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Table of Contents
Introduction 2
Definition of specifications 3
Impact from the specifications 6
Description the different technologies 8
Pros and cons for the different technologies 11
Conclusion 12
References 14
Introduction
A number of different technologies are available for building NIR spectrometers. In this
document we compare FT-NIR Interferometers, Scanning Grating Monochromators and
Fixed Grating Detector Diode Array technologies.
FT-IR Interferometer is at present the preferred technology for IR ( > 2500nm). Grating is the preferred technology for UV/VIS ( < 780nm). In-between, in the NIR region
(780nm < < 2500nm), the advantages of both technologies overlap and they can,
with a proper design, be used for designing excellent analytical instruments.
The preferred spectrometer technology is always application dependent. Different
applications have different requirements to be matched with the advantages and disadvantages of each technology.
In this document we describe the definitions of commonly used specifications, their
impact on measurement performance, the different spectrometer technologies and the
pros and cons of each technology.
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Definition of specifications
Wavelength and Wavenumber
The light is characterized by a wavelength. It is defined as the distance the light passes in
vacuum during one period. The most common unit for wavelength is nm (nano meter)
corresponding to 10-9 m. In the visible range from 400 to 780 nm, the wavelength is
observed as the color of the light.
The light is characterized by a frequency. The relationship between wavelength and
frequency is given by:
c= v
Where c is the speed of light in vacuum, is the wavelength and v is the frequency of
the light. In spectroscopy, it is common to use the units of cm-1 for frequency especially
when using FTIR. The unit cm-1 is called wave number or inverse centimeter, and represents the number of wavelengths that it takes for a length of 1 cm.
Since the units used for the abscissa are reciprocal of each other, praxis of plotting
spectra with cm-1 abscissa with high values to the left has been used.
The conversion from in nm to v in cm-1 and reverse is done by:
v = 107 / and = 107 / v
When transforming resolution between wavelength and wavenumber, this equation
must be used with care. See under the resolution section.
Wavelength range
The wavelength range for NIR is often defined as the range from 780 2500 nm (12820
4000 cm-1) (ref 9). The 2500 nm value is well accepted, but for the short wavelengths
many different values in the range from 600 to 800 nm are used. (ref 1). The spectral
region with shorter wavelengths (400 780 nm) is called the visible range. The spectral
region with longer wavelengths (2500 25000 nm) is called the mid infrared region.
Wavelength accuracy and precision
Wavelength accuracy is how well the wavelength axis of an instrument matches a
reference wavelength axis. Wavelength precision is how well an instrument repeats its
own wavelength axis. The wavelength accuracy and precision is measured in the same
units as the wavelength axis e.g. nm. The same applies for a wavenumber scale where
accuracy and precision is measured in cm-1.
Resolution
The resolution or v of a spectrometer determines the spectral features that can be
separated. Resolution is also called bandwidth, band pass or instrument line shape (
ILS ). The resolution of a spectrometer is normally defined as the full width half height
(FWHH or FWHM) defined by the optical system including a standard processing. The
resolution may also be defined by the Rayleigh criterion which may represent a little
different number. It is important to notice that the resolution is independent of the
distance between the sample points. About 4 sample points are needed to represent
the signal over the resolution. Higher sample density is mostly of cosmetic value.
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The resolution is measured in the same units as the abscissa. Alternatively a dimensionless relative resolution R can be defined.
R() = / and R(v) = v / v
The resolution behaves differently depending on whether it is or v. If is constant
as a function of then v will change proportionally to v2 as function of v.
Resolution of a Monochromator on different scales. Constant on a wavelength scale
To convert a resolution from an abscissa of wavelength to the two wavelengths defining the bandwidth, formula 1 can be used and then subtracted to give the resolution
on the new abscissa. If the relative resolution is small R << 1 then the value of R will
be the same on both abscissas and R can be used to convert the resolution. Note that
in all cases the transformation is only valid for one wavelength.
Noise
Noise is variation in the signal response for repeated measurements on the same stable
sample. In a broad interpretation, noise limits the precision of most measurements. Signal
to Noise Ratio (SNR) is specified as the signal at 100% transmission relative to the noise
calculated as the standard deviation of the same signal for a number of measurements.
A useful measure for signal to noise is absorbance units (Abs), as it relates directly the
absorbencies measured in the spectrum. It must however be also be stated at which
resolution, measurement time and wavelength range the signal to noise is calculated,
as these factors affect the number. The number may be normalized with respect to
time using the unit Abs sqrt(s). This is done by multiplicating the noise measured in
absorbance units with the square root of the measurement time.
