet Lithotripsy Proximal Fiber Failures From Laser and Fiber Mismatch," Urology,
2008, 71(6), 1049-1051.
[38] Knudsen, BE; Glickman, RD; Stallman, KJ; Maswadi, S; Chew, BH; Beiko, DT;
Denstedt, JD; Teichman, JMH. "Performance and safety of holmium: YAG laser optical
fibers," Journal of Endourology, 2005, 19(9), 1092-1097.
[39] Mues, AC; Teichman, JMH; Knudsen, BE. "Evaluation of 24 Holmium:YAG Laser
Optical Fibers for Flexible Ureteroscopy," The Journal of Urology, 2009, 182(1), 348-
354.
[40] Mues, AC; Teichman, JMH; Knudsen, BE. "Quantification of Holmium:Yttrium
Aluminum Garnet optical tip degradation," Journal of Endourology, 2009, 23(9), 1425-
1428.
[41] Harrington, JA. Infrared Fibers and their Applications, SPIE Press, Bellingham, 2004.
[42] Sofer, M; Watterson, JD; Wollin, TA; Nott, L; Razvi, H; Denstedt, JD. "Holmium:
YAG Laser Lithotripsy for Upper Urinary Tract Calculi in 598 Patients," The Journal
of Urology, 2002, 167(1), 31-34.
[43] Watterson, JD; Girvan, AR; Cook, AJ; Beiko, DT; Nott, L; Auge, BK; Preminger, GM;
Denstedt, JD. "Safety and Efficacy of Holmium: Yag Laser Lithotripsy in Patients With
Bleeding Diatheses," The Journal of Urology, 2002, 168(2), 442-445.
[44] Santa-Cruz, RW; Leveillee, RJ; Krongrad, A. Ex vivo comparison of four lithotripters
commonly used in the ureter: what does it take to perforate? 1998.
[45] Corbin, NS; Teichman, JMH; Nguyen, T; Glickman, RD; Rihbany, L; Pearle, MS;
Bishoff, JT. "Laser Lithotripsy and Cyanide," Journal of Endourology, 2000, 14(2),
169-173.
[46] Teichman, JMH; Champion, PC; Wollin, TA; Denstedt, JD. "Holmium: YAG
Lithotripsy of Uric Acid Calculi," The Journal of Urology, 1998, 160(6, Part 1), 2130-
2132.
[47] Corbin, NS; Teichman, JM; Nguyen, T; Glickman, RD; Rihbany, L; Pearle, MS;
Bishoff, JT. "Laser lithotripsy and cyanide," Journal of Endourology, 2000, 14(2), 169-
173.
Chapter 6
COMPUTER MODELLING OF FEMTOSECOND LASER
ABLATION OF SEMICONDUCTORS AND DIELECTRICS
D. P. Korfiatis and K.-A. Th. Thoma
Physics Department, University of Patras
26500 Rio, Patras, Hellas, Greece
ABSTRACT
Ultrafast laser ablation has proved to be a powerful tool for material processing.
Combination of both experimental and theoretical efforts can lead to the determination of
optimum values of laser parameters for the improvement of accuracy which is a most
crucial aspect in micromachining.
Besides experiment and theory, numerical simulation can also provide a significant
research tool in the field for the calculation of parameters of great importance which
influence the micromachining process. Such parameters are ablation threshold as a
function of the laser wavelength, pulse duration and the properties of the particular
material. Especially, the prediction through numerical simulation of the geometry and the
dimensions of the craters formed and the damaged surrounding surface for known laser
and material properties can lead to control and optimization of the micromachining
process. Furthermore, numerical simulation can drop light to the microscopic processes
through which femtosecond laser damage occurs.
In this chapter, the numerical techniques currently used for the simulation of
femtosecond laser ablation of semiconductors and dielectrics are presented and discussed.
These techniques include molecular dynamics simulation, the Fokker-Planck approach
and two temperature models.
1. INTRODUCTION
Ultrashort-pulse lasers have proved to be a powerful tool for material processing offering
many advantages in comparison to long pulses [Amoruso et al 2004, Farsari et al 2005].
Thus, precise micromachining with minimal heat affected zone can be achieved as a result of
D.P. Korfiatis, K.-A. Th. Thoma 154
small thermal diffusion lengths associated with ultrashort pulses. Furthermore, ultrashort
pulses offer low ablation thresholds because of energy localization and the absence of plasma
plume absorption. Energy is localized in a small depth mainly due to the reduction of light
penetration depth because of high laser intensities achieved with femtosecond pulses resulting
to a major contribution of multiphoton absorption processes. Also, a major drawback of
nanosecond laser ablation which is screening of the laser energy, reported to reach up to a
one-half [Bulgakova et al 2004], is totally absent for the case of femtosecond laser pulses,
since in this case plasma is formed after the end of each pulse. .
The understanding of the ultrafast ablation process, the determination of optimum
values of laser parameters for the improvement of the accuracy of micromachining, as
well as the calculation of the associated laser fluence thresholds are of great importance
and efforts towards this goal combining experiment, simulation and theory are highly
required.
In studying physical and physicochemical phenomena one of the big advantages of
simulation (often referred in the literature as numerical experiment) in general is that the
various processes involved can be studied separately. Through simulation one can also
calculate parameters which may not be possible to measure through experiment.
Furthermore, a large number of numerical experiments can be performed easier than the
conventional experiments to reveal the relations between the parameters involved in the
specific problem.
The numerical techniques that are currently used for the simulation of femtosecond laser
absorption and will be discussed explicitly in the following are molecular dynamics
simulation, the Fokker-Planck approach and two temperature models. Special emphasis is
given to the later as it is most frequently found in the literature. Finally, the shape and
dimensions of craters formed by ablation are calculated, the calculations based on recent
publications.
In molecular dynamics simulation the solid is treated microscopically as an assembly of
atoms that absorb energy from the incident radiation. As a result the bond length is altered
causing a phase transition or the emission of some atoms from the solid lattice.
In Fokker-Planck modelling, the electron energy distribution in the conduction band of
semiconductors or dielectrics is described by the Fokker-Planck approximation of the
Boltzmann equation. The free electron production due to the intense laser field is described
through the variation of the electron energy distribution function.
In two-temperature models a system of partial differential equations is constructed which
describes the interaction between laser radiation and the solid target. The construction of the
model is based on the conservation of the total energy of the system radiation-solid. The solid
is divided in two subsystems, the lattice and the electron-hole plasma which is created due the
absorption of the incident photons. For ultrashort pulses where the pulse width is comparable
or shorter than the lattice-plasma energy relaxation time, it is generally accepted that the two
subsystems attain two different temperatures, hence the name of the models.
Computer Modelling of Femtosecond Laser Ablation of Semiconductors 155
2. MOLECULAR DYNAMICS SIMULATION
Molecular Dynamics (MD) simulation is a computational method to investigate the
behaviour of materials by computing the molecular or atomic motion under the influence of a
given potential. The general approach of MD is to obtain at the instant t+dt atomic positions,
velocities, etc, based on positions, velocities, and other dynamic information at the instant t
[Xu et al 2004]. A commonly used potential for the description of atom-atom interaction in
semiconductors and dielectrics is the Lennard-Jones potential given by the relation [Perez and
Lewis 2003]:
( )
=
6 12
6 12
4
c c
r r r r
r V

for
c
r r
and ( ) 0 = r V for
c
r r >

(1)
where
c
r is the cutoff distance at which the potential has been adjusted to vanish and ,
are the energy and length scales respectively.
Alternatively, a diamond-like structure has been modelled by using the Stillinger-Weber
potential [Herrmann et al 1998, Holenstein et al 2004]. In the Stillinger-Weber potential two-
body and three-body interactions are considered. The two-body term is of the form:
( ) ( )

=
a r
e A r A r V

2
4
1 2
(2)
where a is the cutoff distance,
1
A ,
2
A are energy constants and is a length constant.
The three-body term consists of exponential functions and an angular term favouring the
tetrahedral arrangement of the four neighbours of a diamond-like structure.
( )
2
3
3
1
cos , ,

+ =

jik
a r
a r
jik ik ij
ik
ij
e e r r V

(3)
where
ij
r ,
ik
r are the distances between the particles,
jik
is the bonding angle and an
energy constant. Coulomb potential for ion-electron interaction is considered in addition to
the potential describing ion-ion interaction.
The lattice of the solid is simulated through an ensemble of a certain number of atoms
bound via one of the above mentioned potential functions. Each incident photon has a finite
probability of being absorbed by any of the atoms. This probability depends on the density of
the atoms and the linear and multiphoton absorption coefficient of the material. After the
absorption of a photon, the atom by which the photon is absorbed is marked as an excited
atom. Changes in the potential and therefore in the crystal structure, with increasing degrees
of excitation are implemented as a number of randomly broken bonds matching the degree of
excitation. A broken bond is simulated by removing the attractive part of the two-body
potential discarding also the three-body part of the potential [Herrmann et al 1998, Holenstein
et al 2004]. For a solid with valence equal to 4, which is the case of silicon, an atom with a
degree of excitation exceeding 3 is considered not to be bound at all [Herrmann et al 1998].
If after repeated absorption the total energy absorbed by an atom exceeds the workfunction
then the atom is considered as ionized and an electron-hole pair is added to the system
[Holenstein et al 2004]. Ablation threshold is defined as the minimum laser fluence value
required for a certain number of ions to be ejected from the lattice.
A third approach is the study of the increase of the mean bond-length as atoms absorb
energy from the incident laser radiation. In this case the fluence threshold for melting and
ablation can be defined by using the Lindemann criterion [Jeschke et al 2002]. A typical value
of bond-length increase above which the lattice becomes unstable, leading to melting or
ablation, is about 15%.
3. THE FOKKER-PLANK APPROACH
The Fokker-Plank approximation of the Boltzmann transport equation for the electron
distribution function is given by [Apostolova and Hahn 2000, Azzouz 2004, Oh et al 2006]:

( ) ( )
( ) t S
t J
t
t f
,
, ,
(4)
where ( ) d t f , is the number density of electrons with kinetic energy between and
d + at time t and
( )
, S t is related to electron generation and recombination through:

( ) ( ) ( ) ( ) t R t R t R t S
pi rcc imp
, , , , + + =
(5)
where
imp
R is the impact ionization term,
rcc
R is the Auger recombination term and
pi
R
is the multiphoton absorption term. The current in energy space, ( ) t J , , is the number of
electrons per unit volume whose energy increases from a value less than to a value greater
than per unit time. A complete analysis of these terms can be found in the literature
[Apostolova and Hahn 2000].
In Fokker-Plank approach, damage threshold is usually defined in terms of a critical
plasma density as given in section 3 through (14) [Azzouz 2004] or semi-empirically as a
percentage of valence electron concentration.
4. TWO-TEMPERATURE MODELS
In two-temperature models, it is assumed that energy from ultrashort laser radiation is
absorbed by free carriers at a first step, leading to an increase of their temperature and density
with time. At a second step a transfer of energy by free carriers to the lattice is considered,
followed by an increase of the lattice temperature. The above procedure is governed by an
energy relaxation time [Yoffa 1980]. This type of model was proposed for the first time in
1975 in order for the radiation-solid interaction to be described when the pulse width is
shorter than the energy relaxation time [Anisimov et al 1975]. Usually, the two-temperature
models appearing in the literature are 1D since lateral diffusion of carriers and heat can be
neglected in the ultrafast time scale. 2D models though have also been used in certain cases
[Sim et al 2007]. In two-temperature models, electrons and holes are assumed to be at a
common temperature. The thermalization time of the carriers is of the order of fs 10 . This
time sets the lower limit for the laser pulse width in order for the two-temperature model to be
valid.
The creation of electron-hole pairs is due to both linear and multi-photon (usually two-
photon) absorption and also to avalanche ionization. For intense laser radiation multi-photon
absorption is usually dominating over linear absorption, the former being the predominant
mechanism for plasma creation in semiconductors. Multi-photon absorption in dielectrics
results to the creation of an initial plasma density, crucial for avalanche ionization to take
place.
Electron and hole concentrations are considered as equal in all cases, as Dember field
created by charge separation prohibits electron and hole concentrations from becoming
significantly different [Van Driel 1987, Othonos 1998, Chen et al 2005].
The main recombination mechanism for high plasma densities is Auger recombination
(the inverse phenomenon of avalanche ionization) with the recombination time given by a
relation of the form:
2
3
1
n
R
=

(6)
where
3
is the bipolar Auger coefficient and n is the electron-hole pair concentration.
For high enough plasma densities (higher than
3 21
10

cm ), due to screening of the Coulomb
interaction, Auger recombination time tends to take a constant value independent of the
plasma density.
A typical two-temperature model for the description of femtosecond laser absorption by
semiconductors and dielectrics consists of the following equations:

( ) ( ) ( ) ( )
E
L c
L L
t z T t z T
L
z
t z T
z t
t z T
c
, , , ,
+
(7)
( ) ( ) ( ) ( ) ( )
( ) t z n
t z n
hf
t z I
hf
t z I
z
t z n
D
z t
t z n
R
,
,
2
, , , ,
2
+ + +
(8)

( ) ( )
( )
( )
( ) ( ) t z I t z I
hf
E hf
hf
E hf
z
t z n
D
t z n
t z U
z t
t z U
FC
g g
c c
, ,
2
2
,
,
, ,

( ) ( ) ( )
E
c
R
g
t z T t z T
L
t z n
E

, , ,
+ (9)
( )
( ) ( ) ( ) t z I t z I
z
t z I
FC
, ,
,
+ + =
(10)
In the right hand side of (7) the first term describes the heat conduction through the lattice
and the second one the exchange of energy between lattice and plasma. In the right hand side
of (8), diffusion, generation through linear and two photon absorption, recombination of the
carriers and generation due to avalanche ionization, have been taken into account. The terms
in the right hand side of (9) represent the diffusion of energy through carrier diffusion, the
increase of carriers' energy because of the excess of photon energy over the energy gap, free
carriers' absorption and Auger recombination. The last term denotes the exchange of energy
between lattice and plasma. Finally, equation (10) represents the attenuation of light intensity
due to linear, non-linear and free carriers absorption. The value of the absorbed light
intensity I , which is really incident on the sample, is obtained after subtraction of the
reflection.
The relation between carriers energy and temperature and thus the specific heat of
carriers can be obtained from classical statistics as [Lietoila and Gibbons 1982]:

( ) ( ) ( ) t z T t z n k t z U
c B c
, , 3 , =

(11)
and ( ) t z n k c
B c
, 3 = (12)
More precisely, the Fermi-Dirac statistics can be used for the determination of the
carriers specific heat [Chen et al 2005].
As already mentioned, exchange of energy between carriers and lattice is governed by an
energy relaxation time. The energy relaxation time is increased with increasing plasma
density because the rate of energy exchange is reduced due to screening effects. The factor L
in the energy exchange term in equations (7) and (9) is usually considered as equal to the
specific heat of the carriers [Lietoila and Gibbons 1982, Van Driel 1987]. A more symmetric
relation which is also used [Klossika et al 1996, Korfiatis et al 2007a] is:
L c
L c
c c
c c
L
+
= (13)
The meaning of all symbols used in equations (7)-(10) can be found in Table 1. The
subscript L is for lattice and the subscript c is for carriers.

Table 1
Symbol Meaning Symbol Meaning
T
Temperature Thermal conductivity
c Specific heat
a
D
Ambipolar diffusion
coefficient
n Plasma density
g
E
Energy gap
a Linear absorption coefficient

Two-photon absorption
coefficient
FC
a
Free carrier absorption
coefficient
U
Energy

Impact ionization coefficient
hf
Photon energy

The boundary conditions required for solving the above system of partial differential
equations can be that of the semi-infinite medium, namely, at the sample rare boundary lattice
and plasma temperature are fixed at room temperature and plasma concentration at its
intrinsic value. Alternatively, the boundary conditions can be set by defining zero fluxes of
energy and carriers between the irradiated film and the surrounding, namely vanishing
derivatives of lattice and plasma temperatures, as well as plasma density. A combination of
the two types of boundary conditions can also be used.
The initialization of ablation (ablation fluence threshold) has been defined in several
ways in the relevant literature. Some researchers [Pronko et al 1998, Allenspacher et al 2003]
define the ablation fluuence threshold as the point at which plasma density resumes its so
called critical value for which the plasma frequency becomes equal to the laser angular
frequency:
p L
=

(14)

This definition of critical plasma density has the disadvantage that the critical density
obtained depends mainly on laser frequency and not on the material parameters. A more
rational definition of critical plasma density results through the alternative approach given in
the following.
The main ablation mechanisms are thermal vaporization (strong ablation) and Coulomb
explosion (gentle ablation) [Jiang and Tsai 2003]. For the case of strong ablation the melting
of the solid target under the influence of the intense laser radiation can be described by the
system of equations (7)-(10). The solid to liquid transition can be treated numerically as a
moving boundary. Then, the vaporization of the liquid can be treated in a similar manner.
Most semiconductors in liquid phase behave as metals, so a two-temperature model suitable
for the description of metal-radiation interaction can be used. This is of the form [Chichkov et
al 1996, Korfiatis et al 2009]:

( ) ( ) ( )
l
E
c
l
I
l
c
l
I
l
c l
I
t z T t z T
c c
c c
t
t z T
c
, , ,
+

(15)

( ) ( ) ( ) ( )
l
E
c
l
I
l
c
l
I
l
c c l
c
c l
c
t z T t z T
c c
c c
z
t z T
z t
t z T
c
, , , ,
+
(16)
where the superscript l is for liquid, the subscript I is for ions and the other symbols
have the usual meaning. In this framework, the definition of ablation threshold comes directly
as the minimum laser fluence required for the onset of vaporization of the liquid [Glover
2003].
Two-temperature models have also been used for the study of generalized thermo-
elastodynamics of materials subject to ultrafast laser heating [Qi and Suh 2009, 2010a,
2010b].
Finally, it must be pointed out that a combination of both molecular dynamics simulation
and two-temperature models has been used in some cases [Yamashita et al 2006].
5. COMPUTATION OF CRATER GEOMETRY
Ablation threshold is of great importance in laser micromachining since it can lead to the
prediction of the shape of the crater created by ablation on the target surface. In the following
the geometry of a crater created by ablation is calculated, the analysis based on two recent
publications [Korfiatis et al 2007b, 2009].
Neglecting free carriers absorption and taking into account only linear and two-photon
absorption, the attenuation of light intensity in the irradiated sample is given through the
relation:
( )I I
z
I
+ =

(17)
For a rectangular pulse in time I is relating to the incident fluence through:
R
I
F
p
=
1
0

(18)
where
p
is the pulse duration and R the reflectivity. Integration of (17) can lead to the
calculation of damage depth by setting
th
F F =
0
at the damage depth [Korfiatis et al 2007b],
where
th
F is the fluence threshold. The damage depth is given through:

( ) ( )
( ) ( )
+
+
=
0
0
1
1
ln
1
F R F
F R F
d
p th
th p

(19)

For
0
F damage depth tends to a saturation value given by the relation:
( )
( )

+
=
th
th p
F R
F R
d
1
1
ln
1
max

(20)

For a Gaussian pulse in space:
( )
2
0
2
2
0
w
r
e F r F

= (21)
where
0
w is the laser beam waist. So, eq. (19) can be written as:
( )
( ) ( )
( )

+
+
=
2
0
2
2
0
2
2
0
2
0
1
1
ln
1
w
r
p th
th p
w
r
e F R F
F R e F
r d

(22)

The radius of the damaged region can be calculated directly from (22) as the radius at
which ( )
th
F r F = :
=
th
th
F
F
w r
0
0
ln
2
1

(23)

The last equation is used extensively by experimentalists for determining the ablation
threshold given the radius of the ablated region.
Integrating ( ) r d over the entire crater surface, the volume of the crater results to be:
( )
+ =

2
0
2
2
2 2
2
0 2
0
2
0
2 2
0
ln
2
2
w
r
c
a
c
c
c
ye L y L
w
r
y
F
F
w
r w
V
(24)
where
( )
p
a
F R
y
0
1
(25)
and ( ) z L
2
is the dilogarithm function [Abramowitz and Stegun 1965]:
( )
( )

=
0
2
1 ln
z
dt
t
t
z L

(26)
Obviously, by setting the ablation threshold as
th
F in the above equations the shape of
the crater created by ablation can be calculated. If instead of the ablation threshold the
melting threshold is used the shape of the entire heat affected zone can be calculated.
As precision is a major advantage of using ultra short pulses in material micromachining,
it is of great importance that simulation techniques offer the possibility of calculating the
shape and dimensions of the craters formed by ablation in the irradiated materials.
REFERENCES
A. Lietoila and J. F. Gibbons, J. Appl. Phys. (1982) 53 3207.
A. Othonos, J. Appl. Phys. (1998) 83 1789.
B. N. Chichkov et al, Appl. Phys. A (1996) 63, 109.
D. P. Korfiatis, K.-A. Th. Thoma, J. C. Vardaxoglou, Appl. Surf. Sci. (2009) 255, 7605.
D. P. Korfiatis, K.-A. Th. Thoma, J. C. Vardaxoglou, J. Phys. D: Appl. Phys. (2007a) 40,
6803.
D. P. Korfiatis, K.-A. Th. Thoma, J. C. Vardaxoglou, Metamaterials, October 22-26 (2007b)
Rome, Italy.
D. Perez and L. J. Lewis, Phys. Rev. B (2003) 67, 184102.
E. J. Yoffa, Phys. Rev. B (1980) 21, (6), 2415.
H. M. Van Driel, Phys. Rev. B (1987) 35 8166.
H. O. Jeschke et al, Appl. Surf. Sci. (2002) 197-198 839.
H. S. Sim, S. H. Lee and J. S. Lee, J. Mech. Sci. Technol. (2007) 21, 1847.
I. M. Azzouz, J. Phys. B: At. Mol. Opt. Phys. (2004) 37 3259.
J. J. Klossika et al, Phys. Rev. B (1996) 54, (15), 10277.
J. K. Chen, D. Y. Tzou and J. E. Beraun, (2005) Int. J. Heat Mass Tran. 48 501.
L. Jiang and H. L. Tsai, NSF Workshop on Unsolved Problems and Research Needs in
Thermal Aspects of Material Removal Processes, June 10-12 (2003) Stillwater, OK.
M. Abramowitz, I. A. Stegun, Handbook of Mathematical Functions, Dover, 1965.
M. Farsari et al, J. Micromech. Microeng. (2005) 15, 1786.
N. M. Bulgakova, A. V. Bulgakov, L. P. Babich, Appl. Phys. A (2004) 79, 1323.
P. Allenspacher, B. Huettner and W. Riede, Proc. SPIE (2003) 4932, 358.
P. P. Pronko et al, Phys. Rev. B (1998) 58, 2387.
R. F. W. Herrmann, J. Gerlach and E. E. B. Campbell, Appl. Phys. A (1998) 66, 35.
R. Holenstein et al, Proc SPIE (2004) 5579, 688.
S. Amoruso et al, Appl. Phys. A (2004) 79, 1377.
S. I. Anisimov, B. L. Kapeliovich and T. L. Perelman, Sov. Phys. JETP (1975) 39, 375.
T. Apostolova, Y. Hahn, J. Appl. Phys. (2000) 88, 1024.
T. E. Glover, J. Opt. Soc. Am. B (2003) 20, 125.
X. Qi and C. S. Suh, Int. J. Heat Mass Tran. (2010a) 53, 41.
X. Qi and C. S. Suh, Int. J. Heat Mass Tran. (2010b) 53, 744.
X. Qi and C. S. Suh, J. Therm.Stresses (2009) 32, 477.
X. Xu, C. Cheng and I. Chowdhury, J. Heat Transfer (2004) 126, 727.
Y. M. Oh et al, Int. J. Heat Mass Tran. (2006) 49, 1493.
Y. Yamashita et al, Fusion Eng. Des. (2006) 81, 1695.
In: Laser Ablation: Effects and Applications
Editor: Sharon E. Black
ISBN: 978-1-61122-466-5
c _2011 Nova Science Publishers, Inc.
Chapter 7
THERMOPHYSICAL EFFECTS OF FEMTOSECOND
LASER ABLATION OF METAL TARGET
Ranran Fang
1
and Hua Wei
2
1
College of Mathematics and Physics,
Chongqing University of Posts and Telecommunications,
Chongqing 400065, China
2
Department of Physics,
Chongqing University, Chongqing 400044, China
Abstract
The electron-phonon relaxation time as a function of pulse width and uence of
femtosecond laser is studied based on the two-temperature model. The satisfactory
agreement between our numerical results and experimental data indicates that the
electron-phonon relaxation time is reasonably accurate with the inuences of pulse
width and uence of femtosecond laser. An improved two-temperature model to de-
scribe femtosecond laser ablation of metal target is also presented. The temperature-
dependent heat capacity and thermal conductivity of the electron, as well as electron
temperature-dependent absorption coefcient and absorptivity are all considered in
this tailored two-temperature model. The satisfactory agreement between our numer-
ical results and experimental data indicates that the temperature dependence of heat
capacity, thermal conductivity, absorption coefcient and absorptivity in femtosecond
laser ablation of metal target must not be neglected. This chapter nally presents a
unied thermal model, which can describe the thermophysical effects with laser pulse
width ranges from nanosecond to femtosecond. The satisfactory agreement between
our numerical results and experimental results of vaporization threshold indicates that
the unied thermal model is correct and reasonable.
PACS 52.38.Mf; 52.50.Jm; 79.20.Ds
Email address: ranranfang2@gmail.com

164 Ranran Fang and Hua Wei
1. Introduction
It is well known that using femtosecond pulses in laser ablation has two major advantages
over nanosecond pulses: much lower uences are needed to accomplish ablation [1, 2, 3,
4, 5, 6, 7, 8] and considerably sharper contours can be achieved [9, 10]. Femtosecond laser
ablation is useful in various applications concerning laser modication of surfaces (e.g.
drilling, cutting, patterning), lm growth by pulsed laser deposition (PLD), generation of
nanoparticles and so on [11, 12, 13, 14]. In the past two decades, the femtosecond laser
ablation of metals and its nonequilibrium energy transport have been very active research
topics [15, 16, 18, 19, 17, 20, 21, 22, 23, 24].
In most theoretical treatments only electron-phonon collisions are taken into account
for the electron diffusion process during and after femtosecond laser pulse ablation [25,
26, 27, 28, 29]. However, the recent pump-probe measurements have revealed that the
role of electron-electron collisions becomes essential for the electron relaxation at elec-
tron temperature around or above 1 eV [26]. The electron-phonon collisions dominanting
electron diffusion are valid only in the low electron temperature regime. Thus, extending
the conventional two-temperature model from the low temperature regime dominated by
electron-phonon collisions to the high temperature regime through modifying the electron
thermal conductivity associated with the electron-electron collisions is crucial.
Experiments have conrmed that the features of the femtosecond laser ablation process
are greatly inuenced by the quantity of laser energy absorbed by the target [30]. The
absorption coefcient introduced by the Lambert-Beers law accounts for the attenuation of
the absorbed energy in the target [31], and the absorptivity refers to the magnitude of the
ratio of absorbed energy to incident energy [32]. They both describe the ability of absorbing
laser energy for target. For the thermal mechanismdominates almost all the physical effects
in the process of femtosecond laser ablation, the absorption coefcient and the absorptivity
are important optical parameters in the femtosecond laser ablation. A lot of literatures
consider the absorption coefcient and the absorptivity as constant in femtosecond laser
ablation. However, the effect of electron temperature on the absorption coefcient and the
absorptivity is distinctive.
For the important application in technology and the rich subject in which to study,
the researches of pulsed laser ablation and laser processing of materials develop very fast
employing from the nanosecond to the femtosecond time regime [1, 5, 33, 34]. Both the
experimental and theoretical studies have clearly demonstrated the presence of two differ-
ent ablation mechanisms: nonequilibrium ablation [35, 36, 37] and equilibrium ablation
[38, 39, 40, 41, 42, 43, 44, 45, 46], whose criteria is related with ratio of the electron-
phonon coupling time (
R
) and the laser pulse width (
L
), that is, as

R
L
1, it is the
non-equilibrium ablation, while

R
L
1, it belongs to the equilibrium ablation, further-
more

R
L
1, it can be called a mixed ablation.
In section II, we report the numerical solution of the electron-phonon relaxation time
as a function of the heat source term parameters with two-temperature model(TTM). For a
certain laser uence the shorter the pulse width, the shorter the electron-phonon relaxation
time is. However, the electron-phonon relaxation time becomes long for low laser uence
when the pulse width is xed. Besides, the variation of heat-affected zone per pulse with
laser uence is performed. Our numerical results are in good agreement with the experi-
Thermophysical Effects of Femtosecond Laser Ablation of Metal Target 165
mental data [16].
In order to describe the thermophysical effects of femtosecond laser ablation of metal
target, a tailored theoretical model including temperature-dependent heat capacity, thermal
conductivity of the electron, the absorption coefcient and absorptivity is presented in sec-
tion III. The modied model is used to simulate femtosecond laser ablation of copper target.
The satisfactory agreement between our numerical results and experimental data of ablation
rate indicates that temperature dependence of heat capacity, thermal conductivity, absorp-
tion coefcient and absorptivity in femtosecond laser ablation of metal target should not be
neglected. In section IV, we present a unied thermal model which can depict the process.
The electron-phonon coupling time
R
and laser pulse width
L
are introduced in this model
as the criteria to distinguished the two kinds of mechanisms. The well agreement between
our numerical results and experimental results of vaporization threshold indicates that the
unied thermal model is reasonable and satisfactory.
2. Effect of Pulse Width and Fluence of Femtosecond Laser
on the Electron-phonon Relaxation Time
In this section, the electron-phonon relaxation time as a function of pulse width and u-
ence of femtosecond laser is studied on the basis of two-temperature model. The two-
temperature model is solved using a nite difference method for copper target. The tem-
perature distribution of the electron and lattice along with space and time for a certain
laser uence is presented. And the time-dependence of lattice and electron temperature
of the surface for different pulse width and different laser uence are also respectively
performed. Moreover, the variation of heat-affected zone per pulse with laser uence is
obtained. The satisfactory agreement between our numerical results and experimental data
indicates that the electron-phonon relaxation time is reasonably accurate with the inuences
of pulse width and uence of femtosecond laser.
2.1. Two-temperature Model
The interactions of femtosecond laser pulses with metals are very complicated. The energy
transport process in femtosecond laser heating of metals consists of two stages. The rst
stage is the absorption of the laser energy through photon-electron interactions within the
femtosecond pulse duration. It takes a few femtoseconds for electrons to reestablish the
Fermi distribution. Within the duration of a single femtosecond pulse, the change of lat-
tice temperature is generally negligible. The second stage is the energy distribution to the
lattice through electron-phonon interactions, typically on the order of tens of picoseconds.
Although the electron-phonon collision time may be comparable to the electron-electron
collision time, it takes much longer to transfer energy from free electrons to phonons, be-
cause the phonon mass is much larger than the electron mass. The characteristic time for
the free electron and the lattice to reach thermal equilibrium is called the electron-phonon
relaxation time [20].
In order to describe this phenomenon, TTM which takes account of the source term is
used. This model considers the energy relaxation between electrons and phonons and the
thermal diffusion, i.e. Fourier law, as follows:
C
e
(T
e
)

t
T
e
= k
e
(T
e
)

