X-ray Photoelectron Spectroscopy

Dr. B. SREEDHAR
Senior Principal Scientist
Professor, AcSIR
Inorganic and Physical Chemistry Division
Indian Institute of Chemical Technology
(Council of Scientific & Industrial Research)
Hyderabad – 500 607
sreedharb@iict.res.in
April 18, 2019 01
Spectroscopy
Inputs Outputs

e-
γ A+ e- γ A+

Sample
 Electrons Out

Auger electrons Probe: Electrons

Secondary electron
imaging

Backscattered electron
imaging
Photons out
Transmitted electrons
Energy Dispersive
Electrons In Electron diffraction Spectroscopy
e- e-
γ Wavelength
Dispersive
Spectroscopy

Sample
April 18, 2019 3
 Probe: Photons

Photons Out
Fourier Transform Infrared
Spectroscopy
Photons In Raman Electrons Out
Infrared Visible XPS, X-ray
Visible Ultraviolet Photoelectron
Ultraviolet X-Ray Fluorescence Spectroscopy
X-Rays X-Ray Diffraction
γ γ e-

Sample
April 18, 2019 4
Probe: Ions
Ions Out
SIMS, Secondary
Ion Mass
Spectrometry

Ions In ToF SIMS, Time of

A+ Flight SIMS,
A+ ICP MS, Inductively
Coupled Plasma
Mass Spectrometry

Sample

April 18, 2019 5

X-Ray Tools
n X-Ray Spectroscopy
¨ EnergyDispersive X-ray Spectroscopy (EDS)
¨ Wavelength Dispersive X-ray Spectroscopy
(WDS)
n X-ray fluorescence (XRF)
n X-ray photoelectron spectroscopy (XPS)
n X-Ray Diffraction

April 18, 2019 6

 X-ray Photoelectron Spectroscopy (XPS), also known as
Electron Spectroscopy for Chemical Analysis (ESCA) is a widely used
technique to investigate the chemical composition of surfaces.

• Introduction (XPS basic principles)

• Quantification.
• Energy resolution and count rates.
• Wide scan data (low energy resolution)
• Narrow scan data (high energy resolution)
• Chemical state analysis.
• Sensitivity.
• Sputter depth profiles.
• Line scans.
• Maps.
 Information Derived from XPS

Photoelectrons out
X-rays in

d = 3l

• X-ray photoelectron spectroscopy works by irradiating a

sample material with monoenergetic soft x-rays causing
electrons to be ejected.
• Identification of the elements in the sample can be made
directly from the kinetic energies of these ejected
photoelectrons.
• The relative concentrations of elements can be
determined from the photoelectron intensities.
Photo emission process is often
envisaged as three steps

ü Absorption and ionisation - (initial

state effect)

ü Response from atom and creation of

photoelectron -(final state effect)

ü Transport of electron to surface and

escape -(extrinsic loss)
 X-ray Photoelectron Spectroscopy
Small Area Detection
Electrons are extracted only
from a narrow solid angle.
X-ray Beam

X-ray penetration
depth ~1µm.
10 nm
Electrons can be
excited in this
entire volume. 1 mm 2

X-ray excitation area ~1x1 cm2. Electrons are

April 18, 2019
emitted from this entire area 13
 Chemical State Information
• The binding energy of an electron is dependent on the atomic orbital the
electron occupies and the chemical environment of the atom.

Valence electron,
low binding energy

Core level electron,

high binding energy

• The variation of binding energy of a specific photoemission peak provides

information on the chemical state of the atom or ion.
Electron Emission Process

XPS may involve the concurrent emission of both

Photoelectrons and Auger electrons

Photoelectron

L23

L1

K
Auger Electron

L23

L1

K
 Principle of XPS

XPS involves irradiation of a sample under vacuum by x-rays

of known energy which causes photo-ejection of electrons
from atoms near the surface

The emitted electrons have a kinetic energy Ek, which is

given by
Ek = hn - Eb - F

where hn = photon energy

(Planck’s constant = 6.62 x 10-34 Jsec)
Eb = Binding energy relative to Fermi level
F = spectrometer work function
Spectrum of Eb Þ Spectrum of Ek
•XPS probes the first » 5-10 nm of a surface and provides the
following information:

Identification of all elements (except H and He)

present at concentrations >0.1 atomic %
Semi-quantitative information (±5%)
Molecular environment (oxidation states,
bonding atoms)
Surface sensitivity from 5 to 75 angstroms
Conducting and insulating materials
Lateral variations in surface composition
Non-destructive elemental depth profiles and
surface heterogeneity (10 nm)
Destructive elemental Depth profiles (1 µm)
Spactial resolution for surface mapping from > 10 mm
 Surface analysis by XPS requires irradiating a solid in
an Ultra-high Vacuum (UHV) chamber with monoenergetic soft
X-rays and analyzing the energies of the emitted electrons.

