IR Spectrometers
RA Spragg, PerkinElmer Life and Analytical Sciences, Bucks, UK
ã 2017 Elsevier Ltd. All rights reserved.
Abbreviations
ADC analog-to-digital converter
ATR attenuated total reflection
DTGS deuterated triglycine sulfate
FFT fast Fourier transform
FIR far IR
Introduction
Over the past 30 years, Fourier transform IR (FT-IR) spectrom-
eters have almost entirely replaced dispersive instruments. The
most significant feature of FT spectrometers is that radiation
from all wavelengths is measured simultaneously. This is much
more efficient than the dispersive spectrometer where different
wavelengths are measured successively. This difference, known
as the Fellgett advantage, leads to much faster or more sensitive
measurement. For example, a dispersive spectrometer typically
takes at least 3 min to scan from 4000 to 400 cm
1, whereas
most FT instruments can acquire a spectrum in 1 s or less. The
first commercial mid-IR FT spectrometer was introduced in
1969, but initially, the cost of the necessary computing power
confined the use of such instruments to research applications.
More recently, FT-IR spectrometers have become less expensive
in real terms than the dispersive instruments that they have
replaced. As this article will deal with instruments that are
capable of recording complete spectra, it will not consider
laser-based measurements.
The IR Region
The IR region covers wavelengths from approximately 800 nm
to 1 mm. However, spectroscopists generally divide this region
into three: near IR (NIR), from the visible to 2.5 mm; mid IR,
from 2.5 to 25 mm; and far IR (FIR), beyond 25 mm (Figure 1).
The main significance of this division is that most fundamental
molecular vibrations occur in the mid IR, making this region
the richest in chemical information. The NIR region contains
overtones and combinations of the fundamental vibrations,
especially those involving hydrogen atoms. Some electronic
absorptions are also found in this region. The FIR region is
Wavelength (μm)
0.8 2.5 25
Near IR Mid IR Far IR
12 500 4000 400
Wavenumber (cm−1)
Figure 1 The divisions of the IR region.
Encyclopedia of Spectroscopy and Spectrometry, Third Edition
FT Fourier transform
FT-IR Fourier transform IR
MCT mercury cadmium telluride
NIR near IR
OPD optical path difference
mostly of interest for vibrations involving heavy atoms, lattice
modes of solids, and some rotational absorptions of small
molecules.
This article will concentrate on the mid-IR region, which
covers the widest range of applications. However, it is worth
noting that interest in the NIR region has increased steadily in
recent years.
Dispersive IR Spectrometers
The principle of operation of a dispersive spectrometer is very
simple. A beam from a broadband source of radiation is dis-
persed by a prism or grating. The dispersed radiation falls on a
slit through which a narrow range of wavelengths passes to
reach a detector. Rotating the prism or grating brings successive
wavelengths onto the slit, so scanning the spectrum. For the
mid IR, the source is a ceramic rod or wire heated to around
1300 K. In practice, instruments use one or more gratings to
cover the mid-IR region with filters to separate different orders
of diffraction. The most common detector used to be a ther-
mocouple, but the few current models use deuterated triglycine
sulfate (DTGS) detectors. Instruments operate in a double-
beam mode (Figure 2), switching rapidly between two equiv-
alent optical paths, one of which contains the sample. The
transmission of the sample is measured from the ratio between
the detector signals from the two beams directly (ratio record-
ing) or by moving an attenuator into the reference beam until
the detector signal matches that through the sample.
Fourier Transform Spectrometers
Most commercial FT spectrometers are based on the Michelson
interferometer (Figure 3). A collimated beam of radiation falls
on a beam splitter that divides it into two beams with approx-
imately equal intensities. These two beams strike mirrors that
500
return them to the beam splitter where they recombine, creat-
ing interference, and then proceed to a detector. Moving one of
200 the mirrors creates a varying optical path difference (OPD)
between the two beams. As the path difference changes, the
two beams move in and out of phase with each other, so that
there is alternating constructive and destructive interference.
http://dx.doi.org/10.1016/B978-0-12-803224-4.00088-1 419
420 IR Spectrometers

Grating

Slits

Detector

Reference beam

Source

Sample

Sector mirror
Sample beam
Figure 2 The optical arrangement of a double-beam dispersive IR spectrometer.

