25 Instruments for Optical Spectrometry

25A INSTRUMENT COMPONENTS

(1) source of radiant energy
(2) wavelength selector
(3) sample container
(4) detector
(5) signal processor and readout
Fig. 25-1 components of
various types of instruments
for optical spectroscopy. (a)
The arrangement for
absorption measurements is
(a) shown. (b) The configuration
for fluorescence measurements
is shown. Two wavelength
selectors are needed to select
the excitation and the emission
wavelengths. The selected
source radiation is incident on
the sample and the radiation
emitted is measured, usually at
right angles to avoid scattering.
(b) (c) The configuration for
emission spectroscopy is
shown. A source of thermal
energy, such as a flame,
produces an analyte vapor that
emits radiation that is isolated
by the wavelengths selector
(c) and converted to an electrical
signal by the detector.

25A-1 Optical Materials

cells, windows, lenses and wavelength
dispersing element (Fig. 25-2)
silicate glass: for visible region
fused silica or quartz: < 380 nm

Fig. 25-2 Transmittance ranges for

various optical materials.

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25A-2 Spectroscopic Sources
generate a beam of radiation with sufficient and
stable power
(1) continuous sources: emit radiation that changes
in intensity only slowly as a function of
wavelength
(2) line sources: emit a limited number of bands of
radiation, each of which spans a very
limited range of wavelength.
Fig. 25-3 Spectral source types. The spectrum of a continuum source
(a) is much broader than that of a line source (b).
Table 25-1 Continuous Sources for Optical Spectroscopy
Source Wavelength Region, nm Type of Spectroscopy
Xenon arc lamp 250-600 Molecular fluorescence
H2 and D2 lamps 160-380 UV molecular absorption
Tungsten/halogen lamp 240-2500 UV/vis/near-IR molecular
absorption
Tungsten lamp 350-2200 Vis/near-IR molecular absorption
Nernst glower 400-20,000 IR molecular absorption
Nichrome wire 750-20,000 IR molecular absorption
Globar 1200-40,000 IR molecular absorption
Continuous Sources in the UV/Visible Region
provides radiation of all wavelength within a Fig. 25-4 (a) A tungsten lamp of
particular spectral region. the type used in spectroscopy and
(b) its spectrum. Intensity of the
tungsten source is usually quite
low at wavelengths shorter than
about 350 nm. Note that the
intensity reaches a maximum in
the near-IR region of the spectrum
(a) (b) (~1200 nm in this case).
Deuterium (hydrogen) lamps: 160 - 380 nm (Fig. 25-4)
A cylindrical tube (contains deuterium at a low pressure) with a quartz window
(the radiation exits)
Fig. 25-5 (a) A deuterium lamp of the type
used in spectrophotometers and (b) its
spectrum. Note that the maximum
intensity occurs at ~ 225 nm. Typically
instruments switch from deuterium to
tungsten at ~350 nm.
(a) (b)
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Continuous Sources in the IR Region
Globar source: 1 - 40 μm (Globar heated to about 1500℃)
5- by 50-mm silicon carbide rod.
Nernst glower: a cylinder of zirconium and yttrium oxides.
Nichrome wire

25A-3 Wavelength Selectors

enhance both the selectivity and the sensitivity

1. Monochromators and Polychromators

advantage: the output wavelength can be varied continuously over a
considerable spectral range. (the more common type)
2. Grating → disperse radiation into its component wavelengths
qualitative analysis: narrow slits and minimum effective bandwidths
quantitative analysis: wider slits permit operation at lower amplification (greater
reproducibility).
(a)

Fig. 25-6. Types of monochromators: (a) grating

monochromator and (b) prism
monochromator. In both cases, λ1 > λ2.

Fig. 25-7 Output of an exit slit as the

monochromator is scanned from λ1- δλ Fig. 25-8 Mechanism of diffraction from an
to λ1+ δλ. echellette-type grating.

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 The Echellette Grating

Concave Grating

Holographic Grating

Fig. 25-9 Dispersion of radiation alomg the

focal plane AB of a typical prism (a) and
echellette grating (b). The position of A and
B in the scale in (c) are shown in Fig. 25-6.

3. Radiation Filters
advantage: simplicity, ruggedness and cheapness
interference filter: effective bandwidths of 5 to 20 nm
Dielectric material: CaF2 of MgF2
absorption filter: effective bandwidths of 50 to 250 nm

Fig. 20-10 Bandwidths for two types of filter.

Fig. 25-11 (a) Schematic cross section of an interference filter. Note that the drawing is
not to scale, and the three central bands are much narrower than shown. (b) Schematic
to show the conditions for constructive interference.

25A-4 Detecting and Measuring Radiant Energy

detector: indicates the existence of some physical phenomenon.
ex: photographic film
pointer of a balance
mercury level in a thermometer
human eye
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 transducer: converts signals, such as light intensity, pH, mass and temp. into
electrical signals that can be subsequently amplified, manipulated
and finally converted into numbers proportional to the magnitude of
the original signal.
Properties of Radiation Transducers
1. responds rapidly to low levels of radiant energy over a broad wavelength
range.
2. produces an electrical signal that is easily amplified and has a relatively low
noise level.
3. electrical signal produced by the transducer be directly proportional to the
power of the beam P:
G = KP + K' → G = KP
G : electrical response of the detector in units of current, resistance or
potential.
K : proportionality constant (sensitivity of the detector)
K': dark current (produced by a photoelectric detector in the absence of
light).
Types of Transducers
Table 25-2Common Detectors for Absorption Spectroscopy
Type Wavelength Range, nm Type of Spectroscopy
Photon Detectors
Phototubes 150-1000 UV/visible and near-IR absorption
Photomultiplier tubes 150-1000 UV/visible and near-IR absorption,
molecular fluorescence
Silicon photodiodes 350-1100 Visible and near-IR absorption
Photoconductives cells 1000-50,000 IR absorption
Heat Detectors
Thermocouples 600-20,000 IR absorption
Bolometers 600-20,000 IR absorption
Pneumatic cells 600-40,000 IR absorption
Pyroelectric cells 1000-20,000 IR absorption