2
x
2
T
e
g(T
e
T
l
) + (1 R)
b
I
0
(t) exp(
b
x)
(1)
C
l
t
T
l
= g(T
e
T
l
)
(2)
where T
e
and T
l
are the electron and lattice temperature , respectively. C
l
is the specic
heat of lattice. C
e
(T
e
) and k
e
(T
e
) are the specic heat and the thermal conductivity of
electron, respectively. C
e
(T
e
) = A
e
T
e
, and k
e
(T
e
) = k
e,0
T
e
/T
l
[10, 47]. g is the electron-
phonon coupling coefcient. R and
b
are the reectance and the absorption coefcient of
the target. In order to describe the incident laser intensity more accurately, we adopt the
laser incident intensity expressed by a Gauss function [35], i.e.,
I
0
(t) = I
0
exp[
(4 ln2)t
2
(
p
)
2
] (3)
where I
0
is the maximal laser power density,
p
is the laser pulse width.
For the equation (1) and (2), the initial condition is
T
e
(x, 0) = T
l
(x, 0) = T
0
. (4)
and the boundary conditions can be expressed as:
k
e
T
e
x
[
x=0
= (1 R)I
0
(t)
(5)
k
e
T
e
x
[
x=d
= 0
(6)
where d is the target thickness, and T
0
= 300K is the initial temperature which is uniform
across the target.
The analytical solution of electron-phonon relaxation time
ep
used in many papers [16,
47, 48, 49, 50] can be deduced from TTM, but this analytical solution without considering
the uence of femtosecond laser, and
ep
is expressed as
ep

e
p
(
p
+
l
)
e
(
p
+
l
) +
p
l
+

e
e
+
l
(7)
where
i
= C
l
/g and
e
= C
e
/g are the electron cooling and lattice heating times, respec-
tively. From equation (7), we can nd that the analytical solution of the electron-phonon
relaxation time is not uenced by the uence of the source term.
For low laser intensities the analytical solution should be effective. However, for high
laser intensities equation (7) will be invalid. It is the high time for us to obtain the numerical
solution of the electron-phonon relaxation time. The effect of pulse width and uence of
femtosecond laser on electron-phonon relaxation time is studied depending on TTM in the
following section.
Table 1. Thermal and optical properties of copper
R
b
(m
1
) A
e
(J/m
3
K
2
) k
e,0
(W/mK)
0.92 7.1 10
7
96.6 401
C
l
(J/m
3
K) g(W/m
3
K) T
m
(K) T
b
(K)
3.46 2.6 10
17
1356 2811
Figure 1. (a) Electron temperature distribution and (b) lattice temperature distribution at
different times and position predicted by the two-temperature model for the copper target
irradiated by a 100fs, 800nm pulse at 0.4J/cm
2
.
2.2. Electron Thermal Diffusion Length
For high laser uence, the thermal diffusion of electron is driven by the temperature gra-
dient. The hot-electron bath is cooled down by electron-phonon interaction, the strength
of which limits the diffusion range [10]. The electron thermal diffusion length can be ex-
pressed as [16, 47, 48, 49, 50],
l =
D
ep
(8)
where D is the thermal diffusion coefcient, D = k
e
(T
e
)/C
e
(T
e
). The numerical solution
of
ep
is calculated by virtue of TTM in this section.
2.3. Results and Discussion
The thermal and optical properties of copper in Table I are adopted from Ref. [47].
2.3.1. The space- and time-dependence of electron and lattice temperature of target
The space- and time-dependence of electron and lattice temperature in target is represented
in Fig.1. We can see from Fig.1(a) , at a xed location, the electron temperature rstly
Figure 2. The time-dependence of electron and lattice temperature of the surface for the
copper target irradiated by a 100fs, 800nm pulse at 0.4J/cm
2
.
rapidly increases along with the ablation time, while suddenly decreases when it reaches
the maximum. As shown in Fig.1(b), the temperature of the lattice rises gradually. Then,
the lattice temperature doesnt change when it reaches the maximum. For a xed time, the
temperature of electron and lattice decrease along with depth. We can analyze the phe-
nomenons as follows: When the femtosecond laser irradiates the target, it takes a few fem-
toseconds for electrons to absorb of the laser energy through photon-electron interactions.
Within the duration of a single femtosecond pulse, the change of lattice temperature is gen-
erally negligible. Then the energy will be distributed from the electron to lattice through
electron-phonon interactions. The lattice reaches to the same temperature as electron tem-
perature eventually. The evolvement of electron and lattice temperature in this section is
consistent with many experiments [26, 51, 52].
2.3.2. The numerical solution of electron-phonon relaxation time
As shown in Fig.2, it presents the evolvement of electron and lattice temperature of the sur-
face along with time for the copper target irradiated by a 100fs, 800nmpulse at 0.4J/cm
2
.
Along with increasing time, the electron temperature rises rstly, then it suddenly decreases
when it reaches the maximum. However, the temperature of lattice rstly increases gradu-
ally, then it reaches to the same temperature as electron temperature. The electron-phonon
relaxation time
ep
is the time for the electrons and the lattice to reach thermal equilibrium.
The electron-phonon relaxation time
ep
2ps can be obtained from Fig.2.
Figure 3. The time-dependence of electron and lattice temperature of the surface for differ-
ent pulse width with pulse uence of 0.75J/cm
2
and laser wavelength of 800nm.
2.3.3. Effect of pulse width of femtosecond laser on the electron-phonon relaxation
time
The evolvement of electron and lattice temperature of the surface along with time for dif-
ferent pulse width is shown in Fig.3. The time used by the electron temperature reaching
the maximum is the corresponding pulse width. For the same pulse uence, the shorter the
pulse width, the bigger the electron temperature maximum is, and the shorter the electron-
phonon relaxation time is. Because the total incident laser energy is xed, the laser energy
per unit time irradiating the target becomes large for short pulse width. Absorbing much
more laser energy per unit time, the electron temperature will be higher, and the corre-
sponding electron kinetic energy will be bigger. Then the effective electron-ion collision
frequency
ei
becomes higher. The time for energy transfer from electron to ions is ex-
pressed as t
energy
= (
ei
m
e
/m
i
)
1
[17]. We can obtain from this equation that the higher
the effective electron-ion collision frequency, the shorter the time for energy transfer from
electron to ions is. As a result, the electron-phonon relaxation time becomes short for short
pulse width.
2.3.4. Effect of uence of femtosecond laser on the electron-phonon relaxation time
As shown in Fig.4, it presents the evolvement of electron and lattice temperature of the
surface along with time for different laser uences. For higher laser uence, equilibrium
temperature of electron and lattice becomes higher accordingly. It is obvious that the ulti-
mate temperature of the target will be higher when it absorbs much more energy. However,
Figure 4. The time-dependence of electron and lattice temperature of the surface for the
copper target irradiated by a 100fs, 800nm pulse at different laser uences.
the lower uence laser, the longer the electron-phonon relaxation time is. The reason is that
when the high intensity laser irradiates the target, the kinetic energy of the electron will be
bigger. The electron-phonon relaxation time becomes longer for low uence laser.
2.3.5. Heat-affected zone per pulse as a function of laser uence
When considering the transport of absorbed energy into the depth of the material, we have
to distinguish two processes occurring in successive time intervals. The rst process is
electron thermal diffusion by electron-electron collisions and electron-phonon interactions.
The second interval is reached when electrons and the lattice stayed in thermal equilibrium,
where the common thermal diffusion drives the heat dissipation into the material. Fig.5
shows how the heat-affected zone depends on laser uence. The experimental data come
from Ref. [16]. Considering the effect of pulse width and uence of femtosecond laser on
the electron-phonon relaxation time, the numerical solution of electron thermal diffusion
length is obtained. The numerical solution of the heat-affected zone is plotted in Fig.5. It is
clear that the simulated results are proper to describe the ablation process.
In section II, the effect of pulse width and uence of femtosecond laser on the electron-
phonon relaxation time is studied depending on TTM. As an example of copper target, the
numerical solutions are obtained by solving TTM with a nite difference method. For a
certain laser uence the shorter the pulse width, the shorter the electron-phonon relaxation
time is. However, the electron-phonon relaxation time becomes long for low laser uence
when the pulse width is xed. Furthermore, a quite good agreement of numerical results
with the experimental data has been obtained. This suggests that it is signicant to in-
Figure 5. Dependence of the thickness of heat-affected zone following the laser uence.
vestigate the effect of pulse width and unce of femtosecond laser on the electron-phonon
relaxation time.
3. Improved Two-temperature Model and its Application
in Femtosecond Laser Ablation of Metal Target
This section presents a unied thermal model, which can describe the thermophysical ef-
fects with laser pulse width ranges from nanosecond to femtosecond. Take gold target as
an example, the numerical solutions are obtained from the unied model using a nite dif-
ference method. The temperature distribution of the electron and the lattice along with
space and time at a certain laser uence is presented. The time-dependence of lattice and
electron temperature on the surface for different laser uence is also performed. The satis-
factory agreement between our numerical results and experimental results of vaporization
threshold indicates that the unied thermal model is correct and reasonable.
3.1. The Effect of Temperature on Heat Capacity and Thermal Conductivity
of the Electrons
Normally, the thermophysical properties of electron such as the heat capacity and thermal
conductivity of the electrons are all temperature dependent. The electron heat capacity is
usually a linear function of the electron temperature, given by
C
e
(T
e
) = C
e
T
e
, (9)
where C
e
being a constant.
The electron thermal conductivity can be described by
(T
e
, T
l
) = C
e
2
F
/3, (10)
where
F
is the Fermi velocity, and is the electron momentum relaxation time.
For good conductors, such as metals, the electron-electron collision frequency can be
determined by
ee
= AT
2
e
, whereas the electron-phonon collision frequency is propor-
tional to T
l
, namely,
eph
= BT
l
. Here A and B are constants, and both contribute to
the electron collision frequency . A relationship between the electron momentum relax-
ation time and the electron-electron and electron-phonon collision frequency for electron
temperature below the Fermi temperature is given by [53]
1
= =
ee
+
eph
= AT
2
e
+ BT
l
. (11)
Substituting Eq. (11) into the expression of the electron thermal conductivity, we can
obtain the following equation:
(T
e
, T
l
) =

2
F
C
e
T
e
3
1
AT
2
e
+BT
l
=
0
BT
e
AT
2
e
+ BT
l
, (12)
where
0
=
F
C
e
/(3B) is the electron heat conductivity at room temperature ( T
e
= T
l
=
300K).
3.2. Electron Temperature Dependences of the Absorption Coefcient
and the Absorptivity
It is assumed that a pulsed laser beam irradiates on a target surface vertically. The electric
eld intensity in the target can be described as follows:
E = E
0
exp[i(
x
t)], (13)
E
0
is the electric eld intensity at x = 0, is the incident laser angle frequency, is the
laser propagation velocity in target satisfying the following relation:
= c/n
c
, (14)
where c is the laser propagation velocity in vacuum. n
c
is the complex refractive index,
which can describe the optical characters of material,
n
c
= n + i, (15)
where n is the refractive index, is extinction coefcient.
Substituting Eqs. (14) and (15) into Eq. (13) yields
E = E
0
exp(it) exp(i
xn
c
) exp(
x
c
). (16)
By the operation of module to Eq. (16), we have
[E[
2
= EE
= [E
0
[
2
exp(2
x
c
). (17)
According to Lambert-Beer-Bouguer Law, when laser irradiates the target surface, the
laser intensity attenuates in exponent in the target, which can be expressed by [54]
I(x, t) = I(0, t) exp(bx), (18)
I(0, t) is the intensity of the incident laser, is the absorptivity of the target, b is the
absorption coefcient of the target.
In the target, the intensity equals to the square of the module of the electric led inten-
sity, namely [E[
2
= I(x, t). Based on this relation, comparison of Eq. (17) with Eq. (18)
gives the following relation:
b =
2
c
=
4
c
=
4
0
, (19)
where
0
is the laser wavelength in vacuum.
It is well known that Maxwell equation in the isotropical medium can be described
by[55]
_

E =
0

H
t
,
_

H =

E +
0

E
t
,
_

H = 0,
_

E = 0,
(20)
where and
0
are the magnetic conductivities of the target and vacuum. is the target
conductance, is the target relative permittivity,
0
= 8.85 10
12
C
2
N
1
m
2
is the
permittivity of vacuum.
Substituting Eq. (16) into Eq. (20), we obtain the refractive index n and the extinction
coefcient as the functions of the conductance and the permittivity as follows:
n
2
=
1
2
[1 + (

2
0
)]
0.5
+ 1,
2
=
1
2
[1 + (

2
0
)]
0.5
1,
(21)
where
0
= 8.85 10
12
C
2
N
1
m
2
, is the permittivity of vacuum.
The conductance of general metal is generally in the range 10
8
10
12
1
m
1
, the
relative permittivity is in the range 0-100, and in the the conditions of this section, the laser
angle frequency is 2 10
15
, we can regard that
(

)
2
1.
(22)
So Eq. (13) can be simplied into
n

2
0
, (23)
can be presented as a function of electron temperature T
e
[56]
(T
e
) =

0
1 +(T
e
T
0
)
,
(24)
where
0
is the target conductance at initial temperature T
0
, is the target temperature
coefcient of resistance. For general metal, is in the range 40010
5
70010
5
K
1
[57].
Substituting Eqs. (23) and (24) into Eq. (19) yields
b(T
e
) =
4k
0
=
0
c
=
4
0
0
c[1 + (T
e
T
0
)]
. (25)
This is an important relationship that we derived in this section. From this formula,
it can be found that the absorption coefcient monotonously decreases following target
temperature when the resistance temperature coefcient and irradiated laser wavelength are
both constants.
With the same point of view, we discuss the absorptivity, namely the ratio of the ab-
sorbed intensity to incident intensity. When a laser irradiates a target surface vertically, the
target absorptivity is generally described as follows[56]:
= 1 R = 1
(n 1)
2

2
(n 1)
2
+
2
=
2
2
(n 1)
2
+
2
, (26)
where R is the target reectivity.
Substituting Eqs. (22) and (24) into Eq. (25) gives
(T
e
) = 2
4
0
4c
0
(1 + (T
e
T
0
))
0
.
(27)
This is another important relationship that we derived indicating the relation between
the resistance temperature coefcient, the laser wavelength, the target electron temperature
and the absorptivity.
S(x, t) is the heat source, which can be expressed as follows:
S(x, t) = bI(0, t) exp(bx). (28)
In experiments, the laser beam indeed has a transverse intensity prole. Transverse
mode describes the energy distribution of laser spot. Transverse mode is divided into base
transverse mode and high-order transverse mode. Beam quality of the base transverse mode
is the best. Base transverse mode is Gaussian beam. Gaussian pulse can be used to accu-
rately describe the incident laser intensity[18, 19, 17]. In our section, we adopt the Gaussian
pulse to describe the incident laser:
I(0, t) = I
0
exp[
(4 ln2)t
2
(
p
)
2
], (29)
here I
0
is the maximal laser power density.
Substituting of Eqs. (25), (27) and (29) into Eq. (28), we get the heat source as follows:
S(x, t) = bI(0, t) exp(bx) =
4I
0
0
exp[
(4 ln2)t
2
(
p
)
2
] exp[[
4
0
0
c[1 +(T
e
(x, t) T
0
)]
]
0.5
x],
= C exp[
(4 ln 2)t
2
(
p
)
2
] exp[[
D
1 + (T
e
(x, t) T
0
)
]
0.5
x],
(30)
where C = 4I
0
/
0
, D = 4
0
/
0
0
c.
The effects of the copper d-band on femtosecond laser absorption are discussed in liter-
ature [18]. Copper has a fully-occupied d-band, a few electron-volts below the Fermi level.
The Fermi level is located in the half-occupied, nearly free-electron (NFE) s-band, 7-8 eV
above the bottom of the conductivity band. In copper, the d-band is 3-4 eV wide, and its
upper edge lays 2.0-2.2 eV belowthe Fermi level. Thus, the presence of the d-band does not
affect the NFE character of copper for the 800nm central wavelength of the laser at electron
temperature below 1 eV. It is acceptable that it need not to consider the d-band absorption
for the 800nm central wavelength of the laser at electron temperature below 1 eV [18].
3.3. Verication of Absorption Coefcient Analytic Approximation
In order to verify the validity of the absorption coefcient analytic approximation, we
present a comparison between the experimental results [19] and theoretical predictions for
the absorption. The theoretical predictions include theoretical data of the Maxwell equa-
tions and theoretical data of our analytic approximations. The following are Maxwell equa-
tions for radiation propagation in the medium [18],

H + i
c
(x, t)

E = 0,

E i

H = 0,
(31)
Q(x, t) =
1
2
Re(x, t) [E(X, T)[
2
, (32)
(, x) = 1 + i
4(x, t)
,
(33)
where (, x) is the dielectric permittivity of the target at the incident radiation frequency
, and (x, t) is the conductivity of the target.
The absorption coefcient A is evaluated as [19]
A =
2
0
dt
0
Q(x, t)dx
2
0
I(t)dt
(34)
Figure 6. Comparison of the experimental results with the theoretical predictions for 800
nm wavelength.
Fig.6 presents a comparison between the experimental results and the theoretical pre-
dictions for the absorption of = 800nm wavelength, 50 fs FWHM duration laser pulses
in high-quality commercial Cu targets[19]. Solid curve represents the theoretical data of
the Maxwell equations. Dash dot curve indicates the theoretical data of our analytic ap-
proximations. Fig.6 shows that two different theoretical curves are both consistent with
the experimental data. The two theoretical curves and the experimental curve show the in-
crease movement in absorption. However, there is a big difference between the theoretical
data of our analytic approximations and the experimental data after laser intensity exceeds
3 10
14
W/cm
2
. From the above analysis, we can clearly see that our analytic approxi-
mations are accurate when laser uence is not very high (0.2 0.4J/cm
2
). Our analytic
approximations are not very well for high uence, it should be upgraded to obtain better
approximations in the following research.
3.4. The Improved Two Temperature Model
The original two-temperature model was formulated by S.I. Anisimov et al[58]. The fol-
lowing is the improved two temperature model, which considers the effect of electron tem-
perature on the electron heat capacity, electron thermal conductivity, absorption coefcient
and absorptivity.
C
e
T
e
(T
e
)

t
T
e
=
0
BT
e
AT
2
e
+BT
l
2
x
2
T
e
g(T
e
T
l
) + C exp[
(4 ln2)t
2
(
p
)
2
]
exp[[
D
1 + (T
e
(x, t) T
0
)
]
0.5
x],
(35)
C
l
t
T
l
= g(T
e
T
l
).
(36)
For the Eqs. (27) and (28), the initial condition is
T
e
(x, 0) = T
l
(x, 0) = T
0
, (37)
and the boundary conditions can be expressed as:
k
e
T
e
x
[
x=0
= (1 R)I
0
(t),
(38)
k
e
T
e
x
[
d
= 0,
(39)
where T
0
= 300K is the initial temperature which is uniform across the target, d is the
depth of the target.
3.5. Results and Discussion
Under the initial condition (37) and the boundary conditions (38) (39), Eqs. (35) and (36)
are numerically solved by a nite difference scheme. The thermal and optical properties of
gold in Table 3 are adopted from [59].
Table 2. Thermal and optical properties of copper
coefcient of the electron heat capacity (C
e
) 96.6J/m
3
K
2
lattice heat capacity (C
l
) 3.5 10
6
J/m
3
K
e-ph coupling coefcient (g) 1 10
17
W/m
3
K
electron heat conductivity at room temperature (
0
) 400W/mK
coefcient of e-e collision frequency (A) 1.75 10
7
K
2
S
1
coefcient of e-ph collision frequency (B) 1.98 10
11
K
1
S
1
target temperature coefcient of resistance () 4.3 10
3
K
1
3.5.1. The Time-dependence of Electron and Lattice Temperature of Target
The temporal evolution of the electron and lattice temperatures at the metal surface for
different laser uence is shown in Fig.7. The maximum temperature of the electron tem-
perature at the surface is in the range 5500 8000K for the laser uence varying from
Figure 7. Temporal evolution of electron temperature (a) and lattice temperature (b) at the
surface for the copper target irradiated by a 100fs, 800nm pulse at 0.2J/cm
2
, 0.3J/cm
2
,
0.4J/cm
2
, respectively.
0.2 0.4J/cm
2
. The surface electron and lattice temperature increase with increasing laser
uence. For a xed laser uence, the electron temperature rstly rapidly increases along
with the ablation time, while suddenly decreases when it reaches the maximum in Fig.7(a).
And the temperature of the lattice raises gradually in Fig.7(b).
3.5.2. Ablation rate per pulse as a function of laser uence
In order to argue the correctness of the improved two-temperature model in this section, we
compare our calculated ablation rate with the experimental data and the result of the model
without considering electron temperature-dependent heat capacity, thermal conductivity of
the electron, absorption coefcient and absorptivity, shown in Fig.8. Curve 1 represents
how the ablation rate depends on laser uence based on our model Eqs. (30) and (31).
Curve 2 stands for the model without considering electron temperature-dependent heat ca-
pacity, thermal conductivity of the electron, absorption coefcient and absorptivity. In our
simulation, it is assumed the thermal conductivity of electron to be 318W/mK, specic heat
of electron to be 67.7J/m
3
K, the absorptivity to be 0.06, and the absorption coefcient to
be 7.88 10
5
/m [47].
In the experiment, the intensity autocorrelator and the powermeter at the exit of the
amplier periodically monitored the drifts in the pulse width and output energy in order to
ensure a stable pulse energy on the Cu target. An 80 mm focal length fused silica convex
lens is used to focus the attenuated laser pulses onto the Cu substrate. The pulse width and
the center wavelength are 100fs and 800nm, respectively. The ablation rate is estimated as
an averaged value over 300 sbsequent pulses. The ablation depths after laser ablation are
measured using a mechanical stylus (Dektak-3030)[16]. In the simulation, the pulsewidth
p
and the center wavelength
0
are 100fs and 800nm in the the heat source Eq.(22). The
range of the maximal laser power density I
0
is from 0.1J/cm
2
to 2J/cm
2
.
The details on how the ablation dynamics was modeled are given as follow: When the
femtosecond laser irradiates the target, it takes a few femtosecond for electrons to absorb the
Figure 8. Dependence the ablation rate on the laser uence, curve (numerical data 1)
represents the improved model, see text in detail.
laser energy through electron-photon interactions. Within the duration of a single femtosec-
ond pulse, the change of lattice temperature is generally negligible. Then the energy will
be distributed from the electrons to lattice through electron-phonon interactions. The lattice
reaches to the same temperature as electrons temperature, eventually. When the electron
temperature and lattice temperature are equal, the common thermal diffusion drives the heat
dissipation into the material. The electron temperature and the lattice temperature are both
functions of target depth x and time t, that is to say, T = T(x, t). x refers to the spatial co-
ordinate in the direction perpendicular to the target surface. The ablation rate is the depth x
when the lattice temperature reaches the boiling point, 2811 K for copper in the simulation
[16].
Fig.8 displays the relationship between the ablation rate and laser uence. The ablation
rate is estimated from the depth which becomes heated above the boiling point, 2811 K for
copper in the simulation [16]. Both curves 1 and 2 ascend with the increasing time. As
curve 1 takes into account the effect of the variation of heat capacity, thermal conductivity
of the electron, the absorption coefcient and the absorptivity, it is obviously higher than
curve 2 for the increment of absorbed energy. The experimental data come from Ref.[16].
Obviously, this gure shows a better agreement between our model (curve1) and the exper-
iment than curve 2.
Hirayama and Obara said that the MD simulation results are not well consistent with
the experimental results of the ablation rate in their paper[16]. They also explained that
the difference in the ablation rate between the experiment and the simulation may be due
to optical parameters of the material, especially the absorption coefcient which has been
considered as constant. They indicated that the absorption coefcient may be changed due
to the heating up of the laser-irradiated surface[16].
In our section, based on the electron-phonon and electron-electron collision frequency,
we can obtain the temperature-dependent heat capacity and thermal conductivity of the
electron. The electron temperature-dependent absorption coeffcient and absorptivity can
be deduced through a combination of optical properties of solids and Maxwells law. The
temperature-dependent heat capacity and thermal conductivity of the electron, as well as
electron temperature-dependent absorption coeffcient and absorptivity are all considered
in this improved two-temperature model. The tailored two-temperature model is solved
using a nite difference method. It is very easy to precisely dene the initial and boundary
conditions in the nite difference method. The simulation results of the ablation rate are
consistent with the experimental results.
In section III, in order to describe femtosecond laser ablation of metal target, an im-
proved thermal model considering electron temperature-dependent heat capacity, thermal
conductivity of the electron, absorption coefcient and absorptivity has been developed in
this section. The present model is used to simulate femtosecond laser ablation of copper
target. The satisfactorily good agreement between our numerical results and experimental
results of ablation depth conrms that the tailored model is a much more satisfactory theo-
retical framework in femtosecond laser ablation of metal target. The analysis to the ablation
characteristics is important to understand the basic mechanisms involved in the femtosec-
ond laser-target interaction. We hope the present model will be helpful for the experimental
investigation of the application of femtosecond laser.
4. A Unied Thermal Model of Thermophysical Effects with
Pulse Width from Nanosecond to Femtosecond
This section presents a unied thermal model, which can describe the thermophysical ef-
fects with laser pulse width ranges from nanosecond to femtosecond. Take gold target as
an example, the numerical solutions are obtained from the unied model using a nite dif-
ference method. The temperature distribution of the electron and the lattice along with
space and time at a certain laser uence is presented. The time-dependence of lattice and
electron temperature on the surface for different laser uence is also performed. The satis-
factory agreement between our numerical results and experimental results of vaporization
threshold indicates that the unied thermal model is correct and reasonable.
4.1. The Unied Model
4.1.1. Physical background
When laser irradiates the target, the rst stage is the absorption of the laser energy through
photon-electron interactions. It takes a few femtoseconds for electrons to reestablish the
Fermi distribution. The second stage is the energy distributionto the lattice through electron-
phonon interactions, the characteristic scales of which is called the electron-phonon cou-
pling time, typically on the order of tens of picoseconds [20].
For nanosecond laser, the pulse width of which is much more than the electron-phonon
coupling time. This kind of ablation is called thermal equilibrium ablation. However, the
ablation undergoes nonequilibrium process for the femtosecond laser due to that the pulse
width is less than the electron-phonon coupling time. As for the picosecond laser ablated
process, the corresponding mechanism is very complex due to both of the two ablation
mechanisms are coexisting.
We can learn that the ratio of the electron-phonon coupling time and laser pulse width
is the important criteria. As
R

L
, i.e., exp[a
L
] 0, the ablation is nonequilibrium
ablation. Our unied model changes into the simplied two temperature model which can
represent the phenomenon of nonequilibriumablation. When
R

L
, i.e., exp[a
L
]
1, it is equilibriumablation. The unied model can be transferred into the classical equation
of one-dimensional heat-conduction, and the equilibrium ablation can also be described
by this model. However, if
R

L
, i.e., 0 < exp[a
L
] < 1, it is the mix ablation
including equilibrium and nonequilibrium ablation, the complicated ablation mechanism
can be presented by our unied model as well. Therefore, an exponential term is inserted
in the TTM model to make it valid from fs to ns pulse duration.
4.1.2. The contents of our model
The following equations are the unied thermal model, which can describe the thermophys-
ical phenomenon of laser ablation process with laser pulse width ranges from nanosecond
to femtosecond:
C
e
t
T
e
= k
e
exp[a
L
]

2
x
2
T
e
g(T
e
T
l
) + (1 R)
b
I
0
(t) exp(
b
x),
(40)
C
l
t
T
l
= g(T
e
T
l
),
(41)
where T
e
and T
l
are the electron and lattice temperature, respectively. C
e
and C
l
are the
specic heat of electron and lattice. k
e
is the thermal conductivity of electron. g is the
electron-phonon coupling coefcient. R and
b
are the reectance and the absorption co-
efcient of the target, respectively. a is an undetermined coefcient, which is variant for
different material. The value of a is determined by tting theoretical results to experimental
data. The effect of the thermal excitation of electrons on the thermophysical properties is
sensitive to the details of the electron structure of the target material. However, when T
e
is below 3000K, the inuence of the thermal excitation of electrons on the C
e
and k
e
is
very little [60]. On the other hand, when we deal with melting, and in order to simplify the
problem to stress the unied model, it is necessary to assume C
e
and k
e
are independent of
the electron temperature. Since in metal the thermal conduction is dominated by electron,
the diffusion term can be neglected for lattice in Eq. (41) [10].
In order to describe the incident laser intensity more accurately, we adopt a Gaussian
pulse of duration
p
(FWHM) with an intensity [11]:
I
0
(t) = I
0
exp[
(4 ln2)t
2
(
p
)
2
], (42)
here I
0
is the maximal laser power density.
When
R

L
, i.e., exp[a
L
] 0, Eqs. (40) and (41) can be transferred into
C
e
t
T
e
= g(T
e
T
l
) + (1 R)
b
I
0
(t) exp(
b
x),
(43)
C
l
t
T
l
= g(T
e
T
l
),
(44)
they are the equations of the simplied two temperature model (TTM).
For the long pulses, the ablation is thermal equilibrium process, i.e., T
e
= T
l
= T, so
Eq. (41) can be neglected. Under the condition that
R

L
, i.e., exp[a
L
] 1, Eq.
(40) can be changed into
C
v
t
T = k

2
x
2
T + (1 R)
b
I
0
(t) exp(
b
x),
(45)
where C
v
= C
e
+C
l
, k and T are the specic heat, the thermal conductivityand the temper-
ature of the target, respectively. Eq. (45) becomes the classical equation of one-dimensional
heat-conduction. The rst one of the right part in Eq. (45) is the heat-conduction term of
the target.
When 0 < exp[a
L
] < 1, it is the mix process including equilibriumand nonequilib-
rium ablations. Therefore, the unied thermal model can well describe the whole thermal
conduction phenomenon with laser pulse width ranged from nanosecond to femtosecond
timescale.
For the Eqs. (40) and (41), the initial condition is
T
e
(x, 0) = T
l
(x, 0) = T
0
, (46)
and the boundary conditions can be expressed as follows,
k
e
T
e
x
[
x=0
= (1 R)I
0
(t),
(47)
k
e
T
e
x
[
= 0,
(48)
where T
0
= 300K is the initial temperature which is uniform across the target. is the
thermal diffuse depth. In terms of the low-uence ablation case, it has been considered that
the number density of the hot electrons is low enough that the energy transfer occurs only
within the area characterized marked by the skin depth = 1/
b
. However, if the laser
uence is very high, the electron thermal diffusion length should be =
k
e
C
e
R
[49] .
4.2. Results and Discussions
Under the initial condition (46) and the boundary conditions (47) (48), Eqs. (40) and (41)
are numerically solved by a nite difference scheme. The thermal and optical properties of
gold in Table 3 are adopted from Refs. [53, 49, 20, 5].
Table 3. Thermal and optical properties of gold
wavelength() 1053nm
thermal conductivity of electron (k
e
) 318W/mK
specic heat of electron (C
e
) 67.7J/m
3
K
specic heat of lattice (C
l
) 2.30 10
6
J/m
3
K
absorption coefcient (
b
) 7.88 10
5
m
1
reectance (R) 0.94
e-ph coupling coefcient (g) 2.1 10
16
Wm
3
K
1
the electron-phonon coupling time (
R
) 6ps
Figure 9. Damage threshold uences versus pulse width for the gold target irradiated by
1053nm pulse(experimental and computed modeling results).
4.2.1. Determination of the value of a
Damage threshold uences versus the pulse width for gold is presented in Fig.9. The pulse
width dependence of threshold uences measured by Stuart et al. on a 200-nm-thick gold
with laser pulses is generated by a 1053nm Ti:sapphire CPA system. The front end of the
system produced 1-ns stretched pulses as much as 60 mJ at 10 Hz in a TEM
00
Gaussian
mode. The pulses were then compressed in a single-grating compressor of variable length.
Pulses of continuouslyadjustable duration from 300 fs to 1ns can be obtained by varying the
dispersive path length of the compressor. The energy delivered to the damage sample was
adjusted with a half-wave plat before compression. The energy of each pulse was recorded
from calibrated leakage through a mirror. After irradiation, Nomarski microscopy was used
to inspect the sample for damage. The denition of damage includes any visible permanent
modication to the surface observable with the Nomarski microscopy [1].
The simple one-dimension heat-conduction model is used to predict the dependence of
damage threshold on the laser pulse width[1]. The data of the damage threshold only can be
obtained by the heat-conduction model including the heat source term. But the heat source
term is not included in this heat-conduction model, so the damage thresholds can not be
given by the model. However, our unied model includes the heat source term and also
describes the phenomenon of two temperature in the electron and lattice for ultrashort pulse
duration. From Fig.1, we can nd the calculated data of damage threshold from our unied
model increase with the increment of laser pulse width. Especially for ultrashort pulse
duration, our unied model can give the evolvement of damage threshold along with the
laser pulse width. By assuming the damage starts when the maximum lattice temperature
reaches the melting point, 1337.33K for gold [20] in the simulation, the value of a can be
determined as 0.67 through tting the experimental results with computed results.
The absorptance A = 1 R of a pure metal consists of two components, A =
A
INTR
+ A
SR
. A
INTR
is the intrinsic absorptance and A
SR
is the contribution due to
surface roughness. For an optically smooth metal surface, the order of A
SR
is about 12%
of A
INTR
while the role of A
SR
enhances as the surface roughness increases. In Fig.9,
each data point originates from typically 600 shots on one spot. However, for multipulse
ablation, only the rst laser pulse interacts with an undamaged surface. All the subsequent
laser pulses interact with a structurally modied surface and their absorption is determined
by both A
INTR
and A
SR
. For lowpulse duration (i.e., less than 10 ps), the modied surface
is obscure, the value of A
SR
is very small. On the other hand, the modied surface is obvi-
ous for larger pulse duration, so the value of A
SR
becomes bigger accordingly when pulse
width is longer than 10 ps [30]. In our simulation, we only take into account the intrinsic
absorptance A
INTR
without considering A
SR
. So for pulse duration longer than 10 ps, the
theoretical data are a little bit higher than the experimental ones.
For low pulse duration (i.e., less than 10 ps), the electron temperature is much higher
within the ultrashort pulse duration. Within the duration of a single ultrashort pulse, the
change of lattice temperature is generally negligible. Both C
e
and k
e
are functions of the
electron temperature, C
e
= A
e
T
e
and k
e
= K
e,0
T
e
/T
l
. The constants A
e
= 71Jm
3
K
2
and K
e,0
= 318Wm
1
K
1
is for the gold target [10]. In our simulation, it is assumed that
C
e
and k
e
are independent of the electron temperature. Due to the constant electron heat
capacity and electron heat conductivity, the electron temperature in the surface region of the
irradiated target can be transiently brought to higher values [60]. Therefore, the theoretical
data are always below the experimental ones.
4.2.2. The evolvement of vaporization threshold uence with laser pulse width
As shown in Fig.10, it presents the relations of vaporization threshold uence and laser
pulse width. In the experiment, the threshold for vaporization was studied across the pulse
range from 150fs to 7ns using laser radiation at 770 nm. Such a laser (770 nm) was used in
the experiment where the oscillator is pumped with an argon-ion laser and the amplier with
a doubled Nd:YAGoperating at 10 Hz repetition rate. The energy of each pulse is measured
Figure 10. Vaporization threshold uence versus pulse width for the gold target irradiated
by 770nm pulse(experimental and computed modeling results).
by the photodiode and is stored along with the integrated optical emission from that pulse.
Experimental vaporization threshold, as a function of pulse width, is determined by the
extrapolation technique. The extrapolation technique produces a threshold that is dened as
the uence needed to bring the system up to, but not actually at, the onset of electronically
excited vapor as observed with a photomultiplier tube (PMT) [5]. The vaporization will
start when the maximum lattice temperature reaches the vaporization temperature ( 2873K
for gold in the simulations).
The calculated data of vaporization threshold on the laser pulse width are presented by
calculation of the one-dimension heat-conduction model including the heat source term [5].
Nonequilibrium process between electrons and lattice is already signicant for ultrashort
pulses, in which the electron temperature can be much higher than the one of the lattice
[20]. The corresponding thermophysical effects must be described by TTM. The data cal-
culated by the one-dimension heat-conduction model are not change with the pulse width
for ultrashort pulses. However, the experimental data vary with the increment of the pulse
width. The calculated data from our unied model increase with the pulse width. It is
shown that the theoretical results accord with the experimental data approximately. It can
be proved that the unied thermal model is available to describe the thermal phenomenon
of laser ablation with laser pulse width ranges from nanosecond to femtosecond.
In section IV, a unied thermal model which can describe the thermophysical phe-
nomenon with laser pulse width ranges from nanosecond to femtosecond is presented in
this section. As an example of gold target, the numerical solutions are obtained by solv-
ing the heat ow equations using a nite difference method. The parameter of the unied
thermal model is determined through comparing theoretical and experimental value of dam-
age threshold uence with laser pulse width ranges from nanosecond to femtosecond time
regime. The temperature of electron and lattice which is dependent on space and time in
target at a certain laser uence is presented. The time-dependence of lattice and electron
temperature for different laser uence is performed. The satisfactory agreement between
our numerical results and experimental results of vaporization threshold uence indicates
that the unied thermal model is reasonable.
5. Conclusion
We have reviewed our recent research work on Thermophysical effects of femtosecond
laser ablation of metal target. The effect of pulse width and uence of femtosecond laser
on the electron-phonon relaxation time is studied depending on TTM. In order to describe
femtosecond laser ablation of metal target accurately, an improved thermal model consid-
ering electron temperature-dependent heat capacity, thermal conductivity of the electron,
absorption coefcient and absorptivity has been developed in this chapter. This chapter
also presents a unied thermal model, which can describe the thermophysical effects with
laser pulse width ranges from nanosecond to femtosecond.
6. Ackowledgments
This work was supported by the National Natural Science Foundation of China through
Grant Nos.10904177,11004257,10804132, Natural Science Foundation Project of CQCSTC
2010BB9404, and by the Scientic Research Foundation for Doctor of Chongqing Univer-
sity of Posts and Telecommunications No. A2009-15.
References
[1] B.C. Stuart, M.D. Feit, S. Herman, A.M. Rubenchik, B.W. Shore and M.D. Perry,
J.Opt.Soc.Am. B 13, 459 (1996).
[2] M.E. Povarnitsyn, T.E. Itina, M. Sentis, K.V. Khishchenko, and P.R. Levashov, Phys.
Rev. B 75, 235414 (2007).
[3] J. Bonse, G. Bachelier, J. Siegel, and J. Solis, Phys. Rev. B 74 134106
[4] P. Lorazo, L.J. Lewis, M. Meunier, Phys. Rev. Lett. 91, 225502 (2003).
[5] P.P. Pronko, S.K. Dutta and D. Du, J. Appl. Phys. 78(10), 6233 (1995).
[6] R.R. Fang, D.M. Zhang, H. Wei, D.Z. Hu, Z.H. Li, X.Y. Tan, M. Sun, Eur. Phys. J.
Appl. Phys. 42, 229 (2008).
[7] R.R. Fang, D.M. Zhang, H. Wei, Z.H. Li, F.X. Yang, X.Y. Tan,Eur. Phys. Chin. Phys.
Lett. 25(10), 3716 (2008).
[8] R.R. Fang, D.M. Zhang, H. Wei, Z.H. Li, F.X. Yang, y.H. Gao, Laser Part. Beams 28,
157 (2010).
[9] S. Preuss, A. Demchuk, M. Stuke, Appl. Phys. A 61, 33 (1995).
[10] S.-S. Wellershoff, J. Hohlfeld, J. G udde and E. Matthias, Appl. Phys. A 69, S99
(1999).
[11] S. Amoruso, G. Ausanio, R. Bruzzese, M. Vitiello, and X. Wang, Phys. Rev. B 71,
033406 (2005).
[12] S. Amoruso, R. Bruzzese, N. Spinelli, R. Velotta, M. Vitiello, X. Wang, G. Ausanio,
V. Iannotti, and L. Lanotte, Appl. Phys. Lett. 84, 4502 (2004).
[13] D. B auerle Laser Processing and Chemistry, 3rd ed., Springer, Berlin, 2000
[14] D.B. Chrisey, G.K. Hubler(Eds.), Pulsed Laser Deposition of Thin Films, Wiley, New
York, 1994
[15] S. Bashir, M.S. Raque, and F. Ul-haq, Laser Part. Beams 25, 181 (2007).
[16] Y. Hirayama and M. Obara, J. Appl. Phys 97, 064903 (2005).
[17] E.G. Gamaly, N.R. Madsen, M. Duering, A.V. Rode, V.Z. Kolev, and B. Luther-
Davies, Phys. Rev. B 71, 174405 (2005).
[18] D. Fisher, M. Fraenkel, Z. Zinamon, Z. Henis, E. Moshe, Y. Horovitz, E. Luzon, S.
Maman and S. Eliezer, Laser Part. Beams 23, 391 (2005).
[19] D. Fisher, M. Fraenkel, Z. Henis, E. Moshe and S. liezer, Phys. Rev. E 65, 016409.
(2001).
[20] L. Jiang, H.L. Tsai, J. Heat. Trans. 127, 1167 (2005).
[21] B.M. Mirdan, H.A. Jawad, D. Batani, V. Conte, T. Desai, and R. Jafer, Laser Part.
Beams 27, 103 (2009).
[22] T. Ozaki, L.E. Bom, and R.A. Ganeev, Laser Part. Beams 26, 235 (2008).
[23] T. Ozaki, L.B.E. Bom, R. Ganeev, J.C. Kieffr, M. Suzuki, and H. Kuroda, Laser Part.
Beams 25, 321 (2007).
[24] M.S. Trtica, B.B. Radak, B.M.Gakovic, D.S. Milovanovic, D. Batani, and T. Desal,
Laser Part. Beams 25, 321 (2009).
[25] S. Amoruso, G. Ausanio, R. Bruzzese, L. Gragnaniello, L. Lantte, M. Vitiello, and X.
Wang, Appl. Surf. Sci. 252 4863 (2006).
[26] S.D. Brorson, A. Kazeroonian, J.S. Moodera, D.W. Face, T.K. Cheng, E.P. Ippen,
M.S. Dresselhaus, and G. Dresselhaus, Phys. Rev. Lett. 64, 2172 (1990).
[27] W.S. Fann, R. Storz, H.K. Tom and J. Bokor, Phys.Rev.B 46 13592 (1992).
[28] C.K. Sun, F. Vallee, L. Acioli, E.P. Ippen and J.G. Fujimoto, Phys.Rev.B 48 12365
(1993).
[29] C.K. Sun, F. Vallee, L. Acioli, E.P. Ippen and J.G. Fujimoto, Phys.Rev.B 50 15337
(1994).
[30] A.Y. Vorobyev and C.L. Guo, Phys.Rev.B 72, 195422 (2005).
[31] Arun Inam, X.D. Wu, T. Venkatesan, S.B. Ogale, C.C. Chang, and D. Dijkkanp,
Appl.Phys. Lett. 51,1112 (1987).
[32] D.M. Zhang, L. Li, Z.H. Li, L. Guan, S.P. Hou and X.Y. Tan, Acta Phys. Sin. 54 1283
(2005).
[33] Y.C. Lan, D.V. Tran, and H.Y. Zheng, Laser Part. Beams 25, 155 (2007).
[34] D.M. Zhang, L. Li, Z.H. Li, Eur. Phys.J-Appl. Phys. 33, 91 (2006).
[35] S. Amoruso, G. Ausanio, R. Bruzzese, L. Gragnaniello, L. Lanotte, M. Vitiello, X.
Wang, Appl. Surf. Sci. 252, 4863 (2006).
[36] X. Zeng, X.L. Mao, R. Greif, R.E. Russo, Appl. Phys. A7180, 237 (2005).
[37] C.H. Crouch, J.E. Carey, J.M. Warrender, M.J. Aziz, E. Mazur, Appl. Phys. Lett. 84,
1850 (2004).
[38] Q.M. Lu, Phys. Rev. E 67, 016410 (2003).
[39] Q.M. Lu, S.S. Mao, X.L. Mao, R.E. Russo, Appl. Phys. Lett. 80, 3072 (2002).
[40] Q.M. Lu, S.S. Mao, X.L. Mao, R.E. Russo, Proceedings of the SPIE - The Interna-
tional Society for Optical Engineering, 4760, 959 (2002).
[41] J.G. Lunney, R. Jordan, Appl. Surf. Sci. 127-129, 941 (1998).
[42] S. Amoruso, M. Armenante, R. Bruzzese, N. Spinelli, R. Velotta, and X. Wang, Appl.
Phys. Lett. 75, 7 (1999).
[43] V. Craciun and D. Craciun, Appl. Surf. Sci. 138-139, 218 (1999).
[44] D.M. Zhang, D. Liu, Z.H. Li, Appl. Surf. Sci. 253, 6144 (2007).
[45] D.M. Zhang, X.Y. Tan, Z.H. Li, Physica B 357, 348 (2005).
[46] R.R. Fang, D.M. Zhang, Z.H. Li, phys.stat.sol(a) 204,(12) 4241 (2007).
[47] G.L. Eesley, Phys. Rev. B 33, 2144 (1986).
[48] S. Nolte, C. Momma, H. Jacobs, A. T unnermann, B.N. Chichkov, B. Wellegehausen
and H. Welling, J. Opt. Soc. B 14, 2716 (1997).
[49] K. Furusawa, K. Takahashi, H. Kumagai, K. Midorikawa and M. Obara, Appl. Phys.
A 69, S359 (1999).
[50] N.N. Nedialkov, S.E. Imamova and P.A. Atanasov, J. Phys. D: Appl. Phys. 37, 638
(2004).
[51] J.G. Fujimoto, J.M. Liu, E.P. Ippen, and N. Bloembergen, Phys. Rev. Lett. 53, 1837
(1984).
[52] T. Hertel, E. Knoesel, M. Wolf, and G. Ertl, Phys. Rev. Lett.76, 535 (1996).
[53] J.C. Wang and C.L. Guo, Appl. Phys. Lett. 87, 251914 (2005).
[54] P. Andrea, M. Antonio and K. Roger, Phys. Rev. E 50 4716 (1994).
[55] S. Guo, Electric Dynamic, Higher Education Publishing Company.(1997).
[56] C.K. Sun, The Effect of Laser Irradiation, National Defence Industry Press, Bei-
jing.(2002).
[57] B.H. Billings, H.P.R. Frederikse, American Institute of Physics Handbook. 3rd ed.,
McGraw-Hill, New York.(1972).
[58] S.I. Anisimov, B.L. Kapeliovich, and T.L. Perelman, Sov. Phys. JETP 39:375 (1974).
[59] H.E. Elsayed-ali, T.B.Norris, M.A. Pessot and G.A. Mourou, Phys.Rev.Lett. 58,1212
(1987).
[60] Zhibin Lin, Leonid V. Zhigilei, Appl. Surf. Sci. 253, 6295 (2007).
Chapter 8
FORMATION OF NANOPARTICLES UNDER
LASER ABLATION OF SOLIDS IN LIQUIDS
G. A. Shafeev
Wave Research Center, Prokhorov General Physics Institute,
Russian Academy of Sciences, Moscow, Russia
ABSTRACT
The process of nanoparticle formation under laser ablation of solids in liquids is
described. Critical parameters are discussed that govern the properties of nanoparticles
ejected into the surrounding liquid. These parameters are laser wavelength, pulse
duration, interaction of individual nanoparticles with laser beam inside the liquid. A
review of previous results is presented on the properties of nanoparticles of noble metals.
Recent data on laser-assisted generation of other metals is given, including the formation
of alloyed nanoparticles. Micro- and nanostructuring of the target upon its laser ablation
in liquid environment is discussed. Examples are given of the influence of the
surrounding liquid on the chemical composition of generated nanoparticles. The laser
control over the size distribution of nanoparticles in liquids is demonstrated either by
spatial profiling of laser beam intensity or proper tuning of laser wavelength into plasmon
resonance of nanoparticles. Recent results are given on excitation of high energy levels of
media under laser exposure to laser pulses of picosecond range of duration.
INTRODUCTION
The advent of lasers opened a new branch of research of interaction of radiation with
matter. The primary eye-visible effect of laser action on a solid target is removing of some
material from the target surface within the laser spot. This process was called laser ablation
from a Latin word ablatio, which means removal.
The process of laser ablation of solids in liquids has attracted much attention of
researchers during the last decade. This is due mainly to the simplicity of the experimental
G. A. Shafeev 192
setup. Many modern laboratories (and not only physical ones) are equipped with lasers, and
synthesis of nanoparticles is a strong temptation. The process proceeds in one step and results
in immediate formation of nanoparticles in the liquid in which the target is immersed. The
main feature of the process is that ideally the liquid contains only nanoparticles made of the
target material and the liquid. There are no counter-ions or residuals of reducing agents left in
the solution. For this reason laser ablation of solids in liquids can be considered as a method
of nanoparticle synthesis, which is an alternative to chemical methods.
Commercially available laser sources are characterized by a number of parameters, such
as peak power, average power, wavelength of emission, pulse repetition rate, etc. If the final
purpose of ablation of a target immersed into a liquid is the synthesis of nanoparticles with
desired properties, such as their chemical composition, size distribution, concentration, etc.,
then the above mentioned laser parameters are of different importance to the properties of
desired nanoparticles. Also, the nature of the liquid plays a significant role in the final
properties of nanoparticles generated under laser ablation.
The objective of this text is to outline the relative importance of various experimental
parameters to the properties of nanoparticles synthesized by laser ablation of a solid target
immersed into a liquid.
General Setup of Laser Ablation in Liquids
Figure 1 shows a generalized setup of experiments on laser ablation of solids in a liquid
environment. This setup may vary from one research group to another, though their common
features are the same.
Laser radiation is focused onto a solid target immersed in a liquid. It is assumed that the
liquid is transparent at the laser wavelength, otherwise the focalization of the beam would be
problematic due to absorption of laser radiation in it. The simplest way is working with the
free surface of the liquid, which allows avoiding additional reflection at the interface
covering glass/air. However, the use of volatile liquids, such as acetone, ethanol, etc.,
requires covering the liquid with a window that is transparent at the laser wavelength.

