Photoelectron spectroscopy

Electromagnetic radiation has the properties of both a wave and a

particle .The radiation is usually described in terms of its energy, E, or its
wavelength, . The relation between these units is expressed in following
equation:
E=hv=hc/
where h is Plancks constant, v is the frequency of the wave, c is the
speed of light in vacuum and is the wavelength of the light .
Photons are particles of light and with the right energy they can interact
with matter .If an atom or molecule absorbs a photon, the electronic
structure of the atom or molecule will adjust itself to the added quantum
of energy .This process can be used to explore the different energy levels
of atoms or molecules, and one can obtain useful chemical information
about different species.
X-ray photoelectron spectroscopy (XPS) is the most widely used surface
analysis technique to provide both quantitative atomic concentration and
chemical state information of the detected elements .X-ray irradiation
of surfaces results in the emission of photoelectrons whose energies are
characteristic of the elements .The information depth is approximately
57 nm. Angle-resolved XPS offers non-destructive resolution of
structures within the XPS sampling depth, e .g .layer ordering,
composition and thickness can be determined.
Moreover, XPS can be utilized for sputter depth profiling to characterize
thin films and multi-layer systems by quantifying matrix-level elements
as a function of depth.
Principles of X-RAY Photoelectron Spectroscopy
Briefly, XPS is based on the principle that, when a surface is irradiated
with X-rays, i will be ejected. If X-ray lines of sufficiently narrow widths
are used, the photoelectrons have characteristic energies related directly
to the atomic levels from which they came; XPS commonly uses either
the AlK!(1486.6 eV) or the MgK!(1253.6 eV ) lines .With such low -
energy excitation, the photoelectrons must originate in the outer few
monolayers only if they are to escape without energy loss .The resultant
energetic electrons are then collected and counted, after dispersion, by an
electrostatic analyzer .A photoelectron energy spectrum then consists of a
plot of counts as a function of kinetic energy .Such spectra may be used
for analytical purposes or to gain insight into the chemical bonding of the
elements present .The technique is fully quantitative insofar as the area
under a characteristic peak can be related directly to the concentration of
the corresponding atomic species in the surface layer .The sensitivity of
XPS is of the order of 0.1 at% for most elements. Chemical information
can be extracted from the spectrum by detailed considerations of the
position (with a typical resolution of " 0.1 eV) and shape of peak
envelopes .This information can be interpreted readily by comparison
with spectra of standard compounds, recorded in the same experiment,
or by consulting the voluminous and mature literature on XPS
investigations of various compound.
The basic requirements for a photoemission experiment (XPS) are:
1. a source of fixed-energy radiation
2. an electron energy analyzer (which can disperse the emitted electrons
according to their kinetic energy, and thereby measure the flux of emitted
electrons of a particular energy)
3. a high vacuum environment (to enable the emitted photoelectrons to
be analyzed without interference from gas phase collisions)


XPS can provide typical information such as:
determining the composition of a surface )elemental and chemical
composition quantification.
mapping the spatial distribution of the surface constituents.
in-depth profiling these constituents into the bulk of the material.
determining an over-layer or thin film thickness
identifying particles
quantifying light element impurities
Limitations
All elements are detectable except for H and He
Sample has to be a solid at RT and stable under vacuum conditions,
powders are possible
Depending on the chemical composition samples might be sensitive
to X-ray irradiation

Basic Instrument



n For each and every element, there will be a characteristic binding
energy associated with each core atomic orbital i.e. each element
will give rise to a characteristic set of peaks in the photoelectron
spectrum at kinetic energies determined by the photon energy and
the respective binding energies.
n The presence of peaks at particular energies therefore indicates the
presence of a specific element in the sample under study -
furthermore, the intensity of the peaks is related to the
concentration of the element within the sampled region. Thus, the
technique provides a quantitative analysis of the surface
composition and is sometimes known by the alternative acronym ,
ESCA (Electron Spectroscopy for Chemical Analysis).
n The most commonly employed x-ray sources are those giving rise
to :
Mg K
!
radiation : hv = 1253.6 eV
Al K
!
radiation : hv = 1486.6 eV








References
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