Fixed mirror
Detector
signal
Coated surface
Fourier transform

cm−1
Source Path difference

Figure 5 The interferogram from a broadband source and the

Beam splitter corresponding spectrum.
Compensator plate
Scanning mirror

Detector Scanning mirror

Figure 3 The basic optics of a Michelson interferometer. Collimating

mirror
Fixed
mirror

Laser detector
Source
Detector
Laser

Sample

Figure 6 The optical arrangement of an FT-IR spectrometer.

0 0
Individual cosine waves Sum of cosines
Figure 4 The interference of overlapping cosine waves.
Monochromatic radiation produces a sinusoidal signal, the
frequency of which is directly proportional to the wavenumber.
The signal from a broadband source consists of a combination
of overlapping sinusoidal signals, called an interferogram. A
typical interferogram has a strong signal, called the centerburst,
at the point where the paths of the two beams are equal, and
decays as the path difference increases (Figure 4). The interfer-
ogram can be converted into the required spectrum of intensi-
ties at different wavenumbers by an FT (Figure 5).
Unlike dispersive spectrometers, FT instruments operate in
a single-beam mode (Figure 6). The sample is normally placed
between the interferometer and the detector, in contrast to the
arrangement in dispersive spectrometers, where the sample is

placed between the source and the monochromator. Two spec-
tra are recorded, first of the instrument alone and then with the
sample in place. The ratio of these, calculated automatically, is
the transmission spectrum of the sample (Figure 7).
Range and Resolution in FT-IR Spectrometers
The detector in an FT spectrometer sees a range of frequencies
that is limited by the output of the source and the transmission
of the optics. The interferogram is digitized before the Fourier
transformation. The range of frequencies that can be identified
in the Fourier analysis depends on the spacing of the data points
in the digitized signal. There must be at least two data points for
each cycle of the highest frequency in the analysis. This is
known as the Nyquist criterion. If there are fewer than two
data points per cycle, the signal is indistinguishable from that
of another, lower frequency, a phenomenon known as aliasing.
Optical or electrical filtering is therefore needed to remove any
frequencies that are above the Nyquist limit (Figure 8).
Instrument profile
Instrument + sample
Ratio
4000 3000 2000 1000
cm−1
Figure 7 Single-beam spectra and the resulting sample spectrum.
Sampling points
Undersampled signal, <2 points/cycle
Apparent frequency
Figure 8 A signal sampled at less than two points per cycle and a lower frequency with identical values at the sampling points.
IR Spectrometers 421
The resolution in the spectrum depends on the spacing of
the frequencies provided by the FT. This is determined by the
length of the interferogram. The frequencies used in an FT are
such that an exact number of cycles fit the length of the inter-
ferogram from zero to the maximum OPD, D (in centimeters).
Two adjacent frequencies in the analysis, corresponding to
wavenumbers n1 and n2, have n and (nþ1) cycles in this length.
The wavenumbers are given by:
n1 ¼ n=D and n2 ¼ ðn þ 1Þ=D
From this, it follows that the difference between the wave
numbers is:
n2
n1 ¼ 1=D
Thus the spectrum generated by the FT contains wave numbers
separated by the inverse of the maximum path difference in
centimeters. Instruments for routine analytical work typically
have highest resolution of 1 or 0.5 cm
1, requiring a maximum
path difference of 1 or 2 cm. This resolution is constant across
the spectrum. Research instruments have been built with reso-
lutions as high as 0.0009 cm
1, which requires a path differ-
ence in excess of 10 m.
In a practical instrument, the beam passing through the
interferometer cannot be perfectly parallel. There are rays at
different angles, and these experience different changes in the
pathlength for a given displacement of the moving mirror. This
causes line broadening by an amount that is proportional to
the wavenumber. The range of angles admitted to the interfer-
ometer has to be restricted so that the required resolution is
achieved. Incorporating an aperture, called a Jacquinot stop, at
an appropriate point in the optical system controls this. In
some ways, this aperture is analogous to the slit in a dispersive
spectrometer. For a given resolution, the optical throughput of
an FT spectrometer, limited by a circular aperture, can be
higher than that of a dispersive spectrometer with a rectangular
slit. This is referred to as the Jacquinot advantage and contrib-
utes to the higher sensitivity of FT instruments. The size of this
aperture depends on the resolution and the wave number
range. Lowering the resolution by a factor of two allows
the energy reaching the detector to be doubled. However,
422 IR Spectrometers

