X-RAY PHOTOELECTRON

SPECTROSCOPY (XPS)

Paper – 4103 A
SURFACE ANALYSIS by
XPS/ESCA, AES, SIMS
What are X-rays good for?
Photoelectric effect
The BE is determined by the attraction of the electrons to the
nucleus.
If an electron with energy x is pulled away from the nucleus, the
attraction between the electron and the nucleus decreases and the
BE decreases.
Eventually, there will be a point when the electron will be free of
the nucleus.
This is the point with 0
energy , the electron is
free from the atom.

0 B.E.

x These electrons
are attracted to the
p+ proton with certain
binding energy x
XPS is a widely used surface analysis technique because
of its relative simplicity in use and data interpretation.

( By elastic or non elastic

scattering)
Techniques where X-ray are used
X-RAY PHOTOELECTRON
SPECTROSCOPY (XPS)
X-ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for
Chemical Analysis (ESCA), is used to determine quantitative atomic composition
and chemistry. It is a surface analysis technique with a sampling volume that
extends from the surface to a depth of approximately 5-7 nm. XPS is an
elemental analysis technique that is unique in providing chemical state
information of the detected elements, such as distinguishing between sulfate
and sulfide forms of the element sulfur. The process works by irradiating a
sample with monochromatic x-rays, resulting in the emission of photoelectrons
whose energies are characteristic of the elements within the sampling volume.

Signal Detected: Photoelectrons from near surface atoms

Elements Detected: Li-U Chemical bonding information
Detection Limits: 0.01 - 1 at% sub-monolayer
Depth Resolution: 2 - 20 nm (Profiling Mode)
1 - 10 nm (Surface analysis)
Imaging/Mapping: Yes
Lateral Resolution/Probe Size: 10 µm - 2 mm
 Uses for XPS Analysis
• Surface analysis of organic • Aerospace and Automotive
and inorganic materials, • Biomedical/biotechnology
stains, or residues • Compound Semiconductor
• Determining composition • Data Storage
and chemical state
information from surfaces • Defense and Displays
• Depth profiling for thin film • Electronics
composition • Lighting
• Silicon oxynitride thickness • Pharmaceutical
and dose measurements • Photonics and Polymer
• Thin film oxide thickness • Semiconductor
measurements (SiO2, • Solar Photovoltaics
Al2O3 etc.)
• Telecommunications
 Strengths of XPS Analysis Limitations of Analysis

• Chemical state identification on • Detection limits typically ~ 0.1

surfaces at%
• Identification of all elements • Smallest analytical area ~10 µm
except for H and He • Limited specific organic
• Quantitative analysis, including information
chemical state differences • Sample compatibility with UHV
between samples environment
• Applicable for a wide variety of
materials, including insulating
samples (paper, plastics, and
glass)
• Depth profiling
• Oxide thickness measurement
 Related Spectroscopy
• Auger Electron Spectroscopy (AES or SAM) –using energetic
electron (1000 –10,000 eV) to examine core-levels.
• Secondary ion mass spectroscopy: The most sensitive of all
surface analysis techniques. Can detect hydrogen, and depth
profiling is possible. Has pronounced matrix effects that can
cause orders of magnitude variations in elemental sensitivity
and make quantitative analysis difficult

SAM – Scanning Auger Microscopy

 Electron Spectroscopy for Surface Analysis
Spectroscopy Particles involved Incident energy Information
obtained

X-ray X-ray IN 1-4 keV Chemical state,

Photoemission Electron OUT composition
(XPS)
UV Photoemission UV photon IN 5-50 eV Valence band
(UPS) Electron OUT

Auger Electron Electron IN 1-5 keV Composition, depth

(AES) Electron OUT profiling

Inverse Electron IN 8-20 eV Unoccupied states

Photoemission (IPS) Photon OUT

Electron energy Electron IN 1-5 eV Vibrations

Loss (EELS) Electron OUT
 XPS – Historical Developments
1887 Discovery of Photoelectric Effect (Hertz)
1905 Einstein explains the Photoelectric effect (received Nobel Prize on
1921)
1914 First formulation of basic XPS theory
1920 Photoelectron spectra of different elements were recorded
1954 Further development of the method (K. Siegbahn) - received
Nobel Prize on 1981
1970 Firth commercial XPS machine available
ESCA/XPS

Thermo-VG Scientific
ESCALab 250
Courtesy: WATLab, University of Waterloo, ON, CANADA
A typical XPS Spectrum from Gold
Nomenclature from Energy Levels
Nomenclature from Energy Levels
X-ray photoemission process
• XPS spectral lines are identified
by the shell from which the
electron was ejected (1s, 2s, 2p,
etc.).

