Beruflich Dokumente
Kultur Dokumente
Echelle monochromators
contain two dispersing elements arranged in series.
The first of these elements is a special type of
grating called an echelle grating. The second,
which follows, is usually a low-dispersion prism,
or sometimes a grating. The echelle grating,
which was first described by G. R. Harrison in
1949, provides higher dispersion and higher
resolution than an echellette of the same size.
MONOCHROMATOR
SLITS
Exit slights help select the range of wavelengths that exit the
monochromator and strike the detector
More important than entrance slits
Can be:
Monochromator Slits
Good slits
Two pieces of metal to give sharp edges
Parallel to one another
Spacing can be adjusted in some models
Entrance slit
Serves as a radiation source
Focusing on the slit plane
Bandwidth
Defined as a span of
monochromator setting
needed to move the image of
the entrance slit across the exit
slit
Effective bandwidth
Dleff
of the bandwidth
When two slits are identical
D-1 = Dl/Dy
When Dy = w = (slit width)
D-1 = Dleff /w
Example
FIGURE 7-25 The effect of the slit width on spectra. The entrance slit is illuminated with A" A"
and A 3 only. Entrance and exit slits are identical. Plots on the right show changes in emitted
power as the setting of monochromator is varied.
Quantitative analysis
SAMPLE HOLDERS
(CELLS)
Must:
Examples
Sample Containers
The cells or cuvettes that hold the samples must
be made of material that is transparent to radiation
in the spectral region of interest. Quartz or fused
silica is required for work in the ultraviolet region
(below 350 nm), both of these substances are
transparent in the visible region. Silicate glasses
can be employed in the region between 350 and
2000 nm. Plastic containers can be used in the
visible region. Crystalline NaCl is the most
common cell windows in the i.r region.
RADIATION
TRANSDUCERS
RADIATION
TRANSDUCERS
Radiation Transducers
Introduction
The detectors for early spectroscopic
instruments were the human eye or a
PHOTON TRANSDUCERS
photon transducers
Several types of photon transducers are available, including
(I) photovoltaic cells, in which the radiant energy generates a current at the
interface of a semiconductor layer and a metal;
(2)
phototubes, in which radiation causes emission of electrons from a photosensitive
solid surface;
(3) photomultiplier tubes,
which contain a photoemissive surface as well as several additional surfaces that
emit a cascade of electrons when struck by electrons from the photosensitive area;
(4) photoconductivity transducers in which absorption of radiation by a semiconductor
produces electrons and holes, thus leading to enhanced conductivity;
(5) silicon photodiodes. in
which photons cause the formation ofelectron-hole pairs and a current across a
reversebiased
pn junction; and `
(6)
charge-transfer transducers, in which the charges developed in a silicon crystal as a
result of absorption of photons are collected and measured.
a) Photovolatic cell
Structure
metal-semiconductor-metal
sandwiches
350-750 nm
550 nm maximum response
10-100 microA
Barrier-layer cell
Low-price
Amplification difficulty
Low sensensitivity for weak
radiation
Fatigue effect
b) Vacuum Phototube
Structure
High sensitivity
Red response
UV response
Flat response
FIGURE7-31 Photomultiplier tube: (a), photograph of a typical commercial tube; (b), cross:
sectional view; (c), electrical diagram illustrating dynode polanzatlon and photocurrent mea
surement. Radiation striking the photosensitive cathode (b) gives nse to photoelectrons by the
hotoelectric effect. Dynode D1 is held at a positive voltage Withrespect to the photocathode.
~Iectrons emitted by the cathode are attracted to the first dynode and accelerated In the fteld.
Each electron striking dynode D1 thus gives rise to two to four secondary electrons. These
are attracted to dynode D2, which is again positive with respect to dynode D1. The resulting
amplification at the anode can be 106 or greater. The exact amplification factor depends on
the number of dynodes and the voltage difference between each. ThiSautomatic Internal
amplification is one of the major advantages of photomultiplier tubes. With modern Instrumentation,
the arrival of individual photocurrent pulses can be detected and counted Instead
of being measured as an average current. This technique, called photon counting, IS
m = dk
e.g. 5 e- emitted / incident e-10
dynodes.
m = dk = 510 1 x 107
Typical Gain = 104 - 107
Douglas A. Skoog and James J. Leary, Principles of Instrumental Analysis,
Saunders College Publishing, Fort Worth, 1992.
e) Silicon Diodes
Photodiodes
High resistant
e-
Forward biasing
Reverse biasing
MULTICHANNEL PHOTON
TRANSDUCERS
Multichannel photon
transducers
The first multichannel detector used in spectroscopy was a
photographic plate or a film strip that was placed along the
length of the focal plane of a spectrometer so that all the lines
in a spectrum could be recorded simultaneously. Photographic
detection is relatively sensitive, with some emulsions that
respond to as few as 10 to 100 photons. The primary limitation
of this type of detector, however, is the time required to
develop the image of the spectrum and convert the blackening
of the emulsion to radiant intensities. Modern multichannel
transducers 24 consist of an array of small photosensitive
elements arranged either linearly or in a two-dimensional
pattern on a single semiconductor chip.
