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When light, an electromagnetic wave is incident on a material, scattering takes place. Raman
scattering is an inelastic scattering phenomenon where the frequency of scattered light is
different from incident light frequency. Because of the electric field component in the
incident light electric dipole is formed in the sample. This resulting dipole moment is given
by,
p = E where is the polarizability of the sample and E is the electric field given by
E = E0 Cos (20t)
The polarizability depends on the vibrations that exist in the sample system given by
When a system (be it a molecule or atom) absorbs a photon, it gains energy and enters an
excited state. One way for the system to relax is to emit a photon, thus losing its energy
(another method would be the loss of heat energy). When the emitted photon has less energy
than the absorbed photon, this energy difference is the Stokes shift. If the emitted photon has
more energy, the energy difference is called an anti-Stokes shift; this extra energy comes
from dissipation of thermal phonons in a crystal lattice, cooling the crystal in the process.
The instrument has provision for two lasers 514.5 nm and 325 nm. Two different filters are
used for two lasers. Also a neutral filter is used to reduce intensity of the laser used in order
not to damage the samples. There are different modes in the usage of neutral filter which
reduce the power level by different amount. They are:
In the confocal system, the size of the hole can be varied from 53 m to 1000 m. But it is
generally fixed to 100 m during experiment. The confocality is approximately 4 m.
Different lenses of varied magnification are attached to the setup. They are to be selected
based on the sample and the working distance needed for the sample.
Regarding samples, powdered and thin film samples can be used as it is. But if the samples
are volatile, then a cover ship is used to preserve the sample. The sample stage is motorized
and controlled by a stepper motor. Stage motion control is possible in all x, y, z directions but
z movement is generally not used. The resolution is 100 nm.
The edge filter used is a LPF. So we can see only stokes lines. The practical limit of this filter
is:
Min: 50 cm1
Max: 4000 cm1
The slit size determines the resolution of measurement. The slit size here is fixed to 500 m.
Also two detectors are used for different scan ranges. CCD detector scans from 190 1000
nm and InGaAs detector scans from 800 1700 nm thus covering UV, visible and NIR
regions. The resolution of CCD detector is 0.3 cm1 at 514 nm and its working temperature is
70 oC. The resolution of InGaAs detector is 1 nm and its working temperature is 30 oC. Also
the InGaAs detector is not used for Raman analysis but is used in PL analysis.
3. Procedure
Place sample on the sample stage.
Turn ON halogen lamp.
Switch to video mode.
LabSpec software is initialized.
Enable video, use joystick to position the sample and focus properly.
Put it to higher magnification and switch to Raman mode.
Adjust power level of the laser being used. The beam diameter at source is ~2mm.
Acquire the data:
o Real time display (RTD) to focus the sample.
o PIGRUN actual data is acquired using this
Remove shutter to pass laser light.
Select window size and set proper values for acquisition (RTD) time, pigrun time and
accumulation number.
After measurements are done, close shutter to prevent laser into the system.
Stress analysis, phase study as a function of different parameters like pressure etc, structural
studies, concentration of solute in a solvent, particle size using PL, band gap determination.
4. Measurements
Experiment I: To find whether the given two Carbon Samples are crystalline or
amorphous
Raman Spectra of the Amorphous Carbon Raman Spectra of the Crystalline Carbon
By PL measurement we can find the band gap of semiconductors. We can find the wavelength from
the graph and calculate the energy band gap using E= (hc)/ . The semiconductors have a valence and
conduction band separated by an energy gap. When a photon of energy greater than the energy gap is
impinged on the semiconductor, electrons can be excited to the conduction band. These electrons
relax to the edge of the conduction band through non-radiative losses (like transferring heat to crystals
phonons). From the edge of the conduction band to the valence band, the electrons fall emitting a
radiation (photon) of frequency corresponding to the energy gap of the semiconductor. A
semiconductor depending on its band structure can have more than one peak in its PL spectrum.
Experiment III: To study the Raman Spectra of Polypropylene