Pressure
Degree of Vacuum Torr
102 ■ Remove adsorbed gases from
Low Vacuum the sample.
10-1 ■ Eliminate adsorption of
Medium Vacuum contaminants on the sample.
10-4
■ Prevent arcing and high
High Vacuum
10-8 voltage breakdown.
Ultra-High Vacuum ■ Increase the mean free path for
10-11 electrons, ions and photons.

April 18, 2019 19

 Computer
System
Hemispherical Energy Analyzer

Outer Sphere Magnetic Shield

Inner Sphere Analyzer Control

Electron Lenses for Energy

Multi-Channel Plate
Optics Electron Multiplier
Adjustment
(Retardation) Resistive Anode
X-ray Encoder
Source Position Computer
Lenses for Analysis
Position Address
Area Definition
Converter
Position Sensitive
Detector (PSD)
Sample
5 4 .7
Mg Kα = 1253.6 eV and Al Kα = 1486.6 eV
Factors to be considered in selecting an
elemental source:

ü Energy resolution of the X-rays

ü Energy of the photons that are produced
ü Ease of application of the material to an
anode surface
 Six features seen in a typical XPS spectrum

1. Sharp peaks due to photoelectrons created within the first few atomic layers
(elastically scattered).

2. Multiplet splitting (occurs when unfilled shells contain unpaired electrons).

3. A broad structure due to electrons from deeper in the solid which are ineslastically
scattered (reduced KE) forms the background.

4. Satellites (shake-off and shake-up) are due to a sudden change in Coulombic potential
as the photoejected electron passes through the valence band.

5. Plasmons which are created by collective excitations of the valence band

• Extrinsic Plasmon: excited as the energetic PE propagates through the solid after
the photoelectric process.
• Intrinsic Plasmon: screening response of the solid to the sudden creation of the
core hole in one of its atom
The two kinds of Plasmon are indistinguishable.

6. Auger peaks produced by X-rays (transitions from L to K shell: O KLL or C KLL).

 The Photoelectron Spectrum

O 1s

• Both photoemission and Auger peaks observed

in a spectrum.
O KLL Auger
• Peaks are superimposed on a rising
Intensity (CPS)

background, due to inelastically scattered

photoelectrons.

Si 2s Si 2p
Inelastically scattered photoelectrons C 1s

O 2s

Binding energy (eV)

XPS Spectra showing the Chemical State of Si
Thin SiO2 layer on Thick SiO2 layer on Si
Si

300 W Mg Ka
excited
spectra
29
Binding energies of some elements
33
 Quantitative Surface Analysis of
Poly(ethylene tetraphthalate) - PET
O 1s region
C 1s region
O2
1
C1 2 3 3 2 2 2
O1
-(-O-C- -C-O-CH2-CH2-)-
n

=
O O
1 1

experimental theory
C(1) 65 at% 60 at%
C(2) 23 at% 20 at%
C2 C(3) 12 at% 20 at%
C3
O(1) 51 at% 50 at%
O(2) 49 at% 50 at%

180 W Mg Ka
excited spectra
 Binding energy of a core-electron depends on the electron density
around the corresponding atoms

 Energy shift due to the

chemical environment
Oxidation degrees of metals
Coordination
Typical binding energies for C 1s photoemission peaks
from organic materials

functional group Binding energy (eV)

hydrocarbon C-H, C-C 285.0

amine C-N 286.0
alcohol, ether C-O-H, C-O-C 286.5
fluorocarbon C-F 287.8
carbonyl C=O 288.0
2F bound to a carbon -CH2CF2- 290.6
3F bound to a carbon -CF3 293-294

Typical chemical shifts for O 1s photoemission peaks

from organic materials

functional group Binding energy (eV)

carbonyl -C=O, O-C=O 532.2

alcohol, ether -O-H, O-C-O 532.8
ester C-O-C=O 533.7
For p, d and f peaks, two peaks are observed

The separation between the two peaks are named

spin orbital splitting. The values of spin orbital
splitting of a core level of an element in different
compounds are nearly the same.

