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Lesson Objectives

(5) Elements of Spectroscopic
Instrumentation
Jonyl L. Garcia, M.Sc., RCh.
Assistant Professor
Chemistry Department
At the end of this lesson, the student will be able to:
❑Identify the different components of optical
instruments;
❑Differentiate between the different type of optical
components;
❑Illustrate the different assemblies of optical
instruments;
❑Differentiate between the various optical
instrumental designs, with the understanding of
their advantages and disadvantages.

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General Components for Spectroscopic General Assemblies of Spectroscopic

Instruments Instruments
1. Source of radiant energy  Absorption spectroscopy

2. Wavelength selector
3. Sample container
4. Radiation detector or transducer Fluorescence and scattering spectroscopy →

5. Signal processing and read-out

 Emission spectroscopy

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Optical Materials

• Materials used in
construction of
optical devices must
transmit light within
the wavelength range
being studied

RADIATION SOURCES

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Radiation Sources Continuum Sources vs. Line Sources

• Provides energy for

excitation of
electrons
• Output must be
CONSTANT, STABLE
and INTENSE enough.
• Requires a regulated
power supply

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Radiation Sources Radiation Sources

1. Continuum source 3. Pulsed sources

– Emit radiation over a – Emit radiation in
wide band of
wavelength bursts
– E.g. D2 lamp, arc lamp, – E.g. Xenon pulse lamp
tungsten lamp, Nernst
glower, Globar 4. Lasers
2. Line source – Monochromatic
– Limited number of – High intensity
bands of radiation – Tunable lasers
– E.g. Hollow cathode available
lamps

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*Globar – SiC rod

**Nernst glower – oxides of zirconium or yttrium

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Sample Containers

• Cells or cuvettes
• Holds sample – must be transparent with respect to
the radiation used
• Matched and calibrated
• Care / cleaning

SAMPLE CONTAINERS

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Wavelength Selector

• Device that restricts the

radiation being measured to a
narrow band that is absorbed
or emitted by the analyte
(effective bandwidth or
spectral bandpass)
• Narrow wavelength of
radiation
– Enhances sensitivity
– Provide selectivity to both
absorption and emission
methods
WAVELENGTH SELECTOR – Required for obtaining a linear
relation between the optical
signal and concentration

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2 General Types of Wavelength Selector Filters

• Absorption filters
• Filters – operate by – consists of a colored glass
absorbing all but a plate that removes part of
the incident radiation by
restricted band or absorption; rugged, low
cost, suitable for VIS region.
radiation from a Effective bandwidth – 30-
250 nm; low transmittance
continuous source • Interference filters –
• Absorption filter – consists of a thin layer of a
transparent material (CaF2
• Interference filter or MgF2) coated on both
sides with a film of metal
that is thin enough so that it
emits approximately half of
the radiation striking it and
reflects the other half.

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Monochromators
• Consists of the ff. components:
– Entrance slit
– Collimating lens or mirror
– Prism or grating
– Focusing element
– Exit slit (no exit slit = spectrograph*; multiple exit slits =
polychromator)
• Characteristics defined by
– Rotation the dispersion material
– Adjusting the slit width – define band width
• The narrower the slit, the narrower the bandwidth, the better
resolution; however leads to low power

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Types of Monochromators Echellette-type grating

• Grating
monochormator
– Cheaper to fabricate
– Provide better
wavelength separation
– Disperse radiation
linearly

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Prisms

*A major advantage of gratings over prisms is

that, in contrast to a prism, the dispersion along
the focal plane is for all practical purposes
linear.

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Holographic gratings

• Grooves made via

optical techniques
(lasers) rather than
mechanical techniques
• Reflection grating more
popular than
transmission gratings
• Produces spectra free
from stray radiation DETECTORS / TRANSDUCERS
and double images
(ghosts)

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Radiation Detector Types of radiation detectors

• Converts EMR energy into • Photon detectors

electrical energy (voltage, – Based upon the interaction
current or charge)
of radiation with a
• Ideal characteristics reactive surface to emit
– Fast response electrons resulting in the
– High sensitivity development of a
– Respond to low level of photocurrent or to
radiant energy promote electrons to
– High S/N energy states in which
– Constant response over a they can conduct
wide wavelength range electricity
– Minimal output signal in the (photoconduction)
absence of illumination
– Produce electrical signal
– Useful for detecting UV,
directly proportional to VIS, and NIR but not IR and
radiant power longer wavelengths

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Photon detectors Photon detectors

• Phototube • Photomultiplier tube
– Consists of semicylindrical – More sensitive than
cathode and a wire anode photodiode
sealed in evacuated
transparent envelope – Dynodes – maintained at
– Surface cathode – increasing potential on
photoemissive coating, which an accelerated
emits electrons upon being electron produces several
irradiated additional electrons
– Bias potential across – Sensitive to UV-Vis
electrodes allow emitted radiation; extremely fast
electrons to flow to anode response; house in light-
to produce current tight compartment

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Photon detectors Silicon photodiodes

