Collaborative workshop Charge density waves: small scales and ultrashort time

Vukovar, Croatia, 28 31 October 2010.

Pulsed laser deposition technologies (PLD, MAPLE, LIFT): basic phenomena and
applications
Ion N. Mihailescu, Carmen Ristoscu
National Institute for Lasers, Plasma and Radiation Physics, Lasers Department, 409 Atomistilor, PO
Box MG-54, RO-077125, Magurele, Ilfov, Romania
Ion.mihailescu@inflpr.ro.
Since their introduction in 1960, pulsed lasers are
recognized as a flexible and powerful tool for material
processing applications. The plasma generated and
supported by high intensity laser radiation was long time
considered an important loss channel and so, a strong
impediment in the development of efficient laser processing
technologies of materials. In time however, it became clear
that the plasma not only controls the complex interaction
phenomena between the laser radiation and various media
but can be exploited in view of improving laser radiation
coupling and eventually the efficient processing of materials
submitted to intense laser beams [1]. In materials science,
laser plays a significant role either as a passive component
for monitoring or as an active tool for coupling its radiation
energy into material being processed. Pulsed laser action
results in various applications such as localized melting,
laser annealing, surface cleaning by desorption and ablation,
surface hardening by rapid quench, and after 1988, pulsed
laser deposition technologies for synthesizing high quality
nanostructured thin films.
We review herewith recent results we obtained by using
pulsed laser deposition technologies: Pulsed laser
Deposition (PLD), Matrix Assisted Pulsed Laser
Evaporation (MAPLE), Laser Induced Forward Transfer
(LIFT) and Combinatorial-PLD (C-PLD).

Figure 1. PLD experimental setup

The general PLD layout used in experiments of thin film
synthesis can be described as follows (Fig. 1). Laser beam
generated by a pulsed UV laser source enters the reaction
chamber through a quartz window. We used a KrF* excimer
laser source (COMPEXPro 205) generating at 248 nm
pulses of 25 ns duration. The beam is focused onto target

surface by means of an AR cylindrical lens placed outside

the deposition chamber. It hits the target surface at oblique
incidence. The target is rotated and translated during
multipulse irradiation to avoid piercing and improve film
uniformity. A temperature controller is used to monitor
substrate heating and cooling. The reaction chamber is
initially evacuated down to a residual pressure of 10-4 Pa.
The dynamic pressure during experiments is kept constant
using a flow controller.
PLD demonstrated to be a versatile technique for thin film
processing with a high diversity of structural and
morphological characteristics [2,3]. Many independent
parameters can be changed under control in order to select
the optimum deposition regimes of some specific structures
and thin films. Growing thin films by PLD has numerous
advantages, such as:
- the laser source is placed outside the deposition chamber
offering increased flexibility in handling the material, laying
out the geometrical setup, and adjusting deposition
parameters;
- most of the solid and liquid materials can be ablated;
- multistructures can be easy synthesized ;
- laser pulses make possible to control the growth rate of the
coatings very accurately (down to a few fractions of );
- most of the ablated material is located inside the plasma
generated under laser pulse action;
- the stoichiometry of coating materials generally coincides
with that of the target even for complex, highly unstable
compounds (also described as congruent transfer);
- the coatings adhere well due to the high plasma energy
incident onto deposition substrate; and
- species with metastable or nonequilibrium states and new
phases can be synthesized.
The presence of particulates of different geometrical shape
and size was considered for long time one major handicap
for the large scale implementation of PLD for the synthesis
of surfaces with suitable finishing or applications in optoelectronics or lasing media, among other. It took several
years till the origin of these particulates, which could be
present either on surface or deeply embedded into the films,
could be suitably understood and monitored. We know now
that the major physical phenomena involved in particulates
formation are :
1. explosive dislocation of the substance caused by the
subsurface overheating of the target;
2. gas phase condensation of the evaporated material
(clustering);

Collaborative workshop Charge density waves: small scales and ultrashort time
Vukovar, Croatia, 28 31 October 2010.
3. liquid phase expulsion under the action of the recoil
pressure of the ablated substance;
4. blast-wave explosion at the liquid (melt) solid interface;
and
5. hydrodinamic instabilities on target surface.
It was nothing but a matter of time to elaborate protocols
and rules to be applied for particulates limitation or even
complete elimination. Among the most efficient methods to
be applied we mention:
- to avoid the presence of the liquid inside the crater;
- proper choice of laser wavelength;
- to set the incident laser fluence at a level high enough to
vaporize all the melted substance;
- application of electric and/or magnetic fields normally to
expansion; or
- intersection and elimination of particulates by a second
laser beam.
Nevertheless, in case of very complex delicate
biomolecules, PLD fails because of the irreversible damage
of the chemical bonds and consequent compositional
modification of the deposited film. This disadvantage is
eliminated by matrix assisted pulsed laser evaporation
(MAPLE), capable to transfer compounds at low
temperatures. MAPLE was developed after 1998 [4] as a
complementary method to PLD, necessary for delicate (in
respect with thermal and/or biological degradation and
damage) materials transfer (Fig. 2). MAPLE essentially
differs from PLD by target preparation, laser-material
interaction and transfer mechanisms. It provides a more
gentle mechanism for transferring many different
compounds, including large molecular weight species, such
as polymeric or organic molecules [5,6].