• The ejected photoelectron has

kinetic energy:
KE=hn-BE-Φ

• Following this process, the atom

will release energy by the
emission of an Auger Electron.
Binding Energy Reference
Auger Emission Process
• L electron falls to fill core level
vacancy (step 1).

• KLL Auger electron emitted to

conserve energy released in
step 1.

• The kinetic energy of the

emitted Auger electron is:
KE=E(K)-E(L2)-E(L3).
XPS Peaks
 Instrument
• The principal components of a photoelectron spectrometer are:

– -Ultra-high Vacuum System (< 10-9 torr)

– - A X-ray source and Monochromator
– - An analyzer allowing to measure the electrons kinetic energy
– - A system of electron detection (channeltrons and CCD)
 COMPONENTS OF XPS:

üA source of X-rays
üAn ultra high vacuum (UHV)
üAn electron energy analyzer
ü A magnetic field shielding
üAn electron detector system
üA set of stage manipulators
 XPS Instrument

X-Ray Source

Ion Source

SIMS Analyzer

Sample introduction
Chamber
Surface science and UHV
Surface sensitive techniques must be performed under UHV conditions, as the
slightest contamination will alter the results. Ambient pressures of <10-9 Torr
are considered in the UHV range.

Pumping: Each type of pump operates over a limited range, so a combination is

needed to reach UHV

Rotary Pump (760-10-3 Torr):

Turbomolecular Pump (10-2 - 10-11 Torr): Inclination of the high speed stator
blades give incident gas molecules a high velocity away from the UHV region.

Ion Pump (10-4 -10-12 Torr): High voltage causes anode to emit electrons, which
ionize gas molecules as they travel toward the cathode. Ions remain trapped on
cathode.
 X-ray Sources
• Typical materials are Mg and Al.

• A heated filament (cathode) emits electrons which are accelerated toward

a solid anode (water cooled) over a potential of the order of 5 -20 kV.

• Holes are formed in the inner levels of the anode atoms by the electron
bombardment and are then radioactively filled by transitions from higher-
lying levels:
2p3/2 1s
2p½ 1s

Resulting in the emission of X-rays Mg Kα1, 2 at 1253.6 eV

Al Kα1, 2 at 1486.6 eV
Dual X-ray Source
Schematic of X-ray Monochromator

Energy
Analyzer Quartz
Crystal Disperser

e-

Sample

Rowland Circle
X-ray Anode
 Analyzer
An electron energy analyzer is more
correctly a velocity analyzer. Most
instruments use the cylindrical
mirror analyzer or the concentric
hemispherical analyzer. Cylindrical
mirror and concentric hemispherical
analyzers are electrostatic dispersive
units.

A negative potential (relative to the inner surface) is applied to the outer cylinder or
sphere. For a given potential difference between the two cylinders or hemispheres, only
electrons within a very narrow velocity range will follow a trajectory to the detector. The
energy range of the photoemitted electrons can be swept by varying the potential across
the analyzer. Usually incoming electrons are retarded using a lens or grids so that the
kinetic energy of the electrons in the analyzer remains fixed at a preselected value, the
pass energy, as the retarding field is scanned.
Analyzer
• A potential difference between the cylinders or hemispheres
allow only electrons with specific kinetic energies to make it
to the electron detector.
• Varying potentials measure different kinetic energies
• Computer calculates binding energy

(-)
(-)
Hemispherical Plates
(-)

(+) (-)
(-) (+)
X-rays
(+)

Electron
Detector
Sample
Electrons Analyzer
 Pass Energy
The mostly used analyzer on ESCA
spectrometers is the hemispherical
one with constant analysis energy
(CAE). The analyzer plays the role
of a filter, a potential's delay is
applied at the entrance of the
analyzer ensuring a constant
analysis energy (called pass
energy). It permits to scan all the
photoelectron spectrum with a
constant resolution. With this
analyzer type, a high transmission
is achieved along the whole energy
range.
 Detector
Two types:
(a) Channel electron multipliers
(Channeltrons)
(b) Channel plates

The detector is an electron multiplier

or a channel plate multiplier. In most
cases, the data acquisition system
includes a multi-channel analyzer or a
computer that permits repetitive
scans to be made. Multiple scans over
the same energy region improve the
signal-to-noise ratio, enhancing weak
signals.
Channel electron multipliers
(Channeltrons)
Micro Channel Plates
Charge Compensation

Usually ESCA spectrometers are

equipped with an electron gun (called
Flood Gun) in order to avoid charging
effects on insulating surfaces: The
positive charge created by the
photoemission is neutralised during
analysis by a low energy electron gun.
A typical XPS Spectrum from clean Iron

Note that the B. E. scale is drawn from right to left, so that the photoelectron kinetic
energies measured by the spectrometer increase from left to right.
Background
Background signal is comprised of electrons that undergo inelastic collisions before
exiting the sample. Thus the background increases the as we probe deeper into the
sample.