Figure 1. Experimental setup for laser ablation of solids in a liquid environment
Formation of Nanoparticles under Laser Ablation of Solids in Liquids 193
EXPERIMENTAL TECHNIQUE
The experimental setup for laser ablation in a liquid environment is perfectly simple. It is
usually assumed that the liquid that surrounds the solid target is transparent at laser
wavelength while the laser radiation is absorbed by the target. A solid target is placed under a
thin (several millimeters) layer of liquid and is exposed to laser radiation through this layer.
Different pulsed laser sources can be used, e.g., a Nd:YAG laser at 1.06 m output and its
harmonics, a Cu vapor laser, a Ti:sapphire laser, etc. UV excimer lasers are less common,
since most liquids and NP absorb in the UV region. The only necessary requirement is that
the laser beam is sufficiently powerful to induce local melting of the target. Usually the laser
beam is focused onto the target using an appropriate optics to a certain size of laser spot (see
Figure 1). In some experiments the target is rotated under the laser beam to avoid the
exposure of the same area. Some research uses a sealed-off cell to avoid oxidation of NP by
air oxygen, but basically the setup is the same. It is the density of the laser energy (in J/cm
2
),
or so-called fluence, that determines the temperature of the target and the possibility to
produce surface melting and eventual generation of NP. The irradiation of the metal surface
results in fast removal of the material that is confined to the laser spot. The ejected
nanoparticles remain in the liquid that surrounds the target, resulting in formation of a so-
called colloidal solution. Unlike real solutions that contain ionic or molecular species,
colloidal solutions also contain particles, e.g., NP and clusters. Due to accumulation of NP in
the surrounding liquid, their prolonged interaction with laser radiation is possible. Therefore,
the thickness of the liquid layer above the target is also an important experimental parameter
that may influence the properties of generated NP.
Different laser parameters are of different importance to the efficiency of NP generation.
1. Pulse Duration
Usually, pulsed laser sources are used for generation of NP in liquids with pulse duration
from hundreds of femtoseconds to hundreds of nanoseconds. The NP under laser ablation in
liquids are formed owing to sputtering of the molten layer by the recoil pressure of the liquid
that surrounds the target. Therefore, the necessary condition of NP synthesis is melting of the
target material. In general, the temperature distribution under laser exposure of solids can be
found solving a heat conduction equation with corresponding boundary conditions. However,
in the case of short laser pulses of the duration mentioned above, the complicated problem of
temperature calculation can be significantly simplified. This simplification is based on the
fact that the heat diffusion length l
d
from laser-exposed areas of the target during the duration
of the laser pulse t
p
is small compared to laser spot size d. Indeed, in a typical experiment on
pulsed laser ablation d ~ 10 m, while the heat diffusion length is much less. Assuming that
the laser beam has a flat-top profile (typical of excimer lasers, metal vapor lasers, etc.) one
may suggest that the absorbed laser energy is spent for heating of the target layer whose
thickness is of order of (at
p
)
1/2
, where a stands for the heat diffusion coefficient of the target
material, while the area of this layer coincides with the laser spot. Unlike to what one might
believe, the presence of liquid around the target does not alter noticeably the temperature
inside the laser spot. The reason is that the heat diffusion coefficient for liquids is even
G. A. Shafeev 194
smaller than that of solids. Presence of the liquid may affect only the average temperature rise
of the target if the repetition rate of laser pulses is elevated, e.g., of order of 1 kHz and more.
Simple heat balance equation leads for the following expression of the temperature T within
the laser spot:

h c
Aj
T
,
where A stands for absorptivity of the target at the laser wavelength, A = 1- R, where R is the
reflectivity coefficient at laser wavelength, c stands for heat capacity of the target material,
is density of the target material, and h is the heat diffusion length inside the target. One can
see that in a quite natural way the temperature is proportional to the energy density of the
laser beam, or so called fluence j. The heat diffusion length h depends on the heat diffusivity
of the target material:

p
at h ,
where in turn a = k/c , where k is the heat conduction coefficient of the target, and t
p
stands
for laser pulse duration. The longer is the laser pulse t
p
, the thicker is the layer of the material
which is heated by absorbed laser energy. The above-made estimation of the temperature rise
T is made assuming superficial absorption of laser radiation. If is the coefficient of
absorption of laser radiation, then this condition can be written as follows:

-1
<< h
Of course some energy is consumed for heating and evaporation of a liquid adjacent to
the laser spot, but this energy is small compared to the absorbed one due to low thermal
conductivity of liquids.
In case of metal targets laser radiation is absorbed by free electrons that transfer their
energy to the metal lattice within 3- 5 picoseconds. Virtually no heat exchange with the bulk
of the solid target occurs, and the absorbed laser energy is spent for heating of the layer
within the absorption depth
-1
of laser radiation.
The absorptivity A of the target surface is a complex parameter. For a smooth metallic
surface it can be calculated using reference data on both real and imaginary part of a complex
dielectric function of the material. However, as soon as the surface of the target is not flat and
is characterized by a certain relief, the absorptivity of the target may largely deviate from its
theoretical value. This is due to the dependence of absorptivity on the angle of incidence of
radiation. Since the target material is dispersed into surrounding liquid as nanoparticles
during laser ablation in liquids, the formation of the relief indeed occurs.
2. Laser Wavelength
As soon as laser ablation of metals is considered, any wavelength is appropriate.
However, laser radiation can be absorbed by NP that are generated under ablation of the
target. The majority of NP absorb in UV region, which imposes certain drawback on the use
of excimer UV lasers for generation of NP.
3. Repetition Rate
Nanoparticles are ejected from the solid target at each pulse provided that the absorbed
laser energy is sufficient to melt it. Therefore, the higher is the repetition rate of laser pulses,
the higher is the rate of NP generation. However at high repetition rate the target may be
screened from the beam by gas bubbles that have remained from previous pulses. This can be
avoided using either a flow cell or elevated velocity of scanning (rotation) of the target.
HISTORICAL REVIEW
Formation of nanoparticles under laser ablation of solids either in gas or in vacuum has
been extensively explored during the last decade. Understanding of the mechanisms of cluster
formation is needed to control the process of Pulsed Laser Deposition (PLD) that is widely
used now for deposition of a large variety of compounds. Formation of nanoparticles under
laser ablation of solids in liquid environment has been studied to a lower extent. A number of
wet chemical methods of nanoparticles (NP) preparation are known up to date. Laser ablation
of solids in liquid environment emerged as an alternative technique that is capable of
producing pure NP without counter-ions and surface-active substances. Primary motivation
for generation of NP by laser exposure of solid targets in liquids was the hope that pure NP
would be more efficient in the process of Surface Enhanced Raman Scattering (SERS), since
no other compounds can obscure the surface of a metallic NP [1-5]. Formation of both large
variety of NP under laser ablation of corresponding solids has been reported during the last
decade [6-17]. Further studies showed that the laser ablation in liquids is a complex process
with a number of experimental parameters. In particular, chemical interaction of ejected nano-
sized species with hot liquid vapors at high transient pressure results in large diversity of final
particles that remain in the liquid. Also, surface tension at the interfaces is dominant force
that governs the dynamics of interaction of molten target material with vapors of surrounding
liquid on a nanometer scale. Under pulsed laser exposure the liquid also undergoes chemical
changes that may be stipulated by ejected NP that act in this case as a catalyst. Initially liquid
substance may become supercritical in the vicinity of the target, which alters its reactivity and
opens new channels of chemical reactions especially in case of aqueous solutions.
Interaction of metal nanoparticles with laser light proceeds via its absorption by free
electrons. Free electrons exhibit plasmon resonance, whose position is determined by both
their concentration, their effective mass (that depends on the solid) and particle size. NP of
noble metals, e.g., Au or Ag, show a strong selective absorption in the visible, so the
suspensions of these NP in liquids are colored. Plasmon resonances of other metallic NP are
G. A. Shafeev 196
situated in the UV region [18, 19]. Though if the liquid is transparent at the onset of laser
exposure of the target, the appearance of NP may change this situation, and the laser radiation
is absorbed by the colloidal solution. This may lead to poor control of the laser spot size on
the target due to either thermal lensing inside the solution or different non-linear phenomena
induced by laser beam in NP [20-22]. So, the thickness of the liquid layer above the target is
also one of the experimental parameters that are essential during ablation in liquids.
Depending on the dwell time of the laser beam on the target, a more or less significant
amount of the target material is transferred into the surrounding liquid as NP. The target relief
is therefore modified, and a crater is formed in the target in case of its exposure to a stationary
laser beam. To avoid the formation of the crater the target is either rotated or is scanned under
the laser beam. However, a periodic relief arises on the target surface at sufficiently high
number of laser shots of order of 10
4
. The structures are densely packed micro-cones, and
their period linearly varies with the size of laser spot on the target as shown in Figure 2 [23].
These micro-cones are separated by long channels with high aspect ratio that run deep
inside the target body. The formation of these micro-structures alters the properties of NP
generated by laser ablation, since the conditions of vapor expansion inside the channels are
different from those on a flat solid-liquid interface. In other words, the molten areas of the
target are no longer on its surface but are situated mostly in the channels. Indeed, the micro-
cones are oriented in a way to reflect the incident laser beam. Therefore, the properties of NP
generated from a smooth target surface at the onset of laser exposure are different from those
at later stages when the micro-relief has been formed.
The cross section of a brass target subjected to radiation of a Cu vapor laser in ethanol is
presented in Figure 3. One can see deep channels that separate the microstructures formed in
the target upon laser ablation. The melt is formed predominantly on the bottom of channels
due to both increased angle of incidence of laser radiation compared to a flat surface and to
reflection of laser light from side surface of micro-cones.
The molten layer is pushed along the cone surface and is partially dispersed into
surrounding liquid as NP. Other part of melt solidifies on cone surface forming in some cases
typical tips on their tops as can be seen in Figure 2.

Figure 2. SEM top view of a brass target produced by scanning beam of a Cu vapor laser. Inset shows
the enlarged view of the same surface tilted for 35. Scale bar denotes 20 m and 10 m in inset

Figure 3. SEM view of a cross section of a brass target subjected to laser beam of a Cu vapor laser
under the layer of ethanol. Space bar denotes 20 m
Formation of periodic micro-relief on the target surface inexorably alters the character of
temperature distribution along its surface during the laser pulse. The temperature distribution
is smooth on initial flat target surface, and in case of a flat top profile of laser beam intensity
the temperature profile is also almost flat except for side effects. As soon as periodic micro-
relief is formed, the temperature profile consists of numerous hot spots located in the
channels between micro-cones. The energy density (fluence) inside these spots exceeds by far
the fluence on the initial surface without micro-relief. Since the size of NP depends on the
fluence, the size distribution of NP generated via laser ablation of the micro-structured target
should be different from that generated at the first stages of laser ablation when the target is
still flat.
Unlike laser ablation in vacuum where synthesized NP rapidly leave the laser beam and
never come back due to sticking on the chamber walls, NP synthesized by ablation in liquids
remain in it and may return into the laser beam during their motion. The efficiency of
coupling of radiation to nanoparticles depends on the proximity of laser wavelength to
plasmon resonance of charge carriers. The energy from electrons to the lattice is transferred
within 3-5 ps [24], and the temperature T of a nanoparticle of radius R can be estimated on
the basis of conventional heat diffusion equation [25]. For 8kR/l <<1 one obtains T ~
2I
0
kR
2
/k
liq
, that is the temperature of the nanoparticle in the laser beam is proportional to
its geometric cross-section. Here k
liq
stands for the thermal conductivity of the surrounding
liquid which is assumed to be constant during its evaporation for the sake of simplicity. Note
that due to the small size of NP their temperature is proportional to the peak power density of
the laser beam I
0
(Watts per square centimeter). The extinction coefficient under large
detuning from the plasmon resonance is close to that of the bulk metal. However, in the
vicinity of plasmon resonance = () shows resonant behavior, and the temperature T of the
particle strongly depends on the laser wavelength.
The main difference between laser ablation in vacuum and in liquid environment is a
short free path of ablated species in the latter case. Indeed, the formation of NP under laser
irradiation of a metal target immersed into a liquid proceeds via local melting of the metal.
The adjacent liquid layer is heated to almost the same temperature owing to heat transfer from
the metal. The thickness h of this layer can be estimated using the heat diffusion coefficient of
a liquid a = 10
3
cm
2
/s and the diffusion time equal to duration of the laser pulse
p
= 20 ns.
G. A. Shafeev 198
Then the thickness of the liquid layer h ~ (a
p
)
1/2
= 0.3 m. This thin layer has a temperature
much higher than boiling point of the liquid at normal pressure and is hence in the vapor
phase. The pressure in this vapor layer can be roughly estimated as the vapor pressure of the
liquid at temperature of the substrate. This means that in typical experimental conditions all
liquids are in vapor phase at pressure of the order of hundreds atmospheres. The thickness of
the molten layer on the target is about the length of heat diffusion into the metal, h
m
~
(a
m
p
)
1/2
. a
m
= 1.7 and 0.13 cm
2
/s for Ag and Au, respectively, which gives the heat diffusion
length of 1.9 m for Ag and 0.5 m for Au. This is the maximal thickness of the reservoir for
generation of nanoparticles that is gained at fluence much higher than the melting threshold.
That is why the size of nanoparticles is almost independent on the pulse width, from hundreds
of nanosecond through hundreds of femtosecond. At lower fluence the thickness of the melt is
smaller than h
m
. Expanding vapors of the liquid splash this reservoir resulting in the removal
of the molten layer. Note that formation of nanoparticles via evaporation of the metal is
unlikely, since the pressure of metal vapor at a temperature close to melting is too low
compared to vapor pressure of the surrounding liquid. Surface tension stabilizes the molten
drop of the metal, while the pressure of surrounding vapor of the liquid tends to split it. As a
first approximation one may suggest that the size of a stable drop of metal can be found from
the following relation: 2/R ~ p
liq
, where is the surface tension coefficient of the metal, R is
the radius of the drop, and p
liq
is the pressure of the vapor of the liquid surrounding the target.
Substitution of these parameters for Ag ablated in water for R = 30 nm and T = 1000 C gives
p
liq
~10
8
Pa, which is a reasonable value. The melting temperature decreases with the size of
the nanoparticles, so at sufficiently small R the particle melts under the laser pulse, but the
vapor pressure of surrounding liquid is not high enough to cause its further splitting.
LASER ABLATION OF AN AG TARGET IN LIQUID ENVIRONMENT
Historically Ag NP were the first ones synthesized by laser ablation of a silver plate in
water. Various laser sources have been successfully used for this synthesis ranging from a
nanosecond Nd:YAG through Ti:sapphire femtosecond lasers [21,26,27]. Ablation of a
metallic Ag immersed into water by radiation of a Cu vapor laser at wavelength of 510.6 nm
and pulse duration of 20 ns results in visible coloration of the liquid; it takes on a yellowish
color. The optical spectra of Ag NP generated by laser ablation in different liquids are
presented in Figure 3. The maximum of absorption is at about 400 nm, which is typical for so
called plasmon absorption of Ag nanoparticles in water [18,19]. The intensity of the plasmon
band increases with irradiation time, while its position does not vary significantly. Ag NP are
slowly oxidized by air oxygen dissolved in the liquid, and the position of plasmon resonance
shifts to the red with time due to formation of oxide layer with high refractive index [22].
The Transmission Electron Microscope (TEM) view of Ag nanoparticles produced by
ablation of an Ag target in acetone is shown in Figure 5. The average size of particles is
around 15 nm. Moreover, they are flat disks, and their thickness is of order of few nanometers
[15]. This is clearly seen in those areas where the TEM image of intersection of two or more
Ag particles appears darker than each separate particle.

Figure 4. Absorption spectrum of Ag nanoparticles obtained by ablation of Ag in different liquids. The
plasmon peak of Ag is well pronounced at ca 400 nm

Figure 5. TEM view of Ag nanoparticles obtained by ablation of a bulk Ag in acetone. Scale bar
denotes 50 nm
Smaller Ag NP are synthesized using sodium dodecyl sulphate (SDS) as a surface active
substance [26]. Laser pulses of various durations have been used for synthesis of Ag NP in
water ranging from ns to fs domain [21, 27].
400 500 600 700 800

0,00
0,05
0,10
0,15
0,20
acetone
ethanol
water
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength, nm
G. A. Shafeev 200
LASER ABLATION OF AN AU TARGET IN LIQUID ENVIRONMENT
Gold NP exhibit a well-pronounced dependence of their absorption spectrum on their
shape and size. In general, a metallic ellipsoid is characterized by three different plasmon
resonances. In case of a spherical particle all three of them are degenerated, and Au NP show
the maximum of absorption around 520 nm independent on the way of their preparation.
Elongated Au NP (nanorods) are characterized by two absorption bands that correspond to so
called transverse and longitudinal plasmon resonances. The position of the latter varies with
aspect ratio of Au nanorods, and for sufficiently high aspect ratio the longitudinal resonance
moves from the visible to the near IR range of the spectrum [28].
The optical spectra of water after laser exposure of metallic Au show well-pronounced
absorption band at ca 520 nm that is characteristic of transverse plasmon resonance [18, 19].
At higher laser fluence elongated Au NP are also synthesized, which is accompanied by the
appearance of a red wing. Au NP prepared in water in absence of surface-active agents are
metastable against precipitation, and their significant precipitation is observed within several
days after preparation. Precipitation of NP is accompanied by appearance of a wide red wing
that indicates the presence of elongated Au NP with various aspect ratios. Synthesis of a
stable colloidal solution of Au NP in water has been reported by several groups [29-32].
The coupling of laser radiation to the colloidal solution can lead to the modification of
the size distribution of Au NP. This is confirmed by TEM view of Au particles as obtained
after the ablation of Au in water. Laser radiation modifies not only the size of the particles,
but also their shape. As-obtained particles are elongated, while those exposed to laser
radiation are the nano-disks similar to Ag nanoparticles. Average size of Au as-obtained after
ablation by a Cu vapor laser in H
2
O in absence of surface-active substances is 20 nm, while
with further laser exposure of the solution alone their size diminishes to ca 10 nm.
Au NP produced at high laser fluence on the target are characterized by elongated shape
independent of the nature of the surrounding liquid. This effect has been observed for laser
ablation in alkanes [33] as well as in water. Figure 6 shows the TEM view of Au NP
synthesized by laser ablation of a gold target in water. The majority of NP has a spherical
shape, while some NP have aspect ratio ranging from 2 to 10. Accordingly, the absorption
spectrum of this solution is characterized by two maxima, one at ca 540-560 nm and the
second having a wide red wing centered at longer wavelengths.
The rate of generation of Ag and Au NP depends on laser fluence. For instance, it is 0.6
and 1.2 mg/hour, for respective metals, with a laser spot of 30 m and fluence of 30 J/cm
2
.
Nanoparticle size can be drastically reduced by the use of aqueous solutions of
surfactants, which cover the particles just after their ablation and thus prevent them from
further agglomeration. Sodium dodecyl sulphate (SDS) is one of the most popular agents
capable of reducing the mean size of Au nanoparticles down to 5 nm during nanosecond laser
ablation of gold [29-31]. Ablation of a gold target with shorter laser pulses, e.g., femtosecond
ones, results in synthesis of bimodal distribution function of nanoparticle size at elevated laser
fluence and almost mono-dispersed Au NP at lower fluence of 50 J/cm
2
[32]. Another
stabilizing agent for Au NP are cyclodextrins [34]. Their addition provides perfect stability of
Au NP as small as 2-2.5 nm synthesized by laser ablation with femtosecond pulses.
NP of another noble metal Pt can also be synthesized by laser ablation of a metallic Pt
target. In presence of SDS their size can be as small as 5 nm [35].

Figure 6. TEM view of Au NP obtained by ablation of a gold target immersed into water at elevated
laser fluence of 90 J/cm
2
at 1.06 m, pulse width of 130 ns
INTERACTION OF NANOPARTICLES WITH LASER BEAM
Coupling of laser radiation to isolated NP proceeds via its absorption by free electrons.
Then the absorbed energy is thermalized and transferred to NP material. Since these electrons
are characterized by some plasmon resonance, the efficiency of this coupling strongly
depends on the detuning of laser radiation from maximum of absorption. This interaction is
not important in case of laser generation of NP in vacuum, since NP do not come back to the
laser beam. In liquid environment NP remain in the liquid and do come back inside the beam
due to convective flows. Repeated interaction of NP with laser beam leads to observation of
some interesting phenomena described below.
FRAGMENTATION OF NP UNDER LASER EXPOSURE IN LIQUIDS
Fragmentation of NP under their laser exposure in liquids has been reported as early as
the synthesis of NP itself [2, 6, 30]. The process manifests itself as a gradual decrease of the
size of NP upon laser irradiation. As a result, the distribution function of particle size shifts to
lower dimensions. The dependence of the NP size on the laser wavelength has been reported
[36, 37] indicating the spectral dependence of the fragmentation process. Optical constants of
G. A. Shafeev 202
metallic targets do not vary largely in the wavelength range of lasers used for NP synthesis,
so fragmentation of NP should be ascribed to interaction of synthesized NP themselves with
the laser beam inside the liquid.
The physical processes that lead to fragmentation of NP in the laser beam are still under
discussion. The most probable reason leading to reduction of NP size are the instabilities that
develop at the interface of molten NP with the vapors of surrounding liquid [25]. Indeed, a
NP may absorb enough energy from the laser beam to undergo the phase transition into a
liquid state. The temperature of NP exceeds at this moment the boiling temperature of
surrounding liquid. The latter is therefore vaporized and forms a shell around the NP. The
pressure of vapors in this shell is around 10
8
Pa, and its possible asymmetry would result in
the break of molten NP inside it into smaller parts. The most probable process is splitting of
the molten NP into two equal particles, since, first, this corresponds to lowest value of total
surface energy, and second, is the lowest mode of perturbation of the surface of molten NP.
This hypothesis is in qualitative agreement with the fact that the average size of NP exposed
to laser radiation in various liquids decreases with the decrease of boiling temperature of the
liquid. The balance is gained when the pressure inside the NP of radius R is of order of the
pressure of the surrounding liquid p
liq
: 2/R ~ p
liq
, where stands for the surface tension of
molten NP.
Fragmentation of the NP under their laser exposure introduces feedbacks into the system
laser radiation NP. Indeed, the average size of NP under their laser exposure is inversely
proportional to the peak intensity of the laser beam inside the liquid. The size of NP decreases
upon exposure till NP become so small that the energy absorbed from the laser pulse is not
sufficient for melting. The system therefore demonstrates a negative feedback and auto-
stabilization. On the other hand, the melting temperature of a NP decreases with its size,
which is a positive feedback. Finally, small NP formed via fragmentation from bigger ones do
not absorb enough energy from the laser beam to be molten, and the ensemble of NP acquires
its upper limit of NP size.
SHAPE-SELECTIVE FRAGMENTATION
The fragmentation of NP under laser exposure of their suspension in a liquid can be
shape-selective, if the spectrum of plasmon resonance depends on their shape. This can be
illustrated by shape-selective fragmentation of Au NP having elongated shape (nanorods). Au
nanorods are characterized by two absorption peaks, one of them corresponds to so called
transverse resonance (TR), while the second is called longitudinal one (LR). These
resonances correspond to oscillations of free electrons in the directions across the nanorods
axis and along it, respectively [28]. The position of TR near 560-570 nm is common for Au
nanorods with any aspect ratio, while the position of their LR is a linear function of the aspect
ratio and moves to the red with its increase [38-41]. If laser radiation is tuned into TR, then all
nanorods are molten and fragmented into spherical NP at sufficiently high peak power of the
laser beam [40]. However, tuning the laser wavelength into LR allows selective fragmentation
of Au nanorods with aspect ratios which are in resonance with laser radiation [42].