Figure 2. MAPLE experimental setup

Specific to MAPLE is the use of a cryogenic composite

target, a dilute mixture of the organic material to be
deposited, and a light-absorbent, high vapor-pressure
solvent matrix. The material to be deposited is dissolved or
suspended in the solvent, usually 0.110 wt%, and cooled
below the solvent freezing temperature. The solid composite
target is evaporated by a pulsed UV laser and the material is
collected on a nearby substrate as a thin film. The vaporized
solvent does not form a film and is pumped away (Fig. 3).
Other new advanced transfer method is Laser Direct Writing
(LDW), also known as Laser Induced Forward Transfer
(LIFT). LDW technologies are used to produce or deposit
materials on complex 2D or 3D structures. Even the concept
of LDW was introduced at the end of 60, this method
concentrated a very large interest after 2000, when the
technique progressed very much and fully demonstrated its
possibilities. LDW has the potential to revolutionize
manufacturing processes across a broad range of sectors
including
aerospace,
pharmaceuticals,
automotive,
biotechnology, ceramics. A few approaches have been
proposed to date to minimize heat induced damage of the
transferred biomaterials. One of them is to initiate
biomaterial transfer by laser ablation of a thin metal film
(sacrificial layer) placed between the biomaterial layer and
the transparent support. LIFT technique consists in the local
transfer of material from a thin film (ribbon) covering a
transparent support to a close receiving substrate under the
action of a laser pulse (Fig. 4). The laser radiation is
absorbed directly in the ribbon or by the thin metal film.

Figure 4. (a) LIFT schematic. (b) Detail of donor/receiver

substrate showing thick sacrificial film covered with transfer
material. Small shaded region indicates the volume in which
the incident laser is absorbed [7]
A very recent development in the field is the CombinatorialPLD technique (C-PLD). In C-PLD, the targets are located
in two different positions and ablated.
In the following, we will provide some recent examples
illustrating the potential of the four mentioned techniques.

Figure 3. Schematic of the MAPLE evaporation process

The Mg films obtained by PLD in UHV from Mg targets

were characterized by Scanning electron microscopy (SEM)
and X-ray diffraction (XRD). The surface of the films
appeared smooth, with only few particulates of about 300
nm diameter (Fig. 5), with a density of only 0.01 /m2.
XRD spectrum evidenced the deposition of a pure Mg film,

Collaborative workshop Charge density waves: small scales and ultrashort time
Vukovar, Croatia, 28 31 October 2010.
(002) textured (Fig. 6). The measured value of the rocking
curve was 4.0683.

Human osteoblast (hOB) precursor cells were cultured on

all structures for up to 14 days. The cells displayed a normal
morphology, optimal viability and spread. The synergistic
effect of the VN and FN coatings was evidenced by actin
and vinculin staining, MTT assays and SEM studies. The
long elongated actin filaments proved the excellent induced
bioactivity, also showing a uniform distribution of the cells
over the entire surface. The vinculin staining evidenced
intimate contacts with material surfaces by focal adhesion
patches for FN covered structures and small spots in case of
VN ones. The MTT results sustained the higher potential for
spreading and improved viability of protein covered
structures versus Ti/HA and Ti/HA/BSA. SEM
investigations revealed more flattened cell morphology with
long developed filopodia when cultivated on FN and VN
structures (Fig. 9).

Figure 5. Typical SEM image of a Mg film obtained by

PLD (F = 5.6 J/cm2)

Mg
(002) (101)
20

(102)
Intensity (a.u.)

