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C) Echelle Monochromators

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.

Echelle grating: Light is reflected off the short


side of the blazes (grooves) in the grating.

2-D distribution of light and detection


using an array of transducers (for later)

MONOCHROMATOR
SLITS

Slits = hole in the wall

Control the entrance of light into and out from the


monochromator. They control quality!

Entrance slits control the intensity of light entering the


monochromator and help control the range of wavelengths of
light that strike the grating
Less important than exit slits

Exit slights help select the range of wavelengths that exit the
monochromator and strike the detector
More important than entrance slits

Can be:

Fixed (just a slot)


Adjustable in width (effective bandwidth and intensity)
Adjustable in height (intensity of light)

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

Effect of Slit Width on Resolution

Effect of slit width on resolution

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

FIGURE 7-24 Illumination of an exit slit by


monochromatic radiation at various monochromator
settings. Exit and entrance slits are identical.

Calculating slit width

Effective bandwidth(Dleff) and D-1

D-1 = Dl/Dy
When Dy = w = (slit width)
D-1 = Dleff /w

Example

Recpiprocal linear dispersion = 1.2nm/mm


Sodium lines at 589.0 nm and 589.6 nm
Required slit width?
Dleff = (589.6-589.0) = 0.3 nm
W = 0.3 nm/(1.2 nm/mm) = 0.25 mm
Practically, narrower than the theoretical values is necessary
to achieve a desired resolution

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.

Wider slits = greater intensity,


Poorer resolution

Narrower slits = lower intensity,


Better resolution

Choice of slit widths

Variable slits for effective


bandwidth
Narrow spectrum

Minimal slit width


Bet decrease in the radiant
power

Quantitative analysis

Wider slit width


for more radiant power

Effect of bandwidth on spectral


detail for benzene vapor

SAMPLE HOLDERS
(CELLS)

Sample Holders (Cells)

Must:

Examples

contain the sample without chemical interaction


be more-or-less transparent to the wavelengths of light in use
be readily cleaned for reuse
be designed for the specific instrument of interest.
quartz is good from about 190-3000 nm
glass is a less expensive alternative from about 300-900 nm
NaCl and KBr are good to much higher wavelengths (IR range)

Cells can be constructed to:

transmit light absorbed at 180 degrees to the incident light


allow emitted light to exit at 90 degrees from the incident light
contain gases (lower concentrations) and have long path lengths (1.0
and 10.0 cm cells are most common)

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.

Absorbance: usually in a matched pair!

Fluorescence, Phosphorescence, Chemiluminescence

Different Shapes and Sizes of Cells

RADIATION
TRANSDUCERS

RADIATION
TRANSDUCERS

Radiation Transducers
Introduction
The detectors for early spectroscopic
instruments were the human eye or a

photographic plate or film. Now a days


more modern detectors are in use that

convert radiant energy into electrical signal.

properties of the Ideal Transducer


The ideal transducer would have a high sensitivity, a
high signal-to-noise ratio, and a constant response
over a considerable range of wavelengths. In
addition, it would exhibit a fast response time and a
zero output signal in the absence of illumination,
Finally, the electrical signal produced by the ideal
transducer would be directly proportional to the
radiant power P.

Types of Radiation Transducers


As indicated in Figure 7-3b, there arc two general
types of radiation transducers.2o One type responds to
photons, the other to heat. All photon transducers (also
called photoelectric or quantum detectors) have an
active surface that absorbs radiation. [n some types, the absorbed
energy causes emission of electrons and
the production of a photocurrent. In others, the radiation
promotes electrons into conduction bands: detection
here is based on the resulting enhanced conductivity
(photo conduction), Photon transducers are used
largely for measurement of UV, visible, and near infrared
radiation.

the relative spectral response of


the various kinds of transducers that are useful for UV,
visible, and IR spectroscopy.

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

produce voltage when irradiated

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

Wire anode and semi cylinder


cathode in a vacuum tube
Photosensitive material

electrons produced by irradiation


of cathode travel to anode.
l response depends on cathode
material (200-1000 nm)

High sensitivity
Red response
UV response
Flat response

FIGURE 7-29 A phototube and op amp readout. The


photocurrent induced by the radiation causes a voltage
drop across R, which appears as "0 at the output of the
current-to-voltage converter. This voltage may be displayed
on a meter or acquired by a data-acquisition

What do we want in a transducer?


