Introduction

• X-rays are a part of electromagnetic spectrum.

• X-rays have a wavelength in range of 10-5 Å to 100 Å; conventional X-Ray
spectroscopy is largely confined to approximately 0.1 Å to 25 Å .
• X- Ray spectroscopy is based upon
measurement of emission, absorption,
scattering, fluorescence and diffraction of
electromagnetic radiation.

• They are defined as short wavelength

electromagnetic radiation produced by
deceleration of high-energy or

• Electronic transition of electrons in the inner

orbitals of atoms.
 X RAY CHARACTERSTICS
EMISSION
Produced in three ways:
1. By bombardment of a metal target with
a beam of high energy electrons
2. By exposure to primary beam of X-rays
to generate secondary X-Rays
3. By employment of radioactive source
whose decay process results in X-Ray
emission.

X-Ray sources produce both continuous

and line spectrum.
• Continuous radiation also called white
radiation or Bremsstrahlung the latter
meaning radiation arising from retardation of
particles.
• It is dependent on accelerating voltage V but
independent of target material.
• It results from collision between electrons of
beam and atoms of target material.
• The maximum photon energy corresponds to
instantaneous deceleration of electron to zero
kinetic energy in single collision.

• Duane-Hunt Law
hν0 = h c/ λ0= Ve where
Ve, product of accelerating voltage and charge on
electron, is K.E. of all electrons in the beam, h is
Planck’s constant, and c is velocity of light; ν0 is
maximum frequency of radiation that can be
produced at voltage V ( volts) and λ0 (Å) is low
wavelength limit for radiation.
• λ0= 12,398/V (after substituting numerical values)

• Characteristic line spectra result from

electronic transitions involving innermost
orbitals.
Characteristic Line Spectra
• Line Spectra consists of two series of lines.
• The shorter wavelength is called K-series
and longer wavelength L-series.
• The short wavelength produced when high
energy electrons from cathode remove
electrons from orbitals nearest to nucleus
of target atom. The formation of excited
ion results which loses quanta of X-
radiation as electrons from outer orbitals
undergo transitions to vacated orbitals.
• The wavelengths of characteristic X-Rays is
independent of chemical combination
because transitions responsible for these
lines involve electrons that take no part in
bonding.
• Moseley’s Law (1914): A linear
relationship exists between reciprocal
values of wavelength for each transition
series and the square of the atomic no. Z
of the excited atom.
ABSORBTION

• X rays are absorbed by matter and degree of

absorbtion is determined by the nature and
amount of absorbing material.

• A peculiarity of X-Ray spectra is appearance of

sharp discontinuities, called absorption edges,
at wavelengths immediately beyond
absorption maxima.

• At absorption maxima the energy of X-Ray

quantum corresponding to that wavelength
exactly matches the energy required to just
eject the highest energy K electron of the
element; immediately beyond this wavelength,
the energy of the radiation is insufficient to
bring about removal of K electron and abrupt
decrease in absorption occurs.

• The energy of radiation is partitioned between

K.E. of electron and P.E. of the excited ion.
Where x is the sample thickness in cms and I and I0 are intensities of transmitted
and incident beams. ρ is density of sample and μm is mass absorption coefficient,
a quantity independent of physical and chemical state of element. It has unit
cm2/g.

Mass absorption coefficients are additive functions of the weight fractions of

elements contained in a sample. Thus,

μm= WA μA + WB μB+ WC μC +…….

where sample is containing weight fractions WA, WB, WC of elements A,B, and C.
The terms μA , μB , μC are the respective mass absorption coefficients for each of
the elements.
FLUORESCENCE

• The absorption of X-Rays produce electronically excited

ions that return to ground state by transitions involving
electrons from higher energy levels characterised by
emission of X-radiation (fluorescence) of wavelengths
identical to those that result from excitation produced by
electron bombardment.

• When fluorescence is to be excited by radiation from an

X-Ray tube , the operating voltage must be sufficiently
great so that cut off wavelength λ0 is shorter than the
absorption edge of the element whose spectrum is to be
excited.
DIFFRACTION

• Diffraction of x rays is used in analysis of

crystalline materials with high degree of accuracy
and specificity.

