Detectors: Ideal requirements: quantitative response; high sensitivity; low noise; short response time

1. Photovoltaic cells/ Barrier-layer cells: Operates without the use of battery.

Construction: It consists of metal base plate like iron or aluminium or copper which acts as one
electrode. A thin layer of semiconductor metal like selenium or cuprous oxide (Cu 2O) is
deposited which is then coated with thin semi-transparent layer of silver or gold which acts as
second electrode.
Working: When the radiation is incident upon selenium, electrons are generated at selenium-
silver interface. These electrons are collected by silver which creates electric voltage difference
between silver surface & cell basis. If this cell is connected to galvanometer & external circuit
has low resistance, photocurrent will flow which is directly proportional to the intensity of
incident radiation.
Advantages: Sensitive over whole visible region; Requires no external supply.
Disadvantages: Current cannot be amplified because of low internal resistance. These are not
used in spectrophotometers.

2. Phototubes/ Photoemissive cells:

Construction: It consists of a bulb with a light sensitive cathode. Inner surface of cathode is
coated with light sensitive layer such as cesium or silver oxide. A metal ring inserted near the
bulb centre acts as anode for capturing electrons.
Working: When the radiation is incident upon cathode. it emits photoelectrons which are
attracted by an anode. The electrons return via the external circuit which is amplified to read
out readily. It measures the amount of the light striking the photo-sensitive surface and
expressing it in absorbance or transmittance or concentration forms. For the wavelength of
350-450 nm, the cathode should be coated with sodium.
Advantages: More sensitive than Photovoltaic cells

3. Photomultiplier tubes (PMT): It is one of the highly sensitive devices used today.
Construction: It consists of an electrode covered with a photoemissive material. A large
number of plates known as dynodes (usually 9-10) are used. A dynode is cover with a material
like Be-Cu, Cs-Sb which emits several electrons.
 Working: Once electrons are ejected from the cathode and accelerated to the sensitive surface
of the dynode, secondary electrons (2-5 electrons for each electron striking the surface) are
emitted in greater amount than initially striking the plate by a factor of 4 or 5. It is repeated
until large number of electrons arrive at collector. Each dynode is maintained at 75-100 V more
positive than the preceding dynode.
Advantages: Extreme sensitive & prevents from stray light. Overall amplification factor of
about 106 is obtained. So, it can be used to measure the intensities about 200 x weaker than
those by conventional methods.

4. Silicon Photodiode:
Construction: As the name suggests, a silicon photodiode is a semiconductor. These are
semiconductor devices used for the detection of light in UV, visible & IR spectral regions.
Working: A silicon photodiode utilizes the internal photoelectric effect, the phenomenon
whereby the electrical properties of the detector itself change when light strikes it. When light
strikes this semiconductor, if the energy of the light is larger than the band gap, electrons in
the valence band are excited into the conduction band, and holes are left in the original valence
band. These electron-hole pairs are created throughout the semiconductor, but in the depletion
region, the electric field causes electrons to be accelerated toward the N- region and holes to
be accelerated toward the P-region. As a result, electrons accumulate in the N-region and holes
accumulate in the P-region, and the two regions become, respectively, negatively and
positively charged. If this is connected to a circuit, current flows. The band gap of silicon is
approximately 1.12 eV, so current flows only for wavelengths that have an optical energy
greater than this.
Advantages: Because of their small size, low noise, high speed & good spectral response,
silicon photodiodes are being used for both civilian and defence related applications. Silicone
diode detectors have a greater wavelength range than a PMT, usually from 180 nm to 1100 nm.
Apparatus Spectrophotometer
UV Visible
Source of radiation Hydrogen discharge lamp, Deuterium Tungsten lamp
discharge lamp, Xenon discharge lamp, Carbon arc
Mercury arc lamp
Filters/ Grating type monochromator (Diffraction, Prism type monochromator
monochromators Transmission) (Dispersive/Refractive, Reflective type)
Sample cell Quartz Glass
Detector All

Difference between Single & Double beam Spectrophotometer

Single Beam Spectrophotometer Double beam Spectrophotometer
Beams Single beam is produced & made to pass Two beams of equal intensities are
reference & sample at different times produced & made to pass reference
& sample at the same time
Blank & Sample Not possible together Possible to compare both together
comparison in one step
Construction Simple, easy & cheap Complicated, difficult & expensive
Working Tedious & time consuming Non tedious & fast
Radiant energy Changes with voltage fluctuations. Compensates with voltage
intensity fluctuations
Radiant energy Adjust every time Scanning can be done over wide
wavelength wavelength range
Measures Total amount of transmitted light reaching the % of light absorbed by sample
detector
Calibration Done with blank every time, before measuring Done only at start
absorbance or transmittance of sample.

Double beam spectrophotometer