Determination of lattice constant and peak intensities from Powder X-ray

Diffraction (PXRD)

X-ray diffraction (XRD) is one of the non-destructive characterization methods used for
materials. The lattice constant and atomic positions in the unit cell are determined using the X-
ray data. The XRD experiments are primarily classified as single crystal X-ray diffraction
(SCXRD) and powder X-ray diffraction (PXRD), depending on the type of samples used in the
investigation. As the name suggests, single crystals are used in the former case, whereas finely
ground powder samples are required for the PXRD data.

The Bragg peaks are observed for the crystalline samples in the X-ray detector whenever the
Bragg’s law is satisfied by the incoming monochromatic X-ray beam of known wavelength ().
Bragg’s law is given by

 ---------------------(1)
where d is the inter-planar distance and is the Bragg angle and  06 Å for Cu-K
radiation.

For the cubic system, the relationship between the inter-planar distance (d), Miller plane (hkl)
and the lattice constant (a) is written as

-----------------------(2)
√

where (hkl) are Miller planes denoted by Miller indices h, k and l.

From (1) and (2), the below relationship is derived, which can be used to determine the unknown
lattice constant of a cubic system by using the PXRD pattern.


-----------------------(3)

where N = is an integer, ‘a’ is a lattice constant and M is a constant for the given
system.

The atomic scattering factor or form factor (f)

The atomic scattering factor is proportional to the atomic number when the diffraction angle is
zero. The figure given below shows a variation of ‘f’ with the Bragg angle ( ). It also depends on
the temperature of the contributing atom.
The variation of the atomic scattering factor can be obtained by

𝑓 ( ) ∑ 𝑎𝑒 𝑐 ∑ 𝑎𝑒 𝑐-----------(4)

where a, b amd C are constants. 

a1 b1 a2 b2 a3 b3 a4 b4 c
Si 6.2925 2.4386 3.0353 32.333 1.9891 0.6785 1.5410 81.6937 1.1407
Cu 13.338 3.5828 7.1676 0.2470 5.6158 11.3966 1.6735 64.820 1.5910
Cs 20.3892 3.569 19.1062 0.3107 10.662 24.3879 1.4953 213.904 3.3352
Cl 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574
K 8.2186 12.7949 7.4398 0.7748 1.0519 213.187 0.8659 41.6841 1.4228
Br 17.1789 2.1723 5.2358 16.5796 5.6377 0.2609 3.9851 41.4328 2.9557
Na 4.7626 3.285 3.1736 8.8422 1.2674 0.3136 1.1128 129.424 0.676
Fe 11.7695 4.7611 7.3573 0.3072 3.5222 15.3535 2.3045 76.8805 1.0369
Zn 14.0743 3.2655 7.0318 0.2333 5.1652 10.3163 2.41 58.7097 1.3041
S 6.9053 1.4679 5.2034 22.2151 1.4379 0.2536 1.5863 56.172 0.8669

The form factor values of all atoms are available at [Link]

form-factor-calculator-table/

The structure factor of the unit cell (F)

The structure factor (F) of the unit cell is determined by an atomic scattering factor (f) of all
constituent atoms and their geometric positions (x,y,z) of atoms in the unit cell and the specimen
temperature in the form of the Debye-Waller factor . Thus, the structure factor (F) of ‘n’ atoms
in the unit cell is given by

( )
∑ 𝑓𝑒 ∑ 𝑓𝑒 𝑒  -----------------------(5)

where B is the Debye-Waller factor and  is the wavelength of X-ray.

The intensity of the scattered X-ray is directly proportional to the structure factor.

-----------------------(6)

Factors affecting the diffraction intensity

(a) Extinction rules for different lattices

Additionally, either a constructive or destructive interference of diffracted X-ray wave depends

on the symmetry of the lattice, which results in the systematic absence (extinction) of X-ray
intensity contribution from some of the Miller planes (hkl) to the PXRD pattern.

(1) Body centered lattice, 𝑓 for h+k+l = even

= 0 for h+k+l = odd

(2) Face centered lattice, 𝑓 for (hkl) all are either even or odd
= 0 for (hkl) mixed

(3) In KBr, 𝑓 𝑓 for h+k+l = even and

= 𝑓 𝑓 for h+k+l = odd

(4) In CsCl, 𝑓 𝑓 for h+k+l = even and

= 𝑓 𝑓 for h+k+l = odd

(5) In diamond, 𝑓 for (hkl) all are either even or odd and (h+k+l) divisible by 4
= 0 for h, k and l are mixed

(6) In ZnS, 𝑓 𝑓 for (hkl) all even and h+k+l = 4n

𝑓 𝑓 for h+k+l = 2n+2

𝑓 𝑓 for (hkl) all odd

for (hkl) mixed

(b) Lorentz–polarization (LP) correction

Lorentz correction (L) is a geometric correction that accounts for the length of time the
sample remains in the diffracting position for any particular scattered X-ray beam. Different
reciprocal lattice points correspond to different sets of diffracting planes with different
geometries relative to the X-ray instrument. So the Lorentz factor depends both on the Bragg
angle and on the diffraction geometry. It is equal to 𝑐 .

Polarization correction (P) arises due to the electromagnetic nature of the X-ray. The
amplitude of scattered X-rays is proportional to the sine of the angle between the direction of the
electric vector of the incident beam and the scattered beam. It is equal to 𝑐 Both
corrections depend on the experimental geometry, thus applied as a single correction factor, LP.

-----------------------(7)

(c)Debye-Waller (DW) Factor on diffraction intensity

The scattering intensity decreases as the temperature of the sample increases. The
relationship is given by

 B sin 2 
f  f 0 exp 
 2  -----------------------(8)

where B is the Debye-Waller factor and . The U is an isotropic thermal displacement

parameter of atoms. The change in the atomic scattering factor with different B values is shown

below.

(d) The Plane Multiplicity Factor (p)

The number of identically spaced planes cutting a unit cell in a particular (hkl) direction is called
the plane multiplicity factor (p). For example, each cubic crystal face has a diagonal (110) and
equivalent planes. Thus, there are 12 crystallographic orientations with six faces. Similarly, the
(100) will have 6 orientations. Hence, the (110) plane will have twice the intensity of the (100)
because of the multiplicity factor (see below Table).

Other factors such as absorption, stress and strain, preferred orientation, disorder, crystallite size,
fluorescence affect the peak intensity in the experimental data. These should be minimum for
better quality data.

The final intensity of the diffracted X-ray is given by

-----------------------(9)
where p is multiplicity factor and K is an instrumental constant.

Procedure
1. You are given 6 diffraction patterns ( vs intensity). Plot it in origin and note down the
and intensity (I) of Bragg peaks.

2. Calculate ‘d’ and relative intensity and note these values in your record sheets.

3. Make a table in EXCEL with , sin , and .

4. Find common and identify (hkl) and corresponding lattice symmetry. Also
calculate a lattice constant.

5. Calculate form factor for the given atoms (in the manual) using the form factor equation
at all Bragg angles. Using these form factor values, calculate the structure factor using the
extinction rules.

6. Calculate the DW factor with U = 0.1, write the multiplicities, calculate LP factor and the
final intensity of the Bragg reflection in an EXCEL table.

7. Compare the calculated relative intensities with the measured values.