• When X-rays are scattered by ordered

environment in a crystal, interference both
constructive and destructive) takes place among
the scattered rays because distance between
scattering centers are of the same order of
magnitude as the wavelength of the radiation.
Diffraction is the result.
Bragg’s Law (1912)
• The X-Rays appear to be
reflected from the crystal only if
the angle of incidence ϴ
satisfies the condition that

sin ϴ= n λ/ 2 d

where d is the interplanar

distance of the crystal , n is an
integer , λ is wavelength of X-
radiation.

• At all other angles, destructive

interference occurs.
 INSTRUMENTATION FOR X-RAY SPECTROSCOPY
Components for X-ray spectroscopy are :
(1) X-ray generating equipment (X-ray tube)
(2) Collimator
(3) Analyzer Crystal
(4) Monochromators
(5) Detectors
 X-Ray Tube
Determining
the energy of
the X-Ray

100KV!

Controlling
the intensity
of X-Ray
 X-Ray Tube

• X-rays can be generated by an X-ray tube.

• X-rays tube is a vacuum tube that uses a high voltage to accelerate the
electrons released by a hot cathode to a high velocity.
• The high velocity electrons collide with a metal target, the anode, creating the
X-rays.
• Less than 1% of electrical power converted to radiant power so anode cooled
Collimators

• A collimator is a device that narrows a beam of particles or waves.

• Narrow mean to cause the directions of motion to become more aligned in a
specific direction (i.e., collimated or parallel).
• Collimation is achieved by using a series of closely spaced ,parallel metal
plates or by a bundle of tubes ,0.5 or less in diameter.
Analyzer Crystal
• Analyzing crystal acts as diffraction grating (dispersing
element) scanning through entire range of goniometer
(monochromator) and permits radiation at a particular
position to be correlated with wavelength through Bragg’s
condition.
• The range of wavelengths usable with various crystals is
governed by d spacings of the crystal planes and by the
geometric limits to which goniometer can be rotated.
• No crystal can be used over entire range. Ammonium
dihydrogen phosphate has much greater wavelength range
but it slow dispersion prevents its use at low wavelegths.
Topaz , LiF used at low wavelengths .
• Crystal is mounted on rotating table that permits variation
and precise determination of angle ϴ between crystal face
and collimated incident beam.
 Monochromator

• Need of Monochromator

• Types of Monochromator

• Working of Filters

• Filter v/s Monochromator

• Working of diffraction grating

• Advantages of monochrome X-Rays

 Need of Monochromator

Monochromators

• Monochromator crystals partially polarize an unpolarized X-ray beam

• The main goal of a Monochromator is to separate and transmit a
narrow portion of the optical signal chosen from a wider range of
wavelengths available at the input.
 Types of Monochromator

• Metallic Filter Type

• Diffraction grating type

 Working of Filters

• Filters exploit the X-ray

absorption edge of the
particular element.
• At wavelengths longer than
the absorption edge (i.e. just
above the edge), the
absorption of the X-rays is
considerably less than for
wavelengths shorter than the
absorption edge (i.e. just
below the edge) as shown for
nickel metal:
 Working of Filters

• The absorption edge of

nickel metal at 1.488 Å lies
between the Kα
(λ = 1.542 Å) and Kβ
(λ = 1.392 Å) X-ray spectral
lines of copper. Hence nickel
foil of an appropriate
thickness can be used to
reduce the intensity of the
Cu Kβ X-rays as shown:
 Choice of filter metal

• The choice of filter material depends upon the choice of

anode material in the X-ray tube as shown in the following
table:

Anode Cu Co Fe Mo Cr

Filter Ni Fe Mn Zr V
 Limitations of Filter

• X-ray filters were used to reduce the unwanted white radiation

from the X-ray source and to eliminate (as much as possible)
the Kβ radiation.
• The drawback of filters is that the background radiation is still
high and that the transmitted radiation is still not very
monochromatic.
 Working of diffraction grating

• Source (A)

• Entrance slit (B)

• Collimator(C)

• Grating (D)

• Another mirror (E)

• Exit slit (F)

 Advantages of monochrome X-Rays

• Improved resolution
• Minimizing sample damage
• Improved signal to noise ratio
• Analyze of small samples
• Multispotting on samples
• Simplified data processing
 X-ray Detectors

• Solid State Detectors

• Scintillation Detectors

• Gas-filled Detectors
 Solid State Detectors

X-ray
 Solid State Detectors

• The charge carriers in semiconductor are electrons and holes.

