25A — Instrument Components
Most spectroscopic instruments in the UV/visible and IR regions consist of five components: (1) a
stable source of radiant energy; (2) a wavelength selector to isolate a limited spectral region; (3) one or
more sample containers; (4) a radiation detector to convert radiant energy into an electrical signal; (5) a
signal-processing and readout unit (including a computer in modern instruments). These components
are arranged in three configurations depending on the type of measurement: absorption, fluorescence,
or emission spectroscopy.
25A-1 Optical Materials
The cells, windows, lenses, mirrors, and wavelength-selecting elements must transmit radiation in the
wavelength region being used.
• Silicate glass — works well in the visible region and is inexpensive.
• Fused silica or quartz — needed in the UV region (below ~380 nm) because glass absorbs
there.
• Halide salts (NaCl, KBr, AgCl) or polymeric materials — used in the IR region beyond ~2.5 µm,
where glass, quartz, and silica all absorb.
25A-2 Spectroscopic Sources
A good source must produce a beam strong enough to detect easily and must remain stable over time.
There are two main types: continuum sources (intensity changes slowly over a wide wavelength
range) and line sources (emit only a few very narrow spectral lines). Sources can also be continuous
(emit constantly) or pulsed (emit in bursts).
Continuum Sources in the UV/Visible Region
• Tungsten filament lamp — covers 320–2500 nm; operates at ~2900 K; useful from ~350–2500
nm.
• Tungsten/halogen (quartz/halogen) lamp — contains iodine inside a quartz envelope; filament
runs hotter (~3500 K) giving higher intensity and extending range into UV; lasts more than twice as
long as a regular tungsten lamp because sublimed tungsten reacts with iodine to form WI2, which
decomposes back onto the filament, redepositing tungsten.
• Deuterium (and hydrogen) lamps — used for UV continuum radiation; deuterium is excited
electrically and dissociates into two atoms plus a UV photon; produces a true spectral continuum
from ~160 to 375 nm; deuterium lamps are preferred because they are more intense.
Other UV/Visible Sources
• Low-pressure mercury arc lamps — used in liquid chromatography detectors; dominant
emission at 253.7 nm.
• Hollow cathode lamps — line sources used specifically for atomic absorption spectroscopy.
• Lasers — used in many spectroscopic applications, both single wavelength and scanning.
Continuum Sources in the IR Region
These are heated inert solids:
• Globar — silicon carbide rod heated to ~1500°C by electric current.
• Nernst glower — cylinder of zirconium and yttrium oxides heated electrically.
• Nichrome wire — inexpensive spiral wire used as an IR source.
25A-3 Wavelength Selectors
These devices restrict radiation to a narrow band to improve selectivity and sensitivity, and to reduce
Beer's law deviations from polychromatic radiation. The main types are monochromators,
polychromators, spectrographs, and filters.
Monochromators and Polychromators
• Monochromator — contains an entrance slit and exit slit; selects one narrow band at a time;
different bands transmitted sequentially by rotating the diffraction grating.
• Spectrograph — contains a diffraction grating and entrance slit but no exit slit; full dispersed
spectrum falls on a multiwavelength detector simultaneously.
• Polychromator — has multiple exit slits and detectors; allows several discrete wavelengths to be
measured simultaneously.
How a Grating Monochromator Works
Radiation enters through a narrow rectangular entrance slit. A concave mirror collimates it into a
parallel beam that hits a reflection grating. The grating diffracts different wavelengths at different angles
(angular dispersion). A second concave mirror focuses the dispersed wavelengths onto the focal plane.
Rotating the grating brings one wavelength at a time to the exit slit. The governing diffraction equation
is:
nλ = d(sin i + sin r)
where n is the diffraction order, λ is the wavelength, d is the groove spacing, i is the incident angle, and
r is the reflected angle.
Effective Bandwidth
The effective bandwidth (spectral bandpass) is the width of the transmitted band at half-peak height. It
depends on the size and quality of the dispersing element, slit widths, and focal length. High-quality
monochromators achieve a few tenths of a nm or less in the UV/visible. For most quantitative work,
1–20 nm is acceptable.
Adjustable Slits
• Narrow slit → smaller effective bandwidth (better resolution), but less light; may limit sensitivity.
• Wide slit → more light, lower amplification needed, better reproducibility — preferred for
quantitative work.
• Narrow slits are essential for qualitative analysis when the spectrum has narrow peaks.
Grating Details
Modern monochromators use replica gratings made by casting liquid resin onto a master grating ruled
with a diamond tool; the replica surface is coated with aluminum, gold, or platinum. The most common
type is the echellette grating, with broad reflective faces and narrow unused faces for highly efficient
diffraction. UV/visible gratings typically have 50–6000 grooves/mm (1200–2400 most common).
Holographic gratings are made using laser interference patterns on photoresist-coated glass, then
aluminum-coated. They can have up to 6000 lines/mm, nearly eliminate grating ghosts and scattered
light, but are slightly less efficient in light output than ruled gratings.
Filters
Filters block all wavelengths except a restricted band. Two types are used:
Interference Filters
Work by optical interference. Consist of a thin transparent dielectric layer (calcium fluoride or
magnesium fluoride) coated on both sides with a thin metal film, sandwiched between two glass plates.
Bandwidth typically 5–20 nm; narrow-band versions can be as low as 0.15% of the nominal
wavelength. The transmitted wavelength is: λ = 2nt / norder, where t is the dielectric thickness and n is
the refractive index. Used in UV, visible, and IR up to ~14 µm.