in most spectrometers, it is not possible to increase the
energy above that permitted for 4 cm
1 resolution because of
other limitations such as the range of the analog-to-digital
converter (ADC).
Measuring the Interferogram
To establish the wavelength scale of the spectrometer, the
interferogram has to be measured at precisely known intervals
of the path difference. Generally, this is achieved by using a
helium–neon laser at 0.6328 mm (15 800 cm
1) to provide a
reference signal. The laser radiation passes through the inter-
ferometer to a separate detector. This produces a sinusoidal
signal with a period equal to the wavelength of the laser
(Figure 9). Typically, the interferogram signal is measured at
each point where the laser signal passes through zero. With this
spacing of the data points in the interferogram, all wave num-
bers below 15 800 cm
1 can be distinguished. The laser wave-
length is known very accurately and is very stable. As a result,
the wavelength scale of FT spectrometers is much more accu-
rate than that of dispersive instruments. This superiority is
known as the Connes advantage, after the originator of the
laser referencing technique. The absolute accuracy of the scale
depends on the spectrometer resolution, whereas the scan-to-
scan precision is of the order of 0.01 cm
1. Semiconductor
diode lasers have recently been used to build very compact
FT-IR instruments. They lack the absolute wavelength stability
of helium–neon lasers but can achieve scan-to-scan precision
of 0.1 cm
1, which is adequate for many applications.
The data points in the interferogram generally correspond
to the path differences at which the signal from the laser
passes through zero. In earlier instruments, analog electronics
detected when this happened and triggered an ADC to collect
the IR signal. More recently, all-digital systems have adopted
ADCs developed for consumer audio and video products. They
cannot be triggered but have superior linearity and 24-bit
resolution, which significantly reduces noise and improves
ordinate accuracy. There are two synchronized ADCs: one for
the laser and one for the IR signal. The sinusoidal laser signal is
measured many times each cycle, so the zero-crossing points
can be determined very accurately by curve fitting. The digi-
tized IR signal is then interpolated to find the value at these
points (see Figure 9).
The time taken for an interferometer to scan from zero to
the maximum path difference is typically of the order of 1 s. For
most routine measurements, the interferogram signal is aver-
aged over several scans to reduce random noise that is largely
generated by the detector. By averaging N scans, the noise level
in the final spectrum can be reduced by a factor of N1/2 relative
to that from a single scan. For the signal averaging to work
properly, the interferogram must be digitized with sufficient
precision to record the noise in a single scan. The ADC must be
able to handle the very large centerburst and the much smaller
noise component. The precision needed for this is at least
16 bits.
In an ideal interferometer, the complete spectral informa-
tion could be obtained by scanning the path difference from
zero to the value needed to achieve the required resolution.
However, data have to be measured for a limited distance on
both sides of the nominal point of zero path difference to carry
out phase correction. For signal averaging, the data points
corresponding to the same path difference for successive
scans have to be combined. The laser signal measures changes
in the path difference but not its absolute value. In early FT

Laser X X
Zero crossing by fitting
X X

X X

X X
X
X
X X
X X X

Measured points

X X X X X X
X
X Interpolated interferogram point
X
X
IR X
X
X
X
X
X

Path difference
Figure 9 Locating the laser signal zero crossings by curve fitting and calculating the interferogram points by interpolation.
 IR Spectrometers 423

instruments, this was measured by including a broadband
white-light source, the interferogram from which is a very
sharp spike at zero path difference (Figure 10). The optics
were arranged so that zero path difference for the white light
was offset from that for the IR radiation. The white-light signal
was used to trigger data collection. The interferometer scans in
one direction and collects a complete interferogram on one
side of zero path difference only. After each scan, the interfer-
ometer would move back past the starting position to begin the
next scan. Such a scheme is described as unidirectional single-
sided scanning (Figure 11). It was necessary to trigger each scan
separately because the path difference could not be tracked
through the change of direction at the end of the scan. Most
systems now use two detectors with a phase shift between them
to monitor the laser signal, allowing forward and reverse
motion to be distinguished. This quadrature detection arrange-
ment can continuously track the path difference and so control
the coaddition of successive scans without individual trigger-
ing. It also allows the interferometer to collect data from scans
in both directions. This bidirectional scanning achieves more
efficient data collection as there is no fly-back period between
scans.
Processing the Interferogram Signal
The signal processing to convert the interferogram into a spec-
trum usually involves phase correction, zero-filling, and apo-
dization as well as the FT. An ideal interferogram would be

IR signal

Data collection

White-light signal

Laser

Mirror movement
Figure 10 The use of a white-light interferogram to trigger data collection.

