Photoelectron Spectroscopy:

Theory
General Overview of Spectroscopy
Spectroscopy uses interaction of electromagnetic
radiation with matter to learn something about the
matter.
If electromagnetic radiation present is in resonance
with the energy spacing between different states
(electronic, vibrational, rotational, etc) of matter,
radiation will be absorbed and transitions will
occur.
The radiation that is transmitted through the
sample is measured, and spectrum can be reported
as either transmittance or absorbance of radiation.
Photoelectron spectroscopy is entirely different!
 Photoelectron vs Other Spectroscopies
Others  Photoelectron
 Photon must be in resonance  Photon just needs enough
with transition energy energy to eject electron
 Measure absorbance or  Measure kinetic energy of
transmittance of photons ejected electrons
 Scan photon energies  Monochromatic photon
source
 Introduction

Photoelectron spectroscopy involves the

measurement of kinetic energy of photoelectrons to
determine the binding energy, intensity and
angular distributions of these electrons and use
the information obtained to examine the electronic
structure of molecules.
It differs from the conventional methods of
spectroscopy in that it detects electrons rather
than photons to study electronic structures of a
material.
 Introduction
 Photoelectron spectroscopy (PES) is the energy measurements of
photoelectrons emitted from solids, gases, or liquids by the
photoelectric effect.
 Depending on the source of ionization energy, PES can be divided
accordingly into Ultraviolet Photoelectron Spectroscopy (UPS) and
X-ray Photoelectron Spectroscopy (XPS).
 The source of radiation for UPS is a noble gas discharge lamp,
usually a He discharge lamp.
 For XPS, also referred to as Electron Spectroscopy for Chemical
Analysis (ESCA), the source is high energy X-rays (1000-1500 eV).
 UPS, which uses the energy of ultraviolet rays (<41 eV) will only
be sufficient to eject electrons from the valence orbitals, while
the high energy X-rays used in XPS can eject electrons from the
core and atomic orbitals.
Photoelectron spectroscopy involves the ejection of electrons from
atoms or molecules following bombardment by monochromatic
photons. The ejected electrons are called photoelectrons.

Photoelectron spectroscopy involving the use of higher-energy

incident photons and applied to the study not only of solid
surfaces but also of samples in the gas phase.
 UPS
In photoelectron spectroscopy techniques such UPS,
the photon energies range from 10-50eV.
So, electrons can be ejected from surfaces due to the
photoelectric effect.
UPS uses vacuum Ultraviolet radiation with energy
10-50eV to determine work functions, ionization
energies and examine valence levels.
Koopmans’ Theorem and the Photoemission
Process
The binding energy of an electron in state I is
equal to the negative of the orbital energy of the ith
state.

The ionization energy (Ii) for the removal of

electrons from different orbitals in a molecule is
given by the energy difference between the initial
state of the neutral molecule (in the ground state)
and the final state that is the state of the ionized
molecule.
Koopmans’theoremmakespossibletheidentificationo
fcalculatedorbitalenergieswithionizationpotentials.
UV Commonly Used Lines (16.6 to 40.8 eV)
Ionization sources are Ne I (16.6eV), Ne II (26.8eV) and
He I (21.2eV), He II (40.8eV).
I—light emitted from neutral atoms
II—light emitted by singly ionized atoms
These lines are produced by cold cathode capillary
discharge. They represent resonance fluorescence
produced when the gas is excited in the discharge and
then decays back to its ground state.
The resonance line produced by transition from the first
excited state to the G.S is usually the most intense.
He I line is at 584Å or 21.22eV and He II line at 304Å
or 40.8eV.
 Photoemission from Valence Bands
• UPS is the most powerful and versatile technique to
study the electronics structure of the valence bands in
atoms, solids and molecules (ionization energy of
molecules, HOMO) and determine the workfunction of
a material. This PE process depends on parameters
such as:
Emitted electron parameters
– Kinetic energy
– Emission angles
– Spin polarization

