Low-energy ion scattering

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LEIS redirects here; for the Hawaiian garland see Lei (Hawaii).

Image of a Kratos Axis-165 system equipped with XPS, ISS, and AES, from Alberta Centre for Surface
Engineering and Science (ACSES).

Low-energy ion scattering spectroscopy (LEIS), sometimes referred to simply as

ion scattering spectroscopy (ISS), is a surface-sensitive analytical technique used to
characterize the chemical and structural makeup of materials. LEIS involves directing
a stream of charged particles known as ions at a surface and making observations of
the positions, velocities, and energies of the ions that have interacted with the surface.
Data that is thus collected can be used to deduce information about the material such
as the relative positions of atoms in a surface lattice and theelemental identity of those
atoms. LEIS is closely related to both medium-energy ion scattering (MEIS) and high-
energy ion scattering (HEIS, known in practice asRutherford
backscattering spectroscopy, or RBS), differing primarily in the energy range of the ion
beam used to probe the surface. While much of the information collected using LEIS
can be obtained using other surface science techniques, LEIS is unique in
its sensitivity to both structure and composition of surfaces. Additionally, LEIS is one of
a very few surface-sensitive techniques capable of directly observing hydrogen atoms,
an aspect that may make it an increasingly more important technique as the hydrogen
economy is being explored.
Contents
 [hide]
 1 Experimental setup

2 Physics of ion-surface interactions

o 2.1 Elemental composition and two-body

collision model

o 2.2 Getting quantitative

o 2.3 Shadowing and blocking

o 2.4 Diffraction does not play a major role

o 2.5 Variations of technique

3 Comparison to other analytical techniques

4 References

5 External links

6 See also

[edit]Experimental setup
LEIS systems consist of the following:

General experimental setup for LEIS.

1. Ion source, used to direct a beam of ions at a target sample. Electron impact
ionization is typically used to ionize noble gas atoms such asHe, Ne or Ar, while
 heating of wafers containingalkali atoms is used to create an alkali ion beam.
Ions thus created hold a positive charge, typically +1, due to ejection
of electrons from atoms. The range of energies used most often in LEIS is
500eV to 20 keV. In order to attain good experimentalresolution it is important
to have a narrow energy spread (ΔE/E < 1%) in the outgoing ion beam.
2. Ion beam manipulator, including electrostatic lenses for focusing and beam-
chopping. Lensesconsist of a series of either plate or cylindergeometries and
serve to collimate the beam as well as to selectively filter the beam based
on mass andvelocity. Beam chopping is performed using apulsed-
wave generator when time-of-flight (TOF) experiments are performed. Ions only
pass through the chopper when there is no applied voltage.
3. Sample manipulator, allows an operator to change the position
and/or angle of the target in order to perform experiments with
varying geometries. Using directional controls,azimuthal (rotational)
and incident angle adjustments may be made.
4. Drift tube/drift region, used in TOF setup. TOF measurements are used when
analysis of particle velocity is required. By pulsing ions towards the sample with
a regular frequency, and observing the time to travel a certain distance after
surface impact to a detector, it is possible to calculate the velocity of ions and
neutrals coming from the surface. An accelerator may also be used in this
setup, prior to the drift tube, in order to achieve separation of ions
from neutrals when desired.
5. Detector/electrostatic analyzer, used to detect the velocities and/or energies
of scattered particles including ions and, in some cases, neutral species. 
 Diagram of an electrostatic analyzer in the hemispherical geometry. Only ions of a selected energy
pass through to the detector.

As opposed to TOF analyzers, electrostatic analyzers achieve ion energy

resolution using electrostatic deflectors to direct only ions of a particular energy
range into a collector, while all other ions are redirected. This type of analyzer
can give good energy resolution (and thus, selectivity) but typically suffers from
poorsensitivity due to the fact that it only detects ions of a certain energy range
and ignores neutral species altogether. Two types of detectors are
used: channel electron multiplier (CEM) and microchannel plate (MCP)
detectors. CEMs operate in a similar manner to photomultipliers, displaying a
cascade of secondary electron emission processes initiated by ion or fast
neutral (energy > 1 keV) impact to give a gain in signal current. In this way it is
possible to efficiently detect even small ion or neutral particle fluxes. MCP
detectors are essentially 2-dimensional arrays of CEMs, and they allow
additional information about particle position to be obtained at the cost of
sensitivity at any given position.