Peak Types
• Photoelectron Lines: The “main peaks”: sharp lines due to core-level
photoelectrons that reach the analyzer without undergoing inelastic loss.

• Auger Lines: Secondary electrons emitted after photoemission occurs as excited

ions relax
 X-Rays and the Electrons
X-Ray
Electron without collision
Electron with collision

The noise signal comes from

the electrons that collide with
other electrons of different
layers. The collisions cause a
decrease in energy of the
electron and it no longer will
contribute to the characteristic
energy of the element.
X-rays source
 A Typical XPS spectrum
• Sharp peaks due to photoelectrons created within the first few atomic
layers (elastically scattered).
• Multiplet splitting (occurs when unfilled shells contain unpaired
electrons).
• A broad structure due to electrons from deeper in the solid which are
inelastically scattered (reduced KE) forms the background.
• Satellites (shake-off and shake-up) are due to a sudden change in
Coulombic potential as the photo ejected electron passes through the
valence band.
• Plasmons which are created by collective excitations of the valence
electrons
• Auger peaks produced by X-rays (transitions from L to K shell: O KLL or
C KLL).
A typical XPS Spectrum from Gold
Electron loss and compensation

For metal or other conducting

samples that grounded to the
spectrometer

-
X-ray
-
e e-
e e-
-
sample e

Electrons move to the surface

continuously to compensate
the electron loss at the surface
region.
Shift in B.E.
of a polymer
surface

+ + + + + + + +
 Electron source with Low energy
magnetic field electrons and Ar+

analyser +
electrons Low energy Ar beam

-ve X-ray
filament e Low energy
electron beam

Sample
Sample
A single setting for all types of
Magnet samples
 xps is used for :
• What elements and the quantity elements of the sample
surface(1-12nm)
• What contamination in the surface or the bulk of the sample
• Empirical formula of a material
• The chemical state identification of the elements in the sample
• The binding energy of electronic states
• The thickness of different materials
• The density of electronic state
Ø Photoelectron lines: core-level,
valence bands, spin-orbit splitting
Ø Auger lines
Ø Chemical shifts
Ø Shake-up satellite
Ø Multiplet satellite
Ø Energy loss lines
 What can we learn from core level
spectrum?
•Compared to valence electrons, the core levels are
little affected by the bonding

•Core level BE is characteristic of the element, but it is

chemically shifted (0 to 10 eV) by interaction with valence
electrons and surrounding (mostly nearest neighbor)
atoms.

Core level XPS gives qualitative and

quantitative chemical structure around
particular element (excluding H and He).
 Chemical Shifts
The measure shifts in the binding energy of core electrons resulting from a change in
the chemical environment. Such changes in binding energy, termed chemical shifts,
can result from a change in the nearest neighbor, the oxidation state, compound, or
the crystal structure.

For example - Assume that the core electrons

are inside a hollow spherical charged shell.
Each core electron then sees a potential. A
change in Q by ΔQ gives a change in V. where
ΔV is the chemical shift
 Chemical Shift – Electronegativity Effects
Carbon-Oxygen Bond
Oxygen Atom

Electron-oxygen
atom attraction
Valence Level
C 2p (Oxygen Electro-
C 1s
negativity)
Binding
Core Level Energy
C 1s Shift to higher
binding energy
Electron-nucleus
attraction (Loss of
Electronic Screening)

Carbon Nucleus
Chemical Shift

Functional Binding Energy

Group (eV)
hydrocarbon C-H, C-C 285.0
amine C-N 286.0
alcohol, ether C-O-H, C-O-C 286.5
Cl bound to C C-Cl 286.5
F bound to C C-F 287.8
carbonyl C=O 288.0
Oxidized metal surfaces

Oxidized and clean Cr 2p spectra (left). Oxidized and clean Cu 2p spectra (right). The
oxide layer resulted in extra peaks (shoulder at higher BE—left of the main line).
Satellites are also seen on the Cu 2p spectra.
 Chemical Shifts
Each of the four different
chemical environments of carbon
is distinguishable.

