FT-Raman Spectroscopy

The Central Instrument Facilities houses the Nicolet FT-Raman

Spectrometer. The instrument comprises of 1064nm Nd:YVO4
excitation laser, XT-KBr beam splitter, He-Ne laser for sample
alignment, InGaAs detector and Computer for automated spectra
collection and analysis. The unit comprises of several sample holders,
which are routinely used for powders, thin films and liquids.
Capability for cryo-cooling and sample rotation are likely to be added
in the near future.
Raman Spectroscopy is a routine analytical technique used
extensively in semiconductor and pharmaceutical industry. Amongst it advantages are the ease of
sample preparation, non-destructive nature of the technique and rich information content. In
1928 Sir C.V.Raman showed that the radiation scattered by molecules, contain photons with
same frequency as the
incident photon, but may also
contain very small number of
photons with changed or
shifted
frequency.
The
frequency-shifted light is
known as Raman radiation.
Some of the Raman radiation
is slightly lower in frequency
than the incident radiation
and is called Stokes-shifted
radiation. Another portion of
the Raman radiation is higher
in frequency than the incident
radiation and is called antiStokes radiation. The exact characteristics of Raman radiation depend on the chemical
composition of the sample and every compound has unique spectral fingerprint. Since no two
molecules give exactly the same Raman spectrum and the intensity of the scattered light is
related to the amount of material present, it is easy to obtain both qualitative and quantitative
information about the sample. In Raman spectroscopy, monochromatic laser source excites the
molecules residing in the ground
vibrational and electronic state to a
virtual state, equal to the energy of the
laser. When the molecules relax back to
the ground vibrational state, giving
back the same energy. This is Rayleigh
scatter. The small portion that relaxes
to an upper vibrational state, giving off
less energy, is the Raman shift (also
known as Stokes shift). Unlike
quantized energy level transactions,

such as fluorescence or phosphorescence, the Raman scatter event involves virtual excited state
and the process is instantaneous. The energy resulting from this shift (initial laser energy minus
energy emitted) is equal to the same vibrational energy gap that is excited in infrared
spectroscopy. The vibrations that are strong in infrared spectrum, those involving strong dipole
moment, are usually weak in Raman spectrum. Similarly, non-polar functional group vibrations
that give very strong Raman bands usually result in weak infrared signals. The two
vibrational spectroscopy techniques are, in fact, complimentary. Raman spectrometers basically
employ one of the two techniques for the collection of spectra, Dispersive Raman and Fourier
Transform Raman
One of the important advantages of
the Fourier Transform (FT)-Raman
lies in the decreased likelihood of
sample fluorescence. By using the
longer wavelength excitation laser
(~1m) there is less energy supplied,
so the virtual state is lower and it is
less likely that it will overlap an upper
electronic state. This greatly reduces
fluorescence interferences, which can
mask the Raman signals. The FT-Raman spectroscopy uses an interferometer to produce an
interferogram, which encodes the unique frequencies of the Raman scattering into a single
signal. The signal is measured very quickly, making signal averaging fast and accurate. The
interferometer employs a beam splitter optimized for near-infrared (NIR) radiation, which
divides the incoming Raman scatter into two optical beams, one transmitted and one reflected.
The reflected beam travels to and reflects off of a flat fixed mirror. The transmitted beam travels
to and reflects of a flat moving mirror, which has a constant frequency and fixed motion. The
two beams recombine at the beam splitter. Depending on their path difference, the two beams
constructively and destructively interfere with each other. Constant frequency and fixed motion
of the moving mirror modulates the interference patter. The resulting interferogram has the
unique property that every data point (a function of the moving mirror position) has information
about every frequency of the Raman scatter collected from the sample.

Attenuated Total Reflectance (ATR) Kit for Infrared Sampling: Spectra tech
accessory for infrared sampling is available at CIF. It comprises of 45-degree
of incidence ZnSe crystal (flat and trough plates), liquid nitrogen cooled
MCT detector, mirror optics and computer for automated data
acquisition and analysis. It can be used for analyzing thin films,
powders and liquids. ATR is a surface technique, which requires
little or no sampling technique. It can be used for the
quantitative and qualitative analyses. The Spectra Tech
ATR has horizontal face-up sampling surface to allow
convenient sample handling of materials.