• Radiation incident upon the semiconducting junction

produces electron-hole pairs as it passes through it. Electrons
and holes are swept away under the influence of the electric
field, and the proper electronics can collect the charge in a
pulse.
 Scintillation Detector

Photo Cathode Dynodes

e- -
HV
e-
+
Scintillator
Focusing
cup
Resistor
 Scintillation detectors
• Scintillation detectors consist of a scintillator and a device, such as a
PMT(Photomultiplier tubes), that converts the light into an electrical
signal

• Consists of an evacuated glass tube containing a photocathode,

typically 10 to 12 electrodes called dynodes, and an anode.

• Electrons emitted by the photocathode are attracted to the first

dynode and are accelerated to kinetic energies equal to the potential
difference between the photocathode and the first dynode.
 Scintillation detectors
• When these electrons strike the first dynode, about 5 electrons are
ejected from the dynode for each electron hitting it.
• These electrons are attracted to the second dynode, and so on, finally
reaching the anode.
• Total amplification of the PMT is the product of the individual
amplifications at each dynode.
• If a PMT has ten dynodes and the amplification at each stage is 5, the
total amplification will be approximately 10,000,000.
• Amplification can be adjusted by changing the voltage applied to the
PMT.
Gas-filled detectors
 Gas-filled detectors
• A gas-filled detector consists of a volume of gas between two
electrodes, with an electrical potential difference (voltage) applied
between the electrodes.

• Ionizing radiation produces ion pairs in the gas.

• Positive ions (cat-ions) attracted to negative electrode (cathode);

electrons or anions attracted to positive electrode (anode).

• In most detectors, cathode is the wall of the container that holds the
gas and anode is a wire inside the container.
 Geiger Mueller Counter

e- (+) Anode

Resistor (-) Cathode

+ -

Battery or
High Voltage 33
 Geiger Mueller Counter
• GM counters also must contain gases with specific properties
• Most common type of detector
• Electrical collection of ions
• When the gas amplification factor reaches 108, the size of the output
pulse is a constant, independent of the initial energy deposit.
• In this region, the Geiger- Mueller region, the detector behaves like a
spark plug with a single large discharge.
• Simple cheap electronics.
• Energy dependence.
• Large dead times, 100-300µs, result
• No information about the energy of the radiation is obtained or its
time characteristics.
 X-ray Diffractometer
• Diffraction is a phenomena of bending of light around the corners of an
obstacle ,when the size of an obstacle is of the order of wavelength of light.

• Bragg's law n = 2d Sin

where d= distance between similar atomic planes in mineral (inter-atomic
spacing
 = angle of diffraction
= wavelength
n= an integer – 1,2,3.. etc (order of diffraction)

• A diffractometer is a measuring instrument for analyzing the crystallographic

structure of a material from the scattering (diffraction) pattern produced
when a beam of radiation or particles (such as X-rays) interacts with it.
 X-ray Diffractometer
• A typical diffractometer consists of a source of radiation, a
monochromator to choose the wavelength, collimator to make the beam
parallel, a sample and a detector.

• An x-ray diffractometer illuminates a sample of material with x-rays of

known wavelength.

• A strip of X-Ray film is mounted in circular position around the sample.

• The undeviated central beam passes out through a hole E cut in the film
strip P. Diffracted beam falls on the film at various points like d1, d2, d3 etc.

• Intensities of the diffraction peaks are proportional to the fraction of the

material in the mixture.
References:
Principles of Instrumental analysis, Skoog
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