X-ray photoelectron spectroscopy

• X-ray photoelectron spectroscopy (XPS) is a

quantitative spectroscopic technique that
measures the elemental composition,
empirical formula, chemical state and
electronic state of the elements that exist within
a material
• In cooperation with Siegbahn, Hewlett-Packard
in the USA produced the first commercial
monochromatic XPS instrument in 1969.
Siegbahn received the Nobel Prize in 1981 to
acknowledge his extensive efforts to develop
XPS into a useful analytical tool.
Schematic diagram of XPS
 Important parts of the XPS
• A source of X-rays
• An ultra-high vacuum (UHV) stainless steel chamber
with UHV pumps
• An electron collection lens
• An electron energy analyzer
• magnetic field shielding
• An electron detector system
• A moderate vacuum sample introduction chamber
• Sample mounts
• A sample stage
• A set of stage manipulators
 Working principle of
• X-ray photoelectron spectroscopy (XPS) is a surface
analytical technique, which is based upon the
photoelectric effect. Each atom in the surface has core
electron with the characteristic binding energy that is
conceptually, not strictly, equal to the ionization
energy of that electron. When an X-ray beam directs
to the sample surface, the energy of the X-ray photon
is adsorbed completely by from the core electron of an
atom. If the photon energy, hv, is large enough, the
core electron will then escape the atom and emit out
of the surface. The emitted electron with the kinetic
energy of Ek is referred to as the photoelectron. The
binding energy of the core electron is give by the
Einstein relationship:
 Working principle of

• Where h is the X-ray photon energy (for monochromatic Al Ka,

h = 1486.6eV); Ek is the kinetic energy of photoelectron, which
can be measured by the energy analyzer; and is the work
function induced by the analyzer, about 4~5eV. Since the work
function, , can be compensated artificially, it is eliminated,
giving the binding energy as follows:

• For insulating samples, once the photoelectrons are emitted out of the
sample surface, a positive charge zone will establish quickly in the sample
surface. As a result, the sample surface acquires a positive potential
(varying typically from several volts to tens of volts) and the kinetic energies
of core electrons are reduced by the same amount, C.
 XPS is used to measure:
• XPS is also known as ESCA, an abbreviation
for Electron Spectroscopy for Chemical
Analysis.
• XPS detects all elements with an
atomic number (Z). This has limitation that it
cannot detect hydrogen (Z=1) or helium (Z=2).
• XPS is routinely used to analyze
inorganic compounds, metal alloys,
semiconductors, polymers, elements, catalysts,
glasses, ceramics, paints, papers, inks, woods,
plant parts, make-up, teeth, bones, medical
implants, bio-materials, viscous oils, glues, ion
modified materials and many others.
 XPS is used to measure:
• elemental composition of the surface (1–10 nm
usually)
• empirical formula of pure materials
• elements that contaminate a surface
• chemical or electronic state of each element in
the surface
• uniformity of elemental composition across the
top surface.
• uniformity of elemental composition as a
function of ion beam etching