Figure 7. Evolution of optical density of suspension of Au nanorods in water under exposure to
radiation of a Cu vapor laser at 510.6 nm (1) and 578.2 nm laser output. Vertical lines indicate the
position of the laser wavelength. Curve (1) in both figures corresponds to the spectrum of initial
colloidal solution
This fragmentation (splitting) is illustrated in Figure 7 in which the evolution of
absorption spectrum of suspension of Au NP with wide distribution of aspect ratio is
presented. Au NP are especially convenient for this type of experiments since their absorption
spectrum depends on their shape. The radiation of a green line of a Cu vapor laser fits well
the transverse plasmon resonance of Au NP, which is common for all Au NP and does not
400 500 600 700
0,4
0,5
0,6
0,7
0,8
0,9
1,0
1,1
5
4
3
2
1
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength, nm
400 500 600 700 800
0,15
0,20
0,25
0,30
4
3
2
1
O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength, nm
G. A. Shafeev 204
depend on their aspect ratio. On the contrary, the yellow line of a Cu vapor laser is absorbed
by non-spherical (elongated) Au NP. Therefore, the evolution of the absorption spectrum is
different if various laser outputs are used for NP exposure.
One can see gradual decrease of the optical density of the suspension in the red that
corresponds to fragmentation of Au nanorods irrespective to their aspect ratio (Figure 7, 1).
On the contrary, exposure of the suspension to radiation that is preferentially absorbed by Au
nanorods with the aspect ratio 2 3 results in the decrease of the optical density just at the
laser wavelength (Figure 7, 2). This decrease indicates the depopulation of the suspension
with nanorods that are in resonance with laser radiation. Of course the laser fluence should
not be too high otherwise nanorods with non-resonant aspect ratio will also be fragmented,
since their absorption wings are very wide.
Au nanorods with aspect ratio about 10 absorb in the near IR region. Exposure of their
suspension to radiation of a Nd:YAG laser operating at its fundamental output at 1.06 m
results in self-stabilization of fragmentation: no changes of absorption spectrum of the
solution occur as soon as long nanorods are fragmented [42].
Similar fragmentation of Au NP is also observed in ethanol and acetone. Their size in
these liquids is somewhat smaller than in water and is of 7 nm under the same laser fluence.
As a consequence, these colloidal solutions are stable against sedimentation. Finally, the
addition of a surface-active substance, e.g., poly(vinyl pyrrolidone) (PVP) with molecular
mass of 10
4
, to ethanol in which the ablation is carried out further decreases the average size
of Au nanoparticles down to ca 4 nm at otherwise equal conditions.
FORMATION OF THE AU-AG ALLOY UNDER
LASER IRRADIATION OF NANOPARTICLES
Direct interaction of NP with laser beam inside the liquid may lead to their melting
during each laser pulse at sufficiently high laser peak intensity. If the colloidal solution
contains NP of various materials, their absorption of laser radiation may be different. Laser
exposure of a mixture of different NP may lead to formation of alloyed NP, and at least one
kind of NP should be molten by laser beam. Recent publications [43-45] have reported the
formation of gold-silver alloy nanoparticles in liquid environment under laser exposure of
core-shell particles obtained by a chemical method. The spectrum of core shell (non-alloyed)
nanoparticles is not a linear combination of the spectra of monometallic colloids [45]. On the
contrary, the spectrum of a mixture of individual colloids is composed of spectra of
monometallic particles. Upon laser exposure, these peaks disappear, and the single alloy peak
arises. Laser exposure of Ag-Au core-shell NP may lead to both Ag shell removal from Au
NP and their alloying depending on laser wavelength and its fluence [46]. Individual NP of
various materials have to come into contact to form an alloy, and therefore the laser alloying
of NP is concentration-dependent process. The position of plasmon resonance of alloyed NP
is a linear combination of plasmon frequencies of individual NP. Formation of alloyed AuAg
NP is accompanied by peculiar modification of the absorption spectrum indicating an
intermediate phase of the Au-Ag alloy formation [47-49]. The temporal evolution of the
optical density of the mixture is presented in Figure 8.
Fi
la
ra
Fi
g/
Sc
in
A
su
al
po
co
nm
For
igure 8. Evoluti
aser ablation of
adiation (wavele
igure 9. TEM v
/l, Cu vapor lase
cale bar denotes
ndividual colloid
Au-Ag particles
The forma
ufficiently larg
lso show the
osition but thi
The positio
oncentration o
m and 520 nm
rmation of Na
ion of the absor
respective meta
ength of 510.6 n
view of Au-Ag n
er, laser fluence
s 40 nm. Alloye
ds in ethanol du
is 7 nm
ation of an i
ge initial NP o
deviation of
s effect is wea
on of plasmon
of metals and
m of Ag and
anoparticles un
rption spectrum
als in ethanol un
nm)
nanoparticles af
e of 9 J/cm
2
. Br
ed Au-Ag nanop
uring 4 hours (b
intermediate p
of each metal
f the maximu
ak.
n frequency o
is always in
Au, respectiv
nder Laser Ab
m of the mixture
nder laser expos

fter 2 hours of e
righter particles
particles obtain
b). Scale bar den
phase of the
(50 -70 nm).
um of plasmo
f an Au-Ag a
between the m
vely. In case
lation of Solid
of both Au and
sure at 55 J/cm
2
exposure (a). Co
are Ag while th
ned by exposure
notes 100 nm. A
alloy is obs
Smaller NP o
on resonance
alloy varies co
maxima of pl
of individual
ds in Liquids

d Ag NP synthe
2
of a Cu vapor
oncentration of
he darker ones a
e of the mixture
Average size of
served only i
of 10-20 nm i
from its stoi
ontinuously w
asmon resona
l particles, ho
205
sized by
laser

f PVP is 0.1
are Au.
e of
f alloyed
in case of
in diameter
ichiometric
with relative
ance at 400
owever, the
G. A. Shafeev 206
maximum of absorption falls out of this interval after certain exposure time and is
significantly red-shifted after 1-2 hours of exposure. With further exposure the maximum
returns to the interval corresponding to an Au-Ag alloy and remains there for even longer
exposures indicating the formation of the alloy. The TEM view of NP at the stage of
anomalous spectrum (Figure 8, spectrum 2) reveals multiple contacts between Au and Ag
nanoparticles that are well observed due to different atomic mass of both metals.
With further exposure these hybrid particles are alloyed, and the final position of the
absorption maximum corresponds to the Ag-Au alloy (Figure 8, spectrum 4). The size of
alloyed nanoparticles is about 5 nm, which is much smaller than initial ones.
Formation of alloyed nanoparticles is sensitive to the presence of surface-active
substances in the liquid. The rate of alloy formation increases under addition of PVP (10
-5
M).
However, the alloying is inhibited at given laser intensity at elevated concentrations of PVP
exceeding 510
-5
M [48]. The rate of alloying decreases with dilution of the mixture,
presumably due to the increase of the average distance between the nanoparticles. It is
pertinent to note that the surface-active substance, e.g., PVP, apparently remains untouched
under laser exposure of NP in spite of their elevated temperature. Raman analysis shows no
variation in the glassy carbon content before and after laser exposure of suspensions of NP
with PVP, though this should be so if the pyrolysis of the surfactant on hot NP took place.
This might be explained by the preferential localization of PVP at the interface of a vapor
bubble that is formed around the NP during their laser exposure.
The absorption spectrum of the Au-Ag alloyed NP is closer to the wavelength of a Cu
vapor laser (510.6 nm) than the plasmon maxima of individual NP. Therefore, the efficiency
of coupling of laser radiation increases upon formation of the alloy. As a result, the average
size of alloyed Au/Ag NP is much smaller than that of individual ones [48, 49]. This is
illustrated in Figure 9 where TEM images of NP are presented at different stages of Au-Ag
alloy formation.
Similar behavior is observed under exposure of the mixture of colloidal solutions of
Cu/Ag and Cu/Au. The alloyed NP are formed under sufficiently long laser exposure of the
mixture, and the final position of the plasmon resonance depends on ratio of individual
colloids in it.
NANOPARTICLES OF CU, BRASS, AND BRONZE
Copper is chemically active and easily reacts with vapors of surrounding liquid. The
chemical interaction may take place both during the ablation and after it due to contact with
air oxygen dissolved in the colloidal solution. Typically, the plasmon resonance of Cu
nanoparticles lies in the visible. Cu NP synthesized by chemical means in anaerobic
conditions show the absorption peaks from 570 to 590 nm [49, 50].
Laser ablation of Cu target in various liquids also leads to formation of NP that are
characterized by absorption in the visible [51]. The peak position is around 590 nm, which
agrees with previously reported data for Cu NP (see Figure 10). Ablation of a Cu target in
water leads to formation of compounds containing only ionic species Cu
+
without any
plasmon peak. The stability of generated Cu NP to slow oxidation is different. Namely, Cu
NP produced by ablation in ethanol are slowly oxidized. This is manifested by gradual
disappearance of the peak of plasmon resonance (Figure 10). Remarkably, the initial plasmon
peak can be restored by exposure of aged colloidal solution to the radiation of a Cu vapor
laser at sufficiently high fluence of several tens of J/cm
2
.
On the contrary, ablation of a Cu target in acetone results in a stable spectrum of the
colloidal solution of NP. The difference in behaviour of Cu nanoparticles in these two liquids
stems from their images obtained with a transmission electron microscope. Cu NP generated
by ablation in ethanol are low-contrast entities with average size of 5 nm. Cu NP in acetone
are metallic as one can conclude from their high contrast and well pronounced peak of
plasmon resonance. However, in this instance they are embedded into some amorphous cloud
[51]. Raman analysis of the dried suspension indicates that this cloud consists of glassy
carbon. The layer of glassy carbon protects Cu NP from oxidation with air oxygen and
preserves their plasmon resonance in the visible. Note that decomposition of acetone on Cu
NP that occurs during laser ablation of a Cu target is highly chemically selective - it takes
place on Cu nanoparticles but not on Ag ones in similar experimental conditions.
Cu NP can also be synthesized via exposure of a suspension of micro-particles of CuO to
laser radiation [52, 53]. At first stages of the exposure the micro-particles are broken into
smaller entities, and then their reduction occurs by surrounding 2-propanol. It is worth
mentioning that Ag NP can also be produced by exposure of suspended Ag
2
O micro-particles
in an appropriate hydrocarbon liquid to laser radiation. In both cases, fragmentation of micro-
particles into smaller particles occurs due to absorption of laser energy by inter-band
transition of corresponding oxide, while the subsequent formation of metallic NP takes place
due to chemical reduction of oxide by surrounding liquid that acts like a reducing agent.

Figure 10. Absorption spectra of the liquids after laser ablation of a bulk Cu target. Ethanol (1), acetone
(2), and water (3). Cu vapor laser, fluence of 30 J/cm
2

200 300 400 500 600 700 800
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
O
p
t
i
c
a
l

d
e
n
s
i
t
y
3
2
1
Wavelength, nm
G. A. Shafeev 208
Brass NP can be synthesized in a similar way. Unlike Cu NP they are stable to oxidation
for at least several months. The position of the plasma resonance of brass nanoparticles
depends slightly on the type of laser source used for their synthesis and lies near 510-515 nm.
The presence of brass NP in the liquid is corroborated by the X-ray diffractometry of the
evaporated suspension. Bronze NP synthesized by laser ablation of a bronze target do not
show any well-defined absorption maximum, instead a wide plateau in the green range of
spectrum is observed in the absorption spectrum of their colloidal solution. However the
absorption spectrum is merely different from that of Cu NP. The mean size of NP of these Cu
alloys is around 20-30 nm.
INTERNAL SEGREGATION OF BRASS NP
Apart from fragmentation described above brass NP undergo drastic modification under
their laser exposure in a liquid. This is an internal segregation of a nanoparticle that is
repulsion of one of its components to its periphery [54]. The material of the nanoparticle is
subjected to additional pressure due to its small radius. For a liquid nanoparticle, the capillary
pressure is given by the expression p=2 /R, where is the surface tension coefficient and R
is the particle radius, which is equal for Cu NP to 120 MPa for R=20 nm. In addition to this
pressure, the nanoparticle during the laser pulse is subjected to the vapor pressure of the
surrounding liquid, which reaches a maximum simultaneously with the particle temperature
and decreases rapidly upon expansion of the vapor shell. The pressure of ethanol vapors
surrounding the particle with a temperature of 1500 K is estimated at about 20 MPa from the
equation of state of a real gas. Note that the pressure of nanoparticle-substance vapors at the
melting temperature for most metals is negligibly low compared to the above values.
As synthesized Cu NP are not stable towards oxidation by air oxygen. The oxidation is
accompanied by disappearance of the peak of plasmon resonance of Cu NP as shown in
Figure 11. It is pertinent to note that the spectra of NP of Cu alloys are more stable with time.
This is due to the formation of a shell around them as described below.
Laser radiation acting on the ensemble of brass NP in the liquid changes their absorption
spectrum. The absorption spectrum of brass NP evolves to that of Cu NP (Figure 12). With
laser exposure the peak corresponding to Cu NP becomes noticeable. Upon further action on
the colloidal solution, the peak corresponding to brass nanoparticles disappears, and only the
plasmon resonance peak of Cu NP remains. Qualitative evidence of the effect is the absence
of small brass nanoparticles (with a radius smaller than 5 nm) upon the laser ablation of a
brass target in ethanol. Estimates show that the time of diffusion of zinc atoms to a distance of
about the diameter of a nanoparticle in the liquid state is of order of several ns, which is
comparable with duration of the laser pulses commonly used in experiments [54]. Small
nanoparticles rapidly lose zinc upon laser irradiation and are transformed to copper NP
oxidized by air oxygen.
A similar shell is observed under laser exposure of bronze NP. In this case the shell
thickness is only few nm due to lower content of the component with low melting
temperature (Sn) (Figure 13). Plasmon resonance of bronze NP is less pronounced than that
of brass NP though is merely different from both Cu and brass NP.

Figure 11. Evolution of absorption spectrum of Cu NP produced by laser ablation of a bulk Cu target in
ethanol. As prepared (1), 6 months later (2). Ablation was carried out using a Cu vapor laser

Figure 12. Evolution of the absorption spectrum of brass NP upon exposure of their colloidal solution
in ethanol to radiation of a 130 ns Nd:YAG laser. As synthesized brass NP (1), 10 (2), and 90 min of
exposure (3)
300 400 500 600 700 800

0,2
0,4
0,6
0,8
1,0
1,2

O
p
t
i
c
a
l

d
e
n
s
i
t
y
Wavelength, nm
1
2
400 450 500 550 600 650
0,4
0,6
0,8
1,0
3
2
1
A
b
s
o
r
p
t
i
o
n
Wavelength, nm
G. A. Shafeev 210

Figure 13. TEM view of core-shell bronze NP synthesized by laser ablation of corresponding targets
(8% Sn, 92%Cu) and then subjected to laser radiation in suspension. The diameter of big NP is about
40 nm
Small radius of NP is responsible for decrease of their melting temperature compared to
bulk material. Also, it has been theoretically demonstrated that the melting temperature is
different for different shapes of NP composed of the same material [55].
Internal segregation of NP under laser exposure leads to repulsion of the components
with lower melting temperature. In this sense one may speak about purification of the core
material under laser exposure.
SELF-INFLUENCE OF A FEMTOSECOND LASER BEAM
Remarkably, the initial average size of nanoparticles produced by ablation of metallic
targets is almost independent on the duration of laser pulse from 100 fs to 100 ns and is of
order of 10 nm. This implies that the size is determined rather by thermal properties of the
target. Indeed, the layer of metal molten by a laser pulse is the only source from which the
nanoparticles are formed. The difference in size becomes pronounced under sufficiently long
laser exposures when the majority of generated nanoparticles pass through the laser beam in
the liquid. In this case the key parameter that determines the efficiency of coupling is
detuning of laser wavelength from the plasmon resonance. In certain cases a good coupling of
laser radiation to the ensemble of NP is achieved via non-linear transformation of laser
radiation by NP themselves. Indeed, the wavelength of a femtosecond Ti:sapphire laser (810
nm) is too far from the plasmon resonances of both Au and Ag NP. However, prolonged laser
exposure of the colloidal solution leads to drastic difference in their average size (14 nm vs 4
nm) [21]. Also, there is a significant amount of even smaller Ag nanoparticles whose size is
below the measuring limits of the microscope (< 2 nm). The ablation is accompanied by
intense generation of the second harmonics of laser radiation at 405 nm. This wavelength
exactly fits the plasmon resonance of Ag NP, while for Au nanoparticles it is significantly
detuned. The effect of second harmonics generation (SHG) on small metal clusters is well
documented in the literature [56, 57]. Despite too small size of metal clusters compared to the
laser wavelength, SHG can be very effective due to their high density, so that the conditions
of spatial synchronism are easily fulfilled. Several models account for high value of the
second order non-linear susceptibility
(2)
and for efficient generation of the second
harmonics. This is assigned to quantum size effect for wave functions of electrons confined to
small metal spheres, which gives rise to quadruple oscillations and, consequently, to non-zero
(2)
even for nanoparticles with a center of symmetry. The observed difference in particle size
is attributed to the self-influence of laser radiation upon generation of nanoparticles via laser
ablation in liquids. Indeed, appearing nanoparticles double the frequency of laser radiation.
Owing to exact matching to plasmon resonance of Ag NP, their temperature can be much
higher than under exposure to initial laser radiation. This causes fragmentation of
nanoparticles that are in resonance with the second harmonics that is Ag ones.
The third order non-linear susceptibility of NP
(3)
is responsible for non-linear lensing of
laser radiation inside the colloidal solution. As a result, the focusing conditions change during
the accumulation of NP in the beam path, and the ablation rate decreases even though laser
radiation is largely detuned from plasmon resonance of NP.
In general, the limiting factor of interaction of NP immersed in a liquid with a
femtosecond laser beam is generation of a white continuum. This continuum consumes a
significant part of laser energy and reduces the efficiency of interaction with NP. This is well
pronounced for pulse durations less than 60 fs.
INFLUENCE OF THE NATURE OF THE LIQUID
Ablation of a Ti Target
The composition of NP produced by laser ablation of Ti was found to be dependent on
the nature of the liquid [16] (see Figure 14). Namely, laser ablation of Ti in ethanol results in
formation of Ti nanoparticles having the cubic structure. It should be reminded that the initial
polycrystalline Ti plate has tetragonal structure. It is known that the cubic phase of Ti is
metastable and exists only at elevated temperature > 600 C. At the same density of laser
energy laser ablation of Ti target immersed into dichlorethane leads to the formation of
nanoparticles of titanium carbide TiC. Four the most intense peaks of TiC can be
distinguished on the X-ray diffractogram of the evaporated suspension. Finally, laser ablation
of Ti in water results in the formation of nanoparticles having the composition of non-
stoichiometric oxide TiO
x
, where x = 1.04. The width of the peaks indicates the small size of
the nanoparticles. All the diffractograms contains several unidentified peaks.
Formation of TiC via ablation of Ti in dichlorethane may be due to catalytic action of Ti
nanoparticles, since no carbon-containing particles have been observed during ablation of
either Si or Au in this liquid under otherwise equal experimental conditions. It is worthwhile
to mention that the surface of Ti target after laser ablation in dichlorethane does not contain
any detectable by X-ray diffraction amount of TiC. This indicates the formation of TiC
nanoparticles via chemical reaction of ejected metal nanoparticles with liquid vapors.
2
Fi
Et
ca
flu
cr
ev
ch
di
in
ge
un
A
lo
co
aq
la
T
ab
ge
H
to
di
of
to
an
12
igure 14. Difrac
thanol (upper cu
alculated from b
uence of 4 J/cm
Unlike to
rystalline, and
Oxidation
ven in case no
hloroform [58
ifferent degree
n case of ablat
Another ex
enerated via la
nder ablation i
Ablation of S
Tin is a me
ower than fo
omposition on
Non-stoich
queous solutio
aser fluence (l
his is corrob
bsorption spec
Since melt
eneral, this is
However, evap
o aggregation
iameter. A gol
f Sn. Once fix
o the substrate
nd therefore to
ctograms of NP
urve), dichloret
broadening of d
m
2

what is beli
d the fraction o
state of NP m
oble metals, e.
8]. X-ray Phot
e of oxidation
ion of Au in c
xample of the
aser ablation o
in acetone, wh
Sn
etal with low
r other meta
n the concentra
hiometric tin o
ons containing
ess than 0.2 J
borated both
ctra.
ting temperatu
due to high f
oration of the
, and X-ray
ld plate imme
xed on a large
e. Mixing Sn N
o specific core
G.
P synthesized by
thane (middle),
diffraction peak
ieved, NP ge
of amorphous
material is stron
g., Au. It was
toelectron Spe
n of Au. The fo
chloroform wit
e influence o
of a solid targ
hile water and
melting point
als mentioned
ation of a surf
oxide SnO
2-x
g SDS [60]. A
J/cm
2
at nanos
by X-ray dif
ure of bulk Sn
fraction of sur
ir colloidal so
diffraction sh
rsed into collo
substrate, Sn
NP and Au NP
e-shell NP. Th
A. Shafeev
y laser ablation
and water (bott
s is 25, 35, and
enerated by l
component is
ngly influence
s confirmed by
ectroscopy (XP
ormation of a
th 5 ns laser sh
of the liquid
get is copper. I
d ethanol lead t
, and laser flu
d above. A c
face-active sub
is formed un
Ablation of Sn
second pulse d
ffraction of t
n is low, Sn N
rface atoms in
olution in abse
hows narrow
oidal solution
NP are solidi
P in ethanol le
heir TEM view
of metallic Ti t
tom curve). The
25 nm, respect
laser ablation
usually very l
ed by the natu
y ablation of A
PS) analysis o
goldchlorine
hots at wavele
on the chemi
In this case fin
to non-metalli
uence required
certain depen
bstance is foun
nder laser abl
in either wate
duration) leads
the dried susp
NP are liquid
n NP compare
ence of surface
peaks of Sn
is rapidly cov
ified and form
eads to wetting
w is presented

arget in differen
e size of nanopa
tively. Cu vapor
n in liquids a
low.
ure of surroun
Au in water, et
of dried colloi
e compound is
ength of 532 n
ical composit
nal NP are me
ic NP.
d for its ablatio
ndence of th
nd in this case
lation of a tin
er or ethanol a
s to formation
pension and
at room temp
ed to their tot
e-active substa
n NP about 1
vered by nume
m a kind of nan
g of Au NP by
in Figure 15.
nt liquids.
articles
r laser,
are always
nding liquid
thanol, and
ids showed
s suggested
nm.
tion of NP
etallic only
on is much
e particles
e [59].
n target in
at moderate
n of Sn NP.
its optical
perature. In
tal number.
ances leads
100 nm in
erous layers
no-contacts
y liquid Sn
Fi
co
so
A
as
co
W
an
ei
di
di
Fi
va
For
igure 15. TEM
orresponding m
The thickn
olidified just a
Au NP resultin
ssigned to tin
At picosec
onfirmed by th
W and Mo N
Other meta
nd are oxidize
ither W or Mo
ispersed into
iffraction and
igure 16. TEM
apor laser. Scale
rmation of Na
view of Au NP
metallic targets in
ness of the sh
after the conta
ng in a shell
oxide.
cond pulse du
heir characteri
NP
als that might
ed very slowly
o upon their ab
surrounding
optical spectr
view of W NP
e bar denotes 50
anoparticles un
P wetting by Sn
n ethanol using
hell depends
act with Au N
l with homog
uration the re
istic absorptio
interact with
y with air oxy
blation in wat
liquid as me
ra of correspon
synthesized by
0 nm
nder Laser Ab
NP. Both collo
radiation of a C
on the volum
NP, and no she
geneous thick
esulting NP c
on peak at 360
surrounding l
gen that is dis
ter. These met
etallic NP, w
nding colloida
ablation of a W
lation of Solid

ids were synthe
Cu vapor laser.
me of the Sn
ell is formed.
kness. Diffuse
onsist mostly
nm.
liquid during
ssolved in liqu
tals with high
which is corro
al solutions.

W target in ethan
ds in Liquids
esized by ablati
Scale bar deno
n NP. Large S
Smaller Sn N
e entities are
y of tin oxide
ablation rema
uid. This conc
melting temp
oborated by b
nol by radiation
213
on of
tes 200 nm
Sn NP are
NP envelop
tentatively
e, which is
ain metallic
cerns NP of
perature are
both X-ray
n of a Cu
G. A. Shafeev 214
Their morphology alters during several months of storage at room temperature due to
oxidation, which results in the formation of core-shell NP (see Figure 16). Like many other
metals, the oxide layer prevents further oxidation of the metallic core. Similar result has been
reported for W NP obtained by ablation of a W target in ethanol using high-repetition-rate
copper bromide laser radiation [61]. The authors deduce the formation of non-stoichiometric
oxide WO
3x
around W NP on the basis of absorption spectra of the colloidal solution.
Carbon NP can also be obtained by laser ablation of a graphite target immersed into
liquid [62].
A peculiar feature of laser ablation in water is enhanced solubility of some compounds in
it under high temperature and high transient pressure that are established during the laser
pulse. This leads to so called hydrothermal synthesis of NP of unusual morphology, e.g.,
platelets or disks of Pb(Zr,Ti)O
3
[63]. Aqueous solutions at pressure and temperature that
exceed its critical value take on the ability to dissolve solids that are not soluble in normal
conditions. Synthesis of compounds via their dissolution in supercritical compounds is called
the hydrothermal one. In nature this type of synthesis occurs in the vicinity of underwater
volcano, which results in formation of various minerals. Hydrothermal synthesis is typical for
non-metallic compounds, such as oxides of more complex ceramics. The material of the
target is dispersed and dissolved in a supercritical medium during the laser pulse. Upon
cooling the solubility drops, and the formation of NP occurs from oversaturated solution.
Apparently, similar process may take place under laser ablation of single crystal rutile in an
aqueous environment [64].
The specific surface of NP is very high, for instance, 1 ml of Au colloid prepared by laser
ablation of a bulk target at typical density has the surface of 30 m
2
. High surface favors
catalytic reactions in liquids. Not only NP material but also the liquid itself may undergo
chemical changes during laser ablation. In some cases these changes are catalyst-specific that
is occur with NP of some specific metals. Laser exposure of most metallic targets (Sn, brass,
etc.) in ethanol leads to its noticeable modification towards formation of products with higher
molecular mass. Indeed, a wide absorption band centered at 350 nm is observed that
correspond to a viscous non-volatile liquid that remains after evaporation of the colloidal
solution synthesized by laser ablation. This product might be a low-molecular mass
polyethylene, which may also form a kind of shell on the synthesized NP. Formation of this
product occurs mostly on the stage of exposure of NP to laser radiation, and catalytic effects
of its formation mediated by NP of various compositions are not excluded.
Modeling of Distribution Function
Modeling of distribution function of nanoparticles size can be performed by a numerical
solution of kinetic equation on the basis of first principles. The following processes should be
taken into account: generation of nanoparticles by laser ablation of a solid target immersed
into liquid, aggregation of nanoparticles, their fragmentation and escape of NP adsorbed on
the wall of a reactor [25, 65]. In the specific conditions of laser ablation in liquids, the last
term can be negligibly small unlike laser ablation in vacuum. On the contrary, fragmentation
of the particles in the laser beam is the main channel of modification of their distribution
function. The peculiar feature of ablation in liquids is simultaneous action of all 4 processes,
since the generated NP remain in the liquid and, in particular, on the optical path of laser
beam. Formation of NP due to coagulation of individual metal atoms ejected from the target
is unlikely, since the necessary condition of their synthesis is melting of the target. NP are
ejected from the target at the very beginning of ablation.
Melting of NP and their subsequent fragmentation may occur only in those areas of the
liquid where the peak power of laser radiation is sufficiently high. The model takes into
account a factor proportional to the ratio of the volume of laser beam waist to total volume of
the liquid. In typical experimental conditions this factor is about 10
-4
, which explains the need
of prolonged laser exposures required to alter the distribution function at measurable level.
Laser exposure of NP in liquid in absence of the metal target results in their
fragmentation due to absorption of laser energy by individual particles. Under laser fluence
typically used NP are molten during the laser pulse, and their splitting is due to hydrodynamic
instabilities of the molten metal embedded into a vapor pocket. According to the model
derived above, the size of the particles goes to 0 under long exposure. In reality for each value
of laser fluence there is a certain minimal size of particles that are too small to absorb the
energy sufficient for their melting from laser beam. The model that takes into account all
above-mentioned considerations shows good qualitative agreement with the experimentally
measured distribution function [25].
INFLUENCE OF INTENSITY DISTRIBUTION OF THE LASER
BEAM ON THE SHAPE OF NANOPARTICLES
The influence of the laser beam profile onto the morphology of NP generated via laser
ablation of solids in liquids is not studied so far and is often ignored in current scientific
literature. The origin of this influence is a certain value of the energy density of the laser
beam, which is needed to melt the target material. The size and shape of NP generated via
laser ablation are sensitive to the laser fluence. Typically higher fluence leads to higher
average size of generated NP. Also, in case of laser ablation of Au at elevated laser fluence
the generated NP have elongated shape (see Figure 6). The term elevated should be
understood in term of laser fluence needed to melt the target surface. One may suggest that
this is due to specific way of interaction of the melt bath within the laser spot with
surrounding medium. Indeed, sputtering of the melt is due to splashing of the molten layer on
the target surface by high pressure vapors of surrounding liquid. However, the ejection of the
melt in the central areas of the laser spot is different from that at its periphery. The melt
ejected in the spot center has high probability to return to the target surface being pushed by
the expanding vapor cloud. On the contrary, ejection of the melt from the periphery of the
melt bath very likely results in the formation of NP, since the lateral dimensions of the
expanding vapor pocket above the target are quite close to the laser spot size. This means that
only the edges of the molten area contribute to NP formation, while the central part of the
laser spot provides relatively small fraction of NP.
These considerations suggest the following experiment on NP generation in which the
laser beam that causes ablation of a target immersed into liquid has another type of symmetry
of its intensity distribution different from that of a flat-top or Gaussian profile. A good
possibility is formation of a periodic intensity distribution in the plane of the target. Such
G. A. Shafeev 216
periodic distribution may occur spontaneously due to, for example, interference of the laser
beam with Surface Electromagnetic Wave excited in the solid by this beam. Another
possibility is exposure of the target to the interference pattern of two coherent laser beams. In
this case the laser fluence is a periodic function along one of coordinate, so does the
temperature distribution as schematically shown in Figure 17.
If the fluence in the maxima of interference pattern are sufficient to melt the target, then
the melt baths will have elongated shape on the target, which in turn may affect the shape of
ejected NP.
The experimental setup is shown in Figure 18. A Cu vapor laser emits at two laser lines,
either green (510.6 nm) or yellow (578.2 nm). In this particular experiment only one output
was used, namely, the green one. The green laser beam was split into two beams of
approximately equal intensities using dividing glass cube. These two beams were
superimposed on the surface of a gold target placed into liquid ethanol. The angle between
two beams corresponded to the interference pattern on the target surface with period of 4 m.
The cell with gold sample was moved under the laser beams in the direction parallel to the
maxima of interference pattern.

Figure 17. Temperature distribution on a target exposed to two coherent laser beams. Solid line
T(x)=T
m
indicates melting temperature of the target

Figure 18. Experimental setup on laser-assisted synthesis of elongated Au NP. 1 laser beam (Cu vapor
laser, 510.6 nm laser output), 2 splitting cube, 3 dielectric mirror, 4 focusing lens, 5 cell, 6 Au
target, 7 liquid ethanol
1
2
3
4
5
6 7

Figure 19. TEM view of Au nanoparticles obtained by ablation of an Au target in ethanol by two
interfering laser beams of a Cu vapor laser. Scale bar denotes 50 nm
Ablation of the Au target in these conditions results in visible coloration of the liquid, and
the color of the solution has bluish tint typical of elongated Au NP. TEM examination of
generated Au colloid confirms the presence of elongated Au NP, as demonstrated in Figure
19. Some Au NP are indeed elongated, and their aspect ratio (ratio of length to diameter)
exceeds 10.
NANOSTRUCTURING OF SOLIDS UNDER
THEIR LASER ABLATION IN LIQUIDS
The total laser fluence absorbed by a target should be sufficient to melt it in order to
produce NP in the liquids. Ideally smooth surface is characterized by definite threshold laser
fluence needed for melting. In practice the surface of a target has certain micro-roughness,
and this surface may not melt simultaneously. Indeed, any protrusion which is weakly
thermally coupled to the bulk of the target is molten at lower fluence than the smooth target.
Therefore, at certain fluence a rough surface will not be molten only in some protruding
areas. The vapors of surrounding liquid that expands from the target will then carry away the
molten fragments thus forming spikes in its surface. The rate of NP generation in the liquid is
very low, so at threshold laser fluence the material tends to leave the target in the form of NP
but remains on it solidified as nano-spikes or nano-bumps. Period of nano-spikes does not
depend on the laser wavelength and is determined mostly by characteristics of the target
material.
Formation of NS on the target is accompanied by modification of its absorption spectrum.
Indeed, the electrons that oscillate within single NP are also confined, and therefore the spike
edges act like the edge of NP as soon as their dimensions are compared with mean free path
of electrons at Fermi level (see Figure 20).
G. A. Shafeev 218

Figure 20. Origin of the surface coloration. Schematic view of oscillations of free electrons in metallic
nanostructures. Plasmon resonance of these electrons is close to that of nanoparticles of the same lateral
dimensions

Figure 21. Absorption of an Ag target ablated under water layer with 5 ps laser pulses at wavelength of
248 nm. Black curve corresponds to initial Ag target while the red one to Ag with NS
This confinement causes the coloration of some metals with formed NS. For instance, Ag
plate with NS looks yellow in appearance [66]. A macro view of Ag surface with NS is
shown in Figure , a. Yellowish coloration in Ag is typical of silver NP.
Absorption spectrum of both initial Ag target and of Ag with NS is shown in Figure 21.
Initial spectrum corresponds to plasmon resonance of electrons in bulk Ag. Formation of
NS manifests itself in broadening of this resonance. A new maximum appears near 360 nm.
This maximum shifts to red with oxidation of Ag upon storage in air during several days.
Similar modifications of absorption have also been observed in large variety of metals, e.g.,
Ti, W, Cu, etc., subjected to laser ablation in liquids at threshold laser fluence.
Typical morphology of both Ag and Ta target with NS formed by laser ablation in water
is presented in Figure 16. One can see that the period of NS is about 50 nm for Ag and 300
nm for Ta, which is much smaller than laser spot. In this sense NS are self-organized. NS on
Ta are characterized by high aspect ratio, while on Ag they are rather nano-bumps.
Formation of NS on metallic targets ablated in liquids requires sufficiently short laser
pulses. Indeed, no NS are formed with nanosecond pulse duration. The longest tested pulses
that produce NS are 350 ps delivered by a Nd:YAG laser at wavelength of 1.06 m. Another
300 400 500 600 700 800
0,0
0,2
0,4
0,6
0,8
1,0
A
Wavelength, nm
necessary condition for formation of NS is certain initial roughness of the target surface. The
local roughness required for NS formation should exceed 30-50 nm. These two conditions
allow suggesting local melting of the target in the micro-protrusions of the target relief, which
develops with further increase of the number of laser shots into an array of self-organized
nano-spikes.
The process of NS formation under laser ablation of solids immersed into liquids requires
further studies. However the experimental data available so far indicate relation of NS to
some instability that develops at the interface melt-vapor of liquid within the laser spot. In
typical conditions the pressure of vapor of the liquid exceed by at least one order of
magnitude the capillary pressure stipulated by curvature of the melt surface, so the recoil
pressure of vapor that expands from the target plays dominant role.

