XPS TECHNIQUE

CATALYTIC PROCESSES

Quevedo Carlos1, Romero María Jose1, Colina Jose2.

1
VII Semester Chemical Engineering Students 2Professor at the University of Cartagena

ABSTRACT
X-ray photoelectron spectroscopy (XPS) is, in principle, based on a particularly simple process.
Electrons within a sample absorb photons of a particular energy and then emerge from the solid.
The kinetic energy analysis of electrons emitted from the surface yields information on the
electronic states of atoms in the surface region(Engelhard et al., 2017).
XPS technique allows quantitative and qualitative analysis of all elements, except hydrogen. Also,
this method reaches a depth of 3nm for phenomena that take place in very thin layers such as
passivation, the segregation of elements for short periods of time (industrial level), new protective
pretreatments, thin layers of corrosion (interior atmospheres) etc.
Keywords: Layer, electrons, análisis, depth and energy.

INTRODUCTION quantitative analysis is performed using

spectra, even if these spectra derive from
Laboratories are always looking for methods
stacks of images. On the other hand, stigmatic
that helps them how obtain better results and
imaging involves irradiating a larger area but
conclusions in their investigations, because
parallel sets of spectra are possible and
they need the characteristic that the
charge compensation operates in a global
microscope and the human eye do not see.
context(Casa XPS, 2005).
Modern XPS instruments combine
1. THEORETICAL BACKGROUND
technology from a range of fields including
electron optics, X-ray optics, digital/analog 1.1 What is XPS technique?
electronics, mechanical engineering and
X-ray Photoelectron Spectroscopy
software engineering. The complex mixture
(XPS) or Electron Spectroscopy for
of these disciplines is challenging to manage
Chemical Analysis (ESCA) is a
at the best of times but the ever-increasing
technique which analyzes the
demands of a maturing technique coupled
elements constituting the sample
with the need to satisfy both research and
surface, its composition, and
application-orientated customers (from a
chemical bonding state by irradiating
comparatively small market) means that state-
x-rays on the sample surface, and
of-the-art instruments must come at a
measuring the kinetic energy of the
relatively high price. It also requires users to
photoelectrons emitted from the
be relatively sophisticated in order to exploit
sample surface. XPS instrument
the technique to its full potential since they
using Al Kα rays can generally obtain
too must appreciate many of the details
information on elements within a few
wrapped up in the systems. XPS images
nms of the sample surface.
provide the means for assessing a sample, but
The x-ray beam diameter can be set finely focused electron beam to
between several µmφ to several create SEM images for sample
hundred µmφ, and the scan range can viewing and point spectra or images
be changed arbitrarily, enabling for compositional analysis. With the
measurement of the most appropriate PHI XPS instruments, a finely
analysis area for the sample. focused x-ray beam is scanned to
create secondary electron images for
When the surface contamination sample viewing and point spectra or
layer is thick, or when evaluating a images for compositional analysis.
deeper area, ion sputtering is used to
perform surface etching. An element The size of the x-ray beam can be
composition or chemical bonding increased to support the efficient
state depth profile can be obtained analysis of larger samples with
from the spectrum information homogeneous composition. In
gained through alternating between contrast to SEM/EDS which has a
sputtering and measurement. Depth typical analysis depth of 1-3 µm,
profiles are used for film thickness XPS is a surface analysis technique
evaluation of samples with a with a typical analysis depth of less
multilayer structure and cause than 5 nm and is therefore better
analysis for discoloration/corrosion suited for the compositional analysis
of metal. of ultra-thin layers and thin
Generally, argon (Ar) ions are used microscale sample features(Physical
for depth profile analysis for Electronics, 2022).
inorganic materials such as metals
and semiconductors while fullerene 1.2 Limitations.
(C60) and argon gas cluster ions (Ar- X-ray photoelectron spectroscopy is a
GCIB) are used for organic materials, surface sensitive analytical technique,
so different sputter ion guns are used in which x-rays bombard the surface
depending on the material and of a material and the kinetic energy
purpose(ULVAC-PHI, 2022). of the emitted electrons is measured.

XPS is typically accomplished by The two major characteristics of this

exciting a samples surface with technique that make it powerful as
mono-energetic Al kα x-rays causing an analytical method are its surface
photoelectrons to be emitted from the sensitivity and its ability to reveal
sample surface. An electron energy chemical state information from the
analyzer is used to measure the elements in the sample.
energy of the emitted photoelectrons. All elements except hydrogen and
From the binding energy and helium can be detected, and XPS has
intensity of a photoelectron peak, the been used to study the surface of
elemental identity, chemical state, almost every material from plastics to
and quantity of a detected element textiles to soil to semiconductors.
can be determined.
All materials have surfaces, and it is
Physical Electronics XPS instruments those surfaces that interact with other
function in a manner analogous to materials. Factors such as surface
SEM/EDS instruments that use a wettability, adhesion, corrosion,
 charge transfer, and catalysis are all on the nm scale on material
determined by surfaces and surface surfaces.
contamination, and, therefore,
studying and understanding surfaces  Little or no sample preparation is
is important(Stevie et al., 2020). required.

1.3 Advantages.  X-ray beams produce relatively

 An important advantage of XPS little charging effects compared
over other techniques is the ability with electron beam methods.
to determine the chemical
environment of the atoms present  Some modern XPS instruments
in a sample. This chemical have imaging capabilities.
environment, including factors like
nearest neighbors and the oxidation  Mature XPS databases exist to
state of the element, affects the rapidly identify elements and their
binding energy of the chemical state(Mogk, 2022).
photoelectron peaks (and the
Auger peaks)(Stevie et al., 2020). 1.4 Disadvantages.