6. Vacuum pumps; Studies are performed in ultra-high vacuum (UHV) conditions

(< 10−10 torr) in order to prevent unwanted interference with the ion
beam and/or sample. Common UHV pumps
include turbomolecularand ion pumps, with roughing pumping typically
performed using a rotary vane pump. Due to the extreme surface (i.e. first-
layer) sensitivity of LEIS, samples also need to be rigorously cleaned prior to
analysis. Some common processes used to clean samples
include sputtering and annealing. Appropriate equipment for cleaning must be
contained within the vacuum chamber.
7. Other analysis tools; in many cases it is desirable to perform multiple types of
analysis on a sample within the same UHV system, or even at the same time.
Some additional tools may include Auger electron spectroscopy (AES), low-
energy electron diffraction(LEED), and x-ray photoelectron spectroscopy (XPS).
Use of these tools typically requires the presence of additional detectors as well
as electron and/or x-ray sources where applicable.
[edit]Physics of ion-surface interactions
 Diagram of various ion-surface interactions (non-exhaustive). (1) Incoming ion; (2) Scattering; (3) Neutralization
and scattering; (4) Sputtering or recoiling; (5) Electron emission; (6) Photon emission; (7) Adsorption; (8)
Displacement. LEIS is unique in its high sensitivity to the first surface layer in a sample.

Several different types of events may take place as a result of the ion beam impinging
on a target surface. Some of these events include electron or photon emission,
electron transfer (both ion-surface and surface-ion),scattering, adsorption,
and sputtering (i.e. ejection of atoms from the surface). For each system and each
interaction there exists an interaction cross-section, and the study of these cross-
sections is a field in its own right. As the name suggests, LEIS is primarily concerned
with scattering phenomena.

[edit]Elemental composition and two-body collision model

Due to the energy range typically used in ion scattering experiments (> 500 eV), effects
of thermal vibrations,phonon oscillations, and interatomic binding are ignored since
they are far below this range (~a few eV), and the interaction of particle and surface
may be thought of as aclassical two-body elastic collision problem. Measuring the
energy of ions scattered in this type of interaction can be used to determine the
elemental composition of a surface, as is shown in the following:

Two-body elastic collisions are governed by the concepts

of energy and momentum conservation. Consider a particle with mass mx, velocity v0,
and energy given as   impacting another particle at rest with mass my.
The energies of the particles after collision are   and   
where   and thus  . Additionally, we
know . Using trigonometry we are able to
determine

Similarly, we know

In a well-controlled experiment the energy and mass of the primary ions (E 0 and mx,
respectively) and the scattering or recoiling geometries are all known,
so determination of surface elemental composition is given by the correlation
between E1 or E2 and my. Higher energy scattering peaks correspond to heavier atoms
and lower energy peaks correspond to lighter atoms.

[edit]Getting quantitative
While obtaining qualitative information about the elemental composition of a surface is
relatively straightforward, it is necessary to understand the statistical cross-section of
interaction between ion and surface atoms in order to obtain quantitative information.
Stated another way, it is easy to find out if a particular species is present, but much
more difficult to determine how much of this species is there.

The two-body collision model fails to give quantitative results as it ignores the
contributions of coulomb repulsion as well as the more complicated effects of
charge screening by electrons. This is generally less of a problem in MEIS and RBS
experiments but presents issues in LEIS. Coulomb repulsion occurs between positively
charged primary ions and the nuclei of surface atoms. The interaction potential is given
as:

Where   and   are the atomic numbers of the primary ion and surface atom,
respectively,   is the elementary charge,   is the interatomic distance, and   is the
screening function.   accounts for the interference of the electrons orbiting each
nucleus. In the case of MEIS and RBS, this potential can be used to calculate the
Rutherford scattering cross section  :

Repulsive scattering by a point particle.

As shown at right,   represents a finite region for an incoming particle, while   

represents the solid scattering angle after the scattering event. However, for LEIS   
is typically unknown which prevents such a clean analysis. Additionally, when using
noble gas ion beams there is a high probability of neutralization on impact (which
has strong angular dependence) due to the strong desire of these ions to be in a
neutral, closed shell state. This results in poor secondary ion flux. See AISS and TOF-
SARS below for approaches to avoiding this problem.

[edit]Shadowing and blocking

 Shadowing and blocking effects in two dimensions. No ions will be detected at angles below   Primary
ions are approaching from the upper left.