Figure 22. AFM view of NS on Ag (top) and Ta (bottom). NS were generated by ablation of
corresponding metal target in water, pulse width of 350 ps at wavelength of 1.06 m
G. A. Shafeev 220

Figure 23. Schematic picture of detachment of nanodrops from the melt on the surface of a solid target
Nanostructures on Ag generated by its laser ablation in water show the SERS effect of
adsorbed organic molecules [67]. The estimated enhancement factor is about 10
5
. Unlike Ag
colloid in a liquid, Ag plate with nanostructures can be used for SERS measurements many
times, since the NS do not degrade upon measurements.
Different stages of NS development are schematically shown in the Figure 23. These
structures correspond to morphology that can be found within the laser spot on the target. At
sufficiently high laser fluence the nano-drop of the melt is detached from the target surface
into surrounding liquid as nanoparticles.
It is also clear that probe microscopes fail to image correctly the mushroom-like
structures. This type of nanostructures is imaged by an AFM as a cone.
Small size of NS implies another mechanism of their formation, which should not involve
capillary waves. Indeed, capillary waves with period of hundreds of nanometers would be
suppressed since capillary pressure at this scale tends to smooth the melt.
Thus, formation of nanostructures under laser ablation of metals in liquid environment is
a general conformity. It is characterized by several features. First, nanostructures are observed
only in case of sufficiently short laser pulses. Second. Their period foes not depend on the
laser wavelength. Nanostructures are merely different from periodic ripples that are generated
owing to interference of a Surface Electromagnetic Wave with laser beam.
The reviewed results on laser-assisted generation of nanoparticles via laser ablation in
liquids represent only one point of view. Recent review [69] and recent book [70] consider
another processes and approaches that have been developed during last decade.
EXCITATION OF HIGH ENERGY LEVELS
In typical conditions of experiments on laser ablation of solids in liquid environment the
nanoparticles (NP) sputtered into liquid are optically thin at the wavelength of most common
lasers. Despite their small size (about 10 nm), the NP can efficiently absorb the laser
radiation. The efficiency of this interaction is a function of numerous experimental
parameters, such as particle size, detuning of laser frequency from the position of the plasmon
resonance of NP, etc. However in most cases, NP are optically thin, that is almost transparent
at the laser wavelength. Hence, the time required to reach their temperature under laser
exposure is shorter than the duration of laser pulse as soon as the latter exceeds the
characteristic time of electron-phonon relaxation. The temperature of NP inside the laser
beam is proportional to the peak power of the laser radiation. Estimations show that the
temperature of Au nanoparticles inside Cu vapor laser beam with peak intensity of 10
8
W/cm
2

is several kK, and this temperature scales linearly with laser intensity. Therefore, exposure of
NP suspension in liquid environment is a novel approach that allows excitation of high
energy levels of both the NP material and its close environment. The liquid surrounding the
NP in this case turns into a vapor having high temperature and pressure, and eventually into
plasma that perfectly surrounds it. The present paper describes several proofs that laser
exposure of NP suspension in liquid may lead to excitation of high energy levels including
those of nuclei and neutron release. Laser initiation of neutron emission may open new
possibilities for transformation of elements, synthesis of desired isotopes, disposal of nuclear
waste, etc. The suspension of Hg in D
2
O is a model system for laser-assisted transmutation of
Hg into Au since the neutron binding energy in D has the lowest value [71,72].
Two kinds of Hg were used for a model system of transmutation of Hg into Au: (i) Hg of
analytical purity with natural isotopic composition or (ii) enriched Hg containing 55.6% of
196
Hg and 41.4 % of
199
Hg, with much lower content of other isotopes, obtained by selective
photochemical reaction of Hg with oxygen [73].
Exposure of the colloidal solution of Au NP in water to radiation of a 350 ps Nd:YAG
laser is accompanied by visible emission from the solution. The spectrum of this emission
contains several spectral features. The first one corresponds to anti-Stokes Raman scattering
of H
2
O vapors of laser radiation excited at 1060 nm. The second broad peak coincides with
the emission of atomic Au(I) at 627.8 nm during transition from the resonant to the meta-
stable level. The peak at 530 nm coincides with the position of plasmon resonance of Au NP
in H
2
O. One can also see that the laser-produced plasma is characterized by intense UV
radiation at least up to 200 nm where water itself and Au NP have strong absorption [74].
If the laser spark is placed in the vicinity of a Be window of the cell one can get an image
of a metallic grid on Be using an X-ray photo film, though the exposure time has to be at least
2 hours. Therefore, both deep UV and X-ray radiation is produced during exposure of Au NP
colloid in H
2
O to laser radiation with rather moderate intensity. This result is in agreement
with previous observations of X-ray emission under exposure of aqueous solutions to
femtosecond laser radiation [75,76].
The energy of X-ray photons is sufficient to cause the modification of the NP
environment. This has been confirmed in a model experiment on exposure of Au NP in D
2
O
to radiation of a 350 ps Nd:YAG laser at peak intensity of 10
10
W/cm
2
. Raman spectrum of
D
2
O with Au NP subjected to 2 hours laser exposure indicates the formation of HDO
molecules.
Suspension of Hg in D
2
O is characterized by an absorption peak in the range 270-290 nm
even prior to laser exposure. This peak is assigned to the plasmon resonance of Hg NP, which
is close to the theoretical position of 290 nm reported for 10 nm NP of Hg in H
2
O [18].
Therefore, in the initial stages, exposure of Hg suspensions to laser radiation leads to the
formation of Hg NP (size of the order of 10 nm). Using either a Cu vapor laser (8 hours of
exposure) or a 100 femtosecond Ti:sapphire laser (2 hours of exposure), no Au content was
detected within the accuracy of measurements.
After exposure to a 90 ps Nd:YAG laser radiation, the suspension precipitates very
slowly, unlike a freshly prepared suspension in ultrasonic bath. After 1 day of sedimentation
the liquid separated into two parts, the first close to the bottom and the other remaining in
suspension. Analytic data presented in Table 1 show the formation of Au.
Experiments with a 350 ps Nd:YAG laser were carried out with two types of Hg samples,
either of natural isotopic composition or enriched with
196
Hg. Results of analysis of Hg
suspension of natural isotope composition in D
2
O are similar to those obtained with a 90 ps
laser. The formation of Au in exposed suspensions of Hg in D
2
O is confirmed by analysis,
though in general the Au/Hg ratio is lower.
G. A. Shafeev 222
Table 1. Analysis of Hg samples of natural isotope composition exposed
to radiation of a 90 ps Nd:YAG laser, exposure time of 60 min
Sample Hg in D
2
O
initial
Hg in D
2
O
sample 1
Hg in D
2
O
sample 2
Hg, mg/l 35 23 8
Au, mg/l 0.009 0.1 0.024
Au/Hg ratio 0.00026 0.0043 0.003
Table 2. Exposure of suspension of
196
Hg in D
2
O to radiation of a
350 ps Nd :YAG laser. The results are averaged over 4 different exposures
Sample
196
Hg/D
2
O
initial

196
Hg/D
2
O
exposed Hg drop
196
Hg/D
2
O
4 hours of exposure
(averaged over 4 samples)
196
Hg/D
2
O after
sedimentation
Au, mg/l 0.0073 0.38 0.23 0.17
Hg, mg/l 20 8.94 2.31 12.6
Au/Hg 0.00036 0.0425 0.10 0.0135

The results of analysis for Hg enriched with
196
Hg are presented in Table 2. Note that Au
content is found under laser exposure of a Hg drop immersed into D
2
O for about 10 min in
order to disperse the metal. Four hours of laser exposure increases the Au content to almost
10%.
The mechanism of transmutation is still under discussion. The effect is observed only
under sufficiently long laser pulses of picosecond range. One may suggest that the beginning
of a laser pulse ionizes the nanoparticles within the laser beam while the remaining laser
energy is spent for acceleration of electrons as it is observed in the case of interaction of
strong laser beams with plasma [77]. These electrons provide X-ray photons needed for
release of a neutron from Deuterium.
CONCLUSION
The research on the processes of laser ablation in liquids is still in progress. There is a
certain hope that the simplicity of the experimental setup on laser-matter interaction will
allow developing new cost-effective technologies. Several specific features, such as the
absence of a vacuum, may provide wide use of liquid-assisted generation of nanoparticles in
medicine, catalysis, etc. The novel process of laser-assisted nanostructuring of solids via their
laser ablation in a liquid environment is also of high interest for various applications in
medicine, biology, aero- and hydrodynamics.
REFERENCES
[1] Nedersen, J; Chumanov, G; Cotton, TM. Appl. Spectrosc., 1993, 47, 1959.
[2] Sibbald, MS; Chumanov, G; Cotton, TM. J. Phys. Chem., 1996, 100, 4672.
[3] Fojtik, A; Henglein, A. Ber. Busenges. Phys.Chem., 1993, 97, 252.
[4] Henglein, A. J. Phys.Chem., 1993, 97, 5457.
[5] Prochzka, M; tepnek, B; Vickova, I; Srnova, P. Maly, J. Mol. Struct,1997, 410/411,
213.
[6] Prochzka, M; Mojze, P; tepnek, J; Vlkov, B; Turpin, PY. Anal. Chem., 1997, 69,
5103.
[7] Prochzka, M; tepnek, J; Vlkov, B; Sronov, I; Mal, P. J.Mol. Struc., 1997, 410,
213.
[8] Srnov, I; Prochzka, M; Vlkov, B; tepnek, J; Mal, P. Langmuir, 1998, 14, 4666.
[9] Jeon, JS; Yeh, CH. J. Chin. Chem. Soc., 1998, 45, 721.
[10] Yeh, MS; Yang, YS; Lee, YP; Lee, HF; Yeh, YH; Yeh, CS. J. Phys.Chem., 1999, B
103, 6851.
[11] Takami, A; Kurita, H; Koda, S. J. Phys.Chem., 1999, B103, 1226.
[12] Link, S; Burda, C; Nikoobakht, B; El-Sayed, MA. J. Phys.Chem., 2000, B104, 6152.
[13] Mafun, F; Kohno, J; Takeda, Y; Kondow, T; Sawabe, H. J. Phys. Chem., 2000, B 104,
9111.
[14] Mafun, F; Kohno, J; Takeda, Y; Kondow, T; Sawabe, H. J. Phys. Chem., 2001, B 105,
5114.
[15] Simakin, AV; Voronov, VV; Shafeev, GA; Brayner, R; Bozon-Verduraz, F. Chem.
Phys. Lett., 2001, 348, 182.
[16] Dolgaev, SI; Simakin, AV; Voronov, VV; Shafeev, GA; Bozon-Verduraz, F.
Appl.Surf.Sci., 2002, 186, 546.
[17] Kamat, PV; Flumiani, M; Hartland, GV. J. Phys.Chem., 1998, B 102, 3123.
[18] Creighton, JA; Eadon, DG. J. Chem. Soc. Faraday Trans., 1991, 87, 3881.
[19] Mulvaney, P. Langmuir, 1996, 12, 788.
[20] Ganeev, RA; Ryasnyansky, AI; Tugushev, RI; Usmanov, T. J. Opt. A: Pure Appl. Opt,
2003, 5, 409.
[21] Shafeev, GA; Freysz, E; Bozon-Verduraz, F. Appl. Phys., 2003, A78, 307.
[22] Karavansky, VA; Simakin, AV; Krasovsky, VI; Ivanchenko, PV. Quantum Electronics,
2004, 34(7), 644.
[23] Kazakevich, PV; Simakin, AV; Shafeev, GA; Quantum Electronics, 2005, 35, 831-834.
[24] Link, S; El-Sayed, M. J. hys. Chem., 1999, B103, 8410.
[25] Simakin, AV; Voronov, VV; Kirichenko, NA; Shafeev, GA. Appl. Phys., 2004, A79,
1127-1132.
[26] Mafune, F; Kohno, JY; Takeda, Y; Kondow, T. J.Phys. Chem., 2000, 104, 8333.
[27] Tsuji, T; Kakita, T; Tsuji, M. Appl.Surf. Sci., 2003, 206, 314.
[28] Nikoobakht, B; El-Sayed, MA. Chem. Mater., 2003, 15, 1957.
[29] Mafun, F; Kohno, JY; Takeda, Y; Kondow, T; Sawabe, H. J. Phys.Chem., 2000, B104,
9111.
[30] Mafun, F; Kohno, JY; Takeda, Y; Kondow, T; Sawabe, H. J. Phys.Chem., 2001,
B105, 5144.
[31] Chen, YH; Yeh, CS. Colloids Surf., 2002, 197, 133.
[32] Kabashin, AV; Meunier, M. J. Appl. Phys., 2003, 94, 7941.
[33] Compagnini, G; Scalisi, AA ; Puglisi, O. J. Appl. Phys., 2003, 94(12), 7874.
[34] Sylvestre, JP; Kabashin, AV; Sacher, E; Meunier, M; Luong, JHT. J. Am. Chem. Soc.,
2004, 126, 7176.
G. A. Shafeev 224
[35] Mafun, F; Kohno, JY; Takeda, Yo; Kondow, T. J. Phys. Chem. B, 2003, 107, 4218-
4223.
[36] Jeon, JS; Yeh, CH. J. Chin. Chem. Soc., 1998, 45, 721.
[37] Tsuji, T; Iryo, K; Watanabe, N; Tsuji, M. Appl. Surf. Sci., 2002, 202, 80.
[38] Zhang, XY; Zhang, LD; Lei, Y; Zhao, LX; Mao, YQ. J. Mat. Chem., 2001, 11, 1732.
[39] van der Zande, BMI; Bohmer, MR; Fokkink, LGJ; Schonenberger, C. Langmuir, 2000,
16, 451.
[40] Chang, SS; Shih, CW; Chen, CD; Lai, WC; Wang, CRC. Langmuir, 1999, 15, 701.
[41] Yu, YY; Chang, SS; Lee, CL; Wang, CRC. J. Phys. Chem., 1997, B101, 6661.
[42] Kazakevich, PV; Simakin, AV; Shafeev, GA. Chem. Phys. Lett., 2006, 421, 348-350.
See also in: Kazakevich, PV; Simakin, AV; Shafeev, GA; Viau, G; Soumare, Y;
Bozon-Verduraz, F. Appl. Surf. Sci., 2007, 253 7831-7834.
[43] Link, S; El-Sayed, M. J. hys. Chem., 1999, B103, 8410.
[44] Chen, YH; Tseng, YH; Yeh, CS. J. Mater Chem., 2002, 12, 1419.
[45] Kim, Y; Johnson, RC; Li, J; Hupp, JT; Schatz, GC. J. hys. Chem., 2002, 352, 421.
[46] Abid, JP; Girault, HH; Brevet, PF. Chem.Comm., 2001, 829.
[47] Izgaliev, AT; Simakin, AV; Shafeev, GA. Quantum Electronics, 2004, 34(1),
47-52.
[48] Izgaliev, AT; Simakin, AV; Shafeev, GA; Bozon-Verduraz, F. Chem.Phys. Lett., 2004,
390, 467.
[49] Kazakevich, PV; Simakin, AV; Voronov, VV; Shafeev, GA. Appl.Surf. Sci., 2006, 252,
4373.
[50] Kazakevich, PV; Voronov, VV; Simakin, AV; Shafeev, GA. 2004, Quantum
Electronics, 34(10) 951.
[51] Kazakevich, PV; Voronov, VV; Simakin, AV; Shafeev, GA. Appl. Surf. Sci., 2006, 252,
4373.
[52] Yeh, YH; Yeh, MS; Lee, YP; Yeh, CS. Chemistry Letters, 1998, 1183-1184.
[53] Yeh, MS; Yang, YS; Lee, YP; Lee, HF; Yeh, YH; Yeh, CS. J. Phys. Chem., 1999, B
103, 6851-6857.
[54] Voronov, VV; Kazakevich, PV; Simakin, AV; Shafeev, GA. 2004, JETP Letters,
80(11), 684.
[55] Wautelet, M; Dauchot, JP; Hecq, M. Nanotechnology, 2000, 11, 6-9, Wautelet, M;
Dauchot, JP; Hecq, M. Materials Science and Engineering, 2003, C 23 187-190,
Vallee, R; Wautelet, M; Dauchot, JP; Hecq, M. Nanotechnology, 2001, 12, 68-74.
[56] Lo, KY; Lue, JT. Phys. Rev., 1995, B51(4), 2467. Aktsipetrov, OA; Elyutin, PV;
Fedyanin, AA; Nikulin, AA; Rubtsov, AN. Surface Science, 1995, 325(3), 343.
[58] Compagnini, G; Scalisi, AA; Puglisi, O. Phys. Chem. Chem. Phys., 2002, 4, 2787-2791.
[59] Sasaki, T; Liang, C; Nichols, WT; Shimizu, Y; Koshizaki, N. Appl. Phys., 2004, A79
1489.
[60] Liang, C; Shimizu, Y; Sasaki, T; Koshizaki, N. J. Phys. Chem., 2003, B107, 9220-
9225.
[61] Lima, MSF; Ladrio, FP; Riva, R. Appl. Surf. Sci., 2006, 252, 4420-4424.
[62] Chen, GX; Hong, MH; He, Q; Chen, WZ; Elim, HI; Ji, W; Chong, TC. 2004, Appl.
Phys. A, 79, 1079.
[63] Kruusing, A. Optics and Lasers in Engineering, 2004,41, 307.
[64] Iwabuchi, A; Choo, CK; Tanaka, K. J. Phys. Chem., 2004, B108, 10863.
[65] Bozon-Verduraz, F; Brayner, R; Voronov, VV; Kirichenko, NA; Simakin, AV;
Shafeev, GA. Quantum Electronics, 2003, 33(8), 714-720.
[66] Zavedeev, EV; Petrovskaya, AV; Simakin, AV; Shafeev, GA. Quantum Electronics,
2006, 36(10), 978-980.
[67] Lau Truong, S; Levi, G; Bozon-Verduraz, F; Petrovskaya, AV; Simakin, AV; Shafeev,
GA. Appl.Phys., 2007, A89 (2), 373-376.
[68] Lau Truong, S; Levi, G; Bozon-Verduraz, F; Petrovskaya, AV; Simakin, AV; Shafeev,
GA. Applied Surface Science, 2007, 254, 1236-1239.
[69] Yang, GW. Progress in Materials Science, 2007, 52, 648-698.
[70] Kruusing, A. Handbook of Liquids-assisted laser processing, Elsevier, 2008, 454.
[71] Shafeev, GA; Bozon-Verduraz, F; Robert, M. Preprint of GPI, No45, Moscow, April
12, 2006.
[72] Shafeev, GA; Bozon-Verduraz, F; Robert, M. Physics of Wave Phenomena, 2007,
15(3), 131-136.
[73] Viazovetsky, Yu.V; Senchenkov, AP. Journal of Technical Physics, 1998,
68(1), 67.
[74] Shafeev, GA; Simakin, AV; Bozon-Verduraz, F; Robert, M. Applied Surface Science
2007, 254 1022-1026.
[75] Hatanaka, K; Miura, T; Fukumura, H. Appl.Phys.Lett., 2002, 80(21), 3925.
[76] Hatanaka, K; Fukumura, H. X-ray generation from optical transparent materials by
focusing ultra-short laser pulses, Chapter 9 in: Three-Dimensional Laser
Microfabrication: Principles and Applications, H; Misawa, S. Juodkazis, Eds. Wiley-
VCH, 2006, (199-238).
[77] Pukhov, A; Meyer-ter-Vehn, J. Appl. Phys., 2002, B74, 355.
Chapter 9
NANODIAMONDS FROM LASER
ABLATION IN LIQUID
G. W. Yang
*
State Key Laboratory of Optoelectronic Materials and Technologies, Institute of
Optoelectronic and Functional Composite Materials, School of Physics Science and
Engineering, Zhongshan University, Guangzhou, P.R. China
ABSTRACT
Laser ablation in liquid, i.e. pulsed-laser induced liquid-solid interface reaction
(PLIIR) has been developed to synthesize diamond nanocrystals. Chemical and physical
mechanisms of the nanodiamonds synthesis upon PLIIR are addressed based on the
nucleation thermodynamics and growth kinetics. Our studies showed that PLIIR could be
expected to be a general route to synthesize the nanocrystals with the metastable phases.
1. INTRODUCTION
Pulsed-laser ablation of solid materials has been studied intensively in recent years,
because it has shown the great potential in laser material processing including thin solid film
preparation, nanocrystals synthesis, laser surface cleaning, and device fabrication. Since laser
ablations of solid materials are easily carried out in conventional deposition chambers with
vacuum or filled gases, most of researchers have focused their attention on pulsed laser
ablation of solid target in vacuum and diluted gas, i.e. pulsed laser ablation at gas-solid
interface, aiming at various applications above [1]. Compared with applications of pulsed
laser ablation at gas-solid interface, however, the application of pulsed laser ablation of solid
target in a confined liquid are really comparatively limited in the field of interactions between
pulsed laser and materials [4,5]. Recently, Yang et al. and Singh et al. have clarified that

*
Corresponding author: E-mail: stsygw@mail.sysu.edu.cn, Tel. & Fax: +86-20-8411-3692.
G. W. Yang 228
pulsed-laser ablation in a confined liquid is an effective method to syntheses metastable phase
nanocrystals and nanostructures and named the novel method to be the novel method is
named to be pulsed-laser induced liquid-solid interface reaction (PLIIR) [30-37]. Typically,
diamond and c-BN nanocrystals and immiscible alloying nanocrystals and nanorodes have
been synthesized by PLIIR. Following them, many researchers started to express their
interesting in synthesis of a variety of nanocrystals by PLIIR [38-58]. For example,
nanocrystals of element metals and alloys such as Ti, Au, Ag, Fe-Ni, and TiC, quantum dots
of ZnS and US, ultrafine oxide nanocrystals such as SnO
2-x
and CeO
2
, and Ag
2
Se
nanocrystals. To further extend the application of PLIIR in synthesis of nanocrystals and have
a clear insight into laser ablation in a confined liquid, in this review chapter, we therefore
introduce the fundament physical and chemical aspects, and applications of PLIIR in
fabrications of nanostructures.
2. LASER ABLATION IN LIQUID
2.1. Fundamental Processes in Laser Ablation In Liquid
The pioneer work of pulsed laser ablation in liquid for materials synthesis was reported in
1987, in which authors first time synthesized the iron oxides with metastable phase by pulsed
laser ablation of a iron target in water [11]. Since then, few researchers started to use the
novel pulsed laser ablation to prepare new materials such as metallic oxides and nitrides [85-
87], diamond and diamond-like carbon [12-14,88-90], and carbon nanotubes [91]. Generally,
for laser ablation in liquid, three basic processes of the plasma plume from laser ablation of
solid target in liquid, i.e. generating, transforming, and condensing, will play important roles
in materials synthesis. Basically, a plasma plume from the solid target will generate on the
interface when the front part of the incident laser pulse irradiate the interface between the
solid target and the confined liquid through the liquid schematically illustrated in Figure 1 (a),
and we call the plasma to be the laser-induced plasma. Different from free expansion of the
plasma plume from pulsed laser ablation in vacuum and dilution gas, the expansion of the
laser-induced plasma is confined by the liquid once generation. Following Fabbro [7-10,16-
20], there is the formation of the shock wave by the laser-induced plasma. The laser-induced
plasma adiabatically expands at a supersonic velocity to create a shock wave in front when it
absorbed the later part irradiation of the laser pulse and got the continual complement of the
vaporizing species from the solid target. Then, the shock wave will induce an extra pressure
called plasma-induced pressure in the laser-induced plasma. Further, the plasma-induced
pressure will lead to an additional temperature increasing of the laser-induced plasma.
Therefore, the shock wave induced by the laser-induced plasma pushes the laser-induced
plasma into the state of higher temperature, higher pressure, and higher density (HTHPHD).
For example, Berthe et al. reported that the plasma-induced pressure levels reach to 2-2.5
GPa when the 0.308 m XeCl excimer laser with pulse duration of 50 ns and power of 1-2
GWcm
-2
was applied to ablate the Al target in water [18]. Then, Peyre et al. reported that the
short laser pulse such as 3 ns allows the generation of higher plasma-induced pressure than
longer pulse like as 30 ns (10 GPa versus 5 GPa) [19]. In fact, the wavelength and power of
the laser pulse can influence on the value of the plasma-induced pressure [17]. Moreover,
Nanodiamonds from Laser Ablation in Liquid 229
Sakkas measurements showed that the density of the ablation species is 10
22
-10
23
cm
-3
, the
temperature of laser-induced plasma is 4000-5000 K, and the pressure of laser-induced
plasma is about 10 GPa, when the 532 nm Nd:YAG laser with pulse duration of 10 ns and
power of 10
10
Wcm
-2
was used to ablate a isotropic graphite target in water [117].

(a)

(b)

(c)

(d1) (d2)
Figure 1. Three typical stages of the laser-induced plasma evolution in vacuum or dilution gas. (a) The
generation of the laser-induced plasma on the surface when the front part of the laser pulse ablating the
target. (b) The free expansion of the laser-induced plasma in vacuum or gas when the plasma absorbed
the later part of the laser pulse. (c) The ejection of the plasma plume from the target. (d) Two different
condensations of the laser-induced plasma: one is used to deposit thin films on substrates, and another
one is used to synthesize nanoparticles in gases
G. W. Yang 230

Figure 2. The evolution of the laser-induced plasma in liquid. (a) The generation of the laser-induced
plasma due to the irradiation of the front part of the laser pulse on the target. (b) The expansion of the
plasma plume in liquid due to the absorbing the later laser pulse and the plasma-induced pressure
created by the shock wave. (c) Four kinds of chemical reactions taking place inside the plasma and
liquid, and the interface between the plasma and liquid. (d) Two condensations of the plasma plume in
liquid: one is used to prepare surface coatings on the target surface, and another one is used to fabricate
nanoparticles in liquid
Accordingly, the special laser-induced plasma with HTHPHD generates at the liquid-
solid interface when the laser pulse irradiated the surface of the solid target through the liquid,
due to the confined effect of the liquid, shown in Figure 2 (b). Noted that the thermodynamic
state with HTHPHD is obviously favorable for the formation of the metastable phases that are
in the high-temperature and high-pressure region in their thermodynamic equilibrium phase
diagram.
Four kinds of chemical reactions would take place in the laser-induced plasma and at the
interface between the laser-induced plasma and the liquid during the transformation of the
laser-induced plasma. The first kind of the chemical reaction occurs inside the laser-induced
plasma. Owing to the laser-induced plasma being in the state with HTHPHD, the new phase,
especially metastable phase, could form by high-temperature chemical reacting between the
ablations from the target. The second kind of chemical reaction also takes place inside the
laser-induced plasma, then, the reactant species are from the target and the liquid,
respectively. The high temperature and high pressure in front of the laser-induced plasma will
result in the excitation of the liquid molecules at the interface between the laser-induced
plasma and the liquid to create the new plasma of the liquid molecules, called the plasma-
induced plasma. Naturally, the plasma-induced plasma could rapid dissolve into the laser-
induced plasma once generation, then, the chemical reactions between the species from the
laser ablating target and the species from the liquid molecules excitation would appear inside
the laser-induced plasma. The third chemical reactions occur at the interface between the
laser-induced plasma and the liquid, because the state with HTHPHD of the laser-induced
plasma provides a good opportunity to the high-temperature chemical reactions between the
ablation species from the target and the molecules of the liquid, which would directly take
place at the plasma-liquid interface. The fourth kind of chemical reaction is inside the liquid.
The extremely pressure in front of the laser-induced plasma will impinge the ablation species
from the solid target at the plasma-liquid interface into the liquid, then, chemical reactions
between the ablation species and the liquid molecules would form inside the liquid. It is
noticed that three of four kinds of chemical reactions are simultaneously involved in two
species that are from the solid target and the confined liquid, respectively.

Figure 3. The emission spectra and their time dependence of pulsed laser ablation in liquid. (a) BO
molecules were detected by emission spectra when the Nd:YAG laser with wavelength of 1064 nm,
pulse duration of 20 ns, and the energy fluence of 8-9 J/cm
2
was used to ablate a hexagonal boron
nitride target in water. (b) CN molecules were synthesized by the same pulsed laser ablating a graphite
target in benzene solution
Therefore, these chemical reactions provide occasions to fabricate new materials
combining of the elements of the target and the liquid. Importantly, the reported experimental
200
20
150
0
0
5
10
15
350 400 450 500 550

(a)
200 2034 ns
BO
50
284 ns
200 434 ns
10
134 ns
5
44 ns
B
+

5
29 ns
0
10
20
30
0
20
40
60
0
10
20
30
0
50
100
400
10
3

I
n
t
e
n
s
i
t
y

(
a
r
b
i
t
r
a
r
y

u
n
i
t
)

Wavelength (nm)
B
+

0
10
20
0
5
10
20
10
0
10
20
5
10
0
30
0
40
10
3

5
5
5
50
50
150
29 ns
44 ns
59 ns
134 ns
434 ns
89 ns
CN violet system
C2 Swan system
350 400 450 500 550
Wavelength (nm)
I
n
t
e
n
s
i
t
y

(
a
r
b
i
t
r
a
r
y

u
n
i
t
)

15
0
5
10
15
(b)

G. W. Yang 232
data supported the deductions about the chemical reactions above. [11,31,23]. Figure 2 (c)
schematically illustrates these chemical reactions mentioned above. The last stage of the
plasma plume generated by the pulsed laser ablation in liquid is cooling down and
condensation in the confined liquid shown in Figure 2 (d). Clearly, just like as the pulsed
laser ablation in vacuum and dilution gas, the different condensation will result in different
application in materials preparations. A part of the plasma plume would condense and deposit
back on the surface of the solid target during the plasma quenching in the liquid, due to the
confined pressure from the liquid. Naturally, the condensation and deposition of the plasma
plume lead to thin films formation. Another part of plasma plume will condense and be
dispersed into the liquid during the plasma quenching, due to the cooling down of the
confined liquid. Therefore, the condensation of the plasma results in small particles
synthesized in the liquid. Generally, these small particles float on the surface of the liquid, as
they have a large surface tension.
Now, more and more researchers, who are interested in nanocrystals synthesis, have
stated to pay attention on the later [30-58]. Accordingly, it is a very interesting scene: the
productions of pulsed laser ablation in a confined liquid are dived into two parts, one part at
the liquids bottom in thin films, and another part at the liquids top in particles, respectively.
There are unique kinetic characters of pulsed laser ablation in a liquid. Firstly, the higher
ablating rate to the solid target can be created in pulsed laser ablation in a confined liquid than
that in vacuum and dilution gas. Clearly, the plasma with HTHPHD etches the solid target at
the plasma-solid interface to promote the total ablating rate of the laser ablating the target [28
29,118,119]. Zhu et al. reported the laser ablation rate of Si varies with the thickness of the
water layer above the Si target when a 248 nm KrF excimer with pulse duration of 23 ns was
used to ablate a single Si substrate, and found that the laser ablation rate is the most highly
enhanced with a water layer of 1.1 mm shown in Figure 4, as the optimal water layer
thickness can induced the strongest pressure in the laser-induced plasma. These results thus
show that the high producing can appear in the pulsed laser ablation in the confined liquid for
both of thin films deposition and small particles synthesis. Secondly, the shorter quenching
time of the laser-induced plasma can be achieved in the confined liquid. An experimental
comparison of the plasma durations is shown in Figure 5 [117]. Definitely, we can see that the
plasma duration of pulsed laser ablation in air is ten times than that of pulsed laser ablation in
liquid in the case. Accordingly, the plasma plume created by pulsed ablation in a liquid will
rapidly quench in the confined liquid. Noted that the novel kinetics opens a new door to
synthesize nanocrystals and nanostructures by pulsed laser ablation. Based on the three basic
processes of the plasma plume evolution in a confined liquid above, the production of laser
ablation generates in the duration of the plasma, in sequence, cluster forming, nucleating, and
crystals growing. Remarkably, the short quenching times of the plasma plume can effectively
limit the size of the crystals growing. For instance, the size of the synthesized nanocrystals
may be at the nanometer scale, when the quenching time of the plasma plume is the order of
magnitude of ns. In fact, the size distribution of all the small particles is at the nanoscale
when the laser pulses with pulse duration of less than 20 ns are used to synthesize
nanocrystals by laser ablation in a liquid [30-58]. Additionally, the cooling effect of the
confined liquid on the laser-induced plasma should enhance the formation of the metastable
structures generating in the plasma transformation. In other words, some metastable phases
can be frozen in the duration of the transition from metastable to stable, due to the
instantaneous cooling time (quenching time) of the plasma plume in the confined liquid. For
example, Yang et al. observed the intermediate phase from graphite to cubic diamond in the
synthesis of diamond nanocrystals by the pulsed laser ablating the graphite target in water
[30]. Apparently, the kinetics provides an advantage for the metastable phase preparation by
pulsed laser ablation in liquid.