Incident photon parameters

– Photon energy(hn)
– Angle of incidence
– Polarization
 Instrumentation
• The main goal in either UPS or XPS is to gain
information about the composition, electronic state,
chemical state, binding energy, and more of the surface
region of solids.
• The key point in PES is that a lot of qualitative and
quantitative information can be learned about the
surface region of solids.
• The focus here will be on how the instrumentation for
PES is constructed and what types of systems are
studied using XPS and UPS.
• The goal is to understand how to go about constructing
or diagramming a PES instrument, how to choose an
appropriate analyzer for a given system, and when to
use either XPS or UPS to study a system.
There are a few basics common to both techniques
that must always be present in the instrumental
setup

 A radiation source: The radiation sources used in

PES are fixed-energy radiation sources. XPS
sources from x-rays while UPS sources from a gas
discharge lamp.
 An analyzer: PES analyzers are various types of
electron energy analyzers
 A high vacuum environment: PES is rather picky
when it comes to keeping the surface of the sample
clean and keeping the rest of the environment free
of interferences from things like gas molecules. The
high vacuum is almost always an ultra high
vacuum (UHV) environment.
Diagram of a basic, typical PES instrument used in XPS, where the radiation
source is an X-ray source. When the sample is irradiated, the released
photoelectrons pass through the lens system which slows them down before
they enter the energy analyzer. The analyzer shown is a spherical deflection
analyzer which the photoelectrons pass through before they are collected at the
collector slit.
 Radiation sources
• The radiation source for UPS is a gas discharge lamp, with the typical one being an
He discharge lamp operating at 58.4 nm which corresponds to 21.2 eV of kinetic
energy. XPS has a choice between a monocrhomatic beam of a few microns or an
unfocused non-monochromatic beam of a couple centimeters. These beams
originate from X-Ray sources of either Mg or Al K-? sources giving off 1486 eV and
1258 eV of kinetic energy respectively. For a more versitile light source, synchrotron
radiation sources are also used. Synchrotron radiation is especially useful in
studying valence levels as it provides continuous, polarized radiation with high
energies of > 350 eV.

• The main thing to consider when choosing a radiation source is the kinetic energy
involved. The source is what sets the kinetic energy of the photoelectrons, so there
needs to not only be enough energy present to cause the ionizations, but there
must also be an analyzer capable of measuring the kinetic energy of the released
photoelectrons.

• In XPS experiments, electron guns can also be used in conjunction with x-rays to
eject photoelectrons. There are a couple of advantages and disadvantages to doing
this, however. With an electron gun, the electron beam is easily focused and the
excitation of photoelectrons can be constantly varied. Unfortunately, the
background radiation is increased significantly due to the scattering of falling
electrons. Also, a good portion of substances that are of any experimental interest
are actually decomposed by heavy electron bombardment such as that coming from
an electron gun.
 Spectroscopy
Valence electrons Chemical Bonding
Core electrons Non interacting
Ionization Photoelectron Spectroscopy

hn
 Core Levels-Atom Specific Information

Element Sensitive
Chemical Shifts
 Applications of ESCA
-- Surface contamination
-- Failure analysis
-- Effects of surface treatments
-- Coating, films
-- Tribological effects
-- Depth Profiling (Ar+ sputtering)
 Why XPS not good for study of bands?

1. XPS indeed can excite valence bands to get information about

such as density of states, however, it is not suitable for the
study of valence bands, especially for the study of energy
dispersion (k dependence).

2. XPS photon have too large energy which leads the electrons
from valence bands with very high Ekin, eg, too big wave vector
k.

3. XPS photon energy is too high, the transition probability for

valence bands is very small compared with UV light. ( WHY? )

4. Generally it is hard to analyze spectra with high kinetic energy

with high resolution (DE).
 Summary
• PES is a fairly new technique, continuing to
develop
• PES has unique features compared to other
spectroscopies
• Valence spectroscopy: information on bonding
• Core spectroscopy: qualitative and
quantitative analysis, “chemical shift”