• Photonconductive Cells • Most common light

– Based on photoconduction – promotion of electrons to detector used in
energy states where they can conduct electricity instrumentation
– PCTs consists of a thin film of a semiconductor material • p-n junctions – produces
such as PbS, mercury cadmium telluride (MCT), or indium
hole-electron pairs
antimonide
when irradiated
– Useful for MIR and FIR regions

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Silicon photodiodes Photon detectors

• Photovoltaic mode (without
bias) • Photodiode array
– electron hole pairs migrate to – Array of photodiode
opposite sides of the junction
producing voltage (or current if elements (64 to 4096)
device is connected in a circuit)
– Enable detection of
• Photoconductive mode (with
bias) several wavelengths
– reverse bias is applied across the – Detectors used in
junction; light produces multichannel
electron-hole pairs which greatly
increase conductance → current instruments
produced by the bias and the
free carriers is proportional to – Lower sensitivity,
the light intensity over a wide dynamic range, and
range.
S/N compared to PMT

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Photon detectors Thermal Detectors

• Charge Transfer • Based upon the heating effect of radiation

device • Useful for measurement of IR radiation
– Surpass performance • Converts heat energy to electrical energy
of PDAs and can be
used in multichannel
devices
– 2-D array
– Operates like a
photographic film –
pixels

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Types of Thermal Detectors Types of Thermal Detectors

• Thermocouple • Pneumatic detector

– Consists of one or two pairs of – Consists of small
dissimilar metal junctions that
develop a potential difference cylindrical chamber that is
when their temperatures differ; filled with Xe and contains
magnitude of potential a blackened membrane to
difference depends on the absorb radiation and heat
temperature difference the gas.
between metals
• Bolometer • Pyroelectric Detectors
– Consists of a conducting – Manufactured from
element whose electrical crystals of a pyroelectric
resistance changes as a material, such as barium
function of temperature; titanate or deuterated
fabricated from thin strips of triglycine sulfate
metal such as nickel or
platinum or from – Produces a temperature
semiconductors consisting of dependent voltage when
oxides of nickel or cobalt exposed to IR radiation
(thermistors)

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Signal Processors and Read-Outs

• Signal Processors – an electronic device that

amplifies the electrical signal from the detector
– May alter signal from dc to ac (or reverse), change the
phase of signal and filter it to remove unwanted
components Temporal Design (single channel)
– May also be used to perform mathematical operations on Spatial Design
the signal (differentiation, integration, conversion to a Multiplex Design
logarithm)
• Read-out devices
TYPES OF DESIGN OF
– Can be in form of a digital meter, recorder, CRT, OPTICAL INSTRUMENTS
computer monitor, deflecting needle, etc)

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Temporal Design Spectronic-20

• Operates with single detector; successive radiation

bands are examined sequentially in time
1. Non-dispersive
– Filters are interchanged and intensity read
– Advantages: simplicity, low cost, high energy throughput
(better S/N), lower levels of stray radiation
– Disadvantages: do not provide important spectral detail
over a wide range of wavelength
2. Dispersive
– Photometer equipped with a monochromator, with a
dispersing element that is rotated

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Spatial Design

• Based upon multiple detectors or channels to obtain

information about different parts/elements of the
spectrum simultaneously
1. Non-dispersive
– Contains multiple filter systems and detectors
Measurement Steps: 2. Dispersive
1. 0% adjustment – while shutter is imposed b/w source and detector
2. 100% adjustment – reference solution in light path, shutter opened – Contains a monochromator plus a series of slits + number
3. Determination of response for sample of detectors
– Features: more complex, more costly, microprocessor-
Requirement: stable power supply, light source, electronic circuitry to avoid errors resulting
from changes in reading during the time required to make 100% adjustment and response
controlled, faster spectra gathering, enhanced
signal determination for analyte sensitivity/precision

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Double-Beam Design Double-Beam Design

Measurement Steps: Advantages of Double Beam
1. 0% adjustment with a design
shutter in place 1. Compensate for
between selector and fluctuations in the radiant
beam splitter source, drifts in detector
2. Shutter is opened and and amplifiers
response signal 2. Compensate for wide
determined directly variations in source
intensity with wavelength
In the double-beam in-time instrument (c), the beam is
3. Leads to continuous
(b), a double beam-in-space instrument is shown. In this instrument,
radiation from the filter or monochromator is split into two beams
alternately sent through reference and sample cells before recording of
striking a single photodetector. A period of only a few
that simultaneously pass through the reference and sample cells
milliseconds separates the beams as they pass through the
transmittance and
before striking two matched photodetectors.
two cells. absorbance spectra
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Multiplex Design Multiplex Design

• Single channel devices in which all signals are observed
simultaneously
• Requires modulation of signal in a way that permits
subsequent decoding of signal to give its component
parts or elements
• Most depend upon Fourier transform for signal decoding
• Advantages
– Throughput or Jacquinot advantage - few optical
elements, no slits to attenuate radiation; power of
radiation reaching the detector is high (high S/N)
– High wavelength accuracy and precision – makes signal
averaging possible – lead to high S/N
– Multiplex or Felgett advantage – all elements of source
reach detector simultaneously, entire spectrum obtained
in brief period.

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THANK YOU FOR LISTENING!

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