15

10

(110)

(100)
5

Figure 7. Immunofluorescence detection of FN structures

0

30

35

40

45

50

55

60

2theta (deg)

Figure 6. XRD spectrum of a Mg film obtained by PLD

It is generally accepted that the synthesis of pure Mg films

is very difficult, being jeopardized by the extremely high
affinity of this metal for oxygen.
Extracellular matrix proteins (ECM) proved to be efficient
in material bio-activation by adsorption and cell adhesion at
the interface. We therefore tried to synthesize by PLD and
MAPLE a double structure consisting of a hydroxyapatite
(HA) bed and ECM proteins top-layer. The qualitative
distribution of proteins during the MAPLE synthesis was
monitored by Ponceau S Staining Solution on nitrocellulose
membranes. The quantitative reproducibility of fibronectine
(FN) and vitronectine (VN) was established by colorimetric
protein assay using bicinchoninic acid (BCA) solution. The
transfer of either FN or VN was demonstrated by FTIR
studies where the peaks of protein dropcasts were
coinciding with the ones of MAPLE deposited
nanostructures. These results were supported by antibody
staining studies using anti-human FN or VN rabbit
polyclonal serum and FITC-conjugated anti-rabbit IgG
when spot-like fluorescent regions were visualized by
fluorescence microscopy (Figs. 7,8).

Figure 8. Immunofluorescence detection of VN structures

Ti/HA

Ti/HA/BSA

Collaborative workshop Charge density waves: small scales and ultrashort time
Vukovar, Croatia, 28 31 October 2010.
Ti/HA/VN

Ti/HA/FN

rich region, i.e. between those corresponding for pure ZnO

and ITO films.

Figure 9. SEM images of hOB cells at 7 days from seeding

We have revealed that all porphyrin (TPP :SA) patterns
produced by LIFT demonstrate comparable specific red
fluorescence (Fig. 10) independently of thickness of the
titanium film applied [8]. This points out that essential
amount of the transferred porphyrin has retained its
molecular structure in all cases.

Figure 11. XRR spectra acquired from various locations on

a ITO-ZnO mixed film

In conclusion, we foresee a bright avenue for these four

pulsed laser techniques in synthesis of nanostructured thin
films and multistructures of inorganic, organic or composite
materials for applications in all science and technology top
areas from optoelectronics, chemistry, and metallurgy to
biology and medicine.
Acknowledgements: The authors acknowledge the
financial support of the UEFISCSU under the contracts
511/2009 and 547/2009.

References

Figure 10. Specific red fluorescence of TPP:SA pattern

transferred from the thin-film target (dTi = 50 nm, F =
250 mJ/cm2).
We applied C-PLD to obtain ZnO ITO mixed films [9].
The deposition sequence was 20 pulses from the ITO target
followed by 20 pulses from the ZnO target to ensure a good
atomic mixing of the components. The total number of
pulses was varied from 1000 to 5000, which resulted in
films thicknesses from around 50 to 250 nm across a 50 mm
long substrate. The material was collected on Si or quartz
substrates heated from 300 up to 500 C. Films grown
separately from each target have their maximum thickness
positioned at the intersection between the perpendiculars
from the laser impact area on the targets with the substrate.
For film mixtures the critical angle was found to be a
function of the location where the measurement was
performed. By inspecting Fig. 11, where spectra collected
from a mixed film are displayed along those collected from
pure films, one can see that the mixed film possesses a
density that changes along with the location on the
transversal axis. The calculated values were from 5.63
g/cm3 in the ZnO rich region up to 6.51 g/cm3 in the ITO

[1] I. N. Mihailescu, J. Hermann, Chapter 4 in Laser

Processing of Materials: Fundamentals, Applications, and
Developments, Ed. P. Schaaf, Springer Series in Materials
Science, Springer Heidelberg (2010) pp. 51 90
[2] Pulsed Laser Deposition of Thin Films, edited by D. B.
Chrisey and G. K. Hubler (Wiley, New York, 1994)
[3] Pulsed Laser Deposition of thin films: applications-lead
growth of functional materials, edited by R. Eason (Wiley &
Sons, New York, USA 2007)
[4] D. B. Chrisey, A. Pique R. A. McGill, J. S. Horwitz, B.
R. Ringeisen, D. M. Bubb, and P. K Wu, Chem. Rev. 103,
553 (2003)
[5] Chapter 18 in Ref. 3
[6] I. N. Mihailescu, C. Ristoscu, A. Bigi, I. Mayer,
Chapter 10 in Laser-Surface Interactions for New Materials
Production Tailoring Structure and Properties, Series:
Springer Series in Materials Science, Vol. 130, Miotello,
Antonio; Ossi, Paolo M. (Eds.), 2010, pp. 235 260
[7] N.T. Kattamis, P. E. Purnick, R. Weiss, C. B. Arnold
Applied Physics Letters 91, 171120 (2007)
[8] T.V. Kononenko, I.A. Nagovitsyn, G.K. Chudinova,
I.N. Mihailescu, Applied Surface Science 256, 2803 (2010)
[9] D. Craciun, G. Socol, N.Stefan, M. Miroiu, I.N.
Mihailescu, A.-C. Galca, V. Craciun, Applied Surface
Science 255, 5288 (2009)