Shadowing and blocking are important concepts in almost all types of ion-surface

interactions and result from the repulsive nature of the ion-nucleus interaction. As
shown at right, when a flux of ions flows in parallel towards a scattering
center (nucleus), they are each scattered according to the force of the Coulomb
repulsion. This effect is known as shadowing. In a simple Coulomb repulsion model,
the resulting region of “forbidden” space behind the scattering center takes the form of

a paraboloid with radius   at a distance L from the scattering center.

The flux density is increased near the edge of the paraboloid.

Blocking is closely related to shadowing, and involves the interaction between

scattered ions and a neighboring scattering center (as such it inherently requires the
presence of at least two scattering centers). As shown, ions scattered from the first
nucleus are now on diverging paths as they undergo interaction with the second
nucleus. This interaction results in another “shadowing cone” now called a blocking
cone where ions scattered from the first nucleus are blocked from exiting at angles
below  . Focusing effects again result in an increased flux density near  .

In both shadowing and blocking, the "forbidden" regions are actually accessible to
trajectories when the mass of incoming ions is greater than that of the surface atoms
(e.g. Ar+ impacting Si or Al). In this case the region will have a finite but depleted flux
density.

For higher energy ions such as those used in MEIS and RBS the concepts of
shadowing and blocking are relatively straightforward since ion-nucleus interactions
dominate and electron screening effects are insignificant. However, in the case of LEIS
these screening effects do interfere with ion-nucleus interactions and the repulsive
potential becomes more complicated. Also, multiple scattering events are very likely
which complicates analysis. Importantly, due to the lower energy ions used LEIS is
typically characterized by large interaction cross-sections and shadow cone radii.
For this reason penetration depth is low and the method has much higher first-layer
sensitivity than MEIS or RBS. Overall, these concepts are essential for data analysis
in impact collision LEIS experiments (see below).

[edit]Diffraction does not play a major role

The de Broglie wavelength of ions used in LEIS experiments is given as  .
Using a worst-case value of 500 eV for an 4He+ ion, we see λ is still only 0.006 Å, still
well below the typical interatomic spacing of 2-3 Å. Because of this, the effects
of diffraction are not significant in a normal LEIS experiment.

ICISS geometry and its relevance to structural characterization of surfaces. The direction and length of the
surface-subsurface bond may be determined from an intensity vs.   plot. Red: determining the shape of the
shadow cone; Green: determining surface-subsurface spacing and direction with a known shadow cone shape.

[edit]Variations of technique
Depending on the particular experimental setup, LEIS may be used to obtain a variety
of information about a sample. The following includes several of these methods.

 Alkali ion scattering spectroscopy (AISS) uses alkali ions in place of noble gas

ions to give a distinctly different type of interaction. The primary difference between
AISS and normal ISS is the increase in ion survival probability when using alkali
ions. This is due to the relative stability of alkali (+1) ions as opposed to noble gas
ions which have a much stronger energetic incentive for abstracting electrons from
the sample. Increasing the ion survival probability results in an increase in
ion flux and an improvement in sensitivity, which in turn allows for a reduction in
primary ion flux to a point where the method is almost non-destructive. A
disadvantage of using alkali ions in place of noble gas ions is the increased
likelihood of adsorption or deposition to the sample surface.
 Impact-collision ion scattering spectroscopy (ICISS) takes advantage of
shadowing and blocking in order to make precisedeterminations about interatomic
spacing of the first 1-2 layers in a surface. The specific scattering geometry (180
degrees) ensures detection of only those particles which have undergone head-on
collisions with surface atoms (thereby avoiding the complications of multiple
scattering events). Starting sampling at a relatively high angle of incidence and
scanning over varying incidence angles, the intensity of one particular energy peak
is monitored. Scattered ions form shadow cones (see above) behind each atom,
which prevents any backscattering at low incidence angles. A peak in scattering
intensity is observed when the cones line up such that each passes over the
adjacent atom. Performing such an analysis on a sample with known interatomic
spacing enables determination of the shape of the shadow cone, where as shown
at right,   and  . 

A graph of intensity versus angle of incidence for scattering from a subsurface atom in the ICISS geometry.
The directionality of the surface-subsurface bond (see diagram above) may be deduced from  . The
length of this bond may be deduced from   and   when the shape of the shadow cone is known.

