Nanoscience and Nanotechnology
Module-6
Dr. M. Midhun Kumar
Assistant Professor
School of Chemical Engineering (SCHEME)
Vellore Institute of Technology, Vellore
Email ID: midhunkumar.m@[Link]
Characterization Techniques
Optical Interaction-Based Techniques
Techniques
• UV-Vis spectroscopy
• Photoluminescence (PL) spectroscopy
• Raman spectroscopy
Key Applications Diffraction/Scattering-Based
Band gap determination
Electronic transitions
Techniques
Techniques
• X-ray Diffraction (XRD)
Key Applications
Phase identification
Crystallite size
Lattice parameters
Electron/Probe-Matter Interaction Techniques
Techniques
• SEM (Scanning Electron Microscopy)
• TEM / HRTEM
• Atomic Force Microscopy (AFM)
Key Applications
Particle size & shape Surface Chemical Interaction
Surface topography
Crystallographic imaging
Techniques
Techniques
• XPS (X-ray Photoelectron Spectroscopy)
• FTIR spectroscopy
Key Applications
Surface composition
Oxidation states
Functional group analysis
Surface Chemical Interaction Techniques
Transmission Electron Microscopy (TEM)
Atomic Force Microscopy (AFM)
Surface Chemical Interaction Techniques
What is XPS?
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.
What is XPS?
X-ray Photoelectron spectroscopy,
based on the photoelectric effect,1,2 was
developed in the mid-1960’s by Kai
Siegbahn and his research group at the
University of Uppsala, Sweden.3
1. H. Hertz, Ann. Physik 31,983 (1887).
2. A. Einstein, Ann. Physik 17,132 (1905). 1921 Nobel Prize in Physics.
3. K. Siegbahn, Et. Al.,Nova Acta Regiae [Link]., Ser. IV, Vol. 20 (1967).
1981 Nobel Prize in Physics.
X-ray Photoelectron Spectroscopy
Small Area Detection
Electrons are extracted
only from a narrow solid
X-ray Beam angle.
X-ray penetration
depth ~1m.
Electrons can be 10 nm
excited in this
entire volume. 1 mm2
X-ray excitation area ~1x1 cm2. Electrons
are emitted from this entire area
The Photoelectric Process
Ejected Photoelectron
Incident X-ray
Free XPS spectral lines are
Electron identified by the shell from
Conduction Band Level which the electron was
Fermi ejected (1s, 2s, 2p, etc.).
Level The ejected photoelectron has
Valence Band kinetic energy:
KE=hv-BE-
2p L2,L3 Following this process, the
atom will release energy by
2s L1
the emission of an Auger
Electron.
1s K
Energy required to remove an electron from its atomic
level
Auger Relation of Core Hole
Emitted Auger Electron
Free L electron falls to fill core level
Electron vacancy (step 1).
Conduction Band Level
KLL Auger electron emitted to
Fermi
conserve energy released in
Level
step 1.
Valence Band
The kinetic energy of the
emitted Auger electron is:
2p L2,L3
KE=E(K)-E(L2)-E(L3).
2s L1
1s K
XPS Energy Scale
The XPS instrument measures the
kinetic energy of all collected
electrons. The electron signal includes
contributions from both photoelectron
and Auger electron lines.
XPS Energy Scale- Kinetic energy
KE = hv - BE - spec
Where: BE= Electron Binding Energy
KE= Electron Kinetic Energy
spec= Spectrometer Work Function
Photoelectron line energies: Dependent on photon energy.
Auger electron line energies: Not Dependent on photon energy.
If XPS spectra were presented on a kinetic energy scale,
one would need to know the X-ray source energy used to collect
the data in order to compare the chemical states in the sample
with data collected using another source.
XPS Energy Scale- Binding energy
BE = hv - KE - spec
Where: BE= Electron Binding Energy
KE= Electron Kinetic Energy
spec= Spectrometer Work Function
Photoelectron line energies: Not Dependent on photon
energy.
Auger electron line energies: Dependent on photon energy.
