We employ photoelectron spectroscopy to probe the electronic structure directly.

In this technique,
photons are used to excite the electrons from different energy levels, the process is known as
Photoelectric effect. If the energy of the photoexcited electrons due to the absorption of the incident
photons is sufficiently large, these excited electrons are ejected through the sample surface and are
detected by an electron detectors. Depending on the energy of the excitation source and the detection
process, the technique is named as XPS (x-ray photoemission spectroscopy), UPS (ultra-violet
photoemission spectroscopy), ARPES (angle-resolved photoemission spectroscopy), SRPES (spinresolved photoemission spectroscopy) etc.
We have installed a spin-resolved photoemission spectrometer, where one can identify spin of the
photo-electrons from a magnetized ferromagnetic material. Two photographs of the spin resolved
spectrometer installed in our laboratory is shown here.
Since the electrons are charged particles, the influence of strong Lorenz force makes it impossible to
build a spin detector based on Stern-Gerlach kind of setup. Therefore, the detectors in a spin-resolved
photoemission spectrometer is built based on Mott scattering - the asymmetry of scattered electrons
from a metal foil reflects the spin polarization of the incident electron beam due to the spin orbit
coupling - the detector is called a Mott detector.

5.3 Photoelectron Spectroscopy

Photoelectron spectroscopy utilizes photo-ionization and analysis of the kinetic energy
distribution of the emitted photoelectrons to study the composition and electronic state of the
surface region of a sample.
Traditionally, when the technique has been used for surface studies it has been subdivided
according to the source of exciting radiation into :

X-ray Photoelectron Spectroscopy (XPS)

Ultraviolet Photoelectron Spectroscopy (UPS)

- using soft x-rays (with a photon energy of 200-2000

to examine core-levels.

- using vacuum UV radiation (with a photon energy of

45 eV) to examine valence levels.

The development of synchrotron radiation sources has enabled high resolution studies to be
carried out with radiation spanning a much wider and more complete energy range ( 5 - 5000+
eV ) but such work remains a small minority of all photoelectron studies due to the expense,
complexity and limited availability of such sources.

Physical Principles
Photoelectron spectroscopy is based upon a single photon in/electron out process and from
many viewpoints this underlying process is a much simpler phenomenon than the Auger
process.
The energy of a photon of all types of electromagnetic radiation is given by the Einstein relation
:
E = h
where
h - Planck constant ( 6.62 x 10-34 J s )
- frequency (Hz) of the radiation
Photoelectron spectroscopy uses monochromatic sources of radiation (i.e. photons of fixed
energy).
In XPS the photon is absorbed by an atom in a molecule or solid, leading to ionization and the
emission of a core (inner shell) electron. By contrast, in UPS the photon interacts with valence
levels of the molecule or solid, leading to ionisation by removal of one of these valence
electrons.
The kinetic energy distribution of the emitted photoelectrons (i.e. the number of emitted
photoelectrons as a function of their kinetic energy) can be measured using any appropriate
electron energy analyser and a photoelectron spectrum can thus be recorded.
The process of photoionization can be considered in several ways : one way is to look at the
overall process as follows :
A + h A+ + eConservation of energy then requires that :
E(A) + h = E(A+ ) + E(e-)

Since the electron's energy is present solely as kinetic energy (KE) this can be rearranged to give
the following expression for the KE of the photoelectron:
KE = h - ( E(A+ ) - E(A) )
The final term in brackets, representing the difference in energy between the ionized and
neutral atoms, is generally called the binding energy (BE) of the electron - this then leads to the
following commonly quoted equation :
KE = h - BE
An alternative approach is to consider a one-electron model along the lines of the following
pictorial representation ; this model of the process has the benefit of simplicity but it can be
rather misleading.

The BE is now taken to be a direct measure of the energy required to just remove the electron
concerned from its initial level to the vacuum level and the KE of the photoelectron is again
given by :
KE = h - BE
NOTE - the binding energies (BE) of energy levels in solids are conventionally measured with
respect to the Fermi-level of the solid, rather than the vacuum level. This involves a small

correction to the equation given above in order to account for the work function () of the
solid, but for the purposes of the discussion below this correction will be neglected.

Experimental Details
The basic requirements for a photoemission experiment (XPS or UPS) are:
1. a source of fixed-energy radiation (an x-ray source for XPS or, typically, a He discharge
lamp for UPS)
2. an electron energy analyser (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 analysed
without interference from gas phase collisions)
Such a system is illustrated schematically below:
*****************UPS________________8***********************************************
Ultraviolet light is shone at the sample using a Helium lamp emitting at 21.2 eV (He I radiation)
or 40.8 eV (He II radiation), although synchrotron radiation can provide photon energies from
approx. 10 eV up to the XPS region. The low photon energy in UPS means that deep core
electron levels cannot be excited, and only photoelectrons emitted from the valence band or
shallow core levels are accessible. Angle Resolved UPS (ARUPS) can be used to determine
the band structure of the material under investigation. UPS can also be used to identify
molecular species on surfaces by identifying characteristic electron energies associated with the
bonds of the molecules.
By using a synchrotron, the relative change in photoemission cross-section for various electron
states can be used to determine the partial Density of States (DOS). Certain electron states
undergo a 'Cooper minimum' whereby the cross-section drops to a very low value at a certain
photon energy. Hence the shape of the DOS can be determined without the contribution of the
electron state at the Cooper minimum.
Alternatively, a 'resonance' may occur whereby the photoemission intensity for a particular state
may be enhanced at certain photon energies. This is caused when a high binding energy core
level has its electrons excited to states whose energy is just above the Fermi level. The atom
can relax by emitting an Auger electron (see AES ), or a resonant enhancement of a valence
band state can occur. A typical resonance occurs in Ti where a 3p electron jumps to an empty
3d state for photon energies in the region of 33 eV. (see also Spin-Polarised UPS, SPUPS)

SRUPS: SPUPS - Spin Polarised Ultraviolet Photoelectron Spectroscopy and SPXPS - Spin
Polarised X-ray Photoelectron Spectroscopy. These two techniques are identical to the UPS
and XPS techniques, but they have a detector which can determine the spin of the electrons
emitted from the sample surface. Hence their main use is in the study of magnetic samples. The
spin detector is frequently a so-called Mott detector (named after the late Sir Neville Mott). This
detector makes use of an effect discovered by Neville Mott whereby electrons scatter by
different amounts in different directions depending on their spin.
In a magnetic material, the electrons can be divided into spin up and spin down bands. These
bands have energies which are slightly shifted (or split) with respect to each other (in nonmagnetic materials, there is no splitting). Hence, the polarisation of the electrons changes as a
function of binding energy. This can be studied near the Fermi edge using SPUPS and for
deeper core levels using SPXPS. The results can be compared with theoretically determined
spin dependent calculations of the electronic structure of the material.
Hysteresis loops can be measured by detecting the polarisation of the secondary electrons as a
function of the applied field. This technique is therefore complementary to MOKE. Secondary
electrons in the region of twenty electron volts (eV) have a shorter mean free path than
electrons of about one eV and hence the nature of the hysteresis loop as a function of depth
into the sample can be studied.
http://www.uksaf.org/tech/ups.html