ATR
angle

When infrared radiation exits to air from a high refractive

index material, like ZnSe or Ge, it is partially reflected into the
material. If the angle of incidence of the incoming radiation is
sufficiently large it will be totally internally reflected. If a less
dense and partially transmitting sample is placed in contact
with ZnSe, the totally reflected radiation will be partially
absorbed by the sample. The attenuation of the internally
reflected radiation occurs from the penetration of the electromagnetic radiation field into the matter in contact with the reflection surface. N.J.Harrick (1965)
described this field as an evanescent wave. The depth of penetration (DP), effective penetration
(DP) and effective pathlength (EPL) can be calculated for the ZnSe crystal and the wavelength of
the IR radiation. For Spectratech ATR, the values are 2.0, 1.01 and 12.12 m respectively.
Grazing Angle Reflectance Accessory: Grazing Angle Reflectance (GAR) accessory is a fixed
angle surface analysis FT-IR sampling accessory. GAR
accessory (Harrick) provides a fixed angle of 75 degrees,
which is ideal for analyzing thin films on metal and
semiconductor substrates. In the Refractor, the optical
beam is deflected to and from the sample via wedged
ZnSe windows. This design results in a compact accessory
with optimal throughput. The two ZnSe windows are
SuperCharged, which nearly doubles the performance
of the Refractor. A single Brewster's angle silicon
polarizer plate is located below the sampling plane to
provide the required parallel polarization.
Diffuse reflectance
The diffuse reflectance configuration of the Gemini is highly effective at maximizing the
diffusely scattered radiation, while minimizing the specularly reflected component, a source of
spectral interference. High sensitivity and broad sample applicability make the technique
especially popular. To analyze a diffusely scattering sample, the HATR sampling plate is
removed and the diffuse reflectance body of the Gemini is placed on top of the base unit. It is
optimized for high throughput analysis of solid materials such as pharmaceuticals, metabolites,
powders, contaminants, unknown solids in a volatile solution, and any intractable sample that

can be abraded with silicon carbide paper. The

Gemini has a diffuse reflectance sample cartridge
that can be loaded with six macro or micro sampling
cups. Typically, one of the positions is loaded with
a reference material as the background. All six
positions can be efficiently loaded at once and
rotated into the proper sample position for analysis,
without disrupting the instrument purge. Each
macro cup holds approximately 0.3 grams of
sample, while the optional micro sampling cup
holds approximately 0.01 grams. Diffuse reflectance
spectroscopy offers exceptional versatility in sample
analysis. This versatility results from both its sensitivity and optical characteristics. Classically,
diffuse reflectance has been used to analyze powdered solids in a non-absorbing matrix of an
alkali halide, such as KBr or KCl. The sample is typically analyzed at low concentration,
permitting quantitative presentation of the data in Kubelka-Munk units.
Diffuse Reflectance Infrared Fourier Transform Spectroscopy offers a number of advantages as a
sample analysis technique, including minimal or no sample preparation, ability to analyze most
non-reflective materials, including highly opaque or weakly absorbing materials, applicability
across a wide range of sample concentrations, very high sensitivity down to low ppm levels,
ability to analyze irregular surfaces or coatings, suitability for very large, intractable samples
through the use of specialized sampling devices
When an infrared beam is focused onto a fine
particulate material, the incident beam can
interact with the particle in one of several
ways. First, true specular reflection that
involves reflection of the radiation off the top
surface of the particle at an angle of reflection
equal to the angle of incidence without
penetrating into the particle. This reflection is a
function of the refractive index and the
absorptivity of the material. Diffuse specular
reflectance is another mode of reflection, in
which, the light can undergo multiple
reflections off particle surfaces, all without
penetrating into the particle. After these multiple reflections, the resulting beam emerges from
the sample at a random angle relative to the incident beam. This reflection mode is again a
complex function of refractive index. The third mode of interaction, true diffuse reflectance,
results from the penetration of the incident radiation into one or more sample particles and
subsequent scatter from the sample matrix. The resulting radiation may emerge at any angle
relative to the incident radiation and since it has traveled through the particulates it now contains
information about the absorption characteristics of the sample material.