Ultraviolet/Visible Molecular

Absorption Spectrometry II

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Outline

• Instrumentation
– Overview of instrument components
– Light sources
– Sample containers
– Light detectors

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Instrumentation

Schematic diagram of a single-beam spectrophotometric experiment.

Conceptual component diagram of an instrument for absorption measurement.

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 Double-beam spectrophotometers

Double-beam-in-space

Double-beam-in-time

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Light sources

For the purpose of molecular absorption measurement, a continuum source is

required whose radiant power does not change sharply over a considerable range
of wavelength.

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A deuterium lamp and its spectrum
A continuum spectrum in the UV
region is produced by electrical
excitation of deuterium at low
pressure.
D2 + Ee → D2* → D'+ D"+ hν
A heated oxide-coated
filament provides electrons.
Ee = ED* = ED ' + ED" + hν
2
The sum of ED’ and ED” can vary continuously
from zero to ED2*. Æ The energy and the
frequency of the photon can also vary
continuously.
When the two kinetic energies are by chance
small, hv will be large.Æ This produces a
continuum spectrum from ~160 nm to the
beginning of the visible region. 7
A tungsten filament lamp and its spectrum

• Most common source of visible and near

IR radiation.
• Useful for the wavelength region
between 350 and 2500 nm.
• The energy distribution of this source
approximates that of a blackbody.

Blackbody radiation curves 8

Xenon Arc lamp

The passage of current through an atmosphere of

xenon produces a continuum spectrum between 200
and 1000 nm, with the peak intensity occurring at about
500 nm.

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 Sample containers

Glass: ok with
Vis Abs
measurement,
but it absorbs
UV.
Quartz: UV
absorbance
measurement

Common cuvets for visible and ultraviolet spectroscopy.

(Source: Harris, Quantitative Chemical Analysis, pp 414.)
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Light detectors
Photon Transducers: lightÆ electric current

Photomultiplier tubes:
Photovoltaic cells:

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 Types of photon transducers
• Photographic plates
• Photovoltaic cells: The photons generate a current at the interface of a semi-
conductor layer and a metal.
• Phototubes: Photons causes emission of electrons from a photosensitive solid
surface.
• Photomultiplier tubes (PMT): Photons generate electrons from a
photosensitive area. When the electrons strike a successive dynodes, a
cascade of secondary electrons are produced at each strike.
• Photoconductivity transducers: Absorption of photons by a semiconductor
produces electrons and holes, thus leading to enhanced conductivity.
• Silicon photodiodes: Photons cause the formation of electron-hole pairs and a
current across a reverse-biased pn junction.
• Charge-transfer transducers: Charges are developed in a silicon crystal as a
result of absorption of photons are collected and measured.

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 Relative response of
various Light
detectors

Relative response of various types of

photoelectric transducers
(A) Photomultiplier tubes
(B) (D) (G) Photoconductivity transducers
(B) CdS conductivity
(D) CdSe photoconductivity cell
(G) PbS photoconductivity
(C) (E) Photovoltaic cells
(C) GaAs photovoltaic cell
(E) Se/SeO photovoltaic cell
A Golay Cell, or Golay Detector, is a type of
(F) Silicon photodiodes radiometer in which light is absorbed onto a plate in
(H) (I) Thermal transducers contact with a gas chamber, which heats the gas
(H) Thermocouple and causes it to expand against a diaphragm. A
(I) Golay cell measurement of the diaphragm determines the
amount of radiation.
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Phototubes

At saturation potential
(e.g., 90V), photocurrent
Coated with is proportional to radiant
Photoemissive
material
power.

Drive photoelectrons from

cathode to anode

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Photomultiplier tube

Upon striking the

dynode, each
photoelectron
causes emission of
several additional
electrons.

Cross-sectional view

Photoelectron: an e- that is emitted from an atom or molecule by an incident photon.

Dynode: the auxiliary electrode in a PMT that gives rise to secondary emission and
amplification when bombarded by photoelectrons.
Each dynode is held at a more positive voltage than the previous one. 15
Photomultiplier tube

Sensitive to UV and visible radiation.

Need to be kept in dark and avoid
exposure to daylight or other strong
light.

Each dynode is held at a more positive voltage than the previous one.
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Silicon Diode

Diode: a passive electronic component

Si doped with Ga that allows current to flow in only one
Si doped with
(gallium) As direction.
e- from Si for the missing
e- needed for Si-Ga bond,
Photodiode: a type of diode that allows
leaving a + hole current to flow only when light strikes the
diode.
p: positive mobile charge carrier
n: negative mobile charge carrier

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Silicon Diode: semiconductor

Insulators: large band gap

Metals: zero band gap
Semiconductors: band gaps of intermediate energies,
energies that are well matched to solar photons.

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Silicon Diode: p- and n- type semiconductor
An arsenic-doped n-type silicon
semiconductor
As has five valence e-. When As atoms are
mixed into Si lattice, they are surrounded by four
Si atoms. The four bonds utilize four valence e-,
leaving the As atom with an extra electron.
The extra e- on the As atom has a high energy,
close to that of the Si conduction band. It takes
only a little energy for this e- to enter the
conduction band and move freely through the
lattice. Æ negative mobile charge carrier.
A fixed positive charge is left on each As atom.
An gallium-doped p-type silicon
semiconductor
Ga has 3 valence e-. When Ga atoms are
mixed into Si lattice, they are surrounded
by four Si atoms. The four bonds utilize
four valence e-, one e- missing.
The missing e- on the Ga atom can be
supplied by the surrounding Si lattice,
creating a hole in the valence bond, which
becomes the mobile carrier. Æ positive
mobile charge carrier.
A fixed negative charge is left on each Ga
atom. 19
Silicon Diode: p-n junction

When a p-type semiconductor is joined with a n-

type semiconductor, the mobile charge carriers
migrate away from the junction due to repulsion
from fixed charges of the same sign. The result
is an electric potential at the junction.
If a photon is absorbed in the n-type
semiconductor, the electron that is injected into
the conduction band will have a chance of being
accelerated across the junction before it
recombines with a hole .
Similarly, a photo-generated hole in the valence
band of the p-type semiconductor can be
accelerated in the opposite direction before it
recombines with an electron.
This directed movement of the photo-generated
mobile charges produces an electric current in
an external circuit. The current is proportional to
radiant power.

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Multichannel Photon Transducers: Photodiode Arrays

Cross section
view

Photodiode array: one dimensional transducers

in which the photosensitive elements are
arranged in a line.
Top view

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