Photon Detectors
(1) Phototubes
*a semicylindrical photocathode: supports a
layer of photoemissive material, such as
alkali metal or metal oxide; emitted
photoelectrons, producing a current
(photocurrent)
Fig 25-12 A phototube and accompanying
*a wire anode
circuit.
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(2) Photomultiplier Tubes (PMT) (Fig 25-13) more sensitive
cathode: emitted electrons are accelerated toward a dynode
dynode: at 90 V more positive than cathode.
Fig. 25-13 Diagram of a photomultiplier tube: (a) cross-sectional view,
(b) electrical diagram illustrating dynode polarization and
photocurrent measurement.

(3) Photoconductive Cells.

A thin film of a semiconductor: PbS, mercury cadmium telluride or indium
antimonide

(4) Silicon Photodiodes and Photodiode Arrays

crystalline silicon: semiconductor
conduction a semiconductor involves the movement of electrons and holes in
opposite directions.
conductivity of silicone : enhanced by doping, a process whereby a tiny,
controlled amount (≒ 1 ppm) of a Group V or Group III element is distributed
homogenously throughout a silicon crystal.

Ex:1. a crystal is doped with a group V element, such

as As, four out of five of the valence electrons of
the dopant form covalent bonds with four silicone
atoms leaving one electron free to contribute to
the conductivity of the crystal
containing unbonded electrons (negative charges):
n-type
majority carrier: electrons
Extra electron n-type
Fig. 25-14 Two-dimensional representation of n-type silicon showing “impurity” atom.
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 Ex:2. the silicon is doped with a group III element,
such as Ga, which has but three valence
electrons, an excess of holes develops, which
also enhances conductivity (Fig. 25-15)
containing an excess of holes (positive charges):
p-type
majority carrier: holes
Fig. 25-15 Two-dimensional representation of p-type
p-type Vacancy (or hole)
silicon showing “impurity” atom.

pn junction or pn diode

Fig. 25-16 (a) Schematic of a

silicon diode. (b) Flow of
electricity under forward bias.
(c) Formation of depleton
layer, which prevents flow of
electricity under reverse bias.

(5) Diode-Array Detectors

(6) Charge Transfer Devices (CTD)
Charge Injection Devices (CID)
Charge Coupled Devices (CCD)
Fig. 25-17 Cross section of one of the pixels of
a charge transfer device. The positive
hole produced by the photon hν is
collected under the negative electrode.

Heat Detectors, thermal detector

25A-5 Sample Containers

cells or cuvettes:
0.1 to 1-cm path length

Fig. 25-18 Typical examples of

commercially available cells for the
UV/visible region.

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25B UV/Visible Photometers and Spectrophotometers
spctrophotometers: employ a grating or a prism monochromator to provide a narrow
band of radiation for measurements that the wavelength used can be varied
continuously, thus making it possible to record entire absorption spectra.
photometers: use an absorption filter or an interference filter.
advantages: simplicity, ruggedness and low cost.

25B-1 Single-Beam Instruments

Spectronic 20: spectral range 340 - 625 nm
(an accessory phototube extends
the range to 950 nm).
effective bandwidth of 20 nm
wavelength accuracy of ±2.5 nm
0 % T calibration or adjustment:
100 % T calibration or adjustment: blank (a)

(b)
Fig. 25-19 The Spectronic 20 spectrophotometer. A photography of the instrument is shown
in (a), while the optical diagram is seen in (b).
25B-2 Double-Beam Instruments (Fig. 25-20 b,c)

Fig. 25-20 (a) A single-beam instrument

(a) A aingle-beam instrument, radiation from the filter or monochromator passes through
either the reference or the sample cells before striking the photodetector.

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 Fig. 25-20 (b) A double-beam-in-space
instrument
(b) A double-beam-in-space instrument, radiation from the filter or monochromator is split
into two beams that simultaneously pass through the reference and sample cells before
striking two matched photodetectors.

A double-beam-in-time
instrument
Fig. 25-20 (c)
(c) A double-beam-in-time instrument, the beam is alternately sent through reference and
sample cells before striking a single photodetector. Only a matter of millisecons
separates the beams as they pass through the two cells.
25B-3 Multichannel Instruments
possible to record an entire ultraviolet or
visible spectrum
Chips length: 1-6 cm
individual diodes widths: 0.015-0.050 mm

Fig. 25-21 Diagram of a multichannel spectrometer

based on a grating spectrograph with a
photodiode array detector.

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25C Infrared Spectrophotometers
25C-1 Dispersive IR Instruments
cell compartment is located between the source and the monochromator
→ any scattered radiation generated in the cell compartment is largely removed by
the monochromator.
IR sources: heated solids
IR gratings: much coarser than those required for UV/visible
IR detectors: respond to heat rather than photons
optical components of IR: polished salts such as NaCl or KBr.

25C-2 Fourier Transform Instruments

great speed, high resolution, high sensitivity and unparalleled wavelength
precision and accuracy
no dispersing element and all wavelengths are detected and measured
simultaneously.

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