High sensitivity
High S/N
Constant response over many l s (wide range of
wavelength)
Fast response time
S = 0 if no light present
S P (where P = radiant power)
Photon transducers: light electrical signal
Thermal
transducers: response to heat
conduction bands (enhance conductivity)

c) Photomultiplier Tube (PMT)

Extremely sensitive (use for low light applications).

Light strikes photocathode (photons strike emits


electrons); several electrons per photon.

Bias voltage applied (several hundred volts) electrons


form current.

Electrons emitted towards a dynode (90 V more positive


than photocathode electrons attracted to it).

Electrons hit dynode each electron causes emission of


several electrons.

These electrons are accelerated towards dynode #2 (90 V


more positive than dynode # 1) etc.

d) Photomultiplier tubes (found in more advanced,


scanning UV-VIS and spectroscopic instruments)

Also function based on the photoelectric effect

Additional signal is gained by multiplying the number of electrons produced by


the initial reaction in the detector.

Each electron produces as series of photo-electrons, multiplying its signal. Thus


the name PMT!

Very sensitive to incoming light.


Most sensitive light detector in the UV-VIS range.
VERY rugged. They last a long time.
Sensitive to excessive stray light (room light + powered PMT = DEAD
PMT)

Always used with a scanning or moveable wavelength selector (grating) in a


monochromator

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

819 dynodes (9-10 is most


common).

Gain (m) is # e- emitted per


incident e- (d) to the power
of the # of dynodes (k).

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

Constructed of charge depleted and charge rich


regions of silicon (silicon doped with other ions)
Light striking the detector causes charge to be
created between the p and n regions.
The charge collected is then measured as current
and the array is reset for the next collection
Used most frequently these days in instruments
where the grating is fixed in one position and light
strikes an array of silicon diodes (aka the diode array

Can have thousands of diodes on an array


Each diode collects light from a specific wavelength range
The resolution is generally poorer than with a PMT
However, you can scan literally thousands of times a
minute since there are NO moving parts! Then, the scans

Photodiodes

Douglas A. Skoog and James J. Leary, Principles of Instrumental Analysis,


Saunders College Publishing, Fort Worth, 1992.

the relative spectral response of


the various kinds of transducers that are useful for UV,
visible, and IR spectroscopy.

Skoog et al. 2007

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.

Multichannel Photon Transducers


Photographic plate or a film strip
Place along the focal plane of a spectrometer

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

A silicon photodiode transducer consists of a


Reversed Biased pn junction formed on a silicon chip
A photon promotes an electron from the valence bond
(filled orbitals) to the conduction bond (unfilled
orbitals) creating an electron(-) - hole(+) pair
The concentration of these electron-hole pairs is
dependent on the amount of light striking the
semiconductor

Photodiode Array

Semiconductors (Silicon and Germanium)


Group IV elements
Formation of holes (via thermal
agitation/excitation)
Doping
n-type: Si (or Ge) doped with group V element
(As, Sb) to add electrons.
As: [Ar]4S23d104p3
p-type: Doped with group III element (In, Ga) to
added holes
In: [Kr]5S24d105p1

Skoog et al, p43

FIGURE 7-33 A reverse-biased linear diode-array


detector: (a)cross section and (b)top view.

Photodiode Arrays

Charge-Transfer Device

Charge-Transfer Device (CTD)

Important for multichannel detection (i.e., spatial


resolution); 2-dimensional arrays.
Sensitivity approaches PMT.
An entire spectrum can be recorded as a
snapshot without scanning.
Integrate signal as photon strikes element.
Each pixel: two conductive electrodes over an
insulating material (e.g., SiO2).
Insulator separates electrodes from n-doped silicon.

Semiconductor capacitor: stores charges that are


formed when photons strike the doped silicon.
105 106 charges/pixel can be stored (gain
approaches gain of PMT).
How is amount of charge measured?
Charge-injection device (CID): voltage change
that occurs from charge moving between
electrodes.
Charge-coupled device (CCD): charge is moved
to amplifier.

PHOTO CONDUCTIVITY
TRANSDUCERS

Photo conductivity Transducers


The most sensitive transducers for monitoring
radiation 10 the near-infrared region (0.75 to 3
/m) are semiconductors whose resistances
decrease when they
absorb radiation within this range.

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

Signal Processors and Readouts


The signal processor is ordinarily an electronic
device that amplifies the electrical signal from the
transducer. In addition, it may alter the signal from
dc to ac (or the reverse), change the phase of the
signal, and filter it to remove unwanted
components. Furthermore, the signal processor
may be called upon to perform such mathematical
operations on the signal as differentiation,
integration, or conversion to a logarithm.

