X-Ray diffraction Engineering Physics

3.1 Basic principles:-

phenomenon like interference and diffraction. Wavelength of x-rays is of the

order of 1 Ao. So, that x-ray does not produce observable diffraction effects

with ordinary ruled diffraction grating.

In 1912 von Laue suggested that crystals are more suitable to observe

diffraction effects with x-rays. The important condition for observable diffraction

effects is that the wavelength of the rays and inter planar separation should be

of the same order. Here for x-rays,   1Ao where as inter planar separation is

about 2 A. After Fredrich and knipping who demonstrated that x-ray beam

passing through single crystal was broken up into a collection of diffracted

beams. The measurements of diffracted beam intensities and their directions

would provide the desired information about the crystals.

3.2 Bragg’s law: -

Bragg’s law explains the conditions under which diffracted x-ray beams from a

crystal are possible the diffraction pattern so produced can tell us much about

the internal arrangement of atoms in crystals.

Let us consider a crystal made up of equidistant parallel planes of atoms with

inter planar spacing d further, consider a monochromatic x-ray beam of

wavelength  , having a common wave front, falls at an angle  on these

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 X-Ray diffraction Engineering Physics

planes. Each atom scatters the x-ray uniformly in all directions, because of the

periodic arrangement of atoms, the scattered radiation from all the atoms in a

set of planes is in phase, where they interfere constructively and in out of

phase they interfere destructively

Consider two rays ABC and DEF, which are reflected from different planes in a

given set of lattice planes separated by a distance “d “ which is called inter

planar separation.

Let be the angle made by the rays with different set of planes. The two rays

are reflected from different planes. Thus, the rays BC and EF are reflected from

the two points B and E. the path length of ABC and DEF are not same. Extend

the rays AB to cut EF at H and CB to cut DE at G .the path length of the ray

DEF is greater than the path length of ABC by an amount (GE+EH).

 The path difference between two rays reflected from adjacent planes

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 X-Ray diffraction Engineering Physics

= GE+EH------------ (1)

GE
From  BGE sin  =
BE

= > GE =BE sin  = d sin 

EH
From  BEH sin  =
BE

 EH = BE sin 

=d sin 

 Substituting the values of GE and EH in (1), then the total path difference is

∆ = GE+EH

= d sin  + d sin 

= 2dsin  ---------- (2)

∆ = 2dsin 

if this path difference is an integral multiple of the wavelength  ,the

reflected beam will interfere constructively ,giving maximum intensity i.e.,

constructive diffraction.

Thus,

n  2d sin 

This is known as “BRAGG’S LAW”.

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 X-Ray diffraction Engineering Physics

Bragg’s law states that the x-rays reflected from different parallel Planes of a

crystal interfere constructively when the path difference is integral multiple of

the wavelength of x- rays.

We know that  sin  max  1 then we obtain

n
1
2d

This indicates that  must not be greater than twice the inter planar spacing,

otherwise no diffraction will occur.

3.3 Laue method: -

1. In the Laue method a single crystal is stationary in a beam of x-rays of

continuous wavelength. A crystal selects and diffracts the discrete values

of  for which planes exist of spacing‘d’ and incidence angle ‘  ’

satisfying Bragg’s.

2. The experimental arrangement is shown in fig. A source producing a

beam of x-rays over a wide range of wavelengths preferably 0.2 to 2A0is

used. A pinhole arrangement produces a well-collimated beam.

3. The dimensions of the single specimen need not be greater than 1 mm.

A photographic plate placed at certain distance from the crystal to

record the diffracted rays from single crystal.

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 X-Ray diffraction Engineering Physics

4. The diameter of the pin holes is important for the quality of Laue spot,

which are traced on the plate. The diffraction pattern consists of a series

of spots. This pattern will show the symmetry of the crystal

5. The most important point in this pattern is that the x-ray beam contains

many wavelengths. If we take monochromatic x-ray beam and allow it to

pass through single crystal, the diffraction is not to be expected. This is

because very few sets of planes will satisfy the Bragg’s diffraction

condition.

