Instruments for Optical

Spectrometry
Components of Various Types of Instrument for Optical Spectroscopy

1) Absorption measurement

2) Fluorescence measurements

3) Emission spectroscopy
Instrumentation for spectrometry

1. Light sources

a)continuum source

b) line spectrum
Black Body Radiation
Any object surface can
radiate heat to and
receive heat from
outside, if an object can
absorb all the incident
radiation, regardless of
the frequencies and
directions, this object is
called Black Body. A
ball cavity with a small
hole can be regarded as
a black body, since any
radiation entering the
ball cavity can only
reflect inside it, thus
totally absorbed.
Low pressure mercury arc lamp : 253.7 nm Hg line
Hollow cathode lamps : line sources / AA spectrometry
Laser source
 H2 + Ee  H2*
H2*  H’ + H’’ + h
Ee = EH2*
= EH’ + EH’’ + h

A deuterium lamp
A tungsten lamp

Intensity of a tungsten
filament at 3200K and a
deuterium arc lamp.
Light
Laser
Laser is the acronym of Light Amplification by Stimulated Emission of
Radiation. A device which produces light with a narrow spectral width.
Laser is light of special properties, light is electromagnetic (EM) wave in
visible range. Lasers, broadly speaking, are devices that generate or amplify
light, just as transistors generate and amplify electronic signals at audio,
radio or microwave frequencies. Here light must be understand broadly,
since lasers have covered radiation at wavelengths ranging from infrared
range to ultraviolet and even soft x-ray range.
A laser is a cavity that has mirrors at the ends and is filled with lasable
material such as crystal, glass, liquid, gas, or dye. These materials must have
atoms, ions, or molecules capable of being excited to a metastable state by
light, electric discharge, or other stimulus. The transition from this
metastable state back to the normal ground state is accompanied by the
emission of photons which form a coherent beam.
Laser construction 
A laser system generally consists of three important parts:

- An energy source (usually referred to as the pump or pump source);

- A gain medium or laser medium;
- A mirror, or system of mirrors, forming an optical resonator.
Laser cavity. The electromagnetic wave travels back and forth between the
mirrors, and the wave is amplified with each pass. The output mirror is partially
transparent to allow only a fraction of the beam to pass out of the cavity.
(a) Energy-level diagram illustrating the principle of operation of a laser.
(b) Basic components of a laser. The population inversion is created in the
lasing medium. Pump energy might be derived from intense lamps or an
electric discharge.
Amplification of light
All lasers contain an energized substance that can increase the intensity of light
passing through it. This substance is called the amplifying medium or, sometimes,
the gain medium, and it can be a solid, a liquid or a gas. Whatever its physical form,
the amplifying medium must contain atoms, molecules or ions, a high proportion of
which can store energy that is subsequently released as light.
In a neodymium YAG (Nd:YAG) laser, the amplifying medium is a rod of yttrium
aluminium garnate (YAG) containing ions of the lanthanide metal neodymium (Nd).
In a dye laser, it is a solution of a fluorescent dye in a solvent such as methanol. In a
helium-neon laser, it is a mixture of the gases helium and neon. In a laser diode, it is a
thin layer of semiconductor material sandwiched between other semiconductor layers.
The factor by which the intensity of the light is increased by the amplifying medium is
known as the gain. The gain is not a constant for a particular type of medium. It's
magnitude depends upon the wavelength of the incoming light, the intensity of the
incoming light, the length of the amplifying medium and also upon the extent to which
the amplifying medium has been energized. http://members.aol.com/WSRNet/tut/ut1.htm
Schematic of a Nd:YAG laser.
Properties of laser light
Monochromatic : one wavelength
Extremely bright : high power at one wavelength
Collimated : parallel rays
Polarized : electric field of waves oscillates in one plane
Coherent : all waves in phase
Coherence can be devided into spatial and temporal coherence. For any em wave,
if at time t=0 and t0 the phase diference between two points in space remains the
same, we say the em wave has spatial coherence; If at a point P, the em wave at t
and t+dt has same phase difference if dt is the same, temporal coherence exists.