The peak area ratios of a core level of an

element in different compounds are also nearly
the same.

Spin orbital splitting and peak area

ratios assist in element identifications.
40
Orbital = s Orbital = d
l=0 l=2
s = +/-1/2 s = +/-1/2
j = |l + s| j = |l + s|
= 1/2 = 3/2, 5/2

Orbital = p Orbital = f
l=1 l=3
s = +/-1/2 s = +/-1/2
j = |l + s| j = |l + s|
= 1/2, 3/2 = 5/2, 7/2
 O 1s

C 1s Pd 3d

O KLL

I 3d
I 3s

I 3p

Pd 3d

Mg 2s
Mg 2p
C 1s

Cl 2p

Al 2s
Al 2p
Cl 2s

O 2s
XPS Spectra of LDH-Pd Catalyst used for Heck Reaction with iodobenzene

J. Am. Chem. Soc. 2002, 124, 14127

J. Am. Chem. Soc. 2004, 126, 3396
 XPS spectra of PPVA films:
(a) x = 0.09 before heating, (b) x = 0.09, T =130oC, t = 30 min,
(c) x = 0.09, T =130oC, t = 120 min, (d) x = 0.015, T =130oC, t = 60 min.

Advanced Functional Materials

17 (2007) 2550
Au(0) Au(I) complexes
Ferrous saponite – Adsorption and reduction of hexavalent chromium

American Mineralogist
88 (2003) 1983

Patent Number: US2006016757-A1; US7273557-B2

 (b) (b)
Fe
Fe2+
2p
Fe3+
Intensity (cps)

(a)

(a)

[Fe3+]tet-[Fe2+Fe3+]octO4
O 1s

736 728 720 712

C 1s Fe
3p

1000 800 600 400 200 0

Binding Energy (eV)
Satellites (shake-off and shake-up) are due to a sudden change in
Coulombic potential as the photoejected electron passes
through the valence band.

Shake-OFF Shake-UP

Binding Energy (eV)

 Photoelectron

Photoelectron
Shake-OFF Shake-UP

L23 L23

L1 L1

K K
Satellites (shake-off and shake-up) are due to a sudden change in Coulombic
potential as the photoejected electron passes through the valence band.
 Non-destructive & destructive depth profile
Non-destructive
• By rotating the sample about it’s axis, the sampling depth can be
changed.

• collecting data at different angles, will provide a non-destructive depth

profile.

• this is limited to film thicknesses less than the sampling depth (~100 Å).

Destructive

• Destructive depth profile can be achieved by Ar+ bombardment of the

sample to remove surface atoms, followed by data acquisition.

• When the etch / spectrum cycle is repeated a destructive depth profile

of several 1000’s Å through the sample may be acquired.
 X-rays photoelectrons Angular Dependence of XPS

photoelectrons
X-rays
d > d*

d*

Plasma treated Polystyrene

d=3lsinq
(d)
Sample depth of XPS – d = 3l?
 Depth Profile through a TiN/SiO2 thin film on Si

• Thin layer coatings increasingly used in industry to improve surface

properties.
• Depth profiling combined with XPS allows valuable film thickness and
chemical state information to be determined.

TiN

SiO2

Si substrate
 Depth Profile through a TiN/SiO2 thin film on Si

Full Chemical state concentration Si 2p region shows chemical

depth profile through TiN film allowing environment of the Si atom
determination of film thickness
 I
N=
sDJLlAT
Specifications and metal composition of the series of unsupported
reduced Ni-Fe catalysts reported from the EDX and XPS

Catalysts Bulk Composition of Surface Composition of

Nomenclature Catalysts by EDX Catalysts by XPS
Ni wt.% Fe wt.% Ni wt.% Fe wt.%

100Ni0Fe 100.00 0.00 100.00 0.00

90Ni10Fe 89.68 10.32 88.37 11.63

75Ni25Fe 80.12 19.88 74.35 25.65

50Ni50Fe 43.77 56.23 54.71 45.29

25Ni75Fe 30.58 69.42 26.55 73.45

0Ni100Fe 0.00 100.00 0.00 100.00

Unpublished data