 Non-destructive analysis of  XPS uses an ultrahigh vacuum

materials. chamber (< 10-9 Torr) and some
samples are either not stable or
 Ability to detect all elements volatilize under UHV conditions.
except for H and He.
 Small shifts in binding energies  X-ray beams cannot be focused in
can be measured (~0.1 eV) that the same manner as electron
provides information about the beams; so the analyzed surface
bound state of elements present. areas are significantly larger.
these data are obtained by
collecting spectra over limited
energy range to reveal for a given  Although charge compensation is
element. often effective, some samples may
produce severe charging problems
 Surface-sensitive analysis to that compromise the quality of the
determine composition of material analysis.
surfaces a few atomic layers thick  As a surface sensitive method,
(~ 10 nm). XPS is not an appropriate method
for identifying bulk material
 Surface contaminants are usually substrates(Mogk, 2022).
easily removed using ion (Ar)
beam sputtering methods. 1.5 Instrumentation
 Semi-quantitative analyses can be
obtained within ± 10% atomic  Ultrahigh vacuum system:
concentration. Typically, operating conditions
are at <10-9 Torr. This is
 Depth profiles may be obtained to required because the emitted
demonstrate chemical stratigraphy photoelectrons have a relatively
 low energy and are readily used to minimize surface
absorbed by ambient atmosphere. charging under the X-ray beam.
In other words, photoelectrons  Computer and data reduction
have a relatively small mean free software. XPS data are compared
path between sample and detector to inventories or archives of
as they are readily sorbed by gas experimentally determined XPS
molecules in the chamber. data of standard reference
 X-ray source: Al Kα of Mgα X- materials such as the Handbook
rays are typically used to excite of X-ray Photoelectron
the sample; a monochrometer is Spectroscopy, edited by J
used to permit only X-rays of this Chastain, with authors J.F.
fixed energy to impinge on the moulder, W. F. STickle, P. E.
sample. Sobol and K. D. Bomben (PHI
 An electron energy analyzer is Perkin-Elmer Corporation, 1992)
used to discriminate among the or the NIST X-ray Photoelectron
energies of the photoelectrons Spectroscopy Database(Mogk,
that are produced. This is 2022).
typically a Concentric
Hemispherical Analyzer (CHA).

Figure 2. Kratos AXIS Supra at the

University of Western Ontario.installed
2018 (Xpsfitting, 2021)

2 Examples (cases taken from the

literature)
Figure 1. Schematic of XPS
measurement technique(Uddin, 2.2 Further characterization of the
2018).
surface properties of the SiC
.
particles through complementarity
 Ar ion gun is used a) to sputter of XPS and IGC-ID techniques.
material surfaces to "dust off"
environmental contaminants They demonstrated the capability of
(e.g., sorbed adventitious carbon the XPS and IGC-ID techniques to
from the atmosphere) off of evaluate both the chemical com-
material surfaces, and b) to obtain position and the surface energy of the
depth profiles across surface materials and the necessity to use
layers on the material surface. both techniques to complement the
 Charge neutralization capability information extracted from the
analysis.
using an electron "flood gun" is
The surface stoichiometry and 2.3 Hydrogen detection in high
composition of the SiC samples were strength dual phase steel using
analyzed. The surface of the samples scanning Kelvin probe technique
is slightly oxidized because of the and XPS analyses.
milling process or the synthetic The chemical composition of the
procedure, as deduced from the oxide layer on the steel surface was
appearance of the O1s signal in the characterized by XPS. The apparatus
spectra. The results in Table 4 show consists of an Al-Kα X-ray source
an increase of the dispersive (Thermo VG) and a cylindrical
surface energy values as decreasing mirror analyzer from RIBER. The
the particle size. Since the C(1 s) line at a binding energy of
dispersive energy represents the 284.8 eV was used to normalize the
ability of the electron cloud to absolute binding energies.
create a dipole on it, this capability A rather simple deconvolution was
increases when decreases applied in this study to estimate the
the particle size since the atomic relative amount of Fe(II) and Fe(III)
bonds are more distorted in in the oxide layer. Such approach was
low-sized particles (Tamayo et al., considered sufficient as the effect
2018). was really pronounced after hydrogen
permeation. Moreover, the same
fitting parameters were applied in all
cases to keep the comparison
relevant. Several replicates were used
for XPS analyses as detailed hereafter
(Vucko et al., 2022).

Figure 3. XPS spectra of the studied

samples in the range corresponding to
the Si2p signal.

Fig. 5. XPS analyses of the oxide film 24

h after polishing of the surface (black
dash line) and after heat treatment of 1 h
at 100 °C.

3. CONCLUSIONS

XPS technique is an indispensable

Figure 4. XPS spectra of the studied
technique used in many institutions
samples in the range corresponding to
and companies.
the C1s signal.
. The scientists have been trying to
show the utility through XPS
analysis of the surface from
materials of technological interest,
 taking steel or aluminum as analysis/xps/
examples.
Vucko, F., Ootsuka, S., Rioual, S., Diler, E.,
Nazarov, A., & Thierry, D. (2022).
Hydrogen detection in high strength
dual phase steel using scanning Kelvin
probe technique and XPS analyses.
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spectroscopy.
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XPS.pdf
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