The binding energy scale was derived to make uniform
comparisons of chemical states straight forward.
Binding Energy Referencing
BE = hv - KE - spec- Ech
Where: BE= Electron Binding Energy
KE= Electron Kinetic Energy
spec= Spectrometer Work Function
Ech= Surface Charge Energy
Ech can be determined by electrically calibrating the
instrument to a spectral feature.
C1s at 285.0 eV
Au4f7/2 at 84.0 eV
Where do Binding Energy Shifts Come
From?
-or How Can We Identify Elements and Compounds?
Fermi Level
Pure Element
Electron-electron Binding
Energy
repulsion
Look for changes here
Electron by observing electron
binding energies
Electron-nucleus
attraction Electron-
Nucleus
Separation
Nucleus
Elemental Shifts
Binding Energy (eV)
Element 2p3/2 3p
Fe 707 53 654
Co 778 60 718
Ni 853 67 786
Cu 933 75 858
Zn 1022 89 933
Electron-nucleus attraction helps us identify the
elements
Elemental Shifts
Binding Energy Determination
The photoelectron’s binding energy will be
based on the element’s final-state configuration.
Initial State Final State
Free
Electon
Conduction Band Level Conduction Band
Fermi
Level
Valence Band Valence Band
2p
2s
1s
Chemical Shifts-
Electronegativity Effects
Carbon-Oxygen Bond
Oxygen Atom
Electron-oxygen
Valence Level
atom attraction
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 Shifts-
Electronegativity Effects
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
Electronic Effects
Spin-Orbit Coupling
C 1s
Orbital=s
l=0
s=+/-1/2
ls=1/2
290 288 284 280 276
Binding Energy (eV)
Electronic Effects
Spin-Orbit Coupling
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 Coupling
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-OrbitCoupling
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)
Electronic Effects- Spin-Orbit Coupling
Ti Metal Ti Oxide
Final State Effects- Multiplet Splitting
Following photoelectron emission, the
remaining unpaired electron may couple
with other unpaired electrons in the atom,
resulting in an ion with several possible
final state configurations with as many
different energies. This produces a line
which is split asymmetrically into several
components.
XPS of Copper-Nickel alloy
120
Peak Rel. Atomic
Cu 2p
Area Sens. Conc
100 Mct-eV/sec %
Ni 2.65 4.044 49
Cu 3.65 5.321 51
80
Thousands
N(E)/E
Cu
60 Ni 2p LMM Cu
Ni LMM Cu
LMM Ni LMM
40 LMM Ni
LMM
Ni 3p
20
Cu 3p
0
-1100 -900 -700 -500 -300 -100
Binding Energy (eV)
Instrumentation for X-ray
Photoelectron Spectroscopy
Introduction to X-ray Photoelectron
Spectroscopy (XPS)
• What is XPS?- General Theory
• How can we identify elements and
compounds?
• Instrumentation for XPS
• Examples of materials analysis with
XPS
Instrumentation for XPS
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.
Why UHV for Surface Analysis?
Pressure
Degree of Vacuum Torr
Remove adsorbed gases from
102 the sample.
Low Vacuum
Eliminate adsorption of
10-1
contaminants on the sample.
Medium Vacuum
10-4 Prevent arcing and high
High Vacuum voltage breakdown.
10-8 Increase the mean free path for
Ultra-High Vacuum electrons, ions and photons.
10-11
X-ray Photoelectron Spectrometer
X-ray Photoelectron Spectrometer
Computer
System
Hemispherical Energy Analyzer
Outer Sphere Magnetic Shield
Inner Sphere Analyzer Control
Electron Multi-Channel Plate
Lenses for Energy
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
Applications of
X-ray Photoelectron Spectroscopy
(XPS)
Angle-resolved XPS
=15° = 90°
More Surface Less Surface
Sensitive Sensitive
Information depth = dsin
d = Escape depth ~ 3
= Emission angle relative to surface
= Inelastic Mean Free Path
FTIR spectroscopy