Disadvantages of a laser
High maintenance
Limited wavelengths
Laser types
- Gas Laser
HeNe (543 nm and 633 nm)
Argon(-Ion) (458 nm, 488 nm or 514.5 nm)
Carbon dioxide lasers - used in industry for cutting and welding, up to 100 kW possible

Carbon monoxide lasers - must be cooled, but extremly powerful, up to 500 kW possible

- Excimer(excited dimer or trimer) gas lasers, producing ultraviolet light,

used in semiconductor manufacturing and in LASIK eye surgery;
157 nm (F2)
193 nm (ArF)
222 nm (KrCl)
248 nm (KrF)
308 nm (XeCl)
351 nm (XeF)
- Commonly used laser types for dermatological procedures including
removal of tattoos, birthmarks, and hair:
Ruby (694 nm)

Alexandrite (755 nm)

Pulsed diode array (810 nm)

Nd:YAG (1064 nm) YAG : yttrium/aluminum garnet

Ho:YAG (2090 nm)

Er:YAG (2940 nm)

- Semiconductor laser diodes,

small: used in laser pointers, laser printers, and CD/DVD players;
bigger: bigger industrial diode laser are available used in the industry for cutting and welding,
up to 10 kW possible

- Dye lasers

- Quantum cascade lasers

- Neodymium-doped YAG lasers (Nd:YAG), a high-power laser operating in the
infrared, used for cutting, welding and marking of metals and other materials;

- Erbium-doped YAG, 1645 nm

- Thulium-doped YAG, 2015 nm
- Holmium-doped YAG, 2090 nm, a high-power laser operating in the infrared, it is
explosively absorbed by water-bearing tissues in sections less than a millimeter thick. It is usually
operated in a pulsed mode, and passed through optic fiber surgical devices to resurface joints,
remove rot from teeth, vaporize cancers, and to pulverize kidney and gall stones.

- Titanium-doped sapphire
- Erbium-doped fiber lasers, a type of laser formed from a specially made optical fiber,
which is used as an amplifier for optical communications.
2. Wavelength selectors (Monochromator)
1) Filter a. Absorption filter o
30
b. Interference filter
1 2 1
2) Prism a. Transmission prism = Cornu 1
b. Reflection prism = Littrow 2
Cornu prism 2
Dispersion = d  / d 
o
Approximate transmission limits of prism materials 30
Flint glass (contains PbO ) ; 360nm ~ 2 m
Quartz(crystalline silica) ; 190nm ~3.3m Aluminized
NaCl or KCl ; 0.3~15 m surface
KBr ; 0.3~30 m
LiF ; 0.2~ 5 m
CaF 2 ; 0.2~12 m
AgCl ; 0.4~25 m
CsBr ; 0.3 ~ 50 m Littrow prism
CsI ; 0.3 ~ 70 m
KRS-5(TlBr-TlI) ; 1~30 m

3) Diffraction grating

a. Transmission grating
b. Reflection grating
Wavelength selectors for spectrometry

Type Wavelength range Note

(nm)
Continuously variable

Grating 100 ~ 40,000 3000 lines/mm for vacuum UV,

50 lines/mm for far IR
Prism 120 ~ 30,000

Discontinuous

Interference filter 200 ~ 14,000

Absorption filter 380 ~ 750

Dispersion of radiation along the focal plane AB of a typical prism(a) and
echellette grating (b).
Schematic diagram of diffraction from a grating.

n = (a – b)
d sin  = a
– d sin  = b
n = d (sin  + sin  )
Diagram of a Czerny-Turner grating monochromator.
Interference of adjacent waves that are a) 0 o , b) 90o and c) 180oout of phase.
Choosing the monochromator bandwidth
Monochromator bandwidth should be as large as possible, but small compared with
the width of peak being measured.
stray light
In every instrument, inadvertent stray light (wavelength outside the bandwidth expected
from the monochromator) reaches the detector. High qulity spectrometers could have
two monochromators in series to reduce stray light.