Single-sided, unidirectional Double-sided, bidirectional

Detector
signal

Time Time

0
Path
difference

0 −Δ
Time Time
Figure 11 Alternative scanning and data collection schemes.
424 IR Spectrometers
perfectly symmetrical about zero path difference. However, in
practice, there is some asymmetry because of phase differences
between the signals from different wavenumbers. A phase
correction routine is applied before the FT. Phase correction
can be avoided by scanning the full length of the interferogram
on both sides of zero path difference. This allows a magnitude
spectrum to be calculated without phase correction. The FT
itself uses the fast Fourier transform (FFT) algorithm devised
by Cooley and Tukey. This algorithm requires that the number
of points to be transformed be equal to a power of two.
However, the number of data points collected by scanning to
a path difference of 1 cm, for example, does not correspond to
a power of two. The interferogram is therefore extended by
additional data points with the value of zero to give the
required number of points. This process is called zero-filling.
It is a common practice to apply further zero-filling to double
or quadruple the number of points used. This improves the
appearance of the final spectrum by increasing the density of
the data points, although it does not improve the resolution. In
some systems, interpolation in the spectrum is used to give
results that are equivalent to the additional zero-filling.
Apodization is an operation that is necessary because of the
finite length of the interferogram. Monochromatic radiation
produces a sinusoidal interferogram, but the length of this is
limited by the maximum path difference in the interferometer
scan. The FT of such a signal is a line of finite width with
oscillations on either side. This line has the form of a sinc
function (sin x/x) (Figure 12). The oscillations (or sidelobes)
that accompany each line are obviously a problem because
they could obscure smaller features in the spectrum. They can
be reduced at the expense of some broadening of the lines by
multiplying the interferogram with a function that decreases
with increasing path difference. This process is called apodiza-
tion. Various functions are used for this, representing different
compromises between line broadening and the reduction of the
sidelobes. Historically, a simple triangular function was often
used, but other functions can reduce the sidelobes further with
less broadening. By examining a very large number of alterna-
tive functions, Norton and Beer established empirical limits for
the reduction in sidelobe intensity that could be achieved for a
given increase in linewidth. Three functions identified by
Intensity
Sidelobe
Wavenumber
Figure 12 The sinc function generated by Fourier transformation of a
cosine wave of finite length.
Norton and Beer are in common use: weak, medium, and
strong, corresponding to increasing degrees of sidelobe reduc-
tion and line broadening (Figure 13). The use of no apodiza-
tion to achieve the narrowest possible lines is called boxcar
truncation.
Scanning Mechanisms
To create interference, the beams returned from the two mir-
rors in the interferometer must overlap exactly as they meet at
the beam splitter. Any change in the alignment of the mirrors
reduces the efficiency of the interference by an amount that
increases with the square of the wave number. Small mechan-
ical changes, for example, associated with thermal expansion,
can cause the alignment to change slowly. Changes that occur
between measuring the background and sample spectra result
in a curved baseline (Figure 14).
The scanning mechanisms of interferometers have to be
designed to minimize any change in alignment during the
scan that would introduce noise or distortion into the spec-
trum. In systems where a plane mirror moves linearly, the
problem is to avoid any tilting of the moving mirror. In some
spectrometers, the alignment is monitored and corrected con-
tinuously in a process called dynamic alignment. Multiple
detectors measure the laser reference signal from different
points in the beam. Any mirror tilt introduces a phase shift
between the signals from the detectors because the path differ-
ences are not equal. This is automatically corrected in real time
Boxcar Triangular
N−B strong
N−B weak
N−B medium Raised cosine
Figure 13 Some common apodization functions and the resulting
lineshapes.
105
100
%T
95
90
85
4000 3000 2000 1000
cm−1
Figure 14 A parabolic baseline caused by misalignment of the
interferometer.