Photodiode Arrays
Photodiode Arrays
In a PDA, the individual photosensitive elements
are small silicon photodiodes, each of which
consists of a reverse-biased pn junction
Photodiode Transducer
Photodiode Array
Photodiode Arrays
Charge-Transfer Device
PHOTO CONDUCTIVITY
TRANSDUCERS
THERMAL TRANSDUCERS
Thermal Transducers
Thermal Transducers are used in infrared
spectroscopy. Phototransducers are not
applicable in infrared because photons in
this region lack the energy to cause
photoemission of electrons. Thermal
transducers
are
Thermocouples,
Bolometer (thermistor).
Thermocouples
In its simplest form, a thermocouple consists of a pair
of junctions formed when two pieces of a metal such as
copper are fused to each end of a dissimilar metal such
as constantan as shown in Figure 3-13. A voltage develops
between the two junctions that varies with the
difference in their temperatures.
A well-designed thermocouple transducer is capable
of responding to temperature differences of
10-6 K. This difference corresponds to a potential difference
of about 6 to 8 V/W.
Thermocouples
bolometer
A bolometer is a type of resistance thermometer
constructed of strips of metals, such as
platinum or nickel, or of a semiconductor.
Semiconductor bolometers are often called
thermistors .
Pyroelectric transducers
Pyroelectric transducers are constructed from single
crystalline wafers of pyroelectric materials, which
are insulators (dielectric materials) with very special
thermal and electrical properties. Triglycine sulfate
(NH2CH2COOH)3 H2SO4 (usually deuterated or
with a fraction of the glycines replaced with alanine), is
the most important pyroelectric material used in the
construction of infrared transducers.
SIGNAL PROCESSORS
AND
READOUTS
PHOTON COUNTING
Photon counting
The output from a photomultiplier tube consists of
a pulse of electrons for each photon that reaches the detector
surface. This analog signal is often filtered to remove
undesirable fluctuations due to the random appearance
of photons at the photocathode and measured as a de voltage or
eurrent.
FIBER OPTICS
Fiber optics
In the late 1960, analytical instruments began to appear
on the market that contained fiber optics for
transmiting radiation and images from one
component of the instrument to another. Fiber optics
have added a new dimension of utility to optical
instrument designs."
Optical Fibers
PROPERTIES
OPTICAL
FIBERS
OF
Optical Fiber
FIBER-OPTIC SENSORS
Fiber-optic sensors
Fiber-optic sensors, which are sometimes called
optrodes, consist of a reagent phase immobilized on
the end of a fiber optic. Interaction of the analyte with
the reagent creates a change in absorbance,
reflectance, fluorescence, or luminescence, which is
then transmitted to a detector via the optical fiber.
Fiber optic Sensors are generally simple, inexpensive
devices that are easily miniaturized.
TYPES OF OPTICAL
INSTRUMENT
Spectroscope
Colorimeter
Spectrometer
Spectrograph
Fluorometer
Photometer
More(confusing)
PRINCIPLES OF FOURIER
TRANSFORM OPTICAL
MEASUREMENTS
The instruments we have been talking about work over the frequency domain (we are
measuring signal vs. frequency or wavelength)
Fourier transform techniques measure signal vs. time and then convert time to
wavelength or frequency
FT techniques have much greater resolving power than frequency domain techniques
Fewer mechanical parts
No monochromator
Mathematical deconvolution of the spectrum
FT techniques have higher light throughput because there are fewer optical
components.
Widely used in IR and NMR
Originally developed to separate out weak IR signals from astronomical objects.
An interferometer splits the light beam into two beams and then measures the intensity
of recombined beams
The frequency of these beams is related to the frequency of the light that caused
them.
History
In 1950s, astronomy
Fourier transform
Resolution of FT spectrometer
INHERENT ADVANTAGES OF
FOURIER
TRANSFORM SPECTROMETRY
Advantages of FT
High Resolution
TIME -DOMAIN
SPECTROSCOPY
Freq-domain / time-domain
MICHELSON
INTERFEROMETER
modulation
Velocity of moving
mirror(MM)
Time to move l/2 cm
Bolometer, pyroelectric,
photoconducting IR
detectors can
"see changes on 10-4 s
time scale!
Michelson interferometer
Analysis of interferogram
FT
inverse FT
Fourier Transformation of
Interferograms
Interferogram
retardation d
Difference in pathlength
interferogram
Plot signal vs. d
cosine wave with frequency proportional to light
frequency but signal varies at much lower frequency
resolution
resolution
The resolution of a Fourier transform
spectrometer can be described in terms of the
difference in wavenumber between two lines
that can be just separated by the instrument.
That is,
Semiconductor Diodes