CHM1488 – Raman Spectroscopy

Introduction:
Raman spectroscopy is a very useful material characterization method. It is based on the
Raman scattering effect, discovered in the early 20th century by Raman. The Raman
scattering is a form of inelastic scattering. Photons are incident into the material at one
energy, but emerge at slightly different energies (or wavelengths), due to inelastic
scattering. In reality, the photons change their energy by exchanging some energy with
molecular vibrations of the material. The scattered photon can either release a quantum of
vibrational energy, and emerge at a lower energy (longer wavelength), or it can absorb a
quantum of vibrational energy, and emerge at a higher energy (shorter wavelength).
Vibrational modes have relatively low energies (corresponding to mid-IR or far-IR light
wavelengths).

The advantage of Raman spectroscopy is that it allows us to probe these low energy
modes, without having to use light at these wavelengths. We can probe all these modes
with one single visible wavelength, which is by far easier to use. Most materials have
very characteristic signatures in the mid-IR and far-IR. Being able to investigate these
signatures is a very useful tool in determining the constituents of an unknown material, as
well as the different bonds available. This can all be done in a non-destructive manner.

Equipment and setup:

We will be setting up a confocal Raman spectrometer using a green 532 nm laser, a
monochromator, a photomultiplier tube, a long-pass filter and a few lenses and mirrors.

Photomultiplier tube (PMT) safety and descriptions

Because the Raman effect is quite weak (roughly only one photon in a million undergoes
Raman scattering) we need a very sensitive light detector. Photomultiplier tubes are
among the most sensitive detectors available, being able to detect single photons. Their
sensitivity comes from the fact that they can multiply the generated electrons, producing
a few million electrons for each incoming photon. In order to achieve this, they operate
with very high voltages, up to about 2000 V. PMTs are very delicate, very expensive
and very easily damaged. They are damaged irreversibly if exposed to too much light
while under high voltage. We must always keep light levels low enough, to make sure
that the PMT current never exceeds 100 nA. If connected to an oscilloscope, this means
that the maximum reading on the oscilloscope should never exceed 100 mV. The
following are some procedures that should avoid accidents:
• Program the monochromator shutter to block the laser wavelength from entering
the PMT (shutter is described below)
• Perform all alignments with the high voltage off and the monochromator input slit
closed all the way (described below)
• Once everything is aligned, cover the monochromator input with a card turn on
the high voltage
 • Look at the oscilloscope signal and make sure it doesn’t exceed 100 mV, while
removing the card and opening the slits.

Monochromator description
The monochromator acts like a very high resolution tunable optical filter. It has an input
slit and an output slit. It only passes a single wavelength from input to output, and this
wavelength can be tuned. The monochromator uses a grating internally, to make sure that
only one wavelength is diffracted from the input to the output. All other wavelengths are
diffracted elsewhere, in other directions and do not exit the instrument. The
monochromator used here is a very high-quality instrument, with two gratings, to reject
all unwanted wavelengths even more strongly.
The most important elements of the monochromator are:
• The gratings, which are moved by the controlling computer.
• The input and output slits. The width of the slits determines the resolution of the
monochromator, wider slits allow more wavelengths to pass from input to output,
while narrower slits select a single wavelength even more precisely.
• An automatic shutter, meant to protect the PMT. This shutter closes automatically
when the monocrhomator tunes to wavelengths near the laser wavelength. This is
in order to prevent the bright laser light to reach the PMT

Monochromator configuration:
When starting up, the monochromator displays the initial configuration screen. It asks the
following questions:
• Current monochromator position:
o Enter the number you read on the side of the monochromator
• Laser wavelength
o Enter our laser wavelength in wavenumbers (18797 WN)
• Shutter low and high
o This defines the range of wavelengths over which the shutter should open.
The numbers are relative to the laser wavelength. A safe set of numbers is
200 WN to 5000 WN. This means the shutter closes when you get to
within 200 WN of the laser wavelength.
• PMT voltage
o 1500 V is a good start

General setup notes:

• Assemble your setup on the breadboard in front of the monochromator input.
• We want to set up a confocal system, which means the pump laser is focused by
the same lens that also collects the Raman signal. Use the small (0.5 inch) lens for
this purpose.
• In the confocal system we need to separated the pump from the signal somewhere
between the small lens and the monochromator input. You have available a long-
pass filter for this purpose. The filter passess all wavelengths > 550 nm, and
reflects shorter wavelengths. In order for the filter to be effective, however, it
must be nearly perpendicular to the input beam.
 • Start with a small piece of silicon as your sample, because it reflects light well.
Later you can replace it with other samples.
• Using the filter we can proceed as follow:
1. Start with the laser
2. Add two mirrors to give you control over the beam direction
3. Send the laser beam into the filter at almost 90 degrees
4. The reflected laser beam gets focused by the small lens onto your sample
5. From the sample, the light is picked up by the same lens
6. It goes through the filter
7. After the filter it gets focused onto the monocrhomator input by a lens
with 7 cm focal length
• Alignment hints
1. Start without any lenses, and get the reflected beam from the sample to
overlap with the incoming beam and to go straight to the monochromator
input
2. Then add the 0.5 inch lens, and make sure the output light is collimated.
3. Then add the focusing lens in front of the monochromator and focus the
light on the centre of the monochromator slit.

Samples and Data:

Take Raman spectra for silicon, sulfur and benzene over the range from 400 WN to 5000
WN. Since it’s not possible to plot directly on paper, make a note of the significant
Raman peaks in each one of the materials. You may need to zoom in on certain regions of
the spectrum to capture the correct position and linewidth of the Raman features. Change
the resolution of the spectrometer by changing the slit widths, and estimate the resolution
for different slit widths.