6. But if the source has whole range of wavelengths in the continuous x-

ray spectrum, there will be different values of  , which satisfy Bragg’s

condition.

7. We know that atoms of a crystal have an orderly arrangement in all

three dimensions in space. Hence the diffraction of x- rays will occur

from many families of atomic planes. Each family picks out the

wavelength which it can diffract by satisfying Bragg’s law

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 X-Ray diffraction Engineering Physics

8. The diffraction pattern consists of a series of spots. Each dot is called

as Laue spot and the entire spots are called as “Laue diffraction pattern

“. Each Laue spot represents a set miller indices of planes in the crystal.

The shape of the unit cell can be established from the symmetry of the

Laue pattern.

3.4 Powder method: -

1. The powder method was developed by Debye, Scherrer and by Hill. This

method is used to study the structure of the crystals, which cannot be

obtained easily in the form of perfect crystals of appreciable size.

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 X-Ray diffraction Engineering Physics

2. Therefore the sample used is in the form of a fine power containing a

large no. of tiny crystallites with random orientations.

3. A diagram of a powder camera is shown in fig. There is a specimen

holder at the center of the cylindrical camera. The finely powdered

sample is filled in a thin capillary tube (or) is simply passed on wire by

means of binder and mounted at the center of the camera.

4. Then the camera along with the specimen is taken to the dark room

where a thin strip of x-ray film is loaded in the cylindrical cassette.

Before the camera is loaded the film is punched to make two holes one

for entrance of x-rays and the other for exit of x-rays.

5. A monochromatic x-ray beam is allowed to fall on the power sample.

Since the sample contains a large number of tiny crystallites arranged

randomly in all possible orientations.

6. For each set of planes there exist some crystallites, which are oriented in

a direction to satisfy the Bragg’s condition and give raise the diffraction

effect. The diffracted beam forms a cone with half-apex angle 2  .

7. In a similar way, other sets of lattice planes give their diffraction cones

on the x-ray film. These cones are recorded in the form of a pair of arcs

on the x-ray film.

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 X-Ray diffraction Engineering Physics

8. When they diffract through an angle 900, they appear as straight lines

and afterwards the curvature is reversed and when the angle approaches

to 1800 the traces are nearly circular.

9. We know the linear distances between the pair of arcs various diffraction

angles ‘  ’ can be calculated for a known camera radius ‘R’.

They are related as

S
4 
R

 1 
    s radins
 4R 

 180 1 
    s degrees
  4R 

 57.3 
= s
 4R 

10. Since the wavelength is known for a given characteristic x-ray beam.

Substituting value of ‘  ’ in Bragg’s condition 2d sin   n , the value of ‘d’

can be calculated.

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 X-Ray diffraction Engineering Physics

11. By using the relation

a
d
h2  k 2  l 2

The relation between crystallographic axes and Miller indices (h k l) can

be obtained. This powder method also gives the information of the

structure of the unit cell.

3.5. Applications of X-ray diffraction (XRD):-

 XRD is a nondestructive technique

 To identify crystalline phases and orientation

 To determine structural properties: Lattice parameters (10-4Å), strain, grain

size, expitaxy, phase composition, preferred orientation (Laue) order-disorder

transformation, and thermal expansion.

 To measure thickness of thin films and multi-layers.

 To determine atomic arrangement.

 X-ray diffraction is used to determine the structure of biological molecules.

The discovery of the double-helical structure of the DNA molecule is one

example.

 It is used to study lattice imperfections such as foreign impurities,

dislocations, regions of strain, etc. in the presence of such imperfections, the

diffraction pattern no longer corresponds to that of a perfect crystals and

by studying the devation one can obtain information concerning the type of

imperfections and their distributions in the crystal.