Measurement time
The measurement time is composed of an integration time where signal from the sample is measured, and a handling time which is the time used for handling sample and
results. By changing the integration time e.g. the number of scan averages, the noise
in the signal can be altered. If the noise is stationary, the noise is reduced proportionally to the square root of the integration time. Often, the number of averaged scans is
used as the term for integration time, but it needs the additional information of time
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pr. scan to be comparable between instruments. Many fast scans and few slow scans
represent the same integration time and, as such, the same noise, so the number of
scans only makes sense in a predefined context.
Drift
Slow changes of the instrument response are called drift. It may be interpreted as a
low frequency noise. It can be measured in absorbance in a unit time Abs/s. In many
cases, drift limits the signal to noise that can be obtained by increasing integration
time. This is because the error caused by the drift increases while the noise is reduced
as a function time. At some point, the drift exceeds the noise and signal to noise ratio
starts to decline again.
Stray light
Stray light is when unwanted light reaches the detector and distorts the spectrum. Two
different types of stray light are often observed in a system.
The first type is related to the sample handling where some part of the light reaches
the detector without interacting with the sample e.g. in reflection mode where light
reflected from the sample cup reaches the detector and limits the dynamic range in the
spectrum. In transmission the same is seen when light bypasses the sample.
The second type of stray light is when wavelengths outside the selected bandwidth are
included in the light measured by the spectrometer.
Dynamic range and gain
The difference between the highest and the lowest possible absorbance in a spectrum
is called the spectral dynamic range. It can be measured as a ratio of the highest and
lowest signal or in absorbance units as log10 to the ratio. The spectral dynamic range
may be influenced by the stray light. In FT-NIR instruments the spectral dynamic range is
sometime specified as 'photometric accuracy' and presented as transmission percentage
(x %T) (ref. 11). The instrument may have variable gain which offsets the absorbance
scale relative to zero absorbance. The ratio between the noise level in the most sensitive
setting and the maximum tolerable signal is called the instrument dynamic range. It is
measured as a ratio or in absorbance units. Instrument dynamic range is larger than the
spectral dynamic range. The instrument dynamic range is also called photometric range.
Photometric linearity
The linearity of the photometric axis is the deviation from linearity of log10 of the signal
value against log10 to the true signal attenuation. The value is calculated as the root
mean square error at one wavelength. The photometric linearity is affected by stray light
and limited dynamic range. In FT-NIR instruments the 'photometric accuracy' is sometimes specified as a transmission percentage (x %T) (ref. 11). This number is equivalent
to spectral dynamic range as described in the previous section when it is converted to
absorbance units. It assumes that deviation from linearity is caused by an addition of a
constant error signal in the singlebeam spectrum.
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random. Repetetive noise as readout and digitizing noise cannot be reduced by averaging scans.
Measurement time
There is often a trade-off between measurement time and precision. With a shorter
measurement time for each scan, more scans can be averaged during a fixed sample
analysis time. SNR will improve with the square root of number of scans until the point
where drift will start to dominate over random noise.
Drift
The photometric stability is important for instrument performance. The usual cause of
drift is detector and/or lamp temperature shift. Also, changes in water vapor may cause
changes in spectrum. It can be corrected for by measuring a photometric reference
standard at a rate faster than the drift and then using the information for correction.
Typically this correction is done for every sample measured.
Stray light
The type stray light that is related to the sample handling unit limits the maximum
absorbance reading to the level caused by the stray light alone. If, for instance, 1% of
the sample illumination intensity is reaching the detector without interaction with the
sample, the maximum absorbance level that can be measured is 2AU. When approaching this absorbance level the photometric linearity is affected and saturates.
Spectral stray light will also limit the measurement performance. The impact from this
source of error is very sample and application dependant. In general, stray light is less
severe if it occurs at wavelengths close to the selected wavelength.
Dynamic range
The requirements for instrument dynamic range are much larger for transmission
measurements ( 4 - 6 AU ) than for reflectance measurements ( 2 - 3 AU ). To meet the
requirements, programmable gain detector amplifiers and/or optical attenuators for
the reference measurement are used.
Photometric linearity
In NIR spectroscopy, the useful NIR raw signal is a weak modulation superimposed on
a strong background. Good photometric linearity is required to make the measurement independent of the background intensity. The demand for photometric linearity
is higher for FT compared to grating instruments because the signal to background
ratio is more disadvantageous and nonlinearities cause substantial distortion when the
Fourier transformation is performed.
