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X-ray Diffraction (XRD)

Reading materials:Chapter 7:
T. L. Alfrod, L. C. Feldman and J. W. Mayer, Fundamentals of Nanoscale
Film Analysis, Springer, 2007.
Reference Book:
B. D. Cullity and S. R. Stocks, Elements of X-ray diffraction , Prentice-Hall.

Objectives..

Crystal structure determination.

Effect of temperature on crystal structure
Precise lattice parameter determination
Determination of crystallite sizes from macro-nano dimension.
Strain analysis.
Alloy formation.

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Introduction revisited

Quasicrystal

Source:
http://www.ndt-ed.org/EducationResources/CommunityCollege/Materials/Graphics/QuartzGlass.jpg

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Braggs law in real space

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----- (1)

Crystal structure
1. Lattice and Basis

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Crystal structure

2. Bravais Lattices in 3D

Triclinic

Tetragonal

Hexagonal

Monoclinic

Rhombohedral

Cubic

Orthorhombic
Primitive (P): lattice points on the cell corners
only.
Body (I): one additional lattice point at the
center of the cell.
Face (F): one additional lattice point at the
center of each of the faces of the cell.
Base (A, B or C): one additional lattice point
at the center of each of one pair of the cell faces.

Exercise 1: XRD and data analysis of

a powder sample (Cubic)
Geometry..

Typical spectrum

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Continued..
Analysis of BCC and FCC structure

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Continued..

---- (2)

Does a crystal has many values of a0 ?

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Continued..
BCC

Allowed reflections: h+k+l:even

FCC

Allowed reflections: h,k,l unmixed

(all even or all odd)

Exercise 2: XRD and data analysis of

Hexagonal crystal

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Allowed reflections:
h+2k = 3N (N: integer) and l: odd
- Absent
All others are present

Two lattice parameters: a, c

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Previous week..
Importance of X-ray diffraction
Main objectives of XRD
Crystal structure (BCC, FCC and hexagonal) determination
(for known samples)

BCC

FCC

Hexagonal

Crystal structure using JCPDS datasheet

(For information only)

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Continued..
JCPDS of NaCl (For information only)

Continued..

How to distinguish Cu2O and CuO? (For information

only)

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How to distinguish Cu2O and CuO? (For information

only)

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How to identify structure of a completely unknown sample?

(For information only)
Steps to be followed:

Exercise 3: Coefficient of thermal expansion

---- (3)

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Exercise 4: Precise determination of lattice parameter

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Lattice spacing (d) and lattice

Parameter (a) varies with Sin.
Sin varies with , having different
error for different .
Leads to error in d and a.
Task: How to determine true value
of a?

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Bradley Jeans function

a = a0 +a0K Cos2

Ref: B. D. Cullity

Shortcoming: Extrapolation of random data points varies from

person to person
Cohens method

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Exercise 5: Crystallite size and lattice strain analysis

K
Bcrystal
L cos
---Scherer Formula

Comment:Both crystallite size and

Strain leads to broadening
of XRD peak

Intensity (a.u.)

Task:How to decouple them?

Bstrain = tan
26.5 27.0 27.5 28.0 28.5 29.0 29.5 30.0

2(deg.)

Previous week..

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BCC, FCC and Hexagonal structure reviewed.

Determination of crystal structure using JCPDS (for information only)
Temperature effect on lattice parameter.
Precise determination of lattice parameter.
Determination of crystallite size and lattice strain.

Exercise 6: Mixing of two compounds

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Task: Take 100% pure MgO powder sample. Add 20, 40, 60 and 80
mol% of NiO. Heat treat this mixtures at 1500 0C for 8 h and slowly
cool this mixture to room temperature. How can you distinguish these
Mixtures structurally?

Factors influencing XRD intensity

1.
2.
3.
4.

Structure factor
Multiplicity factor
Temperature factor
Lorentz polarization factor

Frequently asked questions (FAQs)

Session 1

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1. What is the difference between a single crystal, a polycrystal, a nanocrystal and an

amorphous material?
2. Define oriented structure and epitaxial growth.
3. Grain boundaries exist in amorphous materials. Yes/No.
4. Each plane of a crystal is uniquely defined by which quantity?
5. Why X-ray is suitable for crystal structure determination?
6. How XRD pattern look like for a single crystal, a polycrystal a nanocrystal and an
amorphous form a same material?
7. How can you distinguish a simple cubic and a body centred cubic structure by
looking at XRD patterns?
8. What do you exactly mean by the term Indexing of x-ray pattern?

XRD Instrumentation (For information only)

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Frequently asked questions (FAQs)

Session 2

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1. A base-centered cubic crystal has two atoms per unit cell located at 000 and 0
positions. What will be the intensity of diffracted x-ray from this structure when
miller indices are mixed?
2. The two x-ray lines K and K are diffracted from a crystalline plane. If the
diffraction angle corresponding to second one is known, how do you get the same
for the first one?
3. Why the best value of a is expected at an angle close to 900?
4. XRD peak broadening is only due to instrumental error. Yes/No.
5. Suppose you dont know the error of the instruments in your XRD set up. Can you
suggest an diffraction experiment only to obtain the instrumental error.

Tutorial session based on Practical Examples:

Q1. Determine a and c values of Mg (Hexagonal, c/a = 1.624) from the given first six
reflections: 2 32.16, 34.38, 36.60, 47.80, 57.36, 63.05. [X-ray: CuK]
Q2. Using method of least squares, determine the best straight line through the following
four points. x = 10
18 30 42
y = 15 11 11 8
Q3. Al crystal (FCC) is studied by CuK x-rays. The following reflections are observed.

hkl

56.017
56.232
58.291
58.523
68.735
69.107

K1
K2
K1
K2
K1
K2

331
331
420
420
422
422

Determine a for each reflection. Using Cohens method calculate the precise value of a.
Q4. An FCC crystal gives following first four reflections.
2 38.51, 44.77, 65.15 78.26. Peak broadening dye to crystallite size and lattice strain
(Br: in radians) corresponding to these lines are, (2.8, 3.4, 4.4, 5.5 )x 10-3 respectively.
Calculate crystallite size (along z direction).

Q5. In a NaCl crystal (a cubic lattice) 4 Na and 4 Cl atoms per unit cells are located as
follows:
Na

000

Cl

00

00

00

Show that the intensity of diffracted x-ray for mixed indices is zero and for unmixed indices
is finite.