If the shape of the shadow cone is known, the interatomic spacing between surface
atoms as well as the spacing and directionality between surface and subsurface
atoms can then be calculated from the resulting peak-and-valley structure in a
graph of intensity versus scattering angle. In the graph at right showing scattering
intensity from a subsurface (second layer) atom,   corresponds to the middle of
 the "valley" where the atom is being blocked by a surface atom.   and   
correspond to the peaks due to intersection of the shadow cone with the subsurface
atom. Interatomic spacing can be directly calculated from these values if the shape
of the shadow cone is known.

 Neutral Impact-collision ion scattering spectroscopy (NICISS) uses detection of

backscattered projectiles to determine concentration depth profiles of the elements.
The NICISS technique uses noble gas ions (usually He +) of energy 1-5 keV. When
the projectile ions are within a few angstrom of the surface they are neutralised,
and proceed to penetrate into the surface. The projectiles may be backscattered (at
an angle of up to 180°) upon collision with a target atom. This backscattering
causes the projectiles to lose energy proportional to the mass of the target and is of
the order of a few hundred eV. The final energy of the projectiles is determined
via time-of-flight (TOF). Hence by knowing the initial and final energies of the
projectile, it is possible to determine the identity of the target atom. The projectiles
also experience an additional energy loss while penetrating through the bulk, of the
order of a few eV per angrstrom. Hence the depth that each target atom was hit can
also be determined. From the TOF spectrum it is then possible to gain the
concentration depth profiles of the elements present in the sample. NICISS is able
able to probe to a depth of approximately 20 nm with a resolution of only a few
angstrom.

 Reactive ion scattering (RIS) utilizes a stream of very low-energy (1-100

eV) Cs+ ions to probe molecules adsorbed at the surface of a sample. Upon impact
the ions may interact with and chemically bind to species present at the surface.
These interactions take place on a rapid (picosecond) timescale and can be used to
analyze for the presence of different molecules or molecular fragments by
observing spectra of Cs-X+ coming from the surface.

 Time-of-flight scattering and recoiling spectroscopy (TOF-SARS) uses the TOF

analysis setup. Elemental analysis may be performed via observation of in-plane
scattering, while structural information may be obtained by following certain spectral
peaks while shifting either sample incident or azimuthal angle.

 Scattering and recoiling imaging spectroscopy (SARIS) takes advantage of

blocking cone geometries to focus ions in a manner similar to conventional optics.
 This gives very large magnifications (~109) when projected onto a 2-d detector and
may be used to give element-specific images of the sample surface. The use of a
wide 2-d MCP detector greatly reduces sample analysis time as opposed to the
TOF geometry with an inherently narrow-angle detector (see drift tube above). J.
Wayne Rabalais at the University of Houston is one of the pioneers of this method,
and a fine image of the output of a SARIS experiment can be found here.
[edit]Comparison to other analytical techniques

 Medium energy ion scattering (MEIS) and Rutherford backscattering (RBS)

spectroscopies involve a similar setup to LEIS but use ions in the energy range of
~100 keV (MEIS) and ~1-2 MeV (RBS) to probe surfaces. Surface sensitivity is lost
as a result of the use of higher energy particles, so while MEIS and RBS can still
provide information about a sample they are incapable of providing true first-layer
sensitivity.

 Secondary ion mass spectrometry (SIMS) involves the detection of ionic species

ejected from a surface as a result of energetic particle impact. While SIMS is
capable of giving depth profiles of the elemental composition of a sample, it is an
inherently destructive method and is generally does not give structural information.

 X-ray photoelectron spectroscopy (XPS) is capable of surface elemental analysis,

but samples a much more broad region of a sample than LEIS and so is not able to
distinguish the first layer from subsurface layers. Since XPS relies on ejection
of core-level electrons from atoms it is unable to detect hydrogen or helium atoms
in a sample.

 Low-energy electron diffraction (LEED) is often used in combination with LEIS in

order to facilitate proper sample alignment. LEED can give detailed structural
information about a sample including surface superstructures and alignment
of adsorbates. LEED is not element-specific and so cannot be used to determine
surface elemental composition.

 Auger electron spectroscopy (AES) involves the detection of electrons emitted as a

result of core hole excitation and relaxation processes. Since the process involves
core levels it is insensitive to hydrogen and helium atoms. AES results may typically
 be used to infer information on the chemical environment of particular atoms in a
surface.
[edit]