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

Used to transmit light waves over non-linear


paths.
Often used in remote sensing, solution sampling
(dipping probes) and field instruments
Based on the fact that light inside a fiber can be
continuously (totally internally reflected) if the
angle it strikes the fiber surface at is correct
(determines radius of bends, etc.).
Used in construction of optodes (optical fiber
based chemical sensor)

PROPERTIES
OPTICAL
FIBERS

OF

Properties of Optical Fibers


Optical fibers are fine strands of glass or plastic that
transmit radiation for distances of several hundred feet
or more. The diameter of optical fibers ranges from
0.05 pm to as large as 0.6 cm. Where images are to be
transmitted, bundles of fibers, fused at the ends, are
used. A major application of these fiber bundles has
been in medical diagnoses, where their flexibility permits
transmission of images of organs through tortuous
pathways to the physician. Fiber optics are used
not only for observation but also for illumination of
objects. In such applications, the ability to illuminate
without heating is often very important.

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

Types of Optical Instruments

Spectroscope

Colorimeter

Record simultaneously the entire spectrum of a dispersed radiation using


plate or film

Spectrometer

A photometer for fluorescence measurement

Spectrograph

Contains a filter, no scanning function

Fluorometer

Human eye acts as detector for absorption measurements

Photometer

Optical instrument used for visual identification of atomic emission lines

Provides information about the intensity of radiaition as a function of


wavelength or frequency

More(confusing)

types of Optical instrument


Spectroscope:an optical instrument used for the
visual identification of atomic emission lines. We use the term
colorimeter: to designate an instrument for absorption
measurements in which the human eye serves as the detector
using one or more color-comparison standards. spectro graph:
is similar in construction to the two monochromators shown in
Figure 7-18 except that the sht arrangement is replaced with a
large aperture that holds a detector or transducer that is
continuously exposed tn the entire spectrum of dispersed
radiation. spectrometer :is an instrument that provides
information
about the intensity of radiation as a function of wavelength or
frequency.

PRINCIPLES OF FOURIER
TRANSFORM OPTICAL
MEASUREMENTS

Fourier Transform (FT)

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

Separate weak signals from noise

Late 1960s, FT-NIR & FT-IR

Fourier transform

Resolution of FT spectrometer

Two closely spaced lines only separated if one complete


"beat" is recorded.
As lines get closer together, d must increase.

INHERENT ADVANTAGES OF
FOURIER
TRANSFORM SPECTROMETRY

Advantages of FT

Throughput / Jaquinot advantage

High Resolution

Few optics and slits


Less dispersion, high intensity
Usually to improve resolution decrease slit width
but less light makes spectrum "noisier" (S/N)
Dl/l = 6 ppm

Short time scale

Simultaneously measure all spectrum at once saves time


frequency scanning vs. time domain scanning
Fellgett or multiplex advantage

TIME -DOMAIN
SPECTROSCOPY

time -domain spectroscopy


Conventional spectroscopy can be termed
frequency domain spectroscopy in that radiant
power data are recorded as a function of
frequency or the inversely related wavelength.
In contrast, time-domain spectroscopy, which
can be achieved by the Fourier transform, is
concerned with changes in radiant power with
time.

Time domain spectroscopy

Unfortunately, no detector can respond on 10-14


s time scale
Use Michelson interferometer to measure signal
proportional to time varying signal

Freq-domain / time-domain

ACQUIRING TIME-DOMAIN SPECTRA


WITH A

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!

This time domain spectrum is made of


different wavelengths of light arriving at the
detector at different times.

Michelson interferometer

Analysis of interferogram

Computer needed to turn


complex interferogram into
spectrum
Figure 7-43

FT

(b) resolved lines


(c) unresolved lines
Time -> Frequency

inverse FT

Frequency -> Time

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

One full cycle when mirror moves distance l/2


(round-trip = l)

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

Diode: is a nonlinear device that has greater


conductance in one direction than in another
Adjacent n-type and p-type regions
pn junction: the interface between the two regions

This process continues for 9 dynodes


Result: for each photon that strikes photocathode
~106 107 electrons collected at anode.
Is there a drawback? Sensitivity usually limited by
dark current.
Dark current = current generated by thermal
emission of electrons in the absence of light.
Thermal emission reduce by cooling.
Under optimal conditions, PMTs can detect single
photons.
Only used for low-light applications; it is possible
to fry the photocathode.

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