X-ray Diffraction (XRD)

Outline
• What is X-ray Diffraction
• Bragg’s Law
• Basics of Crystallography
• XRD Pattern
• Applications of XRD
 Definition
 X-rays are electromagnetic radiation with very
short wavelength ( 10-8 -10-12 m)
 The energy of the x-ray can be calculated with the
equation
E = h = hc/
 For example : the x-ray photon with wavelength
1Å has energy 12.5 keV
 What Is Diffraction?
A wave interacts with

A single particle
The particle scatters the
incident beam uniformly in
all directions.

A crystalline material
The scattered beam may add
together in a few directions
and reinforce each other to
give diffracted beams.
 What is X-ray Diffraction?
The atomic planes of a crystal cause an incident beam of x-rays (if
wavelength is approximately the magnitude of the interatomic distance) to
interfere with one another as they leave the crystal. The phenomenon is
called x-ray diffraction.

Bragg’s Law: n= 2dsin()

~d

2B
atomic plane

X-ray of  B I
d
 Bragg’s Law and X-ray Diffraction

n = 2dsin() n-integer

Diffraction occurs only when Bragg’s Law is satisfied condition for

constructive interference (X-rays 1 & 2) from planes with spacing d

X-ray1

X-ray2

=3Å
=30o Atomic
plane
d=3 Å

2-diffraction angle
 Deriving Bragg’s Law - n = 2dsin
Constructive interference X-ray 2 X-ray 1
occurs only when

n = AB + BC

AB=BC

n = 2AB

Sin=AB/d

AB=dsin

n =2dsin

=2dhklsinhkl
n – integer, called the order of diffraction
 Basics of Crystallography

System Axial lengths Unit cell Rhombohedral

and angles
a a=b=c
Cubic a=b=c ==90o
===90o a
Hexagonal
a=bc c
Tetragonal ==90o
a=bc c =120o a
===90o
Monoclinic
a
abc
==90o c b
Orthorhombic a
c
abc Triclinic
===90o abc c
a 90o
b a
b
Indexing of Planes and Directions

(111)
c c

[111]
(110)

b b
a a [110]

a direction [uvw] a plane (hkl)

a set of equivalent a set of equivalent
directions <uvw> planes {hkl}
 X-ray Diffraction Pattern
BaTiO3 at T>130oC

(hkl)

Simple Cubic
I

20o 40o 2 60o

dhkl

Bragg’s Law: =2dhklsinhkl (Cu K)=1.5418Å

 XRD Pattern
Significance of Peak Shape in XRD
1. Peak position
2. Peak width
3. Peak intensity

2
 Peak Position
Determine d-spacings and lattice parameters

For a simple cubic (a=b=c=a0)

2 a0 = dhkl (h2+k2+l2)½

For example crystal BaTiO3, 2220=65.9o, 220=32.95o,

d220 =1.4156Å, a0=4.0039Å
 Cubic Structures
a=b=c=a

Simple Cubic Body-centered Cubic Face-centered Cubic

[001] BCC FCC
z axis

a
a [010]
a y

[100]
1 atom 2 atoms 4 atoms
x 8 x 1/8 =1 8 x 1/8 + 1 = 2 8 x 1/8 + 6 x 1/2 = 4
Location: 0,0,0 0,0,0, ½, ½, ½, 0,0,0, ½, ½, 0,
½, 0, ½, 0, ½, ½,
 Structures of Some Common Metals
[001] axis  = 2dhklsinhkl
(001) plane
d010
Mo Cu

a
d001 (010)
(002) plane

d002 = ½ a a [010] [010]

a
axis
BCC FCC
[100]
h,k,l – integers, Miller indices, (hkl) planes
(001) plane intercept [001] axis with a length of a, l = 1
(002) plane intercept [001] axis with a length of ½ a, l = 2
(010) plane intercept [010] axis with a length of a, k = 1, etc.
 z
Structure factor and (001)

intensity of diffraction (002)

• Sometimes, even though

the Bragg’s condition is
FCC
satisfied, a strong
diffraction peak is not 1 1’
observed at the expected 2 2’
angle. 3 3’
• Consider the diffraction
peak of (001) plane of a
FCC crystal. d001

• Owing to the existence of
the (002) plane in
between, complications
d002
occur.
 Structure factor and intensity of
diffraction

 ray 1 and ray 3 have

1 1’ path difference of 
2 2’
3 3’  but ray 1 and ray 2 have
path difference of /2.
So do ray 2 and ray 3.
 It turns out that it is in
d001 /4 /4 d002 fact a destructive
condition, i.e. having an
/2 /2 intensity of 0.
 the diffraction peak of
a (001) plane in a FCC
crystal can never be
observed.
 http://emalwww.engin.umich.edu/education_materials/microscopy.html
=2dhklsinhkl
d001sin001=d002sin002 d001=2d002
If sin002=2sin001 002>001
Bragg’s law holds and (002) diffraction peak appears

1 1 1’ 1’
2 2 2’ 2’
001
002
/2 d002
3 3 3’
/4 3’
d001
002

001

When =001 no diffraction occurs, while  increases to 002, diffraction occurs.

 I Simple Cubic

XRD
Patterns of
Simple 2

Cubic and FCC

FCC

Diffraction angle 2 (degree)

Peak Width - Full Width at Half Maximum
(FWHM)

Determine
1. Particle or
grain size
2. Residual
strain
 Effect of Particle (Grain) Size
As rolled As rolled 300oC
t
200oC Grain
I size
K1 B
K2 (FWHM)
o
250 C Grain 450oC
size

300oC
0.9 Peak
B = t cos broadening
450oC
As grain size decreases
hardness increases and
2
(331) Peak of cold-rolled and
peak become broader
annealed 70Cu-30Zn brass
 Effect of Lattice Strain on
Diffraction Peak Position and
Width

No Strain

Uniform Strain
(d1-do)/do
Peak moves, no shape changes

Non-uniform Strain
d1constant
Peak broadens
 XRD patterns from
other states of matter

Crystal
Constructive interference Diffraction
Structural periodicity Sharp maxima
2
Liquid or amorphous solid
Lack of periodicity One or two
Short range order broad maxima

Monatomic gas
Atoms are arranged Scattering I
perfectly at random decreases with 
 Applications of XRD

XRD is a nondestructive technique

• To identify crystalline phases

• To determine structural properties

• To measure thickness of thin films and multilayers

• To determine atomic arrangement

• To image and characterize defects