Figure 4. The ablated depth of the hole left on the target surface vs laser pulse number at a laser fluence
of 4.5 J/cm2 in air and water

Figure 5. A comparison of the plasma durations between pulsed laser ablation in air and liquid. A series
of images of the visible plasma emission generated by the ablation of a pulsed Nd:YAG laser with
wavelength of 1064 nm, pulse duration of 20 ns, and the energy fluence of 10 J/cm
2
to a graphite target
in air (a) and water (b)
G. W. Yang 234
2.2. Synthesis of Nanocrystals Using Laser Ablation in Liquid
As the descriptions of the basic processes of the laser-induced plasma evolution in a
confined liquid above, two condensations of the plasma in the liquid can find their
applications in materials synthesis, respectively, one for nanocrystals fabrications, and
another one for thin films preparation. Actually, most of reports of materials researches
concerning pulsed laser ablation in liquid have focused on the two issues. Additionally, a few
of applications of pulsed laser ablation in liquid are involved in laser-based materials
processing such as drilling and welding, and Fabbro [120] and Kruusing [116] have devoted
two reviews for these special applications. To our knowledge, there are three kinds of
nanomaterails synthesized, i.e. nanocrystals of diamond and related materials, nanoparticles
of element metals, and nanostructures of metallic alloys and oxides, and two kinds of thin
films prepared, i.e. metallic oxides and nitrides, and diamond-like carbon and related
materials, by pulsed laser ablation in liquid in the literature. Accordingly, these applications
of pulsed laser ablation in liquid in materials preparations are briefly summarized as follows.
Researchers first selected diamond nanoparticles as the synthesized object by using
pulsed laser ablation in liquid, because one side that the properties of diamond are quite
extreme compared with that of other materials, and another side that the synthesis of
diamonds under conditions of normal temperature and pressure is not predicted by the
equilibrium thermodynamic phase diagram of carbon. Ogale et al. reported that diamond
particulates was detected from the productions of pulsed ruby laser irradiation of the pyrolytic
graphite target in the benzene solution by Raman spectroscopy, scanning electron microscope
(SEM) and small angle x-ray diffraction (XRD) [13]. Yang et al. [30-32] and Zheng et al.
[90] studied the formation of diamond nanocrystals from the Nd:YAG pulsed laser ablation of
a isotopic graphite target in water, acetone and alcohol, and characterized the structure and
crystalline morphology of diamond nanocrystals by Raman spectroscopy and transmission
electronic microscope (TEM). Importantly, a relatively complete Raman spectra [32] and nice
single crystal morphology and diffraction images of TEM [30] of diamond nanocrystals were
reported. Further, Pearce et al. [48] reported diamond nanocrystals were synthesized by the
Nd:YAG pulsed laser ablation of a pure graphite target in the cyclohexane, and provided the
selected area electron diffraction (SAD) of TEM and Raman spectra of diamond nanocrystals.
Notably, they pointed out that their study first time reproduced the findings of Yang et al.
[30]. Besides diamond nanocrystals, nanocrystals of diamond related materials were also
synthesized by pulsed laser ablation in liquid. -, -, cubic C
3
N
4
and cubic boron nitride
nanocrystals were prepared by the pulsed laser ablation of a hexagonal boron nitride target in
water and the ammonia solution, respectively [31,121], and the Fourier transform infrared
spectroscopy, XRD, energy dispersive x-ray spectroscopy (EDS) and TEM were used to
characterize the structure, composition, and crystalline morphology of the production.
Secondly, very recently, noble metals nanocrystals synthesis was intensively studied
upon pulsed laser ablation in liquid, due to their applications as catalyst. Simakin et al.
synthesized nanodisks of Au and Ag by the Cu vapor laser (wavelength 510.5 nm, pulse
duration 20 ns) ablation of Au and Ag target in water, in which the diameter and thickness of
nanodisks are in the of 20-60 nm range and few nanometers [38]. Meanwhile, nanoparticles
of Au, Ag, Ti and Si were prepared by the same pulse laser ablation of Au, Ag, Ti and Si
targets in the liquid environments (H
2
O, C
2
H
5
OH, C
2
H
4
C
12
) [39,41]. Comagnini et al.
reported that nanocrystals of Au, Ag, and Pt were synthesized with average sizes of 5-30 nm
by the Nd:YAG pulsed laser (wavelength 532 nm, pulse duration 5 ns) ablation of metallic
targets in n-alkanes generates metallic solutions [43-45]. Further, Ni and Co nanocrystals
were prepared by laser ablation of their target in the flowing ethanol [46]. Differently,
Kondow et al. synthesized ultrafine Au, Ag, and Pt particles (less than 5 nm in diameter) by
the 532 nm pulsed laser ablation of metal targets in an aqueous solution of sodium dodecyl
sulfate, and found that the surfactant concentration responding to controlling of the size of the
synthesized nanoparticles [122-125] On the other hand, Jeon et al. and Tsuji et al. produced
silver and copper colloids by synthesized their nanoparticles in various solvents, e.g. Ag
colloids from pulsed laser ablation of an Ag target in water, methanol, and iopropanol, and Cu
colloids by laser ablation of CuO powders in 2-propanol [54,55,126-128], and showed that
the wavelength of the pulsed laser influence greatly on the size of prepared nanoparticales.
Thirdly, alloying and oxides nanocrystals and nanostructures can be fabricated by pulsed
laser ablation in liquid. Singh et al. synthesized metastable silver-nickel alloying
nanoparticles by a continuous wave CO
2
and Nd:YAG laser ablation in the nitrate and acetate
precursors of silver and nickel [36,37], in the same way, they also prepared silver and nickel
oxides nanoparticles [129]. Moreover, the synthesis of Au-Ag alloying nanoparticles was
studied by pulsed laser ablation of the mixture of these nanoparticles in water or ethanol [42],
and Fe-Ni alloying nanoparticles were successively produced by pulsed laser ablation of an
iron-nickel target in the flowing ethanol [47]. Addition to, metal alloy nanoparticles were
fabricated by pulsed laser irradiation of metal powder suspensions in either aqueous or
organic solutions [130]. Remarkably, Yang et al. reported that one-dimensional silver-nickel
alloying nanostructures were fabricated by a Nd:YAG pulsed laser (wavelength 532 nm,
pulse duration 10 ns) ablation of a nickel target in a silver nitrate solution, and typical
diameters and lengths of these nanorods are in the range of 30-50 nm and 300-500 nm,
respectively [35]. Anikin et al. fabricated ZnSe and US quantum dots with sizes of 10-20 nm
by a Cu vapor laser irradiation of corresponding bulk semiconductors in diethyleneglycol and
ethanol [40]. In oxides nanocrystals synthesis, Liang et al. synthesized ultrafine (3-5 nm) tin
oxide nanocrystals by pulsed laser ablation of a tin plate target in water and aqueous solutions
of sodium dodecyl sulfate [49]. Chen et al. prepared CeO
2
nanoparticles by a Nd:YAG pulsed
laser ablation of a CeO
2
target in water [52]. Additionally, nanocrystals of aluminum
hydroxides were fabricated by nanosecond pulse laser ablation of an Al rod immersed in
water, and these nanoparticles show three different shapes: triangular, rectangular, and fibrous
[56], and nanoparticles of magnesium and zinc hydroxides were fabricated by pulsed laser
ablation of a Mg and Zn plate targets immersed in deionized water or aqueous solutions of
sodium dodecyl sulfate surfactant [50,51]. More recently, Nath et al. synthesized novel
inorganic fullerene-like nanostructures of the layered hafnium sulfide Hf
2
S and quasi-
spherical nanoparticles of HfS by the Nd:YAG pulsed laser (wavelength 532 nm, pulse
duration 10 ns) ablation of HfS
3
powders in tert-butyl disulfide solvent [131], and the size of
these nanoparticles is in the range of 20-80 ns. Accordingly, these results mentioned above
indicate that these parameters such as wavelength and pulse duration of the laser pulse and
kinds and concentrations of liquid environments can effectively control the size of
synthesized nanoparticales by pulsed laser ablation in liquid.
Metastable iron oxides synthesized by a pulsed Ruby laser ablation of a iron target in
water stimulated Ogale et al. to develop a new surface oxidation and nitridation of metals by
pulsed laser irradiating the metals targets in liquid environments, and surface coatings of iron
oxides and nitrides, and GaAs oxides were prepared by this method [85-87]. Further, Sharma
G. W. Yang 236
et al. deposited diamond-like carbon films on the substrate surface by pulsed laser irradiation
of a tungsten substrate immersed cyclohexane and decalin liquid, and glancing XRD and
Raman spectra of the as-deposited films indicated that the deposited films consists mainly a
mixture of hexagonal polytypes of diamond [132]. Meanwhile, Singh et al. reported diamond-
like carbon films were synthesized on the copper surface by pulsed laser irradiating a copper
substrate immersed into liquid benzene [88]. Noted that more experimental data late show the
prepared films from pulsed laser ablation of organic liquid on the metal surface are actually
diamond-like carbons not diamonds [99-103], although the authors mentioned above claimed
diamond films were synthesized. Following these studies, Lu et al. reproduced the Sharmas
findings by using a excimer pulsed laser irradiation of a single crystalline silicon surface in
cyclohexane liquid [92], and prepared a series of diamond-like carbon coatings by pulsed
laser irradiating various organic liquid [94,97,98]. Lyalin et al. reported that amorphous
diamond films were deposited on the substrate surface by a copper vapor pulsed laser
irradiating the transparent substrates (glass, fused silica, sapphire, and CaF) immersed in
liquid aromatic hydrocarbons [93,95,96,99]. Moreover, Simakin et al. prepared carbon films
on the Si surface by pulsed laser irradiating a Si substrate immersed into liquid benzene [100].
For the surface coatings preparations of diamond related materials by pulsed laser ablation in
liquid, Sharma et al. synthesized tetrahedrally coordinated crystalline carbon nitride films on
the substrate surface by pulsed laser ablation of hexamethylenetetramine or hexamine
(C
6
H
12
N
4
) thin layer on the tungsten substrate immersed into liquid ammonia [14].
In fact, the ablation of the substrates simultaneity takes place when the laser pulse
irradiated the liquid-substrate interface in these experimental cases. It is noticed that, these
thin films preparations above by pulsed laser ablation in liquid are distinctly different from
those nanocrystals by the same method. Clearly, one can see that compositions of
nanocrystals synthesized by pulsed laser ablation in liquid are mainly from the ablation of
solid targets, then, the as-deposited thin films are usually from the ablations of the liquid at
the liquid-solid interface. However, both of the nanocrystals synthesis and the surface
coatings preparations are within the frame of the laser-induced plasma evolution from pulsed
laser ablation in liquid, which is detailed described above.
3. PULSED-LASER INDUCED LIQUID-SOLID
INTERFACE REACTION
3.1. PLIIR Apparatus
Based on the characters of the laser-induced plasma evolution from laser ablation in
liquid, we named the novel method of pulsed laser ablation in liquid for materials preparation
to be pulsed-laser induced liquid-solid interface reaction (PLIIR). A basic experimental
apparatus is schematically illustrated in Figure 6. A solid target or substrate is fixed on the
rotatable holder at the bottom of the chamber, and the target or substrate is immersed into
flowing liquid environments, and the chamber is maintained at room temperature by water-
cooling. The rotatable holder ensures homogeneous of the laser ablation of targets when the
pulsed laser irradiated the target surface. Since nanoparticles synthesized by laser ablating
solid targets usually float on the surface of liquids due to their large surface tension, flowing
liquids result in the successive producing of nanocrystals. The thickness of the liquid layer
between gas and surface of target or substrate is the order of magnitude of millimeter. Inert
gases such as Ar are guided to eject oxygen gas filled with the chamber before, because the
volatiles of organic liquids, regarded as liquid environments, easily fire induced the laser
pulse when they meet oxygen gas. The incident pulsed laser is focused on the liquid-solid
interface by a lens during materials preparations. Noted that the laser beam need scan the
surface of substrates for the application of pulsed laser ablation in liquid in surface coatings
preparations.
3.2. Thermodynamic and Kinetic Factors of PLIIR
Distinctly, thermodynamic and kinetic factors of PLIIR can greatly influence on the
nanocrystals formation based on the understandings of the evolution of the laser-induced
plasma generated by PLIIR. Taking the pulsed laser ablation of graphite and aluminum
targets in water as typical examples, we contribute a basic description of thermodynamic and
kinetic factors of PLIIR by detailed characterizations of three important thermodynamic
parameters, i.e. density of species, temperature, and pressure, of the laser-induced plasma.

Figure 6. The schematic illustration of PLIIR apparatus. 1. Laser. 2. Lens. 3. Reflected mirror. 4.
Chamber. 5 and 6. Cooling water tubes. 7. Guide tubes of gas. 8 and 9. Guide tubes of liquid for input
and output. 10. Holder. 11. Target. 12. Liquid. 13. Quartz window
1
Laser
3
4
5
6
8
10
11
9
12
7
13

G. W. Yang 238
The density of species in the laser-induced plasma plume from pulsed laser ablation in
liquid can be estimated based on the measurement of the expansion volume of the plasma
plume and the calculation of the amount of the ablated species from the volume of the hole
left on the target surface after ablating. The expansion volume of the plasma plume is
measured from images of the light emitting region on the target surface produced the laser
pulse ablating the target. Figure 7 shows the image and the intensity distribution of the light
emitting region, and the volume of the plasma plume can be estimated to be 9.910
7
cm
-3
by
assuming that the plume is hemisphere with the diameter of the FWHM intensity. Figure 8
displays the vertical section profile of the hole left on the target surface after laser ablation.
Considering volume linearly increasing with number of pulses increasing, the ablating
volume by a single laser pulse is determined to be 7.410
-8
cm
3
from Figure 7b. Therefore,
the density of the ablated species in the plasma plume generated by the Nd:YAG pulsed laser
ablation of a graphite target in water is calculated to be 6.710
-21
cm
-3
.
The optical emission spectra of the ablated species from the laser-induced plasma
confined in liquid are effective method to determine the temperature of the plasma plume
[21,23-26,133-135]. For instance, Sakka et al. obtained the temperature of the laser-induced
plasma plume of about 5000 K on the basis of the measurements of the emission spectra of C
2

molecules fabricated by the ablation of a pulsed Nd:YAG laser with wavelength of 1064 nm,
pulse duration of 20 ns, and the energy fluence of 10 J/cm
2
to a graphite target in water [24].

Figure 7. The image and intensity distribution of the laser-induced plasma plume from the ablation of a
pulsed Nd:YAG laser with wavelength of 1064 nm, pulse duration of 20 ns, and the energy fluence of
10 J/cm
2
to a graphite target in water
Width (m)
-200
200
I
n
t
e
n
s
i
t
y

(
a
u
)


Figure 8. The vertical section profile of the hole produced by laser pulses ablating the graphite target
for 100 times (a), and the relationship between the holes volume and the number of pulses (b)

Figure 9. The schematic illustration of pressure measurements of the laser-induced plasma in the
confined region by characterizations of the shock wave in the target and the acoustic wave in water
The high pressure in the laser-induced plasma originates from the shock wave generation
when pulsed laser ablation in a confined liquid. Fabbro et al. therefore developed a series of
experimental techniques to measure the pressure by characterizations of the shock wave in
Figure 9a, and built the theoretical model of the laser-induced pressure generation in pulsed
laser ablation in water. Similarly, Lu et al. measured the pressure in the laser-induced plasma
by recording the acoustic wave in water induced by the plasma in Figure 9b. Berthe et al.
reported that the maximum pressure in the laser-induced plasma was obtained as high as
5.5GPa with a pulse duration of about 50 ns when a pulsed laser with wavelength of 1064 nm,
power density of 10 GW/cm
-2
, and pulse duration of 20 ns irradiating a aluminum plate in
0 20 40 60 80 100
0
2
4
6
8
V
o
l
u
m
e

(
1
0
-
1
2
m
3
)
The number of irradiation
ACOUSTIC WAVE
SHOCK WAVE
TARGET
WATER
LASER PULSE
PLASMA
G. W. Yang 240
water. Based on a accepted analytical model, the maximum pressure generated by the laser-
induced plasma in water is given by the following relation:
( ) ( ) ( )
2
0
1 2
3
01 . 0

+
= GWcm I s gcm Z GPa P
, (3.1)
where a is the fraction of internal energy devoted to thermal energy (typically a ~ 0.25),
0
I
the incident power intensity, and Z the reduced shock impedance between target and the
confining water defined by the relation:

et t water
Z Z Z
arg
1 1 2
+ = , (3.2)
where Z
water
and Z
target
are the shock impedances of the water and the target respectively. For
example, for aluminum target, Z
water
= 0.16510
6
g cm
-2
s
-1
and Z
target
= 1.510
6
g cm
-2
s
-1
, for
silicon target, Z
target
= 2.110
6
g cm
-2
s
-1
. Noted that the relationship between temperature and
pressure in the laser-induced plasma is not completely consistent with the predictions from
the idea gas state equation of P = nN
A
kT/V (n: gas density, N
A
: Avogadoro constant, k:
Boltzmann constant, V: gas volume), as the formation of the laser-induced plasma in pulsed
laser ablation in liquid is a far from thermodynamic equilibrium process, and the plasma is
usually not regarded as an idea gas. For instance, assuming the plasma as an idea gas, the
estimated pressure by the equation mentioned above is much lower than that measured by
experimental techniques.
4. DIAMOND NANOCRYSTALS SYNTHESIS BY PLIIR
4.1. Synthesis of Nanodiamonds by PLIIR
The interest in preparation of diamond is motivated by its unique combinations of
physical hardness, high thermal conductivity and optical transparency and others. Many
methods have been developed to prepare diamond since the 1950s when diamond was
synthesized first with a high temperature and high pressure method [136]. PLD has been
proved to be an efficient method for the preparation of a variety of functional thin films [2],
[3]. Particularly, the deposition of amorphous carbon films with diamond-like characters has
been widely reported by laser ablation of graphite in vacuum [137-150], in which some
researchers reported the growth of crystalline particles, but the lack of a diamond peak in
Raman spectra was a common result in all reports. It was not until in 1995 that Polo et al first
showed the Raman spectroscopy analysis of the sample that is confirmed to have diamond
cubic structure of the crystals by the presence of a sharp peak at 1332 cm-1 [151]. Ogale et al.
first reported that diamond particulates with cubic structure were detected from the
productions of pulsed ruby laser irradiation of the pyrolytic graphite target in the benzene
solution [13]. Zheng et al. synthesized diamond nanoparticles by the Nd:YAG pulsed laser
ablation of a isotopic graphite target in water [90]. Yang et al. [30-32] studied the formation
of nanodiamonds upon the Nd:YAG pulsed laser ablation of a graphite target in water,
acetone and alcohol, and obtained a relatively complete Raman spectra [32] and nice single
crystal morphology and diffraction images of TEM [30] of nanodiamonds. Taking Yangs
experiments as an example, here we devote a summary of nanodiamonds synthesis by pulsed
laser ablation in liquid.
The synthesis setup of nanodiamonds is shown in Figure 6. The second harmonic is
produced by a Q-switched Nd:YAG laser with wavelength of 532 nm, pulse duration of
10 ns, repetition frequency of 5 Hz, power density of 10
10
Wcm
-2
. The targets are
spectroscopically pure polycrystalline graphite. Water, acetone, and alcohol are regarded as
reaction liquids in our case. The duration of the pulsed laser ablation of the graphite target in
liquid is in the range of 30-60 min. Finally, the powders floating on the surface of the liquid
are collected as the sample to be analyzed. The typical TEM morphologies of nanodiamonds
are shown in Figure 10. Sizes of most nanodiamonds are in the range of 50-100 nm, and these
nanocrystals display spherical (Figure 10 (c)). However, few large diamond particles were
found in the production shown in Figure 10 (a) and (b).

Figure 10. TEM morphologic images of nanodiamonds synthesized by PLIIR. (a) and (b) Large
particles. (c) Nanocrystals
G. W. Yang 242

Figure 11. Corresponding SAD (a) and indexing (b) (B
C
= [112], B
G
= [1010]) patterns of
nanodiamonds. One sees that the hexagonal diamond and cubic diamond are intermixed in the
crystallites investigated here, and the orientation between these two phases is [110]
c
||[1210]
h
, [111]
c
||[0001]
h
and [112]
c
||[1010]
h

Clearly, we can see the crystalline planes and very regular morphology clearly, which is a
common morphology in diamond. The corresponding SAD and indexing are shown in Figure
11. These nanocrystals are identified to be of a mixture of cubic and hexagonal diamond
structures on basis of these results. Accordingly, one can see that the cubic and hexagonal
diamond phases of the resulted sample were intermixed in the crystallites here, and the
oriented relationship between these two phases is [110]
c
[1210]
h
, [111]
c
[0001]
h
and [112]
c

[1010]
h
. For the lattice parameter of the cubic phase, we obtain value of 3.56 0.01 ,
which is in good agreement with values found in the literature [152], and for the lattice
parameters of the hexagonal phase, we obtain values of 2.53 0.01 and 4.11 0.01 ,
which are in excellent agreement with values found in the literature for the Wurzite-like
hexagonal diamond structure often referred to as Lonsdaleite [153].
To our knowledge, the Raman spectrum of nanodiamonds has been not yet understood
both in experiment and theory in detail. Figure 12 shows the Raman spectra of the
synthesized sample. A Raman line at 1579 cm
-1
of single crystal graphite, two broad bands
centered at 1352 and 1100 cm
-1
, and other two peaks centered at 926 and 623 cm
-1
, are
observed in the Raman spectra in Figure 12 (a). The Raman lines of nanodiamonds usually
become broader and weaker, and the peak frequency shifts to lower frequency [154].
Therefore, the Raman spectra of the resulted sample in our study need to be analyzed by
deconvolution method. Although the 1332 cm
-1
Raman line is not observed from Figure 12,
the Raman peak at 1307 cm
-1
is deconvoluted from the broad band centered at 1352 cm-1,
which is usually attributed to cubic-diamond [155]. The detailed analysis of the Raman
spectra in the range of 1000-2000 cm
-1
is displayed in Figure 12 (b).
The detailed analysis of the Raman spectra in the range of 1000-2000 cm
-1
is displayed in
Figure 12 (b). One can clearly see from Figure 12 (b), four peaks considering Gaussian line
shapes are best fitted with the positions of 1152.5, 1125.5, 1090.9, and 1005.8 cm
-1
,
respectively. In the early studies, Nemanich et al. [156] postulated that microcrystalline
hexagonal diamond should give its strongest vibration Raman frequency at 1175 cm
-1
. In the
report by Maruyama et al. [157] on hexagonal diamond, a Raman response was shown at
1150 cm
-1
. Accordingly, we think that observed Raman peak at 1152.5 cm
-1
is attributed to
the microcrystalline hexagonal diamond. The observed band centered at 1090.9 cm
-1
is
consistent with the proposed for nanocrystalline diamond [158], and its position was close to
the main peak of the vibration density of states (VDOS) of the cluster model of diamond
calculated by Beeman et al. [159]. For the 623 cm
-1
Raman peak, the theoretical calculation
and experimental result have proved that it is attributed to diamond. Mao and Hemerly [160]
have measured the Raman spectra of diamonds under ultrahigh pressure and found a broad
band around 590 cm
-1
. Yoshikawa et al. [154] also have observed the broad band around 600
cm
-1
. However, the strongest peak centered at 926 cm
-1
of the Raman spectrum has not yet
known to us. We carefully studied the Raman spectra of the graphite target used in our study,
just two graphite Raman peaks were observed (Figure 12 (c)). The Raman line at 926 cm
-1
is
thus not original from graphite. Based on references [156-159], we deduce that the Raman
line around 926 cm
-1
would be one of the series Raman lines of nanodiamonds.
Accordingly, these experimental data definitely indicate that nanodiamonds are
synthesized by pulse laser ablation of graphite in various liquids.

(a)

(b)
Figure 12. Continued
G. W. Yang 244

(c)
Figure 12. The Raman spectra of nanodiamonds and graphite target. (a) and (b) The Raman spectrum
and its deconvolution. (c) The Raman spectrum of the graphite target
4.2. Thermodynamic Nucleation of Diamonds upon PLIIR
PLIIR is expected to be advantageous in the preparation of metastable nanocrystals that
prefer a state of high pressure and high temperature. Importantly, PLIIR is a relatively new
laser-based material processing method, and the mechanisms involved in the nucleation and
phase transition of nanocrystals upon PLIIR are not well understood. It is therefore important
to provide theoretical tools to investigate the physical and chemical phenomena involved in
this processing method. More recently, taking the surface tension induced by nanosize
curvature of crystalline nuclei into account, we developed a thermodynamic nucleation on the
nanoscale to elucidate the nucleation of nanodiamonds and related materials [163]. To date,
the thermodynamic nucleation theory has been used in the studies of cubic boron nitride
nucleation in high-pressure and high-temperature superfluid systems and chemical vapor
deposition, the homogenous and heterogeneous nucleation of diamond in chemical vapor
deposition, and the nucleation of diamond nanowires inside carbon nanotubes [164]-[169].
Accordingly, to gain a better understanding of the formation of diamond nanocrystals upon
PLIIR from the point of the view of thermodynamics, in this section, we perform a
thermodynamic analysis, with respect to the effect of nanosize-induced additional pressure on
the Gibbs free energy of diamond nuclei, to have a clear insight into the microscopic process
of diamond formation on the nanoscale during PLIIR, based on the thermodynamic
nucleation mentioned above.
Basically, from the previous work [30,32,36], the formation of nanodiamonds during
PLIIR can be outlined as follows. Compared with the laser ablation at gas or vacuum-solid
interfaces, a special plasma plume with HPHTHD could be created at the liquid-solid
interface when a pulsed-laser irradiated a solid target immersed in liquid. Thus, nanocrystals
could form during the plasma rapidly quenching confined in liquid. Accordingly, in our cases
[30-32], diamond nanocrystals form in plasma condensation confined in liquid, as described
below, upon pulsed-laser ablation at the graphitewater interface. Generally, the laser-
induced plasma contains some species, e.g. atomic clusters with sp
2
bonding, and their ions,
from the laser ablated solid. Because of the laser-induced pressure mentioned above, the
laser-induced plasma is driven into the HPHTHD state. For example, in the case of pulsed-
laser ablation at the graphite-water interface, the pressure-temperature region is determined to
be in the range of 10-15 GPa and 4000-5000 K [30,32], which belongs to the stable region of
diamond in the carbon phase diagram shown in Figure 13. Sequentially, diamond nucleation
and the phase transition from graphite to diamond could take place during the plasma
quenching. Since the diamond phase with sp
3
bonding is a stable phase and the graphite phase
with sp
2
bonding is a metastable phase in the region created by PLIIR, the phase transition
from graphite to diamond can take place. Thus, the formation of diamond nuclei is preferable
to that of graphite in the plasma [170]. Moreover, the diameter of the grown crystals is
usually on the nanometer scale, as the growth time (plasma quenching time) of diamond
nuclei is very short. It is noticed that the performance of the phase transition proposed in this
section is limited to the case of the diamond nucleation mentioned above. Meanwhile, there is
another possibility of diamond nucleating directly from the graphite bulk upon PLIIR. It is
well known that the laser-induced plasma includes particulate contaminants and droplets from
the solid target [171], such as graphite particulates or droplets in the case of pulsed-laser
ablation at the graphite-water interface. Naturally, diamonds could nucleate directly from
these graphite fragments in the plasma, because of the higher pressure and temperature, and
the shock wave generated by PLIIR. Since diamond nucleation directly from graphite was not
discussed in previous studies [170], we will not consider it.

Figure 13. P, T phase and transition diagram of carbon established by Bundy. Solid lines represent
equilibrium phase boundaries. A: commercial synthesis of diamond from graphite by catalysis, B: P =
T threshold of very fast (less than 1 ms) solidsolid transformation of graphite to diamond, C: P, T
region of synthesis of diamond by PLIIR, D: single crystal hexagonal graphite transforms to retrievable
hexagonal-type diamond, B,F,G: threshold of fast P=T cycles, however generated, that convert either
type of graphite or hexagonal diamond into cubic-type diamond
GRAPHITE
0 1000 3000 4000 5000 2000
Temperature (K)
6000
0
10
20
30
40
50
P
r
e
s
s
u
r
e

(
G
P
a
)

A
C
F
DIAMOND
G
LIQ
G. W. Yang 246
Based on the understanding from experimental observations until 1994, Bundy provided
a new pressuretemperature phase diagram of carbon [172] (Figure 13). The solid lines
represent equilibrium phase boundaries, and the solid line from low temperature and low
pressure to the triple point (12 GPa-5000 K) of diamond, graphite and liquid carbon is the so-
called Berman-Simon line (B-S line) in the phase diagram. From the phase diagram one can
see that diamond is in the metastable state in the region above the B-S line. The A region is
the pressure-temperature region utilized for the HTHP commercial preparation of diamond
from graphite. The dashed line, B-F-G, marks the threshold of very fast (i.e. ms-s) transition
of highly compressed graphite, or its low temperature derivatives, to cubic-type diamond. The
B region on the dashed line B-F-G marks the temperaturepressure threshold of very fast (<1
ms) and complete solid-solid transformation of graphite to diamond. This transition always
yields cubic-type diamond. Experimentally, it is done by pressurizing graphite above 12 GPa
and heating the sample with a pulse of electric current or laser radiation. Therefore, our
deductions and calculations are focused on the C region. Moreover, this theory is formulated
based on the following assumptions: (i) nanonuclei are perfectly spherical with no
deformation of the internal structure from the bulk, (ii) nanonuclei are mutually non-
interactive.
Generally, the Gibbs free energy is an adaptable measure of the energy of a state in the
phase transformation among competing phases. At the given thermodynamic conditions, both
diamond and graphite phases could co-exist. However, only one of the two phases, with the
minimum free energy, is stable. The other must be metastable and may transform into the
stable state. Thermodynamically, the phase transformation could be promoted by the
difference of the free energies. In detail, the Gibbs free energy of a phase can be expressed as
a function of the pressure-temperature condition, and is determined by a general coordinate or
reactive coordinate [173]. Therefore, the Gibbs free energy difference arising from the
formation of spherical carbon clusters, with the diamond structure, in the gas phase is
expressed as a function of radius r, pressure P, and temperature T
( )
2 3
4
3
4
r V g r r G
m
+ = , (4.1)
where g is the mole volume Gibbs free energy difference, and
m
V are the surface free
energy and the mole volume of diamond, respectively. Furthermore, we have
+ =
P
T P T
VdP g g
0
0
,
from
V
P
T
P T
=

,
, in which V is the molar volume difference
between graphite and diamond, and g
0
T
is the molar Gibbs free energy difference at zero
pressure. Bundys experimental results showed that V usually remains approximately
constant with pressure-temperature condition, i.e. V = 1.77
6
10
m
3
mol
-1
[172]. Under
the assumption of spherical and isotropic nanocrystalline diamond nuclei above, the size-
induced additional pressure P of diamond nuclei is given by the Laplace-Young equation:
P = 2/r. On the other hand, the equilibrium phase boundary between graphite and diamond
in the carbon phase diagram is expressed by P
e
= 2.73
6
10 T + 7.23
8
10 [172]. Due to the
additional pressure P, the external pressure P
e
that is necessary for the transition from
graphite to diamond will decrease by the same amount [164]-[168]. Thus, we can obtain the
size-dependent equilibrium phase boundary
r T P
e
2 10 23 . 7 10 73 . 2
8 6
+ = . (4.2)
When the pressure-temperature conditions are on the equilibrium line given by Eq. (2),
we have g
T, P
= 0. Thus, we can obtain the molar volume Gibbs free energy difference of the
phase transition from graphite to diamond:
( ) r T P V g
d
P T
2 10 23 . 7 10 73 . 2
8 6
,
+ =
.
Then, considering the nano-size effect, the Gibbs free energy difference of the phase
transition from graphite to diamond is expressed as

( ) ( )
2 8 6 3
4 2 10 23 . 7 10 73 . 2
3
4
r V r T P V r r G
m
+ + =
. (4.3)
When
0
) (
=

r
r G
, the critical size of diamond nuclei is deduced as follows

( ) P T
V
V
r
m
+
+ =
8 6 *
10 23 . 7 10 73 . 2
3
2
2
. (4.4)
Substituting Eq. (4) into Eq. (3), we have the critical free energy of diamond nuclei as
follows

( ) ( )
2 * * 8 6 3 * *
4 2 10 23 . 7 10 73 . 2
3
4
r V r T P V r r G
m
+ + =
. (4.5)
According to Eq. (4), V
m
= 3.417
6
10
m
3
/mol [6], and = 3.7 Jm
-2
[13,8], the
dependence of the radius r* of diamond critical nuclei on the temperature is illustrated in
Figure 14(a) under the conditions of the given pressures and temperature in the range of
10-15 GPa and 4000-5000 K, respectively. Naturally, corresponding to the radius r* of
diamond critical nuclei, the G(r*)-T curves are illustrated in Figure 14(b) under the same
conditions. Accordingly, from Figure 1(a) and (b), one can clearly see that these diamond
nuclei with small radius r* and low formation energy G(r*)could be obtained upon PLIIR.
For example, the radius r* of diamond nuclei can reach a value of 3 nm, while the formation
energy is less than 1
15
10
J, when P = 10 GPa and T = 5000 K. Therefore, these results

indicate that diamond nucleation is favorable upon PLIIR. Furthermore, both radius r* and
formation energy G(r*)of diamond critical nuclei decrease with increasing temperature, and
increase with increasing pressure. The theoretical results could therefore be regarded as an
important reference to control the size of nanodiamonds by choosing the relevant
experimental parameters of PLIIR. In fact, the size distribution of diamond nanocrystals
G. W. Yang 248
synthesized by PLIIR just falls in the range expected by the deduction and calculation above
[30], [32].
4.3. Graphite-Diamond Phase Transition upon PLIIR
The synthesis of nanodiamonds by PLIIR has been recognized to be an advance in
diamond synthesis in recent years [48]. However, compared with the experimental studies of
diamond nanocrystals prepared by PLIIR, few theoretical studies involved in the
thermodynamic nucleation of diamond nanocrystals are found in the literature [32,48]. Wang
and Yang proposed a thermodynamic phase transition model to calculate the phase transition
probability from graphite to diamond upon PLIIR [174], however the model didnt take into
account the effect of nanosize induced additional pressure of diamond nuclei on the phase
transition probability. Considering the capillary effect induced by nanosized curvature of
diamond nuclei on the phase transition from graphite to diamond, we therefore calculate the
phase transition probability from graphite to diamond taking place in PLIIR, based on the
thermodynamic nucleation mentioned above.

Figure 14. The dependence of the radius r* and the Gibbs free energy G(r*) of diamond critical nuclei
on the temperature upon PLIIR under the conditions of various pressure, (a) for r*, and (b) for G(r*)
The Gibbs free energy is an adaptable measure of the energy of a state in phase
transformation among the competing phases. For the given pressure-temperature condition,
both diamond and graphite phases can co-exist, but only one of the two phases is stable, with
minimal free energy, and the other must be metastable and may transform into the stable
state. Thermodynamically, the phase transformation is promoted by the difference of the free
energies, the phase transformation is therefore determined quantitatively by the probability of
the carbon atoms crossing a potential barrier of intermediate state [175]. Generally, the Gibbs
free energy G
T,P
of a phase can be expressed as a function of the pressure-temperature
condition, and determined by a general coordinate or reaction coordinate r schematically
illustrated in Figure 15. The probability of the phase transformation from the metastable
phase to the stable phase is determined not only by the Gibbs free energy difference G
T,P
,
but also by an activation energy (E
a
G
T,P
), which is necessary for the transition. When the
two phases are at the equilibrium condition, i.e. G
T,P
= 0, E
a
is the maximum potential
energy for both sides with respect to the general coordinate r. The general expression of the
probability f of the phase transformation from the initial state to the final state is [174]
f= exp [-(E
a
-G
T, P
) / RT] exp [- (E
a
/RT) ], (4.6)
where R is the gas constant. For the phase transformation from graphite to diamond, f = f
d
and
G
d
T, P
= G
g
T, P
(graphite) - G
d
T, P
(diamond). Meanwhile, (E
a
-G
d
T, P
) is the activation energy
of the phase transition from graphite to diamond. Therefore, f
d
can be given by Eq. (6).
Instead, for the phase transformation from diamond to graphite, f = f
g
and G
g
T, P
= G
d
T, P
(graphite) G
g
T, P
(diamond), f
g
should be expressed as
f
g
= exp [- (E
a
/RT) ] exp [-(E
a
-G
g
T, P
) / RT]. (4.7)
It is noted that, for the phase transition from diamond to graphite, V = - 1.77
6
10
m
3

mol
-1
, and then the molar volume Gibbs free energy difference G
g
T, P
can be given by
G
g
T, P
= 1.77
6
10
(2.73
6
10 T + 7.23
8
10 - 2/r P). (4-8)

Figure 15. Schematic diagram of Gibbs free energy vs coordinate
h-BN
c-BN
G
E
a
-G
Coordinate
G. W. Yang 250

Figure 16. The phase transition probabilities between graphite and diamond, in which the probabilities
from graphite to diamond transition are above the B-S line, the probabilities from diamond to graphite
transition are below the B-S line
Substituting Eq. (4) into Eq. (6), Eq. (8) into Eq. (7), and having E
a
= 120 kJmol
-1
[174],
we calculate the phase transition probability between graphite and diamond upon PLLIR. The
P-T curves with the radius r = 5.0 nm are shown in Figure 16. Clearly, comparing with
Wangs calculation without the nanosize effect [174], one can see that the probability
distribution of the phase transition from graphite to diamond moves downwards along the B-S
line in the carbon phase diagram, from Figure 16. This distribution change is caused by the
nano-size-induced surface tension. In other words, considering the nano-size-induced surface
tension of diamond nuclei, the phase transition probability from graphite to diamond goes up
at the same pressure-temperature condition. More importantly, we can see that the probability
of the phase transition is rather high, up to 10
-3
-10
-2
, in the pressure-temperature region
generated by PLIIR in Figure 16. Actually, these results imply that PLIIR would be a very
efficient way to synthesize nanodiamonds. From Eq.(6) and (8), the dependence of the phase
transition probability from graphite to diamond on the radius of crystalline grains is shown in
Figure 3 under the conditions of P = 13 GPa and T = 4500 K. The phase transition probability
markedly decreased with the increasing radius of crystalline grains in Figure 17. Moreover,
the probability increases much more when the size of crystalline grains is less 5 nm.
Accordingly, from the results, we deduce that diamond nanocrystals with a radius of 2-4 nm
would be easily synthesized by PLIIR compared to grains of size 10-20 nm.
Furthermore, the comparison of the dependence of the phase transition probability on the
pressure is shown for various grain sizes and T = 4500 K in Figure 18. One can see that the
probability curves are parallel to each other at the different grain sizes, and almost linearly
increase with increasing pressure under the conditions of the temperatures used in Figure 18.
In fact, Winter and Ree calculated the phase stability of carbon particles as a function of the
size by first-principles and semiempirical molecular orbital calculations [176]. Their results
showed that the diamond phase is more stable than the graphite phase when the carbon
particle includes less 10
4
-10
5
carbon atoms (a cluster size of 4-5 nm). However, the clusters
with diamond structure larger than 10
5
carbon atoms become less stable than three-
dimensional graphite clusters with the same size. Therefore, our theoretical results are
consistent with Winter and Rees calculations. Accordingly, the thermodynamic analysis
above implies that PLIIR could be expected to be advantageous in the synthesis of
ultrananocrystalline diamonds.