by using piezoelectric transducers to tilt the nonscanning mir-
ror. The problem can also be addressed by using a cube-corner
reflector instead of a plane mirror. Tilting the cube corner does
not alter the direction of the reflected radiation, but lateral
movement would affect the alignment. There are also scanning
arrangements that completely avoid alignment errors during
scanning. One of the simplest generates the path difference by
rotating a pair of parallel mirrors in one arm of the interfer-
ometer (Figure 15). The mirror pair does not alter the direction
of radiation passing through it, whatever its orientation, so that
it cannot affect the alignment as it rotates.
Some commercial instruments use a scanning mechanism
that does not involve moving mirrors. Changing the refractive
index instead of the physical length can alter the optical path. By
moving a wedge of a material such as KBr into one arm of an
interferometer and displacing air, the optical path is increased.
Because the mechanical tolerances are less severe than for sim-
ple moving mirror systems, these instruments are mostly used in
nonlaboratory applications. One disadvantage is that the refrac-
tive index varies with wavelength so that the wavenumber scale
is not inherently linear as it is in conventional instruments.
The range covered by a spectrometer depends primarily on
the properties of the source and the beam splitter, and is
sometimes limited by the detector. The sources used in mid-
IR spectrometers typically operate at temperatures around
1300 K. Their output has a fairly similar profile to a black
body and so provides significant energy across the entire mid-
IR region. An ideal beam splitter would provide uniform reflec-
tivity of 50% and no absorption across the region of interest. In
practice, a single beam splitter made from KBr with a multi-
layer coating can be used from the NIR to approximately
400 cm
1, where KBr absorbs strongly. Most interferometer
designs incorporate a compensator plate so that both beams
pass through the same thickness of KBr. An FT spectrometer
can cover the entire mid-IR region in a single measurement. As
can be seen from Figure 16, the single-beam energy falls off
toward the ends of the range. In consequence, the noise level in
the final spectrum increases at either end.
Detectors
For routine measurements, the most common detector mate-
rial is DTGS. This is a thermal detector, the signal being
Variable path
Fixed path
Out
Rotating mirror
pair
Beam splitter
In
Figure 15 A scanning mechanism with a rotating mirror pair.
IR Spectrometers 425
generated in response to the change in temperature caused by
absorption of the IR radiation. It is generally operated at a
temperature close to ambient. The response time of these detec-
tors is less than 1 ms, allowing them to follow changes occur-
ring at rates up to several kilohertz. In spectrometers with DTGS
detectors, the OPD is typically scanned at approximately
0.3 cm s
1 because faster scanning would reduce the response
of the detector. The time taken to scan the 0.25 cm needed for a
spectrum at 4 cm
1 resolution is therefore approximately 1 s.
Lithium tantalate is an alternative room-temperature detector
material with somewhat lower performance but also lower cost.
When higher speed or sensitivity is needed, liquid nitrogen-
cooled MCT (mercury cadmium telluride) detectors are used.
These are photon detectors in which electrons are excited
directly by the absorption of radiation. Cooling to liquid nitro-
gen temperature is needed to avoid excitation of electrons by
thermal motion. These detectors do not cover the complete IR
range because there is a minimum energy needed to excite an
electron, corresponding to a long wavelength limit. Changing
the composition can vary this limit, but extending the range
reduces the sensitivity. The highest sensitivity is obtained with
narrowband detectors, which have a limit of approximately
750 cm
1, whereas wideband detectors reach 450 cm
1, close
to the limit for KBr optics. Scan rates are not limited by the
detector response, and indeed, the detector performance
improves as the scan rate is increased. This allows data to be
acquired at rates up to 100 scans per second in commercial
instruments. The response of MCT detectors is inherently non-
linear (Figure 17). This restricts their use to low signal levels,
typically less than 10% of the energy available. However, this is
not a problem in applications where the signal level is
restricted, such as microscopy. Because of the nonlinearity,
the centerburst signal is compressed relative to the rest of the
interferogram. After Fourier transformation, the primary con-
sequence is an offset in transmission, so that totally absorbing
bands do not appear at zero. The presence of nonlinearity can
be detected by examining the single-beam signal in the region
beyond the long wavelength limit of the detector. Any non-
linearity causes this signal to be nonzero. Various methods,
both in electronics and in software, have been employed to
minimize the effects of nonlinearity. None of these is entirely
successful. For this reason, room-temperature detectors are
preferred for quantitative measurements.
Relative noise
Energy
4000 3000 2000 1500 1000 400
cm−1
Figure 16 The instrument profile for a mid-IR spectrometer and the
resulting variation of the noise level.
426 IR Spectrometers

