CHAPTER 7

COMPONENTS OF OPTICAL INSTRUMENTS

- based on absorption, fluorescence, phosphorescence, scattering, emission and chemiluminescence
- 5 components: stable source of radiation, transparent sample holder, monochromator (for isolating
restricted region of spectrum), radiation detector (converts energy to electrical signal) and a signal
processor/readout
- absorption, fluorescence and phosphorescence require external sources of energy
- in phosphorescence and fluorescence, emitted radiation is measured at an 90 angle w.r.t the source
- no external source is - can be used with flame and thermal conductivity detectors (universal) for
emission and chemiluminescence spectroscopy since the sample itself is the emitter

Sources of radiation
- must be stable and powerful enough
- continuum source (intensity changes slowly as a function of wavelength); used widely in absorption and
fluorescence spectroscopy
- line source (bands of radiation each spanning a limited range of wavelengths); used widely in atomic
absorption, atomic and molecular fluorescence and Raman spectroscopy

Lasers
- lasers are highly useful sources because of their high intensities, narrow bandwidths, and coherence
- light amplification by stimulated emission of radiation

- the lasing medium is pumped (activated) by external radiation to form a cascade of photons that are
passed back and forth by a pair of mirrors => amplification of highly parallel radiation

- laser action: pumping, spontaneous emission, stimulated emission and absorption

- pumping: excites the active species in lasers, causing several higher electronic and vibrational energy
levels to become populated
- spontaneous emission: random, yields incoherent monochromatic radiation
- stimulated emission: the excited laser species is struck by photons with the same energies as those
produced by spontaneous emission, causing it to relax and emit a photon of the same phase and energy as
the one that stimulated this process => stimulated emission is totally coherent with incoming radiation
- absorption: produces the same result as pumping and competes with stimulated emission

- for there to be light amplification in a laser, # photons from stimulated emission > # photons lost to
absorption => population inversion via pumping

Wavelength selectors
- filters and monochromators
- the effective bandwidth is an inverse measure of the quality of the device

Filters
- interference filters: relies on optical inerference to provide narrow bands of radiation; consists of a
transparent dielectric sandwiched between two glass plates => thickness determines the wavelength of
transmitted radiation; follows Bragg's rule

- absorption filters: absorb selected portions of the spectrum; consists of colored glass or of a dye
sandwiched between glass plates

Monochromators
- designed for spectral scanning => continuously varying the wavelength of radiation over a broad range
- monochromators for UV, visible and IR all use slits, lenses, mirrors, windows, gratings or prisms
- consist of: an entrance slit, collimating lens/mirror, prism/grating, focusing element, exit slit

Sample containers
- needed for all spectroscopic studies except emission spectroscopy
- the cells or cuvettes that hold the samples must be transparent to radiation in the spectral region of
interest
- NaCl is the most commonly used substance for the IR region
Radiation transducers
- real transducers exhibit a small constant response in the absence of radition => dark current
S= kP + k'
- respond to either heat or photons (photoelectric or quantum)
- photon transducers are used mostly for UV, visible and near-IR
- although the relative sensitivity of thermal transducers is independent of wavelength, it is significantly
lower than that of photoelectric transducers
Photon transducers
- photovoltaic cells: energy generates current at the interface of a semiconductor layer and a metal
- phototubes: radiation causes emission of electrons from a photosensitive solid surface
- photomultiplier tubes: photoemissive surface that emits cascades of electrons when struck by electrons
from photosensitive area
- photoconductivity transducer: absorption of radiation by a semiconductor produces electrons and holes,
thus enhancing conductivity
- Si photodiodes: photons cause the formation of electron-hole pairs and a current across a reverse-biased
pn junction
- charge transfer transducers: charge developed in a silicon crystal as a result of photon absorption is
collected and measured

Thermal transducers
- used for the IR region since photons from phototransducers do not have enough energy to cause
photoemission in the IR region
- radiation is absorbed by a small blackbody and the resultant temperature rise is measured; since the
power from an IR beam is extremely small, the heat capacity of the absorbing element must be as small as
possible for the temperature change to be detected; housed in a vacuum to avoid thermal noise from
surroundings
- thermocouple: pair of junctions formed when two pieces of metals are fused to each end of a dissimilar
metal, causing a voltage that changes with the temperature difference to develop between the two
junctions
- thermopile: thermocouples connected in series; higher sensitivity
- bolometer: resistance thermometer constructed from strips of metal that exhibit large changes in
resistance as a function of temperature
- thermistor: semiconductor bolometer
- pyroelectric transducer: temperature-dependent retention of electric field polarization that is temperature
=> pyroelectric crystal sandwiched between two electrodes; change in charge distribution upon irradiation
produces a current that is proportional to the rate of change in polarization with temperature; lose their
polarization when heated above the Curie point
Signal processors and readouts
- electronic device that amplifies and processes the signal from the transducer
- include digital meters, cathode ray tubes, LCD panels, computer displays
Types of optical instruments
- a spectroscope is an optical instrument used for the visual identification of atomic emission lines
- a colorimeter is an instrument for absorption measurements in which the human eye serves as the
detector
- a photometer consists of a source, filter and a photoelectric transducer as well as a signal processor and
readout; fluorometers are photometers designed for measuring fluorescence
- a spectrometer provides information about radiation intensity as a function of wavelength or frequency
- polychromators are multichannel dispersing modules that allow >2 frequencies to be viewed
simultaneously
- spectrophotometer is a spectrometer equipped with >1 exit slits and photoelectric transducers that
permit the determination of the ratio of the radiant power of two beams as a function of wavelength
FT Optical Measurements
- throughput (Jaquinot) advantage: few optical elements and no slits to attenuate the radiation => greater
radiant power and S/N ratio
- high resolving power and wavelength reproducibility

- rapid data acquisition since all elements reach the detector simultaneously => Fellgett/multiplex
advantage
- frequency domain to time domain

- signal power usually decreases with time because the closely spaced wavelengths become more and
more out of phase
- time and frequency domains can be interconverted via:

- the time domain data is acquired using a Michelson interferometer

Michelson interferometer consists minimally of mirrors M1 & M2 and a beam splitter M. In Fig 2, a
source S emits light that hits the beam splitter (in this case, a plate beamsplitter) surface M at point C. M
is partially reflective, so part of the light is transmitted through to point B while some is reflected in the
direction of A. Both beams recombine at point C' to produce an interference pattern incident on the
detector at point E (or on the retina of a person's eye). If there is a slight angle between the two returning
beams, for instance, then an imaging detector will record a sinusoidal fringe pattern as shown in Fig. 3b.

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