Figure 17. The dependence of the phase transition probability from graphite to diamond on the size of
the crystalline grain under the conditions of P = 13 GPa and T = 4500 K

Figure 18. The dependence of the phase transition probability from graphite to diamond on the pressure
under the conditions of T = 4500 K and various sizes of the crystalline grain
G. W. Yang 252
4.4. Structural Transformation of Diamonds upon PLIIR
The hexagonal diamond (hex-d) so-called Lonsdaleite, as the metastable phase with
respect to cubic diamond (cub-d), was first prepared by shock-wave (SW) [177]. Then, Bundy
also obtained the hex-d by using the static high-pressure pressing the hex-g along the c axis at
the high temperature [178]. However, recent attempts to reproduce the conversion of graphite
to hex-d under static pressure failed [179,180]. It is therefore so far not completely confirmed
that the conversion of graphite to hex-d could be achieved under static high-pressure. For the
theoretical side, the highly symmetric transformation path from rhombohedral graphite (rh-g)
to cub-d was first considered, i.e. rh-g as an intermediate phase of hex-g to cub-d
transformation [181,182], and the transformation path would lead a final [111] diamond
orientation parallel to the original graphite c axis. These deductions are in agreement with the
catalyst-aided conversion in HTHP [178], in which catalyst was suggested to aid the mutual
orientation formation of hex-g and cub-d [183]. The orthorhombic graphite (or-g) was also
considered to be the transformation path of hex-g to cub-d and hex-d [184,185], and this path
would lead to the final [112] diamond orientation parallel to the c axis of the hex-g, similar to
the shock-wave experimental results [186]. Considering a large activation barrier from
graphite to diamond, we would like to know whether the intermediate phase with metastable
structure as the transformation path would exist in the conversion of graphite to diamond.
However, the existence of the hypothesized intermediate phase, i.e. rh-g and or-g, in the
conversion of graphite to diamond has never been truly substantiated by the direct
experiments [181,187,188].
On the other hand, PLIIR is a very fast and far from equilibrium process, so that all
metastable and stable phases forming at the initial, intermediate and final stages of the
conversion could be reserved in the final products, especially, for the metastable intermediate
phase. In other words, the quenching times of PLIIR are so short that the metastable phase
forming at the intermediate stage of the conversion could be frozen in the obtained final
products. However, HTHP and SW methods Hardly have the two features (the quenching
times of SW are much longer than those of PLIIR) simultaneously. It is therefore very
unlikely that these possible metastable intermediate phases in the conversion of graphite to
diamond could remain in the two methods, because these phases maybe transform into the
stable phase at the final stage. Therefore, PLIIR provides a good experimental method to
detect the intermediate phase forming in the conversion of graphite to diamond, if these
phases are existing. Using PLIIR, here we show the observation of an rh-g phase, the
intermediate phase as the transformation path of graphite to diamond in experimental [170].
The basic experimental results have been described in the section of nanodiamonds
synthesized by PLIIR. Figure 11 shows the indexing of the SAD. The cubic and hexagonal
phases of diamond are intermixed in the crystallites investigated here, and the oriented
relationship between these two phases was [110]
c
||[1210]
h
, [111]
c
||[0001]
h
, and
[112]
c
||[1010]
h
. Noted that the ratio of diamonds to whole powders synthesized by PLIIR
increases with the pulsed laser energy increasing, which means the transition probability of
graphite to diamond would increase with the used pulsed laser energy increasing. In addition,
the conversion of graphite to diamond was achieved by various radiated pulsed laser energies
from 250 mJ to 350 mJ. To detect the possible metastable intermediate phase, the pulsed
lasers having energy values of 280 mJ, 300 mJ, and 330 mJ were used to produce the
conversion of graphite to diamond, respectively. Figure 19 shows the corresponding X-ray
diffraction spectra (XRD). In the XRD of the graphite target in Figre 19, one can see that that
all the diffraction peaks belong to the hex-g, and the diffraction lines of the rh-g are not
found. However, with the used laser energy increasing, the remarkable diffraction peaks of
the rh-g were clearly observed in the XRD of the sample prepared by using the 330 mJ laser
pulse. The strongest (003) diffraction line, 2 = 26.6, of the rh-g overlaps the strongest (005)
diffraction line of the hex-g, and the second strongest (101) diffraction peak of the rh-g, 2 =
43.44, was in between the hex-g (101) and hex-g (102) lines. These experimental results only
show the experimental evidence that the metastable rh-g phase indeed formed in the
conversion of graphite to diamond upon PLIIR. To gain further insight into the
transformation of the intermediate phase rh-g, the second strongest (101) diffraction of the rh-
g was selected as the mark line to study the dependence of intensity of the mark line on the
used laser energy. The results are shown in Figure 20. One clearly sees that the intensity of
the (101) diffraction peak of the rh-g rapidly increases with the used laser energy increasing.
This observation means that the transformation probability of the hex-g to rh-g increases with
the used pulsed laser energy values increasing. Therefore, the above experimental results
indicate two important evidences.

Figure 19. XRD of the prepared samples by PLIIR. (a) The XRD of the original solid graphite target.
(b) The XDS of the powders obtained by using 330 mJ pulsed laser
25 50
100
2
8K
C
P
S

a
b

G. W. Yang 254

Figure 20. The dependence of the (101) diffraction peak of the rhombohedral graphite on various used
pulsed laser energies
First, excluding the metal catalyst effect, the conversion of graphite to diamond was
strikingly confirmed upon PLIIR. Second, the metastable rh-g phase as the intermediate phase
in the hex-g to cub-d conversion was firmly obtained in this experiment. Accordingly, the
formation mechanism of two structural diamonds are suggested that hex-g would be directly
transformed to hex-d, however, cub-d was obtained by an indirectly transforming, i.e. from
hex-g first to an intermediate phase rh-g, then to the final state cub-d by a solidsolid
transformation manner [30]. Figure 21 shows this structural evolution. In other words, the
basal planes of the hex-g could become boat-buckled and di-intermediate phase rh-g could be
remained. Obviously, the deductions are well in agreement with the experimental result.
A thermodynamic analysis of the graphite-to-diamond transition could aid the
understanding of the various transformation paths. Based on Figure 13, one can see that
diamond is in the metastable state in the region below the B-S line, and the A region (512
GPa, 20003000K) is the pressuretemperature region utilized for HTHP commercial
preparation of diamond from graphite, and the conversion of graphite to diamond via the rh-g
intermediate phase as a transformation path seems to exist in this region [178].

Figure 21. Geometric path for graphite-to-diamond transformation: hexagonal graphite
rhombohedral graphite cubic diamond, the different stackings of the hexagonal planes are viewed
along the sideways
C
P
S

280 300
2242
2247
3270
Pulsed-laser energy (mJ)
330

[111]
The B region (15 GPa, 1000 K) represents the conversion of graphite to diamond via an
or-g intermediate phase as the transformation path found in SW. Furthermore, we mainly paid
attention to the C region (1015 GPa, 40005000K) in the PT phase diagram, in which the
pure conversion of graphite to diamond via a rh-g transformation path is achieved upon
PLIIR. Our previous studies showed that the transformation probabilities of the carbon atoms
over a potential barrier to transform diamond structure in these regions above were different
[174]. For A, B, and C regions, the transiting probabilities of C region are the highest, and in
turn the transiting probabilities of B region are lowest. Based on the analysis above, it is
suggested that two conversions of graphite to diamond, i.e. or-g and rh-g transformation
paths, could exist in B and C regions in the carbon phase diagram, respectively. Since the
parallelism of the [111] orientation of the final cub-d with the c axis of the initial hex-g was
found in the catalyst-aided conversion of graphite to diamond by HTHP [189], the model of
the rh-g transformation path seems to find the experimental evidence. However, the use of the
metal catalysts is known to drastically decrease the transiting pressure and temperature, and is
therefore expected to alter significantly the conversion mechanism (possibly through a metal-
induced buckling of the graphite basal planes) [183]. However, in our results, the graphite-to-
diamond conversion was more pure, i.e. there were not any metal catalysts, the observations
in this study were therefore the true experimental evidences of the above model. Considering
the conversion of graphite to diamond upon PLIIR taking place in C region of the carbon
phase diagram, it is suggested that the hex-g to rh-g to cub-d phase transformation may not be
achieved in A region if the transition metal catalysts are not used.
The parallelism of the [112] orientation of the final cub-d with the c axis of the initial
hex-g was found in SW-induced graphite-to-diamond conversion, which takes place in B
region. It is therefore believed to be the experimental proof of the theoretical model of the
graphite-to-diamond conversion through an or-g path, but the or-g phase had never been
obtained in the corresponding experiment [183]. Interestingly, using the constant-pressure ab
initio molecular dynamic simulations recently confirmed this model [190]. From these results,
again, it is suggested that the different graphite-to-diamond conversions may exist in the
different pressuretemperature regions in the carbon phase diagram [172], for example, the
two mentioned above. However, it is not comprehensible why the transforming by the rh-g
path never appeared in Scandolo et al. simulation [190]. According to HTHP, SW, and PLIIR,
a reasonable deduction was that the important factor about the conversion of graphite to
diamond, i.e. the temperature, was not considered in their simulations. In other words, the
temperature did not play a relevant role due to the overwhelming effect of the pressure in the
molecular dynamic simulations. In fact, the pressure of SW-induced conversion (B region) is
not much larger than that of the pressures of HTHP (A region) and PLIIR (C region), but the
temperatures of the conversions upon HTHP and PLIIR are much higher than that of SW.
Therefore, for the conversion of graphite to diamond, the pressure favorably induces an or-g
transformation path, then the temperature favorably produces a rh-g transformation path.
4.5. Stability of Nanodiamonds Synthesized by PLIIR
Compare diamond with the cubic structure, it is well known that hexagonal diamond is a
metastable phase. Naturally, the formation of the cubic structure of diamond would be prior to
G. W. Yang 256
that of the hexagonal structure in competing growth of cubic and hexagonal phases from the
point of the view of thermodynamics [190]. Interestingly, nanocrystalline diamonds with
cubic and hexagonal structures were synthesized simultaneously by PLIIR [30]. Similarly,
nanocrystalline boron nitrides with cubic and explosion phase that is a high-temperature and
high-pressure phase were also prepared simultaneously by PLIIR [32]. Then, it is noted that
the explosion phase boron nitride is a metastable phase compared with cubic structure boron
nitride. To gain a better understanding to the stability of nanodiamonds with different phases
upon PLIIR from the point of view of structure energy, first-principles calculation using the
CASTEP code (version 2.2 Ab Initio Total Energy Program) [192] was therefore employed to
perform the phase stability of the allotropes of nanodiamonds upon PLIIR [193]. The
CASTEP code is based on the density-functional theory to describe the electronelectron
interaction and a pseudopotential description of the electron-core interaction, and has been
publicized as a Cambrigde Serial Total Energy Package (CASTEP). Usually, it can give the
sum of electronic energy of a large system, as well as its band structure. Transferability and
robustness of the assumed pseudopotentials of each element seem to be confirmed by success
in reproducing the physical properties such as lattice parameters of many compounds.
Therefore, it can be expected to give the relative stability of crystalline allotrope.
The detail experimental procedure was described in the section of nanodiamonds
prepared by PLIIR. We calculated the total energy of cubic diamond, hexagonal diamond, and
graphite versus the various volumes (V) by ab initio calculation. The curves of the total
energy versus various atomic volumes (V) with regard to cubic diamond, hexagonal diamond,
and graphite using the CASTEP code are shown in Figure 22.
Clearly, one can see that graphite phase is equilibrium phase. The result is in agreement
with our case that the ratio of graphite to the whole prepared powders was more 95%. In
addition, we can see that cubic and hexagonal are far from the equilibrium phase and the
energy difference between cubic diamond and hexagonal diamond is very small, with a
magnitude of about 30 meV/atom. Moreover, the total energy of hexagonal diamond is
slightly higher than that of cubic diamond. As the expected, these results indicated that
hexagonal diamond is less stable than the cubic one. Generally, the origin of the small total
energy difference of the cubic and hexagonal diamond is attributed to their similar structural
properties. The crystal structures of the cubic and the hexagonal diamond were shown in
Figure 23. Distinctly, one can see that the atomic arrangement is very similar between cubic
diamond and hexagonal diamond. Both the two structures have covalent tetrahedral bonds
and contain only six-atom rings of bonds. Moreover, the two structures have the same
environments of the first and the second nearest neighbors, and but different environments of
the third nearest neighbors. In detail, along <111> atomic planes direction of cubic diamond
and the c direction of the hexagonal diamond, the difference between the two structures is
better understanding by considering the crystals to be constructed.
In both structures, atomic layers are stacked on top of one another with successive layers
displaced sidewise. In cubic diamond, every fourth layer atoms are stacked on top without
any sidewise displacement, giving rise to the stacking sequence ABC ABC.... as shown in
Figure 23 (a). On the other hand, the stacking sequence is the type of AB AB... in hexagonal
diamond, as shown in Figure 23 (b). Moreover, in cubic diamond, all six atoms form the ring,
in which four atoms lie on a plane and the remaining two atoms occur on the opposite sides of
this plane. Then, it forms the so-called chair shapes, such as the shade part shown in
Figure 23 (a). However, in the hexagonal diamond, it has both the chair shapes as well as the
boat shapes. In contrast to the chair shapes, the boat shapes have four atoms on a plane
and the remaining two atoms occur on the same side of this plane, as shown in the shade part
Figure 23 (b). Whereas the space groups of the cubic diamond and hexagonal diamond are the
O
h
7
and O
6h
4
group, respectively. The structure of hexagonal diamond has lower symmetry
than the cubic diamond.
However, why could cubic diamond and hexagonal diamond coform and coexist in our
synthesis system? It was proposed that PLIIR would be a very fast and far from equilibrium
process, so all metastable and stable phases forming at the initial, intermediate, and final
stages of the conversion could be reserved in the final products, especially, for the metastable
intermediate phase [170] In other words, the quenching times of PLIIR are so short that those
metastable phases forming at the intermediate stage of the conversion could be frozen in the
final products. On the other hand, owing to the similarities of cubic and hexagonal diamond
in structures as the mentioned earlier, and the total energy difference of the two structures is
very small. Accordingly, the hexagonal diamond could not only form at the intermediate
stage of the conversion, but also could exist in the final products in a far-from equilibrium
process, such as PLLIR. Importantly, the energy, pressure, and temperature are always
shifting periodically with the repetition-frequency operation of the laser beam in the pulse-
laser ablation system, even though the shift is very small. It is therefore possible that the cubic
and hexagonal diamond nanocrystals were synthesized one after the other under the
difference energy, pressure, and temperature conditions. More importantly, Wu et al. [194]
pointed out that the formation of hexagonal diamond is usually favored under the conditions
of the high carbon supersaturation, whereas the cubic diamond grows at much lower
supersaturation levels. In the PLIIR, at the initial stage of pulsed-laser ablating graphite
target, the density of the enabled carbonelement supersaturation is always much high, that
time, hexagonal phase formation should be favored. With the pulse over, the density of
carbon supersaturation will greatly decrease. Thus, cubic phase growth will be favored at the
stage. Therefore, hexagonal and cubic phases could form by turns when the density of carbon
supersaturation shifts periodically with the repetition-frequency operation of the laser beam.

Figure 22. Total energies of cubic diamond, hexagonal diamond, and graphite calculated for various
volumes
4 5 6 7 8 9 10
-156.2
-156.0
-155.8
-155.6
-155.4
-155.2
E
t
o
t

(
e
V
/
a
t
o
m
)
Volume
(
3
/atom)

hexagonal diamond
--- cubic diamond
graphite
G. W. Yang 258

Figure 23. Crystal structures of the cubic and hexagonal diamond. (a) Cubic diamond. (b) Hexagonal
diamond
CONCLUSION
There are the concluding remarks of pulsed laser ablation in liquid on the basis of
experimental and theoretical studies above. (i) The plasma plume with HTHPHD is created at
the liquid-solid interface when the laser pulse ablated the solid target in the confined liquid.
Meanwhile, the higher ablating rate to the solid target and shorter quenching time of the
plasma plume in liquid can be achieved. These traits offer a potential to synthesize
nanomaterials and nanostructures. (ii) PLIIR has been verified to be an effective and general
route to synthesize nanostructures, especially, metastable nanostructures that prefer high
temperature and high pressure. New phase formation of nanostructures may involve in both
liquid and solid. (iii) Diamonds nanocrystals have been synthesized by PLIIR in our studies.
The relevant thermodynamics and kinetics of the nanostructures formation upon PLIIR are
suggested in theoretical. (iv) PLIIR could allow researchers to choose and combine
interesting solid targets and liquid to fabricate nanostructures of new compounds for purpose
of fundamental research and potential applications.
ACKNOWLEDGMENTS
The National Science Foundation of China and the Ministry of Education of China
funded this work. The author is grateful to Dr. J. B. Wang of Xiangtan University, Dr. Q. X.
Liu of Guangdong University of Technology, and Dr. C. X. Wang of Tokyo Institute of
Technology, who ever worked in the authors group and made the important contributions to
the research field covered by this review chapter.
REFERENCES
[1] Ashfold, M. N. R., Claeyssens, F. & Henley, S. J.(2004). Chem. Soc. Rev., 33(1), 23.
[2] Cheung, J. T. (1994). In Pulsed Laser Deposition of Thin Films, eds. by D. B. Chrisey,
& G. K. Hubler, New York: John Wiley & Sons, Chapt. 1.
[3] Tornan, V., Zafiropulos, V., Vainos, N. A. & Fotakis, C. (2000). Optics laser Eng., 34,
309.
[4] Lowdnes, D. H., Geohegan, D. B., Puretzky, A. A., Norton, D. P. & Rouleau, C. M.
(1996). Science, 273, 898.
[5] Amoruso, S., Bruzzese, R., Spinelli, N. & Velotta, R. (1999). J. Phys. B, 32, R131.
[6] Willmott, P. R. & Huber, J. R. (2000). Rev. Mod. Phys., 72, 315.
[7] Fabbro, R., Fourntier, J., Ballard, P. & Virmont, J. (1990). J. Appl. Phys., 68, 775.
[8] Devaux, D., Fabbro, R., Tollier, L. & Bartnicki, E. (1993). J. Appl. Phys., 74, 2268.
[9] Peyre, P. & Fabbro, R. (1995). Optics. Quantum Electron, 27, 1213.
[10] Berthe, L., Fabbro, R., Tollier, L. & Bartnicki, E. (1997). J. Appl. Phys., 82, 2826.
[11] Patil, P. P., Phase, D. M., Kulkarni, S. A., Ghaisas, S. V., Kulkarni, S. K., Kanrtkar, S.
M., Ogale, S. B. & Bhide, V. G. (1987). Phys. Rev. Lett, 58, 238.
[12] Ogale, S. B. (1988). Thin Solid Films, 163, 215.
[13] Ogale, S. B., Malshe, A. P., Kanetkar, S. M. & Kshirsagar, S. T. (1992). Solid State
Comm., 84, 371.
[14] Sharma, A. K., Ayyub, P., Multani, M. S., Adhi, K. P., Ogale, S. B., Sunderaraman, M.,
Upadhyay, D. D. & Banerjee, S. (1996). Appl. Phys. Lett, 69, 3489.
[15] Singh, J. J. Mater. Sci., (1994). 29, 5232.
[16] Peyer, P., Scherpereel, X. & Fabbro, R. (1998). J. Mater. Sci., 33, 1421.
[17] Berthe, L., Fabbro, R., Peyer, P. & Bartnicki, E. (1999). J. Appl. Phys., 85, 7552.
[18] Berthe, L., Sollier, A., Fabbro, R., Peyer, P., Bartnicki, E. (2000). J. Phys. D, 33, 2142.
G. W. Yang 260
[19] Peyer, P., Berthe, L., Fabbro, R., Sollier, A. (2000). J. Phys. D: Appl. Phys., 30, 498.
[20] Sollier, A., Berthe, L. & Fabbro, R. (2001). Eur. Phys. J. Appl. Phys., 16, 131.
[21] Agee, V. V., Bakbonov, A. F. & Yankovskii, A. A. (1997). J. Appl. Spectr, 64, 187.
[22] Romain, J. P. & Auroux, E. (1997). J. Appl. Phys., 82, 1367.
[23] Sakka, T., Iwanage, S., Ogata, Y. H. & Takemoto, T. (2000). J. Chem. Phys., 112,
8645.
[24] Sakka, T., Ogate, Y. H. & Mabuchi, M. (2002). J. Phys. D, Appl. Phys., 35, 65.
[25] Sakka, T., Saito, K. & Ogata, Y. H. (2002). Appl. Surf. Sci., 197, 246.
[26] Saito, K., Takatani, K., Sakka, S. & Ogata, Y. H. (2002). Appl. Surf. Sci., 197, 56.
[27] Saito, K., Sakka, T. & Ogata, Y. H. (2003). J. Appl. Phys., 94, 5530.
[28] Zhu, S., Lu, Y. F., Hong, M. H. & Chen, X. Y. (2001). J. Appl. Phys., 89, 2400.
[29] Zhu, S., Lu, Y. F. & Hong, M. H. (2001). Appl. Phys. Lett, 79, 1396.
[30] Yang, G. W., Wang, J. B. & Liu, Q. X. (1998). J. Phys-Condens. Mat, 10, 7923.
[31] Yang, G. W. & Wang, J. B. (2000). Appl. Phys. A-Mater, 71, 343.
[32] Wang, J. B., Zhang, C. Y., Zhong, X. L. & Yang, G. W. (2002). Chem. Phys. Lett, 361,
86.
[33] Wang, J. B., Zhang, C. Y., Zhong, X. L. & Yang, G. W. (2003). Chem. Phys. Lett, 367,
10.
[34] Wang, J. B., Zhong, X. L., Zhang, C. Y. & Yang, G. W. (2003). J. Mater. Res., 8, 2774.
[35] Liu, Q. X., Wang, C. X., Zhang, W. & Yang, G. W. (2003). Chem. Phys. Lett, 382, 1.
[36] Poondi, D. & Singh, J. (2000). J. Mater. Sci., 35, 2467.
[37] Poondi, D., Dobbins, T. & Singh, J. (2000). J. Mater. Sci., 35, 6237.
[38] Simakin, A. V., Voronov, V. V., Shafeev, G. A., Brayner, R. & Bozon-Verduraz, F.
(2001). Chem. Phys. Lett, 348, 182.
[39] Dolgaev, S. I., Simakin, A. V., Voronov, V. V., Shafeev, G. A. & Bozon-Verduraz, F.
(2002). Appl. Surf. Sci., 186, 546.
[40] Anikin, K. V., Melnik, N. M., Simakin, A. V., Shafeev, G. A., Voronov, V. V. &
Vitukhnovsky, A. G. (2002). Chem. Phys. Lett, 366, 357.
[41] Bozon-Verduraz, F., Brayner, R., Voronov, V. V., Kirichenko, N. A., Simakin, A. V. &
Shafeev, G. A. (2003). Quantum Electron, 33, 714.
[42] Izgaliev, A. T., Simakin, A. V. & Shafeev, G. A. (2004). Quantum Electron, 34, 47.
[43] Compagnini, G., Scalisi, A. A. & Puglisi, O. (2002). Phys. Chem. Chem. Phys., 4, 2787.
[44] Compagnini, G., Scalisi, A. A. & Puglisi, O. (2003). J. Appl. Phys., 94, 7874.
[45] Compagnini, G. (2004). Appl. Surf. Sci., 226, 216.
[46] Zhang, Y., Chen, W. Z. & Zhang, W. Z. (2003). Chem. J. Chinese U, 24, 337.
[47] Zhang, W. G. & Jin, Z. G. (2004). Sci. Chin. Ser. B, 47, 159.
[48] Pearce, S. R. J., Henley, S. J., Claeyssens, F., May, P. W., Hallam, K. R., Smith, J. A. &
Rosser, K. N. (2004). Diamond Rel. Mater, 13, 661.
[49] Liang, C. H., Shimizu, Y., Sasaki, T. & Koshizaki, N. (2003). J. Phys. Chem. B, 107,
9220.
[50] Liang, C. H., Shimizu, Y., Masuda, Y. & Koshizaki, N. (2004). Chem. Mater, 16, 963.
[51] Liang, C. H., Shimizu, Y., Sasaki, T. & Koshizaki, N. (2004). Chem. Phys. Lett, 389,
58.
[52] Chen, J. W., Dong, Q. Z., Yang, J., Song, S. L. & Lian, J. S. (2004). Mater. Lett, 58,
337.
[53] Jiang, Z. Y., Huang, R. B., Xie, S. Y. & Zheng, L. S. (2001). J. Solid State Chem., 160,
430.
[54] Yeh, Y. H., Yeh, M. S., Lee, Y. P. & Yeh, C. S. (1998). Chem. Lett, 11, 1183.
[55] Yeh, M. S., Yang, Y. S., Lee, Y. P., Lee, H. F., Yeh, Y. H. & Yeh, C. S. (1999). J.
Phys. Chem. B, 103, 6851.
[56] Chen, Y. H. & Yeh, C. S. (2001). Chem. Comm., 4, 371.
[57] Kabashin, A. V. & Meunier, M. (2003). J. Appl. Phys., 94, 7941.
[58] Chen, G. X., Hong, M. M., Lan, B., Wang, Z. B., Lu, Y. F. & Chong, T. C. (2004).
Appl. Surf. Sci., 228, 169.
[59] ElShall, M. S., Li, S., Turkki, T., Graiver, D., Pernisz, U. C. & Baraton, M. I. (1995). J.
Phys. Chem. B, 99, 17805.
[60] Burr, T. A., Seraphin, A. A. & Kolenbrander, K. D. (1997). Phys. Rev. B, 56, 4818.
[61] Geohegan, D. B., Puretzky, A. A., Duscher, G. & Pennycook, S. (1998). J. Appl. Phys.
Lett, 72, 2987.
[62] Geohegan, D. B., Puretzky, A. A., Duscher, G. & Pennycook, S. J. (1998). Appl. Phys.
Lett, 73, 438.
[63] Becker, M. F., Brock, J. R., Cai, H., Henneke, D. E., Keto, J. W., Lee, J. Y., Nichols,
W. T. & Glicksman, H. D. (1998). Nanostructured Mater, 10, 853.
[64] Geohegan, D. B., Puretzky, A. A. & Rader, D. J. (1999). Appl. Phys. Lett, 74, 3788.
[65] Lowndes, D. H., Rouleau, C. M., Thundat, T. G., Duscher, G., Kenik, E. A. &
Pennycook, S. J. (1999). J. Mat. Res., 14, 359.
[66] Wu, K. T., Yao, Y. D., Wang, C. R. C., Chen, P. F. & Yeh, E. T. (1999). J. Appl. Phys.,
85, 5959.
[67] Link, S. & El-Sayed, M. A. (2000). International Rev. Phys. Chem., 19, 409.
[68] Marine, W., Patrone, L., Lukyanchuk, B. & Sentis, M. (2000). Appl. Surf. Sci., 154,
345.
[69] Hata, K., Fujita, M., Yoshida, S., Yasuda, S., Makimura, T., Murakami, K., Shigekawa,
H., Mizutani, W. & Tokumoto, H. (2001). Appl. Phys. Lett, 79, 692.
[70] Nakata, Y., Muramoto, J., Okada, T. & Maeda, M. (2002). J. Appl. Phys., 91, 1640.
[71] Lu, Y. F. & Aoyagi, Y. (1994). Jpn. J. Appl. Phys. Part 2, 33, l430.
[72] Lu, Y. F., Takai, M., Komuro, S., Shiokawa, T. & Aoyagi, Y. (1994). Appl. Phys. A, 59,
281.
[73] Lu, Y. F. & Aoyagi, Y. (1995). Jpn. J. App. Phys. Part 2, 34, L1557.
[74] Lu, Y. F., Song, W. D., Hong, M. D. & Chong, T. C. (1996). Appl. Phys. A, 64, 573.
[75] Lu, Y. F., Song, W. D., Ang, B. W., Chan, D. S. H. & Low, T. S. (1997). Appl. Phys. A,
65, 9.
[76] Lu, Y. F. (2002). Laser Microprocessing and Applications in Microelectronics, Chapter
in International Trends in Applied Optics (Ed. by Arthur H. Guenther, President,
International Commission for Optics) SPIE.
[77] Kelly, R. (1994). Miotello In Pulsed laser deposition of thin films. Eds. by D. B.
Chrisey, & G. K. Hubler, John Wiley & Sons: New York.
[78] Bekefi, G. (1976). Principles of Laser Plasmas. Wiley: New York.
[79] Angleraud, B., Girault, C., Champeaux, C., Garrelie, F., Germain, C. & Catherinot, A.
(1996). Appl. Surf. Sci., 96, 117.
[80] Balasz, L. Gijbels, Vertes, A. (1991). Anal. Chem., 63, 314.
G. W. Yang 262
[81] Zhang, C. Y., Wang, J. B., Zhong, X. L. & Yang, G. W. (2003). Chem. Phys. Lett, 370,
522.
[82] Ogale, S. B., Patill, P. P., Rooeda, S. & Saris, F. W. (1987). Appl. Phys. Lett, 50, 1802.
[83] Ghaisas, S. V., Malshe, A. P., Patill, P. P., Kanetkar, S. M., Ogale, S. B. & Bhide, V. G.
(1987). J. Appl. Phys., 62, 2799.
[84] Shushtarian, S. S., Ogale, S. B. & Madhukar, A. (1992). Mater. Lett, 13, 325.
[85] Singh, J., Vellaikal, M. & Narayan, J. (1993). J. Appl. Phys., 73, 4351.
[86] Yang, G. W., Liu, Q. X. & Wang, J. B. (1996). Unpublished.
[87] Wang, Y. H., Yu, R. Q., Liu, Z. Y., Huang, R. B., Zheng, L. S., Zhang, X. F., Hu, G. &
Zhang, Z. (1997). Chem. J. Chin. U, 18, 293.
[88] Cheng, D. D., Yu, R. Q., Liu, Z. Y., Zhang, Q., Wang, Y. H., Huang, R. B., Zhan, M.
X. & Zheng, L. S. (1995). Chem. J. Chin. U, 16, 948.
[89] Lu, Y. F., Huang, S. M., Wang, X. B. & Shen, Z. X. (1998). Appl. Phys. A, 66, 543.
[90] Lyalin, A. A., Simakin, A. V., Shafeev, G. A. & Loubnin, E. N. (1999). Appl. Surf. Sci.,
68, 373.
[91] Lu, Y. F., Huang, S. M., Huan, C. H. A. & Luo, X. F. (1999). Appl. Phys. A, 68, 647.
[92] Lyalin, A. A., Simakin, A. V. & Shafeev, G. (1999). A Thin Solid Films, 357, 144.
[93] Simakin, A. V., Lubnin, E. N. & Shafeev, G. A. (1999). Appl. Phys. A, 69, S267.
[94] Huang, S. M., Lu, Y. F. & Sun, Z. (1999). Appl. Surf. Sci., 151, 244.
[95] Huang, S. M., Lu, Y. F., Sun, Z. & Luo, X. F. (2000). Surf. Coat. Tech., 125, 25.
[96] Simakin, A. V., Lubnin, E. N. & Shafeev, G. A. (2000). Appl. Surf. Sci., 154, 405.
[97] Simakin, A. V., Obraztsova, E. D. & Shafeev, G. A. (2000). Chem. Phys. Lett., 332,
231.
[98] Huang, S. M., Lu, Y. F. & Sun, Z. (2000). Jpn. J. Appl. Phys.1, 39, 1154.
[99] Simakin, A. V., Lubnin, E. N. & Shafeev, G. A. (2000). Quantum Electron, 30, 263.
[100] Simakin, A. V., Loubnin, E. N. & Shafeev, G. A. (2002). Appl. Surf. Sci., 186, 227.
[101] Chang, T. C. & Molian, P. A. (1999). J. Manuf. Syst., Supp 1, 1.
[102] Wang, J., Niino, Y. & Yabe, A. (2000). Appl. Surf. Sci., 154, 571.
[103] Yasui, Y., Niino, H., Kawaguchi, Y., Yabe, A. (2002). Appl. Surf. Sci., 186, 552.
[104] Choo, K. L., Ogawa, Y., Kanbargi, G., Otra, V., Raff, L. M., Komanduri, R. (2004).
Mat. Sci. Eng. A, 372, 145.
[105] Vogel, A., Lauterborn, W. (1988). J. Acoust. Soc. Am., 84, 719.
[106] Yavas, O., Leiderer, P., Park, H. K., Grigoropoulos, C. P., Poon, C. C., Leung, W. P. &
Do N. Tam, A. C. (1993). Phys. Rev. Lett., 70, 1830.
[107] Yavas, O., Leiderer, P., Park, H. K., Grigoropoulos, C. P., Poon, C. C. & Tam, A. C.
(1994). Phys. Rev. Lett., 72, 2021.
[108] Yavas, O., Leiderer, P., Park, H. K., Grigoropoulos, C. P., Poon, C. C., Leung, W. P.,
Do, N. & Tam, A. C. (1994). Appl. Phys. A, 58, 407.
[109] Park, H. K., Grigoropoulos, C. P. & Tam, A. C. (1996). Appl. Phys. Lett, 68, 596.
[110] Park, H. K., Zhang, X., Grigoropoulos, C. P., Poon, C. C. & Tam, A. C. (1996). J. heat
Trans.-T, 118, 702.
[111] Park, H. K., Kim, D., Grigoropoulos, C. P. & Tam, A. C. (1996). J. Appl. Phys., 80,
4072.
[112] Kim, D., Park, H. K. & Grigoropoulos, C. P. (2001). Int. J. Heat Mass Tran., 44, 3843.
[113] Kruusing, A. (2004). Optics Laser Eng., 41, 329.
[114] Sakka, T. (private communication)
[115] Geiger, M., Becker, W., Rebhan, T., Hutfless, J. & Lutz, N. (1996). Appl. Surf. Sci., 96-
98, 309.
[116] Kim, D. S., Oh, B. & Lee, H. (2004). Appl. Surf. Sci., 222, 138.
[117] Fabbro, R., Peyre, P., Berthe, L. & Scherpereel, X. (1998). J. Laser Appl., 10, 265.
[118] Wang, J. B. & Yang, G. W. (1998). SPIE, 3550, 65.
[119] Mafune, F., Kohno, J., Takeda, Y., Kondow, T. & Sawabe, H. (2000). J. Phys. Chem.
B, 104, 9111.
B, 105, 5114.
B, 106, 7575.
B, 107, 12589.
[123] Tsuji, T., Iryo, K., Watanabe, N. & Tsuji, M. (2002). Appl. Surf. Sci., 202, 80.
[124] Tsuji, T., Kakita, T. & Tsuji, M. (2003). Appl. Surf. Sci., 206, 314.
[125] Tsuji, T., Tsuboi, Kitamura, N. & Tsuji, T. (2004). Appl. Surf. Sci., 229, 365.
[126] Dobbins, T. A., Pooni, D. & Singh, J. (1999). J. Mater. Synth. Proces., 7, 261.
[127] Zhang, J., Worley, J., Denommee, S., Kingston, C., Jakubek, Z. J., Deslandes, Y., Post,
M., Simard, B., Braidy, N. & Botton, G. A. (2003). J. Phys. Chem. B, 107, 6920.
[128] Nath, M., Rao, C. N. R., Popvitz-Biro, R., Albu-Yaron, A. & Tenne, R. (2004). Chem.
Mater, 16, 2238.
[129] Sharma, A. K., Vispute, R. D., Joag, D. S., Ogale, S. B., Joag, S. D., Ayyub, P.,
Multani, M., Dey, G. K. & Banerjee, S. (1993). Mater. Lett, 17, 42.
[130] Wakisaka, A., Gaumet, J. J., Shimizu, Y., Tamori, Y., Sato, H. & Tokumaru, K. (1993).
J. Chem. Soc., Faraday Trans. 89, 1001.
[131] Takami, A., Kurita, H. & Koda, S. (1995). J. Phys. Chem., 99, 875.
[132] Nakamura, M., Kitamori, T. & Sawad,a, J. (1999). Phys. Chem. B, 103, 1226.
[133] Graebner, E., Jin, S., Kammlott, G. W., Herb, J. A. & Gardinier, C. F. (1992). Nature,
359, 401.
[134] Holland, L. & Ojha, S. M. (1979). Thin Solid Films, 58, 107.
[135] Vora, J., Moravec, T. J. (1981). J. Appl. Phys., 52, 6151.
[136] Sawabe, A. & Inzuka, T. (1985). Appl. Phys. Lett., 46, 2.
[137] Kurihara, K., Sasaki, K. & Koshino, N. (1988). Appl. Phys. Lett., 52, 437.
[138] Weissmantel, C., Bewilogua, K., Dietrich, D., Erler, H. J., Hinnen, H. J., Klose, S.,
Nowich, W. & Rcisse, G. (1980). Thin Solid Films, 72, 19.
[139] Miyasato, T., Kawano, Y. & Miraki, A. (1984). Japan. J. Appl. Phys., 23, L234.
[140] Kitabataske, M. & Wasa, K. (1985). J. Appl. Phys., 58, 1693.
[141] Dijkkamp, D., Venkatesan, T., Wu, X. D., Shaheen, S., Jisrawi, N., Min-Lee, Y. H.,
Mclean, W. L. & Croft, M. (1987). Appl. Phys. Lett., 51, 619.
[142] Horwitz, J. S., Grabowski, K. S., Chrisey, D. B. & Lenchter, R. E. (1991). Appl. Phys.
Lett, 59, 1565.
[143] Sarchez, F., Varela, M., Queralt, X., Aguiar, R. & Morenza, J. L. (1988). Appl. Phys.
Lett, 61, 2228.
[144] Sato, T., Furuno, S., Iguchi, S. & Hanabuso, M. (1988). Appl. Phys. A, 45, 355.
[145] Collins, C. B., Davanloo, F., Lee, T. J., Park, H. & You, J. H. (1993). J. Vac. Sci.
Technol. B, 11, 1936.
G. W. Yang 264
[146] Bourdon, E. B. D., Kovarik, P. & Prince, R. H. (1993). Diamond Relat. Mater, 2, 425.
[147] Seth, J., Padiyath, R., Rasmussen, D. H. & Babu, S. V. (1993). Appl. Phys. Lett, 63,
473.
[148] Polo, M .C., Cifre, J., Sanchez, G., Aguiar, R., Varela, M. & Esteve, J. (1995). Appl.
Phys. Lett, 67, 485.
[149] Bundy, F. P. & Kasper, J. S. (1967). J. Chem. Phys., 46, 3437.
[150] DeCarli, P. S. & Jameson, J. C. (1961). Science, 133, 1821.
[151] Yoshikwa, M., Mori, Y. & Maegawa, M. (1993). Appl. Phys. Lett, 62, 3114.
[152] Scandolo, S., Bermasconi, M. & Chiaron, G. L. (1995). Phys. Rev. Lett, 74, 4015.
[153] Nemanich, R. J., Glass, J. T., Lucovsky, G. & Shroder, R. E. (1988). J. Vac. Sci.
Technol., A6, 1783.
[154] Maruyama, K., Makino, M. & Shiraishi, M. (1992). J. Mater. Sci. Lett, 11, 116.
[155] Prawer, S., Nugent, K. W. & Jamieson, D. N. (1998). Diamond Relat. Mater, 7, 106.
[156] Beeman, D., Silverman, J., Lynds, R. & Anderson, M. R. (1984). Phys. Rev. B, 30, 870.
[157] Mao, H. K. & Hemerly, R. J. (1991). Nature, 351, 721.
[158] Wang, C. X., Liu, Q. X., Yang, Y. H. & Yang, G. W. (2004). J. Phys. Chem. B, 108,
728.
[159] Zhang, C. Y., Wang, C. X., Yang, Y. H. & Yang, G. W. (2004). J. Phys. Chem. B, 108,
2589.
[160] Liu, Q. X., Wang, C. X., Yang, Y. H. & Yang, G. W. (2004). Carbon, 42, 585.
[161] Wang, C. X., Yang, Y. H., Liu, Q. X. & Yang, G. W. (2004). Appl. Phys. Lett, 84,
3034.
[162] Liu, Q. X., Wang, C. X., Yang, Y. H. & Yang, G. W. (2004). Appl. Phys. Lett, 84,
4568.
[163] Wang, C. X., Yang, Y. H., Xu, N. S. & Yang, G. W. (2004). J. Am. Chem. Soc., (in
press).
[164] Wang, C. X., Li,u, Q. X. & Yang, G. W. (2004). Chem. Vapor Deposition, (in press).
[165] Yang, G. W. & Wang, J. B. (2001). Appl. Phys. A, 72, 475.
[166] Simon, A. & Kantor, Z. (2002). Nuclear Instr. Methods in Phys. Res. B, 190, 351.
[167] Bundy, F. P., Bassett, W. A., Weathers, M. S., Hemley, R. J., Mao, H. K. & Goncharov,
A. F. (1996). Carbon, 34, 141.
[168] Yang, G. W. & Liu, B. X. (2000). Phys Rev B, 61, 4500-02 and references therein.
[169] Wang, J. B. & Yang, G. W. (1999). J. Phys: Condens Matter, 11, 7089.
[170] Zhang, Y. F., Zhang, F. Q. & Chen, G. H. (1994). Carbon, 32, 1415.
[171] Winter, N. W. & Ree, F. (1998). J. Computer-Aided Mater. Design, 5, 279.
[172] Aust, R. B. & Drickamer, H. G. (1963). Science, 140, 817.
[173] Bundy, F. P. & Kasper, J. S. (1967). J. Chem. Phys., 46, 3437.
[174] Endo, S., Idani, N., Oshima, R. & Wakatsuki, M. (1994). Phys. Rev. B, 49, 22.
[175] Yagi, T., Utsumi, W., Yamakata, M., Kikegawa, T. & Shimomure, O. O. (1992). Phys.
Rev. B, 46, 6031.
[176] Fahy, S., Louie, S. G. & Cohen, M. (1987). Phys. Rev. B, 35, 7623.
[177] Kertesz, M. & Hoffmann, R. (1984). J. Solid State Chem., 54, 313.
[178] Clarke, R. & Uher, C. (1984). Adv. Phys., 33, 469.
[179] Kurdyumov, A. V. (1975). Sov. Phys. Dokl, 20, 218.
[180] Kurdyumov, A. V., Ostrovskaya, N. F., Pilyankevich, A. N. & Frankevich, I. N.
(1087). Sov. Phys. Dokl., 23, 278.
[181] Wheeler, E. J. & Lewis, D. (1975). Mat. Res. Bull, 10, 687.
[182] Utsumi, W. & Yagi, T. (1991). Science, 252, 1542.
[183] Takano, K. J., Harashima, H. & Wakatsuki, M. (1991). Jpn. J. Appl. Phys., 30, L860.
[184] Vereshchagin, L. F., Kalashnikov, Y. A., Feklichev, E. M., Nikolskaya, I. V. &
Tikhomirova, L. M. (1965). Sov. Phys. Dokl., 10, 534.
[185] Scandolo, S., Bernasconi, M., Chiarotti, G. L., Focher, P. & Tosatti, E. (1995). Phys.
Rev. Lett, 74, 4015.
[186] Goncharov, A. F. (1996). Carbon, 34, 141.
[187] Segall, M. D., Lindan, P. J. D., Probert, M. J., Pickard, C. J., Hasnip, P. J., Clark, S. J.
& Payne, M. C. (2002). J. Phys. Condens. Matter, 14, 2717.
[188] Wang, C. X., Yang, Y. H., Liu, Q. X. & Yang, G. W. (2004). Appl. Phys. Lett, 84,
1471.
[189] Wu, B. R. & Xu, J. (1998). Phys. Rev. B, 57, 13355.

