Lec.

6,7

DETERMINATION OF CRYSTAL STRUCTURES BY XRAY DIFFRACTION

X-Ray Diffraction

Diffraction gratings must have spacings

comparable to the wavelength of diffracted
radiation.
Cant resolve spacings
Spacing is the distance between parallel planes
2
of atoms.

X-Ray Diffracton Methods

Von
Lau
Orientatio
e

n
Single
Crysta
l
Polychrom
atic
Beam,

Rotating
Crystal
Lattice
constant
Single
Crystal
Monchromat
ic
Beam,
Variable

Powde
r
Lattice
Parameters
Poly Crystal
Monchromat
ic
Beam,
Variable
3Angle Many

Laue Method
The Laue method is mainly used to determine the
orientation of large single crystals while radiation is
reflected from, or transmitted through a fixed crystal.
The diffracted beams form arrays of
spots, that lie on curves on the film.

The Bragg angle is fixed

for every set of planes in the
crystal. Each set of planes picks
out & diffracts the particular
wavelength from the white radiation
that satisfies the Bragg law for

the values of d & involved.

Transmission Laue Method

In the transmission Laue method, the film is
placed behind the crystal to record beams which
are transmitted through the crystal.
In the transmission Laue method,
the film is placed behind the
crystal to record beams which are
transmitted through the crystal.

Single
Crystal

One side of the cone of Laue

reflections is defined by the
transmitted beam.
The film intersects the cone,
with the diffraction spots
X-Rays
generally lying on an ellipse.

Film

Crystal Structure Determination

by the Laue Method
The Laue method is mainly used to determine the

crystal orientation.
Although the Laue method can also be used to
determine the crystal structure, several

wavelengths can reflect in different orders

from the same set of planes, with the different
order reflections superimposed on the same spot
in the film. This makes crystal structure
determination by spot intensity diffucult.
The rotating crystal method overcomes this problem.
6

Rotatng Crystal Method

In the rotating crystal
method, a single crystal
is mounted with an axis
normal to a
monochromatic x-ray
beam. A cylindrical film
is placed around it & the
crystal is rotated about
the chosen axis.
As the crystal rotates, Sets of lattice planes will at some

point make the correct Bragg angle

for the monochromatic incident beam, & at that point a diffracted
beam will be formed.
7

Rotatng Crystal Method

The Lattice constant of the crystal can
be determined with this method. For a
given wavelength if the angle at
which a reflection occurs is known, d can
be determined by using Braggs Law.

a
h k
2

2d sin n
8

Rotatng Crystal Method

The reflected beams are located on the surfaces
of imaginary cones. By recording the diffraction
patterns (both angles & intensities) for various
crystal orientations, one can determine the shape
& size of unit cell as well as the arrangement of
atoms inside the cell.

Film
9

 For electromagnetic radiation to be diffracted the

spacing
in the grating should be of the same order as the
wavelength
In crystals the typical interatomic spacing ~ 2-3
so the
suitable radiation is X-rays
Hence, X-rays can be used for the study of
crystal structures
Beam of electrons

Target

X-rays

ccelerating (/decelerating) charge radiates electromagnetic radiat

10

Relationship of the Bragg angle () and the

experimentally measured diffraction angle
(2).

X-ray
intensity
(from
detector)

n
d
2 sinc

11

Mo Target impacted by electrons accelerated by a 35 kV potentia

Intensity

K
White
radiation

0.2

0.6

Characteristic radiation
due to energy transitions
in the atom

1.0

1.4

Wavelength ()
12

Target Metal

Of K radiation ()

Mo

0.71

Cu

1.54

Co

1.79

Fe

1.94

Cr

2.29

13

BRAGGs EQUATION

Deviation =
2

Ray 1

Ray 2

dS
in

The path difference between ray 1 and ray 2 =

2d Sin

14

15

16

Note that in the Braggs equation:

The interatomic spacing (a) along the plane does not appear
Only the interplanar spacing (d) appears
Change in position or spacing of atoms along the plane should not affect
Braggs condition !!
Note: shift (systematic) is
actually not a problem!
d

17

 Braggs equation is a negative law

If Braggs eq. is NOT satisfied NO reflection can occur
If Braggs eq. is satisfied reflection MAY occur
Diffraction = Reinforced Coherent Scattering
Reflection versus Scattering
Reflection

Diffraction

Occurs from surface

Occurs throughout the bulk

Takes place at any angle

Takes place only at Bragg angles

~100 % of the intensity may be reflected

Small fraction of intensity is diffracted

X-rays can be reflected at very small angles of incidence

18

 n = 2d Sin,

n= 1, 2, 3,

n is an integer and is the order of the reflection

For Cu K radiation ( = 1.54 ) and d110= 2.22
n

Sin

0.34

20.7

First order reflection from (110)

