Fundamentals of X-Ray Photoelectron Spectroscopy (XPS) : June 2020
Fundamentals of X-Ray Photoelectron Spectroscopy (XPS) : June 2020
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XPS Mechanism:When a beam of X-ray hits the surface of a sample, the electrons
in the surface can absorb the photon energy and be excited. In some cases, these
electrons can escape the host material (ionization). By measuring the kinetic energy of
the escaping electrons, one can determine the binding energy (EB) of the electrons
using the Einstein’s photoelectric equation. EB reflects the type and valence of the
elements in the tested sample.
1. What is XPS?
➢ Why only surfaces?
Although X-ray can easily penetrate samples, only photoelectrons close to the sample
surface (~10 nm thickness) can escape without significantly losing energy.
XPS signal (shallow surface): without significant energy loss; characteristic of
elements. Escaping electrons with energy partially lost — baseline.
X-Ray Detector
hv e-
Ek = hν – EB – φsp
d
Detection depth (d) depends on the escape depth of photoelectrons (λ, a function of X-
ray wavelength and sample composition).
General d values: 0.5-3 nm (metal); 2-4 nm (inorganic); 4-10 nm (organic)
2. What Can XPS Do?
n=I/S
Attention:
➢ Peaks of one element can differ in the intensity and S. Selecting peaks with high
intensity and large S improves sensitivity.
➢ Sensitivity of one element can vary due to its presence in different compounds, e.g.,
mixtures.
2. What Can XPS Do?
➢ Why semi-quantitative?
Peak area also depends on the mean free path of photoelectrons, cleanness of
sample surface, valence, X-ray intensity, and spectrometer condition. Therefore, XPS
can give relative contents but not absolute values.
XPS EDS
Photoelectron
Spectrum Satellite Peaks
In: 1s22s22p63s23p63d104s24p64d105s25p1
main peak
The main peak of In is its 3d peak. Besides, there are In 4d and In 3p peaks due to
the multiple inner electrons of In.
2. Spin-Orbital Coupling
➢ The coupling of electron movements in orbitals and self-spin leads to
peak separation.
Auger electrons
KLL, KLM, LMM
C KLL, O KLL, Na KLL are Auger electron peaks from C, O, Na, respectively. O KLL has three
peaks: vacancy level (left), re-filling electron level (middle), and Auger electron level (right).
4. Satellite Peaks (Shoulder Peaks)
➢ “Impurities” of the energy in the X-ray source (non-monochromaticity):
e.g., Al/Mg Kα1,2 include Kα3,4,5 and Kβ
C 1s main peak (α1,2) and shoulder peaks (α3,4,5 and β). The intensity of the main
peak is much stronger than those of the shoulder peaks.
X-Ray Photoelectron
Spectroscopy (XPS)
Example
Example 1:
➢ [Left] What elements? Ni, Mo, O, S
➢ [Right] Is the N-doping successful? Yes.
2. Presence of Peak
Example 2:
➢ After cycling, the N element in the compounds was lost or significantly reduced
➢ Reasons for peak absence: no element or content below 0.1 atom%
2. Peak Position
Example 3:
➢ What elements should these peaks be assigned to?
Look up in references, databases, or handbooks.
3. Peak Shift
Example 4:
➢ The Zn 2p peak of 13%ZnO-ZrO2 shifts 0.5 eV compared to that of ZnO.
➢ Which direction? Toward lower binding energy – Zn gets electrons (from ZrO2).
4. Peak Intensity or Area
Example 5:
➢ peak area → relative content → surface composition
In this example, temperature ↑, Ru ↑ (determine from peak intensity)
4. Peak Intensity or Area
Example 6:
➢ peak area → relative content → surface composition
CHx/CH4 ratio changes with CeO2 coverage and reaches the highest when the
coverage is around 0.5 ML.
X-Ray Photoelectron
Spectroscopy (XPS)
Data Analysis
1. Survey Spectroscopy
2. Charge Correction
3. Baseline Subtraction
4. Peak Deconvolution and Fitting
5. Semi-Quantitative Analysis
Charging Effect: The surfaces of insulators and semiconductors can build up positive
charges due to continuous escape of electrons without replenishment. The generation
of positive charges due to loss of surface electrons is termed charging effect.
Charging effect creates a steady, positive potential. This potential restrains electrons
from escaping. Therefore, charging effect deviates the binding energy and reduces
accuracy. Charge correction is performed to eliminate the charge-effect-induced
deviation.
1. Four Methods for Charge Correction
➢ When fitting doublets induced by spin-orbital coupling, one needs to check that the
peak separation, intensity ratio, and FWHW are reasonable. For example, intensity
ratio:
2p1/2:2p3/2 = 1:2 (except TiO2 and V2O5. Their 4p electrons do not follow)
Coster-Kronig transition
3d3/2:2d5/2 = 2:3
4f5/2:4f7/2 = 3:4
➢ Pay extra attention to overlapped peaks
Al 2p & Pt 4f
Ni 3p & Cu 3p Pd 3d & Au 4d
Ref.: Appl. Catal. B 2016, 185, 77-87; RSC Adv., 2017, 7,
41847-41854;Chin. J. Catal. 2020, 41 (8), 1240-1247
Summary of Overlapped Peaks
Mg Kα Al Kα
N KVV & Ce 3d F KLL & La 3d
O KVV & Co 2p, Ba 3d Na KLL & Sn 3d
F KLL & Mn 2p Mg KLL & Ca 2p, Rh 3d
Na KLL & C 1s, K 2p, Ca 2p Fe LMM & Co 2p
Ti LMM & La 3d, Ni 2p Co LMM & Co 2p, Fe 2p
V LMM & Co 2p, Ba 3d Ni LMM & Mn 2p
Mn LMM & Mn 2p, Fe 2p Zn LMM & Sn 3d
Co LMM & Sn 3d Ce M45N45N45 & La 3d5/2
Ni LMM & Sn 3d O KVV & Nd 3d
Cu LMM & Pd 3d, Cd 3d
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