Materials Characterization

X-ray Diffraction (XRD)

Recap Intensity controlling factor
2
I 0   e  M ( hkl)
3 2
2  1  cos 2 (2 ) cos 2 (2 m )  v
I ( hkl)   
2 
F( hkl)  
64r  me c  V2
 sin  cos
2
 hkl  s
where:
I(hkl)= Intensity of reflection of (hkl) in phase .
I0 = incident beam intensity
r = distance from specimen to detector
 = X-ray wavelength
2nd term = square of classical electron radius
Mhkl = multiplicity of reflection hkl of phase 
Next to last term on right = Lorentz-polarization (and monochromator)
correction for (hkl)
In that term, 2m = diffraction angle of the monochromator
v = volume of the unit cell of phase 
s = linear absorption coefficient of the specimen
F(hkl) = structure factor for reflection hkl of phase  (i.e., the vector sum of
scattering intensities of all atoms contributing to that reflection).
 Intensity controlling factor
Factors affecting
the relative intensity of Bragg reflections
Scattering factor
Structure factor
Polarization factor
Multiplicity factor
Lorentz factor
Absorption factor
Temperature factor
 Lorentz-Polarization factor
Lorentz-Polarization factor is combination of geometric and polarization factors (LP). It
depends on the relative opportunity of a plane to diffract as a function of θ.

LP =

θ is the Bragg angle

θm is the Bragg angle of
θ LP
monochromator crystal

2
I 0   e 2  M ( hkl)
3
2  1  cos 2 (2 ) cos 2 (2 m )  v
I ( hkl)   
2 
F( hkl)  
64r  me c  V 2
 sin  cos
2
 hkl  s

I LP
 Multiplicity factor
The multiplicity factor refers to the relative proportion of the planes contribute to diffraction.
i.e., the number of different planes having the same spacing.
More the number of planes under same family greater is the intensity.
• For example; {100} family in cubic crystal:

(100) , (010), (010), (100), (010), (001)

Intensity Intensity
m(100) = 6
Cubic crystal > Tetragonal crystal
for {100} for {100}
•{100} family in tetragonal crystal:

(100) , (010), (100), (010),

m(100)= 4
 Absorption factor
Absorption factor depends on loss of intensity of X-ray beam with in the crystal. The net
result is that the diffracted beam is of lower intensity than one would expect for a
specimen of no absorption.

 For ray 1, absorption of both incident and diffracted

beams occurs along a path of AB and BC respectively.
2

 Similarly for ray 2, absorption of both incident 1

and diffracted beams occurs along a path of DE

and EF respectively.
 Temperature factor
 Atoms in a crystal at a given temperature oscillate about their mean
position. As the
temperature increases, this vibration amplitude increases.

 If the thickness of the plate-like plane in which atoms are vibrate is “2u”,
where “u” is the average amplitude of an atom from its mean position.

 With increasing temperature reinforcement is no longer perfect, and it

becomes more imperfect as the ratio u/d increases.

 Therefore thermal vibration decrease intensity of a diffracted beam

because it has effect of
spreading out the lattice plane.

 But broadening of the diffraction lines does not cause by thermal vibration
; they remain sharp right up to the melting point.
 Instrumental parts of Diffractometer

X-ray source Sample Detector

Incident beam Diffracted beam

Single crystal OR
Powder (Polycrystalline)

Basic assumption of Powder samples is that the crystals are randomly

oriented so that there are always some crystals oriented to satisfy the
Bragg condition for any set of planes
 Instrumental parts of Diffractometer
➢X-ray Tube: The source of X-rays

➢Incident-beam optics: Control and monitor X-ray beam before it hits the sample

➢Sample holder: Stage that hold sample

➢Receiving-beam optics: Control and monitor reflected X-ray by the sample

➢Detector: Count the reflected X-rays scattered by the sample

➢The goniometer: Platform that rotates the sample, optics, detector, and/or tube
 Instrumental parts of Diffractometer

Detector
Incident- beam
optics
X-ray Tube Receiving- beam
optics
Sample holder

The goniometer
Instrumental parts of X-ray Diffractometer

Limit Side divergence

Clean-up diffracted beam, fluorescence,

Set required divergence incoherent scatter
for sample
 XRD component

Optic Function
Source Generate X-ray
Filter Remove unwanted wavelength
Monochromators
Soller slit Allow parallel X-rays
Divergence slit Block highly diverge X-ray
Anti-scatter slit
Receiving slit Control receive X-ray opening
Detector Detect diffraction pattern
Instrumental parts of X-ray Diffractometer

➢ An X-ray beam diffracted from a lattice plane can

be detected when X-ray source, the sample and the
detector are correctly oriented to give Bragg
diffraction

➢ The detector is scanned around the sample along a

circle, in order to collect all the diffracted X-ray
beams.

X-ray beam diffracted from a lattice

 X-ray source

 An atom as consisting of a central nucleus surrounded by electrons lying in various shells. Electrons
bombard the target has sufficient kinetic energy, it can knock an electron out of the K shell, leaving the atom
in an excited, high-energy state. Then one of the outer electrons immediately falls into the vacancy in the K
shell and the atom is once again return in its normal energy state. The energy emitted is in the form of
radiation of a definite wavelength is called X-ray.

 The K-shell vacancy may be filled by an electron from any one of the outer shells
such as L or M, thus giving rise to a series of K lines; Kα and Kβ lines. Therefore
one atom of the target may be emitting Kα radiation while its neighbor is emitting
Kβ. And X-ray source may have mix of both.

 “L” characteristic lines originate in a similar way while an electron is

knocked out from the “L” shell
 X-ray source

❖ X-rays are produced whenever high-speed electrons collide with a metal target.

❖ Essential parts of X-ray tube are: (i) source of electrons, (ii) high accelerating voltage, and (iii) metal
target .

❖ Electron are produced by two ways (i) Filament tubes, in which the source of electrons is a hot filament,
or (ii) gas tubes, in which electrons are produced by the ionization of a small quantity of gas in the tube.

❖ X-ray tube contains an anode (the metal target) and a cathode maintained at a high negative potential
in the order of 30,000 to 50,000 volts for diffraction work. High voltage accelerate the produced
electron and heat the target anode

❖ Since most of the kinetic energy of the electrons is converted into heat in the metal target, therefore
X-ray tube must have water-cooling system to prevent its melting.
X-ray source

X-ray tube
X-ray source

X-ray tube
 X-ray source
 Electrons from the filament strike the target anode (Cu), producing characteristic radiation
via the photoelectric effect.

 The wavelengths of characteristic radiation depends on the material of Anode .

 The X-ray beam actually consists of several characteristic wavelengths of X rays.

For copper, the λ are:

CuKα1 = 1.540 Å
CuKα2 = 1.544 Å
CuKβ = 1.39 Å
 X-ray source

Common X-ray Sources