Absorbance error introduced by different levels of stray light. Stray light is

expressed as a percentage of the irradiance incident on the sample.
 Nominal wavelength

Output of an exit slit as monochromator is scanned from  to 

Filters
It is frequently necessary to filter (remove) wide bands of radiation from a signal.

Bandwidths for two types of filters(interference filter vs

absorption filter).
(a) Schematic cross section of an interference filter.
(b) Schematic to show the conditions for constructive interference
Transmission spectra of interference filters.
(a) Wide band pass filter has ~90% transmission in the 3- 50 5- m wavelength range
but <0.01% transmittance outside this range.
(b) Narrow band-pass filter has a transmission width of 0.1 m centered around 4 m.
3. Optical Materials and sample containers

Transmittance range for various cell construction materials.

 CAT-Lab
Quartz cell for / SWU
UV spectrophotometer
 4. Detectors for spectrometry

Type Wavelength range(nm)

Photon detectors
Phototubes 150 ~ 1,000
Photomultiplier tubes 150 ~ 1,000
Silicon diodes 350 ~ 1,100
Photoconductive cells 1,000 ~ 50,000

Thermal detectors
Thermocouples 600 ~ 20,000
Bolometers 600 ~ 20,000
Pneumatic cells 600 ~ 40,000
Pyroelectric cells 1,000 ~ 20,000

A transducer is a type of detector that converts various types of chemical and physical
quantities into electrical signals such as electrical charge, current, or voltage.
Response of several different detectors.
The greater the sensitivity, the greater the output (current or voltage) of the detector
for a given incident power of photons.
Phototube

Schematic diagram of
photomultiplier with nine dynodes.
Comparison of spectra recorded in 5 min Absorption spectra of hemoglobin with
by a photomultiplier tube and a charge
identical signal levels but different amount
coupled device.
of noise.
Silicon photodiode array
Charge transfer device (CTD)
An operational amplifier current-to-voltage converter used to monitor the current in
a solid state photodiode.

Eout = – IR = – kPR = k’P

P= radient power
G = KP + K’
G = electrical response of the detector in units of current, voltage, or charge.
K’ = dark current
Components and materials of spectroscopic instruments.
Instrumentation of UV-visible spectrophotometer
Types of UV-visible spectrophotometer
1) Single beam spectrophotometer

2) Double beam spectrophotometer

Block diagram for a double-beam in-time scanning spectrophotometer .
3) Diode-array spectrophotometer

Block diagram for a diode array spectrometer.

 Power indicator light Absorbance & Transmittance display

Sample Wavelength
holder selector

Power switch
Zero control Absorbance & Transmittance control

Spectronic 20 spectrophotometer
 Procedure
1) Power on
2) Select wavelength
3) 0% T adjustment

Scale of spectronic 20 spectrophotometer (Calibration)

4) Blank (Reference cell) is
LED inserted into cell holder
5) 100% T adjustment
6) Sample cell is placed in
the cell compartment
7) Readout absorbance
8) Power off

Spectronic 20 spectrophotometer
Schematic diagram of optical system of Spectronic 20 single beam UV-visible spectrophotometer
The dual-beam design greatly simplifies this process by simultaneously measuring P and
Po of the sample and reference cells, respectively. Most spectrometers use a mirrored
rotating chopper wheel to alternately direct the light beam through the sample and
reference cells. The detection electronics or software program can then manipulate the P
and Po values as the wavelength scans to produce the spectrum of absorbance or
transmittance as a function of wavelength.
HP8452A diode array UV-visible spectrophotometer
Optical schematic of the Hewlett-Packard HP-8450A diode array UV-visible spectrophotometer.
 Q n A
Thanks

Home page http://www.swu.ac.kr/~dslee

Electronic mail dslee@swu.ac.kr