X-Ray Photoelectron
Spectroscopy
Deependra Kumar Singh
Assistant Professor
Metallurgical and Materials Engineering
Principles of X-Ray Spectroscopy
X-Ray Diffraction
X-Ray Photoemission Spectroscopy
X-Ray Fluorescence Spectroscopy
X-Ray Absorption Spectroscopy
Introduction
• Photoemission spectroscopy: Energy
measurement of emitted electrons
• Surface sensitive technique
• Based on photoelectric effect
• Developed in mid 1960s by Kai
Siegbahn
• Binding energy of electrons is
determined
𝑩𝒊𝒏𝒅𝒊𝒏𝒈 𝑬𝒏𝒆𝒓𝒈𝒚 𝑩𝑬 = 𝒉𝝂 − 𝑲𝒊𝒏𝒆𝒕𝒊𝒄 𝑬𝒏𝒆𝒓𝒈𝒚 (𝑲𝑬)
Photoelectron Spectroscopy
X-ray Photoelectron Ultraviolet Photoelectron
Spectroscopy Spectroscopy
X-ray Photoelectron Spectroscopy
• Also known as electron spectroscopy
for chemical analysis (ESCA)
• Chemical composition of surfaces
• Al Kα (1486.6 eV) and Mg Kα (1253.6
eV)
• Spectrum contains information only
from top 3-10 nm of sample
Why do we use XPS: Thin film samples
• elements present at surface • thickness of film
• oxidation states of elements • uniformity of film
• chemical states of elements • uniformity in chemical
• band alignment at heterojunctions composition of film
An Introduction to Surface Analysis XPS And AES, Wiley-VCH, 224 (2003)
Instrumentation
1. Ultra-high vacuum: <10-9 torr
2. X-rays source
3. Neutralizer
4. Lens system
5. Hemispherical energy analyzer
6. Electron multiplier
7. Electron detector system
Neutralizer
X-ray source
Spectrum
Sample
Anodised TiO2 nanotubes: synthesis, growth mechanism and thermal stability, University of Bath (2008)
Inelastic Mean Free Path
Inelastic mean free path: An index of how far an electron travels through
a solid before losing its energy
𝑎 0.5
𝜆 = 538 2 + 0.41𝑎 𝑎 ∗ 𝐸
𝐸
E: KE of electron 𝛌: IMFP in nm
a3: volume of atom in nm3
Inelastic Mean Free Path (Ǻ)
• Most elements have inelastic
mean free path in range of ~1-3
nm
• XPS is surface sensitive
technique due to short mean
free path of low energy
electrons in solids
Surface and interface analysis, 1, 1, 2-11 (1979)
Sampling Depth
Sampling depth: depth from which 95% of all photoelectrons are
scattered by the time they reach the surface (3 )
Intensity of electron beam reaching the surface (IS) is attenuated
according to Beer-Lambert law.
−𝑑
𝐼𝑆 = 𝐼0 exp( )
𝜆
d = , IS = (I0/e) = 0.63 I0
d = 2 , IS = (I0 /e2) = 0.86 I0
d = 3 , IS = (I0 /e3) = 0.95 I0
• Most ’s are in the range of ~1-3 nm for Al Kα radiation
• Sampling depth (3 ) for XPS is 3-10 nm
An Introduction to Surface Analysis XPS And AES, Wiley-VCH, 224 (2003)
Features of XPS Spectrum
Sharp peaks:
Auger peaks:
elastically
Transitions from
scattered
L to K shell
photoelectrons
Satellites
Multiplet peaks: loss of
splitting: spin energy of
orbit coupling Background: photoelectrons to
inelastically valence electrons
scattered
electrons deeper
inside surface
Sharp Peaks and Background
dddd
dddd
Sharp peaks – Elastic processes
• Electrons close to surface: escape without energy loss
Background – Inelastic processes
• Electrons deeper in surface: loose energy and emerge with
reduced KE
• Increased BE, electrons very deep in surface loose all energy and
cannot escape
Auger Process
• Core hole created due to emission of photoelectron
• Electron falls from higher level to fill initial core hole in K-shell
• Energy liberated is simultaneously transferred to second electron
An Introduction to Surface Analysis XPS And AES, Wiley-VCH, 224 (2003)
Depth Profiling
• Non destructive
depth profiling (angle
resolved XPS)
Sampling depth decreases
as we go towards higher
angles - information from
surface only
• Destructive depth
profiling (ion
sputtered)
In thin film samples, if
we want characteristics
of a specific layer -
XPS depth profiling
Applied Surface Science; 252, 7730–7733 (2006)
Quantitative Elemental Analysis
𝐼𝑖
Ii =J ni σi K λi 𝑛𝑖 =
𝐽𝐾𝜎𝑖λ𝑖
Inelastic mean free path
Instrumental factors S: the atomic sensitivity factor
Photoionization cross-section • Scales measured areas -
Concentration of atom in solid meaningful atomic
Photon flux concentrations obtained,
regardless of the peak
The atomic concentration
Ci of element i:
Ci = ni /n
Ci = (Ii /Si)/(In/Sn)
An Introduction to Surface Analysis XPS And AES; Wiley-VCH, 224 (2003)
Quantitative Elemental Analysis
Step 1: acquire survey scan to
check what elements are present in
the sample
Step 2: acquire details of each
element and calculate the peak area
To calculate concentration of Si
Element Area S Area/S At%
C 2944 1 2944 0.30
O 12745 2.85 4471.93 0.46
N 457 1.77 258.19 0.03
Si 1663 0.83 2003.61 0.21
ISi /SSi
ISi/SSi /In/Sn =
ISi/SSi + IC/SC + IO/SO + IN /SN
Applications of Surface Science; 15, 1-4, 1-35 (1983)
Thank You!!