Absorption Filters
Less expensive and more rugged; limited to the visible region. Consist of colored glass that absorbs
unwanted wavelengths. Effective bandwidths of 30–250 nm (much wider than interference filters).
Narrower bandwidth versions absorb a significant fraction of desired radiation; transmittance can be 1%
or less at peak. Adequate for routine applications.
Filters in general are simple, rugged, and cheap, but since each covers only one wavelength band, they
are used only when measurements are at a fixed wavelength or wavelength changes are infrequent.
IR Wavelength Selection
Most modern IR instruments use an interferometer and apply Fourier transformation to obtain
spectral information, rather than dispersing the spectrum.
25A-4 Detecting and Measuring Radiant Energy
A detector identifies or records a change in its environment and converts it to a measurable quantity. A
transducer converts non-electrical quantities (like light intensity) into electrical signals. The output is
linearly proportional to radiant power P: G = KP (ignoring dark current). Dark current is a small
constant electrical response even with no radiation; modern instruments subtract it automatically.
Types of Transducers
Two general types: photon detectors and thermal detectors.
Phototubes and Photomultiplier Tubes (PMT)
A phototube has a semicylindrical photocathode coated with photoemissive material and a wire anode
in an evacuated envelope. Light ejects electrons from the cathode; collected at the anode to produce a
photocurrent proportional to radiant power.
A photomultiplier tube (PMT) is more sensitive. It has a photocathode plus a series of dynodes. Each
electron is accelerated to dynode 1 (held 90–100 V more positive), producing 2–4 secondary electrons
per impact. This cascades through all dynodes, giving an amplification of 106 to 107 electrons per
incident photon. This internal amplification is the major advantage of PMTs. At low light levels,
individual photon pulses can be counted — called photon counting.
Photoconductive Cells
A thin film of semiconductor (PbS, MCT, or InSb) on a glass surface in an evacuated envelope.
Absorbed radiation promotes electrons, reducing electrical resistance. PbS and InSb are popular in
the near-IR; MCT (cooled with liquid N2) is used in mid- and far-IR, especially in Fourier transform IR
spectrometers.
Silicon Photodiodes and Photodiode Arrays
Silicon can be enhanced by doping: n-type (Group V dopant, e.g., arsenic — extra free electrons) or
p-type (Group III dopant, e.g., gallium — excess positive holes). A p-n junction diode conducts in one
direction only. Under reverse bias, UV/visible photons create electron-hole pairs, producing a current
proportional to radiant power. More sensitive than a phototube but less than a PMT.
Diode arrays: 1000+ photodiodes on a small silicon chip (~0.02 mm each), placed at the focal plane of
a monochromator to monitor all wavelengths simultaneously — enabling high-speed spectroscopy.
Response time is in nanoseconds.
Thermal Detectors
Used for IR radiation (IR photons lack enough energy for photoemission). They measure the tiny
temperature rise caused by IR absorption. All are housed in a vacuum and shielded from surroundings.
A rotating slotted disk called a chopper converts the signal to AC for easier amplification. IR
measurements are less precise than UV/visible.
Four types:
• Thermocouple/Thermopile — most widely used; measures temperature-induced voltage.
• Bolometer — conducting element whose resistance changes with temperature.
• Pneumatic detector — xenon-filled chamber; IR heats the gas causing pressure changes.
• Pyroelectric detector — crystal (barium titanate or deuterated triglycine sulfate) produces a
temperature-dependent voltage when exposed to IR.
25A-5 Signal Processors and Readout Devices
A signal processor amplifies the detector signal and may also convert DC to AC, change phase, filter
unwanted components, or perform mathematical operations (differentiation, integration, conversion to
logarithms). Readout devices include digital meters and computer monitors. Computers also control
instrument parameters, process and store data, and compare results with databases.
Measuring Photocurrents with Operational Amplifiers
Photocurrents (0.1 µA to 100 µA) are too small to measure directly. An operational amplifier (op amp)
converts this current to a measurable voltage using Ohm's law: E = IR. Since I = kP, the output voltage
is directly proportional to radiant power: E = kRP. Works for photodiodes, vacuum phototubes, and
PMTs.
25A-6 Sample Containers
Sample containers (cells or cuvettes) must have windows transparent in the spectral region used.
• Quartz or fused silica — required for UV (below 350 nm); usable up to ~3000 nm in IR.
• Silicate glass — used for 375–2000 nm; cheaper than quartz.
• Plastic cells — used in the visible region.
• Crystalline NaCl — most common window material for IR; note it is water soluble.
The most common path length for UV/visible cells is 1 cm. Windows should be perpendicular to the
beam to minimize reflection losses.
Cell Care and Maintenance
• Fingerprints, grease, or deposits significantly alter transmission — cells must be thoroughly
cleaned before and after use; windows must not be touched after cleaning.
• Matched cells must not be dried by heating (oven or flame) as this can cause damage or
change path length.
• Matched cells should be calibrated regularly against each other using an absorbing solution.
Feature 25-5: Signals, Noise, and the Signal-to-Noise Ratio
All instrument outputs fluctuate randomly — this is called noise, caused by uncontrolled variables (e.g.,
random photon arrival, 60-Hz line pickup, vibrations, temperature changes, voltage fluctuations). The
signal is the average output value; the noise is its standard deviation.
Signal-to-noise ratio (S/N) = average signal / standard deviation of signal.
• S/N ≈ 100 → peaks clearly visible.
• S/N ≈ 2 → peaks barely visible.
• S/N ≈ 1 → peaks disappear entirely into noise.
Methods to improve S/N include analog filtering, lock-in amplification, boxcar averaging, smoothing,
and Fourier transformation.