Chemical state of an element by its chemical shift

is sometimes not possible especially for transition
metals that have broad lines. Deconvolution used
by many of the commercial instruments have
software packages needs extreme care to fit a
spectrum. Thus, it is useful to obtain "fingerprint"
spectra for compound identification. Multiplet
splitting and shake-up
phenomena sometimes introduce features into a
spectrum that aid interpretation.

XPS spectrum of the carbon 1s lines in ethyl

trifluoracetate
Chemical Shifts
 Multiplet Splitting
Multiplet splitting can occur when there are one or more electrons in the valence
shell with unpaired spins and photoionization occurs in another shell. This situation
typically arises for the transition and rare-earth metals that have unfilled d and f
levels, respectively. When a hole is created in a filled level by photoionization, two
orbitals will exist with uncoupled spins. These two orbitals will couple, leading to a
splitting in the energy levels.

Multiplet splitting is usually most pronounced when the unpaired electrons are in
orbitals with the same principal quantum number.
Electronic Effects – Spin-Orbit Splitting

Cu 2p 2p3/2

2p1/2
Orbital=p
l=1
s=+/-1/2
ls=1/2,3/2
19.8
Peak Area 1 : 2

965 955 945 935 925

Binding Energy (eV)
Electronic Effects – Spin-Orbit Splitting

Ag 3d 3d5/2
3d3/2
Orbital=d
l=2
s=+/-1/2
6.0 ls=3/2,5/2
Peak Area 2 : 3
378 374 370 366 362
Binding Energy (eV)
Electronic Effects – Spin-Orbit Splitting

Au 4f 4f7/2
4f5/2
Orbital=f
l=3
s=+/-1/2
ls=5/2,7/2
3.65
Peak Area 3 : 4
91 87 83 79
Binding Energy (eV)
Plasmon Peak

This feature is specific to clean surfaces. The

photoelectron excites collective oscillations
in the conduction band (free-electron gas),
so called Plasmons. (discrete energy loss).

For Al, Mg, Na etc…the energies are 15.3 eV,

10.6 eV and 5.7 eV, respectively.
Electron Scattering Effects
Plasmon Loss Peak
Al 2s
a a a a

Metal A=15.3 eV
Electron Scattering Effects
Plasmon Loss Peak

O 1s
21 eV
Insulating
Material x4
 Satellite Peaks
Arise when a core electron is removed by a photoionization. There is a sudden
change in the effective charge due to the loss of shielding electrons. (This
perturbation induces a transition in which an electron from a bonding orbital can be
transferred to an anti-bonding orbital simultaneously with core ionization. Two types
of satellite are detected.

Shake-up: The outgoing electron interacts with a valence electron and excites it
(shakes it up) to a higher energy level. As a consequence the energy core electron is
reduced and a satellite structure appears a few eV below (KE scale) the core level
position.

Shake-off: The valence electron is ejected from the ion completely (to the
continuum). Appears as a broadening of the core level peak or contribute to the
inelastic background.
Satellites
Vacancy created by photoionization (unpaired electron left behind (after
ionization) couples with a unpaired electron in the originally incompletely
filled shell and generates splitting of the orbital ( p, d or f orbitals).

Example: Fe2O3 has 5 unpaired electrons in the 3d shell as shown below.

Following photoionization in the 3s shell, there are 2 possible final states.

Schematic of Multiplet Splitting following photoionization in Fe3+ and

XPS spectrum
Ø Data collection is slow compared with other surface analysis
techniques, but analysis time can be decreased substantially when high
resolution or chemical state identification is not needed
Ø Some samples get damaged by X-rays.
Ø Charging effects may be a problem with insulating samples. Some
instruments are equipped with charge-compensation devices
Ø The accuracy of quantitative analysis is limited
 Conclusion

Ø XPS devices is also named ESCA(Electron Spectroscopy Chemical Analysis)

It’s work is based on the photoelectric effect .
Ø XPS is primarly used for chemical analysis as determining thicknesses and
emprical formulas of different elements and,binding energies,densities of
electronic states.
Ø XPS is used from starting Li(A>2) because of smaller orbital’s radius and
analysis of organic compounds cannot be done with XPS because of
degredation with radiation.
Ø XPS is also used for determination of
metals,ceramics,semiconductors,papers,etc.