Superlattice Reflections

1. Concept/Meaning
2. Structure Identification
3. Example
Meaning of Superlattice

A superlattice is a material with periodically alternating layers of distinct atoms.

Alternate Arrangement of layers B

The American metallurgist Bain in 1923, obtained evidence for a gold-copper solid solution.

Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.

 Above the critical temperature Below the critical temperature

Positions
are fixed

• These probabilities are the same for every site and, considering the structure as a whole,
a statistically “average” gold-copper atom occupies each site.
• Gold atoms in a perfectly ordered alloy occupy only the corner positions of the unit cube
and the copper atoms in the face-centered positions, as illustrated in Figure above.
Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.
Structure Factor Calculation

• Atom positions decide the Intensity of the peak.

• Unit cell decides the position of 2Θ.
Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.
• Structure factor is dependent on the presence of order or
disorder within a material.

Probability of atoms A and B

are the same for all lattice sites
Complete Ordering (Superlattice Structure)
B at (1/2, 1/2, 1/2)
A at (000)
 Example
Identification of Ordering from
XRD Pattern.

Ideal XRD Pattern for Ordered Alloy

(Superlattice Structure)
Reflections are allowed for All mixed and Unmixed hkl.
(i.e. Simple Cubic Structure)

Note: The intensity of the peak is weak. Tsai, M. H., & Yeh, J. W. (2014). Materials Research Letters, 2(3), 107-123.
LRO
By XRD
 Disordered

Partially ordered

Completely ordered

Figure: Powder patterns of (very coarse-grained) made with filtered copper radiation: (a) quenched from 440°C (disordered):
(b) held 30 min at 360°C and quenched (partially ordered): (c) slowly cooled from 360°C to room temperature (completely
ordered)
Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.
 Long Range Order 𝒓 𝑨− 𝑭 𝑨
𝑳=
𝟏− 𝑭 𝑨
Long Range Order Parameter
Fraction of Sites occupied by ‘right’ atoms
Fraction of A atoms in the alloy

‘Value varies between 0-1’

Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.

Determine the L experimentally,

Comparing the integrated intensity ratio of a superlattice and fundamental line.

From line profile.

Must have Standard Data Base information

Muralikrishna, G. M., Esther, A. C. M., Guruvidyathri, K., Watermeyer, P., Liebscher, C. H., Kulkarni, K. N., ... & Murty, B. S. (2020). Metals,  10(11), 1411.
 Superlattice-line intensity is generally proportional to (

Let’s understand with example:

It is possible to get
Intensity by experiment

Much difficult to get

Intensity by experiment

Cullity, B. D. (1956). Elements of X-ray Diffraction. Addison-Wesley Publishing.

If standard data is not available, then

The long-range order parameter (L) with the relative intensity ratios (I100/I110) are linear fitted.