X-Ray Photoelectron
Spectroscopy (XPS)
XPS Background
XPS technique is based on Einstein’s idea about the
photoelectric effect, developed around 1905
The concept of photons was used to describe the ejection of
electrons from a surface when photons were impinged upon it
During the mid 1960’s Dr. Siegbahn and his research
group developed the XPS technique.
In 1981, Dr. Siegbahn was awarded the Nobel Prize in Physics
for the development of the XPS technique
X-Rays
Irradiate the sample surface, hitting the core electrons (e-) of the
atoms.
The X-Rays penetrate the sample to a depth on the order of a
micrometer.
The X-Ray source produces photons with certain energies:
MgK photon with an energy of 1253.6 eV
AlK photon with an energy of 1486.6 eV
Normally, the sample will be radiated with photons of a single
energy (MgK or AlK). This is known as a monoenergetic X-Ray
beam.
Why the Core Electrons?
An electron near the Fermi level is far from the nucleus,
moving in different directions all over the place, and will
not carry information about any single atom.
Fermi level is the highest energy level occupied by an
electron in a neutral solid at absolute 0 temperature.
Electron binding energy (BE) is calculated with respect to the
Fermi level.
The core e-s are local close to the nucleus and have
binding energies characteristic of their particular element.
The core e-s have a higher probability of matching the
energies of AlK and MgK.
Valence e-
Core e- Atom
Binding Energy (BE)
The Binding Energy (BE) is characteristic of the core
electrons for each element. The BE is determined by the
attraction of the electrons to the nucleus. If an electron with
energy x is pulled away from the nucleus, the attraction
between the electron and the nucleus decreases and the BE
decreases. Eventually, there will be a point when the
electron will be free of the nucleus.
XPS Instrument
X-Ray Source
Ion Source
SIMS Analyzer
Sample introduction
Chamber
XPS
XPS is also known as ESCA (Electron Spectroscopy for Chemical
Analysis).
The technique is widely used because it is very simple to use and the
data is easily analyzed.
XPS works by irradiating atoms of a surface of any solid material with
X-Ray photons, causing the ejection of electrons.
How Does XPS Technology Work?
A monoenergetic x-ray beam Ultrahigh vacuum
emits photoelectrons from environment to eliminate
the surface of the sample. excessive surface
contamination.
The X-Rays either of two
energies: Cylindrical Mirror Analyzer
Al Ka (1486.6eV) (CMA) measures the KE of
Mg Ka (1253.6 eV) emitted e-s.
The x-ray photons penetrates The spectrum plotted by the
about a micrometer of the computer from the analyzer
sample signal.
The XPS spectrum contains
information only about the The binding energies can be
top 10 - 100 Ǻ of the sample. determined from the peak
positions and the elements
present in the sample
identified.
X-Rays on the Surface
The X-Rays will penetrate to the core e- of the atoms in the
sample.
Some e-s are going to be released without any problem
giving the Kinetic Energies (KE) characteristic of their
elements.
Other e-s will come from inner layers and collide with other
e-s of upper layers
These e- will be lower in lower energy.
They will contribute to the noise signal of the spectrum.
XPS
Spectrum
O 1s
O Auger
O because
of Mg source
C O 2s
Al
Al
Sample and graphic provided by William Durrer, Ph.D.
Department of Physics at the Univertsity of Texas at El Paso
Identification of XPS Peaks
The plot has characteristic peaks for each
element found in the surface of the sample.
There are tables with the KE and BE already
assigned to each element.
After the spectrum is plotted you can look for the
designated value of the peak energy from the
graph and find the element present on the
surface.
XPS Technology
Consider as non- Applications in the
destructive industry:
because it produces soft Polymer surface
x-rays to induce
Catalyst
photoelectron emission
from the sample surface Corrosion
Adhesion
Provide information Semiconductors
about surface layers Dielectric materials
or thin film structures Electronics packaging
Magnetic media
Thin film coatings
