11/28/2014

NE 201 RAMAN SPECTROSCOPY

Rahul Singh Kotesa | PhD 2014

1. Introduction
Raman Spectroscopy is a spectroscopic technique that observes vibrational, rotational and
other low frequency nodes and is used to find the following information:-
Composition of the material - from characteristic Raman peaks
Crystal structure from the change of width of the peaks obtained
Mechanical properties like pressure, stress, strain, temperature from the change in
frequency of peaks obtained

It relies on Raman (inelastic scattering) scattering of monochromatic light, usually from a

laser. The laser light interacts with molecular vibrations, phonons or other excitations in the
system, resulting in the energy of the laser photons being shifted up or down. The shift in
energy gives information about the vibrational modes in the system.

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

Qk = Qk0 Cos (2kt)

Neglecting higher orders, polarizability can be expanded as

Now the dipole moment can be written as,

We can observe that the output has the frequency components: 0, 0 k, 0+ k. Out of
these, 0 k, 0+ k components are used for analyzing the samples. Signals corresponding to
0 k are called stokes and that of 0+ k are called anti stokes lines. These can be obtained by
using appropriate filters.

Fig.1: Energy Diagram of Stokes and Anti Stokes Raman Scattering

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.

Fig.2: Absorption and Emission spectra with Stokes shift

2. Instrument used
The instrument used for lab session is Horiba Jobinyvon make and LabRAM HR model. The
instrument can be used for both Raman and photo luminescence (PL). The signal flow/block
diagram of the instrument is shown below:

Confocal Monochromat Spectrum

Laser Filter Sample Edge Filter Slit Detector
System or + Grator Normalization

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:

D0.03 > P/2

D0.06 > P/4
D1 > P/10
D2 > P/102
D3 > P/103
D4 > P/104

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.

The applications of this instrument are:

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

Experiment II: Obtain the photoluminescance measurement of ZnO sample

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

Raman spectra have four parts:-

a) upto 400 cm-1 phonon interaction
b) 400-1000-1 cm gives information about the composition of the molecule
c) 1000- 2500 -1 cm gives information about the double or triple bond
d) after 2500 -1 cm fives information about the functional groups.

Experiment IV: Analysis of samples containing Rhodamine with gold nanoparticles

Rodamine is highly fluorescent sample. So we will not obtain any peaks. So inorder to obtain the
Raman spectra we need to go for Surface Enhanced Raman Scattering where the gold or silver
nanoparticles are grown or sputtered on the sample. Gold and silver nanoparticles use their property
of Surface Plasmon Resonance which makes the sample fit for Raman scattering. This property is
highly useful for biosamples.