Q.9) Write a short note on XPS, PL, Raman spectroscopy, AES, ESR.

Answer:
1) X-ray photoelectron spectroscopy (XPS):

Figure: Schematic of photoemission

Photon of fixed energy hʋ incident on an atom ejects an electron of binding

energy
EB with kinetic energy EK according to the equation;
hʋ= EK + EB.
Knowing hʋ and by measuring with an energy analyzer, the kinetic energy EK
of
electron, binding energy of electron in an atom can be determined. The
equation is valid for atoms in gases, liquids or solids. In a solid additional
energy (ϕ) the work function of the solid is required for the electron to get
emitted as;
hʋ= EK + EB + ϕ
Work function of solids changes from material to material. It also depends
on their cleanliness and purity. Fortunately, it is not necessary to know ϕ of
the solid. Kinetic energies of emitted electrons are measured with reference
to Fermi level and ϕ can be replaced by ϕSP, the work function of the
spectrometer. Therefore, one gets the measured EK, which differs from the
kinetic energy of photoelectron coming out from the sample.
One obtains intensity of electrons versus electron energy which is the
Electron Distribution Curve (EDC). Core level electrons in atoms of the solid
are very sensitive to their neighboring atoms. Therefore, analysis of
photoelectrons was originally known as ‘Electron Spectroscopy for Chemical
Analysis’. However, there are many electron spectroscopies available now,
which yield chemical information. It is therefore safer to call the technique
as X-ray Photoelectron Spectroscopy(XPS), which specifically indicates that
photoelectrons are produced using X-rays. This is used for elemental
analysis.
 2) Auger Electron Spectroscopy(AES)-

Figure: Schematic of Auger Process

Auger effect- When a core electron is removed, leaving a vacancy, an electron from
a higher energy level may fall into the vacancy, resulting in a release of energy.
Although most often this energy is released in the form of an emitted photon, the
energy can also be transferred to another electron, which is ejected from the atom;
this second ejected electron is called an Auger electron and the effect as Auger
effect. Energy of an Auger electron in above figurecan be written as,
EK-LI-ELII-III = EK – ELI- ELII-LIII
where EK, ELI and ELII-LIII are binding energies of electrons in K, LI and LII-III levels
respectively. Emissions of photons and Auger electrons are competing processes.
This is also used for elemental analysis.
Experimental setup-

Basic requirements of photoelectron and Auger spectroscopy are illustrated.

Except for the source of excitation, instrumentation required by both the
techniques is same. Photoelectrons and Auger electrons are analyzed in the same
analyzer. Electrons passing through them are selected according to their energies,
are detected and amplified using channeltron or channel plate. Amplified signal
after suitable noise filtering is an input for an X-Y recorder or a computer. An X-Y
plot or a spectrum of intensity versus electron kinetic/binding energy can be
obtained. One can make use of readily available data books to identify the
elements.
 3) Raman spectroscopy-
Raman effect- This is sensitive to the vibration spectrum of molecules. However, it
is complementary to the IR analysis. Unlike IR active molecules, Raman active
molecules do not depend upon the presence of a dipole moment but on the
polarizability of the molecule. Whenever scattering of the light occurs, the
scattered light consists of two types viz. Rayleigh scattering and Raman Scattering.
Rayleigh scattering is strong and has the same frequency (elastic scattering) as the
incident beam (ʋ0), and the other is called Raman scattering. Raman scattering is
inelastic scattering and has frequencies ʋ0± ʋm where ʋmis a vibrational frequency
of a molecule. The decreased frequency (ʋ0 -ʋm) and increased frequency ʋ0 -ʋm)
lines are called the Stokes and anti-Stokes lines, respectively.
Experimental setup-
A Raman spectrometer comprises four components which are: (1) excitation source
(laser), (2) sample illumination and collection system, (3) wavelength selector and
(4) detector and computer processing system. FT-Raman spectrometer is preferred
over the normal Raman spectrometer due to the advantage of measuring
information of all frequencies at the same time. The laser is incident on the sample
by means
of a lens and a parabolic mirror. The scattered light from the sample is collected
and passed to a beam splitter and to the moving and fixed mirrors in the
interferometer head. It is then passed through a series of filters and focused onto
a liquid-nitrogen cooled detector.

Figure: Schematic of FT-Raman spectrometer

4) Photoluminescence(PL) spectroscopy –
 Some materials when excited with an external source of stimulus like electrons
or light emit light in the visible range, UV or IR. This phenomenon is known as
luminescence. There are various types of luminescence like photoluminescence,
cathodoluminescence, electroluminescence and so on depending upon the
external stimulus used to excite the material. Luminescence investigations are
useful to analyze the electronic structure of the material. It not only gives
information about the transitions between conduction and valence band but
also the localized states due to impurities or doping.
Experimental setup-

Figure: schematic of PL setup

There has to be a source of photons ranging from UV (200 nm) to IR (800 nm), a
filter to throw away large band of wavelengths, wavelength selectors or
monochromators, sample holder, a detector and a recording system like an X-Y
recorder or a computer. Two types of arrangements viz. transmission type and
reflection type layouts are normally used. The transmission type of geometry is,
however, unsuitable for solid samples.

5) Electron Spin Resonance Spectroscopy(ESR)-

 Figure: Schematic of ESR setup
The principle of ESR is quite analogous to those of NMR.
Since the electron has an intrinsic magnetic moment µe = -gβeS
where g = 2.0023, βe = eh/4ᴨmc = 9.2741 × 10-24 J T-1 (Bohr
magneton), and S = ½. The first order Zeeman Effect splits the two m s states of the
unpaired electrons in a paramagnetic material. The resonance condition is
therefore hʋ = gβB. The klystronis the source of microwave radiation of “fixed”
frequency. The cavity is a hollow rectangular or cylindrical box, the dimensions of
which are matched to the wavelength of the microwaves so that the sample is held
in a region where the magnetic field component of the radiation is maximized and
the electric field is minimized. The spectrometer is tuned so that the waveguides
and cavity contain standing waves, and the detectorrecords a constant intensity.
When the magnetic field is swept to achieve the resonance condition, radiation is
absorbed by the sample, and a smalldecrease in radiation intensity should be
observed at the detector. Since it is much more efficient to detect an AC signal in
the presence of a large DC background, the magnetic field is modulated (typically
at 100 KHz) by means of coils embedded in the walls of the cavity.
Any sample that contains unpaired electrons can, in principle, yield an ESR
spectrum. g-values are determined by careful measurement of the frequency and
magnetic field, or more commonly by using a
reference of known g-value by ESR spectroscopy.