The combinations of components found in use for the three
regions are summarized in Table 1.
Step-Scan Instruments
In most spectrometers, the path difference is scanned continu-
ously, but in recent years, so-called step-scan instruments have
become important for some research applications. In these
instruments, the path difference is held constant at one point,
whereas the interferogram signal is measured before being
moved to the next point. The IR signal has to be modulated
to match the frequency response of the detector. This is
achieved by applying a small amplitude oscillation to the
fixed mirror. In practice, a constant path difference can be
maintained either by moving the two mirrors synchronously
or by holding both stationary. Step-scan instruments can
address a much wider range of dynamic measurements than
continuously scanning systems because the signal modulation
frequencies are not restricted by the velocity of the moving
mirror (Figure 18).
The principal applications have been to very rapid kinetics
and photoacoustic spectroscopy. The kinetic applications
involve processes that are repeated for each step of the path
difference. The signal can be measured at time intervals lim-
ited only by the detector response and electronics. At each
path difference, measurements are made at the same times
after initiation of the process. The data are then reshuffled to
create a series of interferograms in which each point was
measured at the same time in the process. This approach has
allowed FT-IR measurements to reach the nanosecond time-
scale. In photoacoustic spectroscopy, there are advantages
because the modulation frequency is constant across the spec-
trum, making it feasible to measure the spectra of subsurface
layers.
Linear
Nonlinear
Energy
Commercial Instruments
Present-day commercial laboratory spectrometers can be
grouped into those intended for routine measurements and
research instruments. In general, the routine instruments are
designed to simplify operation, whereas research instruments
aim to offer versatility. In virtually all cases, the instrument is
controlled by a personal computer that handles an increasing
amount of the digital signal processing in the system. There are
also instruments with an integrated microscope that are used
for very small samples or imaging. However, more commonly,
microscopes are seen as accessories to normal spectrometers.
Recent years have seen the introduction of a number of more
compact and robust spectrometers for field or process
applications.
A typical routine mid-IR spectrometer has KBr optics, with a
best resolution of around 1 cm
1, and a room-temperature
DTGS detector. Noise levels below 0.1% T, peak to peak, can
be achieved in a few seconds. To reduce the problem of fluctuat-
ing levels of atmospheric water vapor and carbon dioxide, much
of the optical path is sealed and desiccated. The sample compart-
ment will accommodate a variety of sampling accessories such as
those for ATR (attenuated total reflection) and diffuse reflection.
In most cases, the output from the interferometer can be directed
through an external port, principally for coupling to an IR micro-
scope. Other external accessories provide coupling to a gas chro-
matograph or thermogravimetric analyzer. These instruments
often have versions for NIR operation in which the source,
beam splitter, and detector are different.
Research spectrometers are generally larger, permitting
higher optical throughput and hence better signal-to-noise
performance and higher resolution. There may be multiple
external ports for the interferometer output so that several
experiments can be installed simultaneously. The major com-
ponents – source, beam splitter, and detector – are generally
exchangeable, so that a wide spectral range can be covered. A
common arrangement is to have alternative sources and detec-
tors permanently installed and selectable by switching mirrors.
Different ranges can then be selected simply by changing
the beam splitter. For FIR operation, the beam splitters are

Continuous scan Step scan

Path difference

Detector cutoff
700 cm−1 Nonzero
signal

4000.0 3000 2000 1500 1000 500 100.0

cm−1
Time Time
Figure 17 The instrument response with a cooled detector showing
nonlinearity. Figure 18 The difference between continuous and step scanning.

Table 1 Combinations of components found in use for mid-IR, near-IR, and far-IR regions

Range (cm
1) Source Beam splitter Detector

Mid IR 7000–400 Ceramic, wire, SiC KBr, ZnSe DTGS, LiTa, MCT, InSb
Near IR 15 000–4000 Tungsten halogen CaF2, quartz DTGS, PbS, InGaAs, InSb
Far IR 400–20 Ceramic, wire, mercury arc Mylar, wire grid, CsI (>200 cm
1) DTGS, Si

