Instruments for Optical Spectroscopy

Phenomena used for optical measurements

Absorption
Fluorescence
Phosphorescence
Scattering
Emission
Chemiluminescence

Five Components of typical spectroscopic instruments

stable radiation source

wavelength selector
transparent sample holder
radiation detector
signal processor and readout
 wavelength
source
selector detector readout

sample
holder
 Components of Various Types of Instruments

Emission
Chemiluminescence

Absorption

Fluorescenece
Phosphorescence
Scattering
Components and Materials for Spectroscopic Instruments

Spectral region VAC UV UV VISIBLE NEAR IR MID IR FAR IR

(1) Sources Argon

lamp Xenon lamp
H2 or D2
continuous lamp Tungsten lamp
Nernst glower (ZrO2 + Y2O3)
Nichrome wire (Ni + Cr)
Globar (siC)
Hollow cathode
line lamps

1. Radiation Sources
- must generate sufficient power for easy detection
- output should be stable
Radiant power varies exponentially with voltage of electrical supply
- voltage regulator should be employed
- double-beam design circumvents the problem
Continuous Sources
UV source: Deuterium lamp (160 - 400 nm)

D2 + Eenergy D2* D(KE1) + D(KE2) + hν

UV-Visible-NIR source: Quartz Tungsten Halogen (QTH)

(200 - 3000 nm)

At 3500 K, Evaporation: W(s) W(g)

W(g) + I2(g) WI2(g)
Redeposition: WI2(g) + W(s) W(s) + I2(g)
Line Sources

D2 lamp or Hg/Xe arc

lamp ( > 400 nm)
Fig. 9-11
Electrodeless discharge lamps (EDL)
Fig. 9
(a) Ar ions created by RF energy (b) ions collide with gaseous
metal Electrodeless
Electrodeless
atoms which then (c)Discharge
discharge lamps Lamp
(EDL)(Fig.
emit excite 9-12) (EDL)
(a) Ar ions created by RF energy (b) ions collide with gaseou
Atomic emission metal atoms which then (c) emit excite (Fig. 9-12)
Hallow Cathode Lamp (HCL)

involves:
- electron bombardment of cathode
- sputtering of cathode atoms
- emission from excited atoms
involves:
- ionization of Ar by RF energy
CEM 333 page 3.6
- collision of Ar ions with gaseous metal atoms
- emission from excited atoms
CEM 333 page 3.6
LASERS
Light Amplification by Stimulated Emission of Radiation
involves:

The active species of a

laser is excited by electrical
discharge, electrical
current, radiant source

Radiation produced by different

A species in an excited state may lose by
particles differ in direction and phase
spontaneous emission of radiation
(incoherent radiation)
In stimulated emission, the excited laser particles are struck by photons
having the same energies as the photons produced by spontaneous emission.
Emission of this type causes immediate relaxation and emission of photon of
exactly the same energy as the photon that stimulated it.
The emitted photon travels in exactly the same direction and is precisely in
phase (coherent) with the photon that caused the emission.

The absorption process competes with stimulated emission.

 Population Inversion and Amplification
Light amplification in a laser requires that the number of photons produced by
stimulated emission exceed the number lost by absorption.
Population inversion from the normal distribution of energy must exist.
Population Inversion and Amplification:

In the non-inverted system, 3

molecules are in excited state and 6
are in lower energy.

The photons are absorbed by 3

molecules and stimulate 2 excited
molecules. There is a net absorption
of 1 molecule - results in light
attenuation.

In the inverted system, more

molecules undergo stimulated
emission than those that absorb.
Here, there is light amplification.
Fig 7-6
Population Inversion is needed in lasing.
Need population
Population inversion
inversion for lasing
cannot be produced in 2-level system.
3- Cannot
and producesystems
4-level population favor
inversion in 2-level system
population (stimulated
inversion.
emission becomes increasingly dominant). Need 3- or 4- levels

In 4-level system, the required

pumping energy is smaller
because the population of Ex is
usually negligible - inversion is
easily achieved.

Fig 7-7
Lasing medium can be
Lasing medium can be solid (Nd:YAG, semiconductor diode laser
solid:
AlGaAs), gas (noble gas Ar+, He/Ne, CO2, N 2) or liquid (dye)
ruby crystal (Al2O3 with CrIII) (694 nm); Nd:YAG (1.064 µm) (ytrrium aluminum garnet);
semiconductor diode laser Al Ga As
gas: noble gas Ar+ or Kr+, He/Ne (633 nm)(widely used), CO2, N2 (337 nm)
liquid: dye (tunable: (20 - 50 nm)
 Lasing medium can be solid (Nd:YAG, semiconductor diode laser
AlGaAs), gas (noble gas Ar+, He/Ne, CO2, N 2) or liquid (dye)
Components of Lasers

The heart of the device is a lasing medium (e.g. ruby, dye, etc.)
(Fig. 7-4)
The radiationAdvantages • lasing
produced by the action is caused to pass back and forth through the medium.
intense
Additional photons are generated
• with each passage,(line
monochromatic leading to enormous amplification.
sources)
The repeated passage also•produces
pulsed (10-15
a beam -10
that is -6 s) orparallel
highly continuous
becausewave (cw) radiation
nonparallel
escapes from the sides after being reflected a few times.
• coherent
Advantages • small beam divergence

intense CEM 333 page 3.9

monochromatic line source

pulsed (10-15 - 10-6 s), or continuous wave
coherent
small beam divergence