Chapter 2 Synthesis and Characterization

2.2.1 X-ray Diffractometer (XRD)

X-ray diffraction (XRD) is a very important experimental technique in revealing
the crystal structure of bulk solid microstructure of thin films. Apart from providing the
structural phase of the nanocrystals, this technique also provides an estimate of the size of
the nanocrystals, as discussed later in this section. The XRD methods are generally
applied to films thicker than several angstroms on account of the strong penetrating
power of the x-rays. Information related to the crystal structure of the films, including
lattice constants, grain size, preferred orientation of polycrystals, defects, stress, etc. can
be determined from the x-ray diffraction measurement.
X-rays are electromagnetic waves. The phenomenon of the x-ray diffraction by
crystals results from a scattering process in which x-rays are scattered by the electrons of
the atoms without change in wavelength. As the wavelength of X-rays is close to atomic
size (~ 1.5 Ǻ), they get diffracted by atoms and ions. If, as in the case of crystals, the
atoms or ions are arranged in a particular fashion then the diffracted x-rays interfere
constructively or destructively with each other depending on the path difference. W.L.
Bragg formulated the condition for constructive interference as,

2d sin   n

where, d is the spacing between two adjacent atomic planes, θ is the angle between the

atomic plane and the x-rays, n is the order of diffraction maximum, and λ is the
wavelength of the x-rays. The resulting diffraction pattern comprising both the positions
and intensities of the diffraction effects is a fundamental physical property of the
substance. Analysis of the positions of the diffraction effect leads immediately to a
knowledge of the size, shape and orientation of the unit cell. For our studies we have used
the Bruker D8 Advance X-ray diffractometer as shown in Figure 2.4.

21
Chapter 2 Synthesis and Characterization

Figure2.4: X-ray diffractometer

The finite size of the crystallites has a marked effect on the X-ray diffraction line
widths. With reduction in the particle size, observed X-ray diffraction lines broaden
significantly. This is due to the finite size of the nanocrystals. The particle size can be
estimated from the width of the diffraction line corresponding to a particular (hkl)
refection from the Scherrer formula [18]. The origin of such broadenings of the
diffraction peaks due to the finite size effect can be understood by considering the effect
of diffraction from a finite number of planes as shown schematically in Figure 2.5.
Considering an ideal crystal having p atomic (hkl) planes of spacing d parallel to the
surface, the approximate thickness of the crystal is close to pd. The amplitude of a
diffracted ray will be maximum when the path difference between the rays reflected from
successive planes is equal to a multiple of the wavelength

δl  2dsinθ  nλ (2.1)

22
Chapter 2 Synthesis and Characterization

A characteristic shift towards lower angle compared to the reflex of ideal crystals
indicates a lattice expansion. The lattice distortion (∆d/d0) is defined as:

d d 0  ( d exp  d hkl ) d hkl (2.2)

Figure 2.5: A schematic diagram of X-ray diffraction from finite number of planes.

When the incident angle differs from θ by a small amount  , the resulting path
difference is given by

l = 2d sin (θ +  ) = 2d sin θ cos  + 2d sin  cos θ = n  cos  = 2d sin  cos θ

(2.3)

Since,  is small, the above expression can be written as

l  n  2  d cos  (2.4)

The corresponding phase difference between the first and the pth plane is given by

4p  d cos 
 (2.5)

The resultant amplitude of the reflected wave is given by the vector sum of the amplitude

of each of the p vectors successively differing by increasing phase of  , by

23
Chapter 2 Synthesis and Characterization

2p  d cos
ap sin
A 
2p  d cos (2.6)


The amplitude of the reflected ray is maximum when  = 0; in this case A0 = ap. The
full width at half maximum intensity can be calculated by
2 
A 2 sin ( 2 ) 1
=  (2.7)
A02  2 2
( )
2

The above equation holds when


=  1.40
2
(2.8)
or using equation,
4p  d cos 
= 1.40 (2.9)
2
The full width at half maximum,  hkl for the diffraction peak at 2 θ angle is then given
by

0.89
 (2.10)
B cos 

This expression is known as the Scherrer formula. We have used the above
formula for determining the size of the nanocrystallites, as will be discussed in the
subsequent chapters.

24