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The key component for this design is the diffraction grating. A grating is an optical
component with a periodic structure, which splits and diffracts light into several beams
travelling in different directions. The directions of these beams depend on the spacing
of the periodic structure and the wavelength of the light. This relationship between
the spacing and the angles of the incident and diffracted beams of light is known as
the grating equation.
m = d (sin + sin)
m: diffraction order
: wavelength
: entrance angle vs. grating normal
: exit angle vs. grating normal
d: grating period
Light from source enters the monochromator through the entrance slit and is dispersed
by the grating and focused at the exit slit plane. A limited wavelength region of the
spectrum exits from the monochromator through the exit slit and illuminates the sample to be analyzed. A broad band detector detects the light transmitted through (or
reflected by) the sample.
Wavelength selection is performed by rotating the grating by means of a motor. The
angle of the grating is continuously measured and converted to represent the center
wavelength of the wavelength region exiting through the slit.
The wavelength range is determined by the angular range of grating rotation and the
dispersion of the grating. The resolution is determined by the dispersion of the grating
and the width of entrance and exit slits.
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Light from source illuminates the sample to be analyzed. Light transmitted through (or
reflected by) the sample enter the spectrometer through the entrance slit and is dispersed
by the grating and focused at the detector array where the detection is performed.
Wavelength selection is performed by reading different pixels of the detector array.
The wavelength range is determined by the width of the detector array and the dispersion of the grating. The optical resolution is determined by the dispersion of the grating
and the width of entrance slit. The detector must have a number of pixels required by
wavelength range and resolution.
FT-NIR
Different manifestations exist, but the characteristics are common. A FT-NIR spectrometer is based on the principal of the Michelson interferometer. This is illustrated on the
figure below. A parallel light bundle is passed through the interferometer and is split
in two bundles by a beamsplitter. They are reflected back from two mirrors onto the
beamsplitter and recombine. When the distances are equal they add constructively, but
if the path length is different an interference pattern results. This interference pattern
changes in intensity as one of the mirrors is moved. The interference pattern as function of the mirror movement is called the interferogram.
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The NIR interferogram is sampled at equal path differences determined from the laser
interferogram and Fourier transformed to a spectrum. This raw spectrum is called the
single beam spectrum. See figure below. Because the units on the abscissa for the
interferogram is length, the units on the abscissa for the spectrum is length-1. This is
proportional to wave number and this is the reason that cm-1 is used as the abscissa
in FT-NIR systems.
Interferogram
Spectrum
The spectral resolution gets narrower when the travel of the mirror is increased. This
limits the light passed through the interferometer. This is equivalent to the slit width in
a monochromator. The spectral resolution is constant on a wave number scale which
implies that the relative resolution decreases with increasing wavelengths. The noise
on the single beam spectrum is the same all over the spectrum.
By placing a sample in the path of the light a measurement of the sample spectrum
can be done. Both transmission and reflection measurements are possible. All the light
of the interferometer hits the sample all the time.
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Conclusion
FT-NIR Interferometers, Scanning Grating Monochromators and Fixed Grating Detector
Diode Array technologies -the three spectrometer technologies in this comparison all
have their individual advantages and disadvantages.
Major distinctions between spectrometer technologies
+
Scanning Grating
Robustness
FT-NIR
Wavelength accuracy
Resolution
Vibration Sensitive
Sample heating
Process instrumentation
FT-NIR
Process instrumentation
For measurements close to production processes, for example in a feed mill where an
analyser is used close to the processing line or is mounted directly in the process for
continuous in-line measurements, fixed grating DDA is the best option.
A fixed grating DDA spectrometer can be used to create robust and vibration-tolerant
instruments ideal for use inside production plants. The simultaneous measurement of
the full spectrum also makes it tolerant to sample movement. In other words, it is the
preferred technology for in-line applications.
Downsides need to be considered however. In particular, a tradeoff between wavelength
range, resolution and signal to noise ratio must be made. Inevitably, the wavelength
range must be restricted to achieve an acceptable signal to noise ratio.
Qualitative measurements in the laboratory
For spectroscopic assignments of pure chemicals where narrow instrument bandwidth is
needed, FT-NIR has advantages. The high resolution makes it applicable for pin-pointing
substances having narrow absorption bands. The wavelength axis accuracy makes it
easy to transfer spectra and the resolution can be adjusted to obtain the best tradeoff
between wavelength resolution and signal to noise ratio.
Disadvantages include a lower signal/noise ratio than a monochromator, particularly at
short wavelengths and the omitted visible wavelength range (below 850 nm). FT NIR
is also a vibration-sensitive technology and the design of an instrument must take this
into account for applications in a production environment.
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References
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FOSS
Foss All 1
DK-3400 Hilleroed
Denmark
Tel.: +45 7010 3370
Fax: +45 7010 3371
info@foss.dk
www.foss.dk
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