INDEX

A
absorptionspectra,212,214
accounting,33,34
aceticacid,54
acetone,192,198,199,204,207,212,234,241
acid,53,54,145
activationenergy,137,249
aerosols,5,20
AFM,219,220
aggregation,128,137,212,214
agingprocess,129,131
algorithm,107,114
alloyednanoparticles,x,191,206
alters,195,196,197,214
aluminium,2,3,6,7,9,13,15,24,26,31
ambientair,5,32
ambientgas,vii,1,3,5,8,11,13,17,19,23,25,26,
27,29,31,32,33,35,39,100,107
ammonia,234,236
amplitude,120
aqueoussolutions,195,200,212,221,235
archaeologicalskeletalmaterials,vii
argon,17,20
aromatichydrocarbons,236
aspiration,54,55
asymmetry,202
atmosphere,4,33,55,128,129
atmosphericpressure,11,18,31
atomicpositions,102,155
atoms,5,8,17,22,26,32,33,34,107,108,109,
110,112,137,154,155,156,208,212,215,251,
256
attachment,137
Aunanoparticles,200,204,211,217,220
B
backgroundgas,ix,32,99,103,107,109,110,111,
112
backgroundnoise,25
bandgap,139
bandgap,118
barium,84,85
baths,216
beams,vii,1,4,5,25,28,37,216,217,222
bending,146,147
benefits,15
benzene,231,234,236,240
bias,52
bicarbonate,25
bindingenergy,221
biomedicalapplications,146
BMI,224
BNnanocrystals,228
Boltzmannconstant,8,114,240
bonding,155,245
bonds,155,256
bone,46,50,96
bones,52,93,96
borealforest,47
brass,9,11,12,17,20,24,31,196,197,208,209,
214
breakdown,3,6,14,32,37,39,42,102,119,120,
147
C
calcification,51,52
calcium,viii,46,51,52,55,82,83,85,91,93,144
calculus,143,150
Index 268
caliber,143,147
calibration,24,54,55
Cambrian,48
candidates,52
capillary,208,219,220,248
carbon,95,206,207,211,228,234,236,240,244,
245,246,249,250,255,257
carbonatoms,249,250,255
carbonfilm,236,240
carbonnanotubes,228,244
casestudy,94,96
catalysis,101,222,245
catalyst,195,214,234,252,254,255
catalyticeffect,214
cation,54
cattle,95
cesium,84
chaos,110
chemical,vii,viii,x,1,8,45,47,51,92,103,107,
128,131,148,150,191,192,195,204,206,207,
211,212,214,228,230,231,244
Chicago,94
China,227,259
chlorine,212
chloroform,212
circadianrhythm,50
cladding,147
classification,4
cleaning,100,101,227
climate,47
clustermodel,243
clustering,81
clusters,15,20,101,103,115,193,211,245,246,
250
CO2,2,28,235
coatings,101,230,235,236,237
collateral,100
collineargeometry,vii,1,10,37
collisions,107,109,110,113,119
combinedeffect,17
compatibility,131
complement,228
complexity,19,47,92,103
complications,35,148
composites,133
composition,viii,x,3,8,15,17,20,45,47,52,53,
56,82,150,191,192,211,212,221,222,234
compoundsemiconductors,101
compounds,195,206,214,256,259
compression,103,110,113
computing,155
condensation,20,103,115,232,244
conduction,33,117,118,119,121,154,158,193,
194
conductivity,24,101,102,122,159,194,197,240
configuration,vii,viii,1,2,4,5,6,7,8,10,11,12,
13,14,16,17,18,19,20,22,24,25,26,27,28,
30,31,33,35,36,37,39,145
confinement,ix,13,25,26,35,127,128,134,144,
218
conformity,220
consent,128
conservation,146,154
construction,154
contour,110,112
cooling,115,121,214,232,236
copper,9,13,17,24,49,208,212,214,235,236
correctionfactors,79
correlation,16,83
correlations,85,88
cost,14,128,132,147,149,222
Coulombinteraction,157
covering,47,192
criticaldensity,119,159
criticaltemperature,viii,2,31,106,113
criticalvalue,32,33,159,214
crown,49,51,55
crystalstructure,51,134,155,256
crystalline,101,129,131,133,134,136,212,234,
236,240,242,244,250,251,256
crystallites,242,252
crystallization,105
crystals,51,232,240,245,256
cubicboronnitride,234,244
culture,49
cyanide,145,148,150,152
cycles,245
cyclodextrins,200
cysteine,145
cystine,144
D
database,56
decay,4,11,13,24,25,26,35,38,115,116,122,
133
decomposition,ix,99,103,113,114,115,116,117,
122,150,207
deconvolution,242,244
deduction,248,255
Index 269
defects,133
deformation,246
degradation,146,148,151
densityvalues,6,8
deposition,14,28,50,101,113,140,195,227,232,
240,244,261
deposits,48
derivatives,159,246
desorption,100,105,107
detachment,220
detection,6,7,26
detonation,29,32
deviation,92,115,205
diamonds,234,236,243,245,251,252,254,256
dichotomy,viii,46,84
dielectrics,x,103,153,154,155,157
diet,51,81,82,96
dietaryintake,50
differentialequations,117
diffraction,133,212,234,241,253,254
diffusion,ix,28,36,37,38,99,102,110,154,157,
158,159,193,194,197,208
diffusiontime,28,37,38,197
diffusivity,16,36,194
dilutegas,110
dimensionality,107
directmeasure,15
discontinuity,31,32,104
discs,49
dispersion,120,130,133
displacement,13,31,36,39,256
dissociation,26,107,138
distributionfunction,154,156,200,201,214,215
divergence,52,92,147
diversity,195
doping,132,134
DoublePulse(DP)Laserablation,viii,2
doublepulselaserablation,vii
drainage,47
drawing,92
drying,133
dynamicevolution,vii,2,22
E
EarlyBronzeAge,viii,45,49
electriccurrent,246
electrolyte,130
electron,ix,6,8,10,11,22,25,26,30,32,33,37,
87,100,102,108,109,113,115,117,118,120,
121,122,133,139,149,154,155,156,157,207,
220,234,256
electrondiffraction,133
electronicmaterials,140
electronphononcoupling,102
electrons,27,32,101,102,103,108,109,110,113,
117,118,119,120,132,156,157,194,195,197,
201,202,211,217,218,222
elephants,96
elongation,24
emission,3,4,5,8,9,10,11,12,13,14,15,17,18,
20,22,24,27,32,36,37,38,133,135,139,150,
154,192,221,231,233,238
employment,131
enamel,viii,45,50,51,53,55,79,82,85,86,87,93,
95,96
enamelmatrix,viii,45,50,51,79,82
endoscopiclaserlithotripsy,ix,143
energy,vii,viii,ix,xi,2,3,6,7,8,9,10,11,13,14,
15,16,18,19,20,25,26,27,28,29,31,33,34,
36,37,38,55,99,102,105,108,109,111,113,
115,117,137,139,143,144,146,147,148,150,
154,155,156,158,159,191,193,194,195,
197,201,202,207,211,215,220,221,222,231,
233,234,238,240,246,247,249,252,256
environmentalcharacteristics,39
environmentalconditions,19
epithelium,148
equilibrium,28,37,101,102,106,107,115,234,
245,246,247,249,252,256,257
equipment,79
etching,128,130,134
ethanol,130,131,136,139,192,196,197,204,205,
206,207,208,209,211,212,213,214,216,217,
235
evaporation,27,28,100,101,104,105,107,113,
194,197,198,212,214
excimerlasers,193
excitation,ix,xi,2,9,10,26,33,100,102,107,117,
118,122,131,135,155,191,220,230
exclusion,37
experimentalcondition,viii,2,3,4,6,18,25,30,33,
37,100,103,122,198,207,211,215
exploitation,14
exponentialfunctions,155
exposure,xi,11,97,191,193,195,196,200,201,
202,203,204,205,206,207,208,209,210,214,
215,216,220,221,222
expulsion,31
extinction,197
Index 270
F
fabrication,ix,101,127,128,129,131,138,139,
227
faith,92
faunalsamples,viii,45,49
femtosecond,ix,x,3,4,99,100,101,102,113,121,
122,149,153,154,157,163,164,165,166,168,
169,170,171,175,178,180,181,182,185,186,
198,200,210,211,221
femur,49
Fermilevel,217
fiber,143,144,145,146,147,148,149
fibers,146,147,148,151
filmformation,132
films,101,102,130,139,140,234,236
filters,54
fish,47
fishing,47
flexibility,131,146,147
flight,106,107,137
fluid,102,108
FokkerPlanckapproach,x,153,154
formula,131,132
fragmentationprocessing,ix,127,128,134,135
fragments,53,132,144,145,146,149,217,245
France,99
freeenergy,139,244,246,247,248,249
freedom,107
fullerene,128,235
functionalization,136
G
gel,51
geochemicalcomposition,viii,45
geochemicaldata,viii,46,82
geography,51,81,82,84
geometry,vii,x,1,3,10,15,28,146,153,160
Germany,95
Gibbsenergy,137
glasses,3
graphite,214,229,231,233,234,237,238,239,
240,241,242,243,244,245,246,247,248,249,
250,251,252,253,254,255,256,257
Greece,93
growthtime,245
Guangdong,259
Guangzhou,227
guidance,148
guidelines,51
H
hafnium,235
hardness,240
heatcapacity,102,194
heatconductivity,113
heattransfer,33,34,197
heavyparticle,108,113,114
helium,17
hemisphere,238
histology,96
holmium,150,151
hotspots,25,197
HRTEM,133,134
Hunter,45,47,94,95
huntergatherers,viii,46,84
hybrid,107,206
hydrodynamicmodel,ix,99,102,113
hydrothermalsynthesis,214
hydroxyapatite,82,85
hydroxyl,146
hydroxylgroups,146
hypothesis,15,20,26,27,28,32,36,106,202
I
ideal,33,34,108
image,136,198,220,221,238
images,11,12,22,23,24,35,132,133,206,207,
233,234,238,241
immigrants,56,84
impurities,119
incidence,5,32,119,194,196
indexing,242,252
inequality,106
inferences,94
infraredspectroscopy,234
initialstate,249
initiation,29,31,32,221
initiationtime,29,31,32
insulation,25
insulators,16,36
integration,131
interface,xi,33,105,128,147,192,196,202,206,
219,227,228,230,232,236,244,258
Index 271
interference,viii,46,52,53,54,85,86,92,94,216,
220
intracorporeallaserlithotripsy,ix,143,146,149
intrinsicvalue,159
ionimplantation,38
IonMobilitySpectrometry,vii,1
ionization,ix,8,11,15,16,22,25,26,27,33,35,46,
100,102,103,108,109,110,117,118,120,122,
156,157,158,159
ions,5,26,38,52,85,101,103,108,109,113,156,
160,192,195,245
iron,17,228,235
irradiation,2,101,103,108,115,116,130,133,
134,135,137,138,139,144,145,146,148,193,
197,198,201,208,228,230,234,235,236,240
isobaricinterference,viii,46,52,54
isotope,46,47,49,51,54,55,84,85,86,87,88,93,
94,95,96,97,221,222
Italy,162
J
Japan,127,139,263
K
kidney,147,148
kinetics,xi,102,227,232,259
L
LAAtomicFluorescenceSpectrometry,vii,1
LakeBaikal,viii,45,47,48,49,94,95
LAMicrowaveInducedPlasmaAtomicEmission
Spectrometry,vii,1
landscape,50
laserablation,vii,ix,x,1,4,13,15,17,29,30,31,
32,34,35,36,39,46,50,52,53,54,55,56,84,
86,89,93,95,97,99,100,101,103,104,107,
110,112,113,121,122,127,128,129,131,132,
133,134,135,137,138,149,150,153,154,191,
192,193,194,195,196,197,198,200,205,207,
208,209,210,211,212,214,215,218,219,220,
222,227,228,231,232,233,234,235,236,237,
238,239,240,241,243,244,257,258
Laserablation,vii,xi,54,55,57,78,90,93,96,97,
100,128,140,195,206,227
laserbeam,vii,x,1,4,5,25,28,32,100,103,107,
120,129,130,135,138,145,146,147,148,161,
174,191,193,194,196,197,201,202,204,210,
211,214,215,216,217,220,222,237,257
laserenergy,vii,viii,2,18,29,31,32,33,36,108,
111,113,115,117,143,144,148,154,164,165,
168,169,179,180,193,194,195,207,211,215,
222,252
laserflux,vii
LaserInducedBreakdownSpectroscopy(LIBS),vii,1
laserradiation,32,38,103,104,109,146,147,154,
156,157,159,192,193,194,195,196,200,201,
202,204,205,206,207,210,211,214,215,220,
221,246
laserwavelength,x,118,153,169,173,174,191,
192,193,194,197,201,202,203,204,210,217,
220
LaserAblationInductivelyCoupledPlasma(LAICP),
vii,1
laserablationquadrupole,viii,45
lasermatterinteractions,vii,ix,99,100
lasers,3,19,20,28,40,100,101,129,130,132,
139,143,144,145,147,149,151,153,191,192,
193,195,198,202,220,252
latticeparameters,242,256
leaching,54
lead,vii,viii,x,1,2,13,22,24,51,82,97,101,135,
153,160,196,200,202,204,212,221,228,232,
252
leakage,147
lens,54,129,147,216,237
lifetime,13,27,47,49,113,114,115,139
lightscattering,133
lighttransmission,147
LimitOfDetection(LOD),vii,1
lineardependence,38
linearfunction,202
liquidphase,104,105,114,116,117,135,159
liquidgasmixture,ix,100
liquids,ix,x,5,127,128,191,192,193,194,195,
197,198,199,201,202,204,206,207,211,212,
214,215,217,218,219,220,222,236,241,243
lithium,25
lithotripsy,ix,143,144,145,146,147,148,149,
150,151,152
localization,154,206
lowerplasmashielding,viii,2,35
LSD,3,29,31,32,33,35,36
luminescence,ix,127,133
Luo,262
lying,115
Index 272
M
magnesium,235
magnitude,5,14,17,25,37,110,219,232,237,256
majority,49,87,195,200,210
management,147
manganese,82
manufacturing,101
massspectrometry,46,93,95,97
matrix,viii,5,6,8,13,15,24,25,38,45,50,51,52,
55,79,82,84,92,93,133
media,ix,xi,127,128,129,137,138,139,191
Mediterranean,96
melt,13,28,30,31,36,39,195,196,198,215,216,
217,219,220
melting,16,37,101,104,105,113,116,144,156,
159,161,193,197,202,204,208,210,212,213,
215,216,217,219
meltingtemperature,198,202,208,210,212,213,
216
melts,198
metalnanoparticles,195,211
metals,x,5,16,25,31,36,39,101,102,103,113,
122,159,191,195,200,205,208,212,213,214,
218,220,228,234,235
metastableliquidregion,ix,100,116
metastablephases,xi,227,230,232,257
methanol,235
methodology,52,79,92
Mexico,97
microcrystalline,242
microelectronics,38
microhabitats,47
Microsampling,viii,45
microscope,207,210,234
microscopy,13
microstructure,51
microstructures,101,128,196
migration,49,95
MinistryofEducation,259
mixing,23,51,93,96,112
modelsystem,221
modelling,17,35,36,39,113,154
models,33,93,101,102,103,104,106,113,122,
154,157,160,211
moderates,47
molarvolume,106,246,247,249
mole,246
moleculardynamics,ix,x,100,102,153,154,160
molecularmass,100,204,214
molecules,26,53,107,110,112,137,220,221,230,
231,238
moltenpool,viii,2,13,36
momentum,29,146
Mongolia,47
monolayer,26
MonteCarlomethod,107,110
morphology,11,13,15,31,35,82,214,215,218,
220,234,241,242
Moscow,43,94,99,191,225
Moses,144,145
motivation,195
MP,93,96,97
MPI,117,118
mucosa,148
multicollector,viii,45,97
multiphotonexcitation,ix,100
N
nanocrystals,xi,4,128,227,232,234,235,236,
237,241,242,244,247,248,250,257,259
nanomaterials,259
nanometer,195,232,245
nanometerscale,195,232,245
nanometers,137,198,220,234
nanoparticleformation,x,101,191
nanoparticles,x,4,5,39,103,128,131,136,191,
192,193,194,195,197,198,199,200,204,205,
206,207,208,210,211,212,214,218,220,222,
229,230,234,235,236,240
nanorods,200,202,203,204,235
nanosecondlaserablation,ix,4,99,129,154,200
nanostructuredmaterials,101
nanostructures,ix,127,128,136,218,220,228,
232,234,235,259
nanowires,244
NationalResearchCouncil,1
nebulizer,54
neglect,119
nickel,102,235
nitrides,228,234,235,256
nitrogen,17
noblemetals,x,191,195,212,234
nonequilibrium,106
nonmetals,39
nucleation,xi,4,114,227,244,245,247,248
nuclei,221,244,245,246,247,248,250
null,33
numericalaperture,147
Index 273
O
OH,146
operations,92
opportunities,47,101
opticaldensity,203,204
opticalfiber,x,143,146,148,151
opticalgain,139
opticalproperties,16,19,36,134
optimization,x,6,101,153
optoelectronicproperties,ix,127
optoelectronics,38,128
orthogonalgeometry,vii,1
overlap,2,25,28,47,147
oxalate,144
oxidation,86,139,193,206,207,208,212,214,
218,235
oxygen,17,95,96,111,112,137,139,193,198,
206,207,208,213,221,237
P
parallel,vii,1,4,19,28,55,145,216,250,252
parallelism,255
partialdifferentialequations,154,159
particlemass,105
partition,8
passivation,131,134,139
pathways,51
perforation,148
permeability,138
permission,iv
permit,133
permittivity,118
phaseboundaries,245,246
phasediagram,114,115,230,234,245,246,250,
255
phaseexplosionmechanism,viii,2,36
phasetransformation,246,249,255
phasetransitions,103,113
phosphates,93
phosphorous,82,134,135
phosphorus,83,130,134
photographs,2,12,131
photoluminescence,127,128,135,139
photonics,101
photons,118,154,221,222
physicalmechanisms,viii,xi,2,227
physicalproperties,256
physics,ix,101,127
pilotstudy,95
PLspectrum,133,134,135
plants,47,50
plasma,vii,viii,ix,2,3,4,5,6,8,10,11,13,15,17,
19,20,22,23,24,25,26,27,28,29,31,32,33,
34,35,37,38,46,53,86,93,95,97,99,100,107,
108,110,117,118,119,121,122,127,128,129,
136,138,139,140,144,154,156,157,158,159,
208,221,222,228,229,230,232,233,234,236,
237,238,239,240,244,258
plasmaplume,ix,3,4,11,29,38,99,100,108,110,
122,154,228,229,230,232,238,244,258
platelets,214
poison,148
polarization,101
polymer,ix,106,127,131,132,133,134,135,136,
137,139
polymermaterials,106
polymermatrix,133
polymersolutions,131,139
polymers,16,36,128,129,131,133,134,139
populationdensity,112
positivefeedback,202
potassium,25
practicalknowledge,149
precedent,17
precipitation,200
preparation,iv,46,53,54,130,139,195,233,236,
240,244,246,254
prevention,100
probability,120,155,215,248,249,250,251,252
probabilitydistribution,250
probe,220
project,139
propagation,29,102,103,117,120,121,138
pulp,95
pulseduration,x,29,100,102,108,109,144,146,
150,153,160,165,181,184,191,193,194,198,
211,212,213,218,228,231,232,233,234,235,
238,239,241
pulsedlaser,vii,101,107,122,127,128,130,137,
139,143,146,164,172,193,195,227,228,231,
232,233,234,235,236,237,238,239,240,241,
252,253,254,258
pulsedlaserinducedliquidsolidinterfacereaction
(PLIIR),xi,227,228,236
purification,210
purity,128,131,221
PVP,204,205,206
Index 274
pyrolysis,206
pyrolyticgraphite,234,240
Q
quantumconfinement,ix,127,128,129,131,132,
133,134,136,137,139
quantumdot,228,235
quantumdots,228,235
R
radiation,3,33,110,119,146,147,154,157,159,
191,192,193,194,196,197,198,200,201,202,
203,204,207,208,209,210,211,213,220,221,
222
radius,23,24,33,34,35,107,111,112,161,197,
198,202,208,210,246,247,248,250
Ramanspectra,136,234,236,240,242,244
Ramanspectroscopy,234,240
rareearthelements,46,84
reactant,230
reactions,107,214,230,232
reactivity,195
reading,54
reality,215
recognition,viii,46,52,144
recombination,27,107,109,110,118,131,134,
139,156,157,158
recombinationprocesses,110
recommendations,iv
reconstruction,94
referenceframe,105
reflectivity,16,19,24,27,113,119,160,194
refractionindex,119
refractiveindex,13,118,131,198
relaxation,37,102,115,117,118,154,157,158,
220
relaxationprocess,117
relaxationprocesses,117
relevance,38
reliability,46,52
relief,194,196,197,219
renalcalculi,143
replication,55
researchers,52,128,159,191,227,228,240,259
residuals,192
resolution,46,94
ResonantLA,vii,1
resources,47,92,107
rhenium,84
rings,49,256
rodents,50
roomtemperature,35,128,129,130,131,133,139,
159,212,214,236
roughness,217,219
Rouleau,140,259,261
RoyalSociety,97
rubidium,46,79,84
Russia,99,191
rutile,214
S
sapphire,193,198,210,221,236
saturation,17,37,161
scatter,101
scattering,38,133,221
seasonality,viii,45
secretion,50
sedimentation,204,221,222
seed,120
segregation,107,208,210
selectedareaelectrondiffraction,234
selfassembly,ix,127,128,136
semiconductor,102,136
semiconductors,x,16,103,128,153,154,155,157,
159,235
sensitivity,3,6,25,26,38
shade,256
shape,23,36,100,101,109,129,132,154,160,
161,200,202,203,215,216
sheep,96
shock,11,13,23,24,26,27,29,33,34,35,106,
107,110,115,121,129,132,138,139,144,145,
146,228,230,239,240,245,252
shockwaves,23,24,107,110,129,132,138,139,
144,145
shores,viii,45,48
Siberia,viii,45,47,48,94,95
sideeffects,197
signals,25,50,51,53,82
silica,38,118,119,120,146,147,236
silicon,ix,127,128,129,130,131,132,133,134,
135,136,137,138,139,156,236,240
siliconnanocrystals,ix,127,129,133,135,138
silver,37,102,198,204,218,235
simulation,ix,x,99,101,102,107,110,117,122,
153,154,155,160,161,255
Index 275
simulations,ix,100,117,122,255
SiO2,32,128,131,134
skin,115,116
sodium,25,199,235
software,55,133
solidstate,115
solidification,130,132,133,134
solubility,214
solvents,235
soundspeed,114
SouthAfrica,96,97
species,ix,2,3,5,8,11,17,19,20,26,29,46,47,
50,52,55,86,99,103,107,110,111,121,193,
195,197,206,228,230,237,238,245
specificheat,108,158
specificsurface,135,214
spectroscopy,6,101,133,234
speedoflight,118
spin,ix,127,128,132,139
spinonglass(SOG),ix,127,128,132,139
stabilization,136,138,202,204
stagesofmineralization,viii,45
standardization,24
stars,117
states,114,115,134,243
statistics,158
steel,6,7,10,14,15,18,25
stoichiometry,38,107
storage,214,218
striae,50
strictures,56
strontium,46,47,48,49,50,51,52,54,55,79,82,
85,86,89,92,94,95,96
structuring,101
subsistence,47
substitutes,85
substrates,229,236,237
subtraction,54,158
sulfate,235
sulfur,145
Sun,262
supercooling,105
superfluid,244
suppression,137
surfacechemistry,138
surfaceenergy,202
surfacelayer,38
surfaceproperties,100,128
surfacestructure,49
surfacetension,114,195,198,202,208,232,236,
244,250
surfacetreatment,101
surfactant,136,206,235
surgicaltechnique,143
susceptibility,211
suspensions,130,195,206,221,235
symmetry,107,211,215,257
synthesis,xi,5,101,129,192,193,198,199,200,
201,208,214,215,216,221,227,228,232,234,
235,236,241,245,248,251,257
T
technology,128,131,139
teeth,viii,45,47,51,52,53,55,56,57,78,79,82,
85,89,90,92,93,97
TEM,198,199,200,201,205,206,210,212,213,
217,234,241
temperaturedependence,105,114
tension,114,198,250
territory,46,50
thermaldecomposition,116,122,145
thermalenergy,38,108,111,240
thermalevaporation,109,113
Thermalmodel,ix,99
thermalproperties,102,210
thermalization,157
thermodynamic,vii,viii,2,6,8,15,22,34,106,108,
113,114,115,230,234,237,240,244,246,248,
251,254
thinfilms,101,107,132,139,229,232,234,236,
240,261
tin,212,213,235
tissue,136
titanium,28,211
toothenamel,viii,45,51,93,95,96,97
totalenergy,vii,1,10,11,27,154,156,256,257
totalinternalreflection,147
toxicity,131,149
traceelements,53,85,94,95
tradeoff,52
traits,258
transformation,210,221,230,232,245,246,249,
252,253,254,255
transitionmetal,255
transmission,3,38,148,207,234
transparency,240
transport,33,102,104,110,156
tungsten,236
Index 276
tunneling,102,117,118,120
tunnelingeffect,117,120
U
UK,97,110
ultrashortlaserpulses,viii,2,14,37
underlyingmechanisms,37
uniform,26,110,137,146
ureter,147,148,151
uricacid,148,150
urinarycalculi,ix,143,144,149,150
urinarytract,143
UV,193,195,196,221
V
vacancies,137
vacuum,ix,19,28,29,99,101,103,106,107,114,
118,121,128,195,197,201,214,222,227,228,
229,232,240,244
valence,118,156
vapor,106,108,109,114,115,144,145,193,196,
197,198,200,203,205,206,207,208,209,212,
213,215,216,217,219,220,221,234,235,236,
244
variables,86,87
variations,15,34,95,107
varieties,53
vector,108,146
velocity,33,34,105,106,108,109,110,111,112,
131,137,195,228
Vereshchagin,265
vibration,242
viscose,108
visualization,133
volatilization,24
W
waste,221
water,ix,3,48,50,51,54,85,127,128,129,130,
131,132,133,134,135,136,137,139,144,148,
198,199,200,201,203,204,206,207,211,212,
214,218,220,221,228,232,233,234,235,237,
238,239,240,241,245
waterevaporation,136
watershed,48
wavelaserbeam,vii
wavepropagation,121
wavelengths,200
wealth,107
wear,53
welding,234
wetting,212,213
widebandgap,ix,100,117,118,128
windows,18
workers,107
X
XPS,212
Xraydiffraction,211,212,213,253
XRD,133,134,234,236,253
Y
yield,viii,37,45,79,92
yttrium,150
Z
zinc,81,84,208,235
zirconium,86,92

Black SH e Ed Laser Ablation Effects and Applications

Uploaded by

Document Information

Original Description:

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Black SH e Ed Laser Ablation Effects and Applications

Uploaded by

Copyright:

Available Formats

LASERS AND ELECTRO-OPTICS RESEARCH AND TECHNOLOGY

LASER ABLATION: EFFECTS

is the heat of vaporization that can be assumed approximately

Modeling of Laser Ablation Induced by Nanosecond and Femtosecond 113

Email address: ranranfang2@gmail.com

400 500 600 700 800

300 400 500 600 700 800

J, when P = 10 GPa and T = 5000 K. Therefore, these results

You might also like