generally Mylar films, which have a narrow range, or metal
grids on a polymer substrate. Cooled silicon bolometers are the
detectors of choice for high resolution and sensitivity. Some
instruments have a vacuum version that removes the very
strong water absorption in this region, allowing measurement
out to 5 cm
1. Although there have been relatively few reported
applications, some spectrometers are also capable of measur-
ing throughout the visible region.
The range of scan speeds is greater than in routine instru-
ments. The higher speeds provide better performance with
cooled detectors and allow kinetics measurements whilst the
lower speeds are used with photoacoustic detectors. Digital
signal processing is increasingly being used to facilitate exper-
iments involving external modulation where two channels of
information have to be acquired simultaneously. Examples
include polarization modulation in reflection–absorption of
species on metal surfaces and in measuring the dynamic
dichroism associated with polymer stretching. Research instru-
ments generally have both continuous-scanning and step-scan
modes as discussed earlier.
In the 40 years since the introduction of the first commer-
cial FT instrument, there have been great improvements in
speed and sensitivity. Routine measurements using the com-
mon sampling techniques now take only seconds, so that
further improvements in performance will bring little benefit.
Future advances are more likely to be seen in the development
in smaller and more robust spectrometers. Although a number
of instruments for field applications have appeared, it is prob-
able that the simpler sampling possible with Raman spectrom-
eters will make these the instruments of choice. There are areas
where improved performance is desirable, such as the sensitiv-
ity of chromatographic interfaces and the spatial resolution of
IR microscopes. However, recently, there has been little pro-
gress, and there is little prospect of significant advances in these
areas. One area where advances can be expected is in imaging
where there is real potential for medical diagnoses based on
spectroscopy. The advent of step-scan spectrometers has led to
great advances, but these have been in rather specialized appli-
cations. Thus, FT-IR instrumentation can be classified as
mature. There is little prospect of any alternative methods of
measuring IR spectra replacing FT instruments for most pur-
poses. An exception is gas analysis where the development of
mid-IR quantum cascade lasers operating at room temperature
is likely to lead to novel analyzers.
IR Spectrometers 427
See also: ATR and Reflectance IR Spectroscopy, Applications;
Chromatography-IR, Applications; Chromatography-IR, Methods and
Instrumentation; Computational Methods and Chemometrics in Near
Infrared Spectroscopy; Far Infrared Spectroscopy Applications;
Forensic Science, Applications of IR Spectroscopy; FT-IR and Raman
Spectroscopies, Polymorphism Applications; FTIR Spectroscopy of
Aqueous Solutions; High Resolution Gas Phase IR Spectroscopy
Applications; High Resolution Gas Phase IR Spectroscopy
Instrumentation; High-Pressure IR; Infrared and Raman Spectroscopy
of Minerals and Inorganic Materials; IR and Raman Spectroscopies,
Matrix Isolation Studies; IR and Raman Spectroscopies of Inorganic,
Coordination and Organometallic Compounds; IR and Raman
Spectroscopies, Polymer Applications; IR and Raman Spectroscopies,
Studies of Hydrogen Bonding and Other Physicochemical Interactions;
IR and Raman Spectroscopies, The Study of Art Works; IR and Raman
Spectroscopy, Industrial Applications; IR, Biological Applications; IR,
Medical Science Applications; IR Spectral Group Frequencies of
Organic Compounds; IR Spectroscopic Data Processing; IR
Spectroscopy Sample Preparation Methods; IR Spectroscopy, Soil
Analysis Applications; IR Spectroscopy, Surface Studies; IR
Spectroscopy, Theory; Near-Infrared Spectra, Interpretation; Near-
Infrared Spectroscopy; Near-IR Spectrometers; Protein Structure
Analysis by CD, FTIR, and Raman Spectroscopies; Raman and Infrared
Microspectroscopy; Spatially Resolved IR; Vibrational CD,
Applications; Vibrational CD Spectrometers; Vibrational CD, Theory
and Application to Determination of Absolute Configuration; Vibrational
CD, Theory; Vibrational, Rotational and Raman Spectroscopy,
Historical Perspective; Vibrational Spectroscopy Applications in Drugs
Analysis; Vibrational Spectroscopy, Flame and Temperature
Measurement; Vibrational Spectroscopy in Food Processing.
Further Reading
Chalmers JM and Griffiths PR (eds.) (2002) Handbook of Vibrational Spectroscopy, vol.
1. Wiley The first volume of this comprehensive work covers theory and
instrumentation.
Griffiths PR and de Haseth JA (2007) Fourier Transform Infrared Spectroscopy.
New York: Wiley This is the standard book on the subject with detailed discussion of
the principles of operation and design of FT-IR spectrometers.