Laboratory based XPS[edit]

In laboratory systems, either 10–30 mm beam diameter non-monochromatic Al Kα or Mg

Kα anode radiation is used, or a focused 20-500 micrometer diameter beam single
wavelength Al Kα monochromatised radiation. Monochromatic Al Kα X-rays are normally
produced by diffracting and focusing a beam of non-monochromatic X-rays off of a thin disc
of natural, crystalline quartz with a <1010> orientation. The resulting wavelength is 8.3386
angstroms (0.83386 nm) which corresponds to a photon energy of 1486.7 eV. Aluminum
Kα X-rays have an intrinsic full width at half maximum (FWHM) of 0.43 eV, centered on
1486.7 eV (E/ΔE = 3457).[citation needed] For a well–optimized monochromator, the energy width of
the monochromated aluminum Kα X-rays is 0.16 eV, but energy broadening in common
electron energy analyzers (spectrometers) produces an ultimate energy resolution on the
order of FWHM=0.25 eV which, in effect, is the ultimate energy resolution of most
commercial systems. When working under practical, everyday conditions, high energy-
resolution settings will produce peak widths (FWHM) between 0.4–0.6 eV for various pure
elements and some compounds. For example, in a spectrum obtained in 1 minute at a pass
energy of 20 eV using monochromated aluminum Kα X-rays, the Ag 3d5/2 peak for a clean
silver film or foil will typically have a FWHM of 0.45 eV. [citation needed] Non-monochromatic
magnesium X-rays have a wavelength of 9.89 angstroms (0.989 nm) which corresponds to a
photon energy of 1253 eV. The energy width of the non-monochromated X-ray is roughly
0.70 eV, which, in effect is the ultimate energy resolution of a system using non-
monochromatic X-rays.[citation needed] Non-monochromatic X-ray sources do not use any crystals to
diffract the X-rays which allows all primary X-rays lines and the full range of high-
energy Bremsstrahlung X-rays (1–12 keV) to reach the surface. The ultimate energy
resolution (FWHM) when using a non-monochromatic Mg Kα source is 0.9–1.0 eV, which
includes some contribution from spectrometer-induced broadening. [citation needed]

Synchrotron based XPS[edit]

A breakthrough has been brought about in the last decades by the development of large
scale synchrotron radiation facilities. Here, bunches of relativistic electrons kept in orbit
inside a storage ring are accelerated through bending magnets or insertion devices
like wigglers and undulators to produce a high brilliance and high flux photon beam. The
beam is orders of magnitude more intense and better collimated than typically produced by
anode-based sources. Synchrotron radiation is also tunable over a wide wavelength range,
and can be made polarized in several distinct ways. This way, photon can be selected
yielding optimum photoionization cross-sections for probing a particular core level. The high
photon flux, in addition, makes it possible to perform XPS experiments also from low density
atomic species, such as molecular and atomic adsorbates.

Data processing[edit]
Peak identification[edit]
The number of peaks produced by a single element varies from 1 to more than 20. Tables of
binding energies that identify the shell and spin-orbit of each peak produced by a given
element are included with modern XPS instruments, and can be found in various handbooks
and websites.[12][13] Because these experimentally determined energies are characteristic of
specific elements, they can be directly used to identify experimentally measured peaks of a
material with unknown elemental composition.
Before beginning the process of peak identification, the analyst must determine if the binding
energies of the unprocessed survey spectrum (0-1400 eV) have or have not been shifted
due to a positive or negative surface charge. This is most often done by looking for two
peaks that are due to the presence of carbon and oxygen.

Charge referencing insulators[edit]

Charge referencing is needed when a sample suffers a charge induced shift of experimental
binding energies to obtain meaningful binding energies from both wide-scan, high sensitivity
(low energy resolution) survey spectra (0-1100 eV), and also narrow-scan, chemical state
(high energy resolution) spectra. Charge induced shifting is normally due to a modest excess
of low voltage (-1 to -20 eV) electrons attached to the surface, or a modest shortage of
electrons (+1 to +15 eV) within the top 1-12 nm of the sample caused by the loss of photo-
emitted electrons. If, by chance, the charging of the surface is excessively positive, then the
spectrum might appear as a series of rolling hills, not sharp peaks as shown in the example
spectrum.
Charge referencing is performed by adding a Charge Correction Factor to each of the
experimentally measured peaks. Since various hydrocarbon species appear on all air-
exposed surfaces, the binding energy of the hydrocarbon C (1s) XPS peak is used to charge
correct all energies obtained from non-conductive samples or conductors that have been
deliberately insulated from the sample mount. The peak is normally found between 284.5 eV
and 285.5 eV. The 284.8 eV binding energy is routinely used as the reference binding
energy for charge referencing insulators, so that the charge correction factor is the difference
between 284.8 eV and the experimentally measured C (1s) peak position.
Conductive materials and most native oxides of conductors should never need charge
referencing. Conductive materials should never be charge referenced unless the topmost
layer of the sample has a thick non-conductive film. The charging effect, if needed, can also
be compensated by providing suitable low energy charges to the surface by the use of low-
voltage (1-20 eV) electron beam from an electron flood gun, UV lights, low-voltage argon ion
beam with low-voltage electron beam (1-10 eV), aperture masks, mesh screen with low-
voltage electron beams, etc.