43.92

Second order reflection from (110)

Also written as (220)

d hkl

0.69

a
h2 k 2 l 2

a
d 220
8
a
d110
2

d 220 1

d110 2
19

In XRD nth order reflection from (h k l) is considered as 1st order reflection

from (nh nk nl)

n 2d hkl sin
d hkl
2
sin
n

2d nh nk nl sin

20

21

The Powder Method

If a powdered crystal is used instead of a single
crystal, then there is no need to rotate it, because
there will always be some small crystals at an
orientation for which diffraction is permitted.
Here a monochromatic X-ray beam is incident on
a powdered or polycrystalline sample.
Useful for samples that are difficult to obtain in
single crystal form.
The powder method is used to determine the
lattice parameters accurately. Lattice parameters
are the magnitudes of the primitive vectors a, b
and c which define the unit cell for the
crystal.
22

The Powder Method

For every set of crystal planes, by chance,
one or more crystals will be in the correct
orientation to give the correct Bragg angle
to satisfy Bragg's equation. Every crystal
plane is thus capable of diffraction.
Each diffraction line is made up of a large
number of small spots, each from a separate
crystal. Each spot is so small as to give the
appearance of a continuous line.
23

The Powder Method

If a monochromatic X-ray beam is directed
at a single crystal, then only one or two
diffracted beams may result. See figure
For a sample of several randomly orientated
single crystals, the diffracted beams will lie
on the surface of several cones. The cones
may emerge in all directions, forwards and
backwards.
See figure
For a sample of hundreds of crystals
(powdered sample), the diffracted beams
form continuous cones. A circle of film is
used to record the diffraction pattern as
shown. Each cone intersects the film giving
diffraction lines. The lines are seen as arcs
on the film.
See figure

24

THE POWDER METHOD

Cone of diffracted rays

25

POWDER METHOD
Diffraction cones and the Debye-Scherrer geometry
Different cones for different reflections

Film may be replaced with detector

26

Debye Scherrer Camera

A small amount of powdered material is sealed into a fine
capillary tube made from glass that does not diffract X-Rays.

The sample is placed in the Debye Scherrer camera and

is accurately aligned to be in the center of the camera. XRays enter the camera through a collimator.
The powder diffracts the X-Rays
in accordance with Braggs Law to
produce cones of diffracted
beams. These cones intersect a
strip of photographic film located
in the cylindrical camera to
produce a characteristic set of
arcs on the film.
27

Powder Diffraction Film

When the film is removed from the
camera, flattened & processed, it shows
the diffraction lines & the holes for the
incident & transmitted beams.

28

Some Typical Measurement Results

Laue - white X-rays
Yields stereoscopic projection of reciprocal lattice

Rotating-Crystal method: monochromatic Xrays

Fix source & rotate crystal to reveal reciprocal lattice

Normalized Counts

Powder diffraction - monochromatic X-rays

Ce all
Y CoIn
1Powder sample to reveal
of RL
0.8 0.2 directions
5
I/Imax
CeCoIn5 Theory
0.5

20

30

40

50

60

70
29

80

90

Photograph of a

XRD Diffractometer
(Courtesy H&M Services.)

30

(a) Diagram of a
diffractometer
showing a powdered
sample, incident &
diffracted beams.
(b) Diffraction
Pattern
from a sample of
gold powder.
31

Example (From the Internet)

The results of a diffraction experiment using X-Rays
with = 0.7107 (radiation obtained from a
molybdenum, Mo, target) show that diffracted peaks
occur at the following 2 angles:

Find: The crystal structure, the indices of the plane

producing each peak, & the lattice parameter of the
32
material.

Example (Solution)
First calculate the sin2 value for each peak, then
divide through by the lowest denominator, 0.0308.

33

Example (Solution Continued)

Then use the 2 values for any of the peaks to
calculate the interplanar spacing & thus the lattice
parameter.

Picking Peak 8: 2 = 59.42 or = 29.71

So, for example:
d 400

0.7107

0.71699
2 sin
2 sin( 29.71)
2

a 0 d 400 h k l

(0.71699)( 4) 2.868

This is the lattice parameter for body-centered cubic iron.

34

Applications of XRD
Note: XRD is a nondestructive technique!
Some uses of XRD include:
1. Distinguishing between crystalline & amorphous
2.
3.
4.
5.
6.

materials.
Determination of the structure of crystalline
materials.
Determination of electron distribution within the
atoms, & throughout the unit cell.
Determination of the orientation of single crystals.
Determination of the texture of polygrained
materials.
Measurement of strain and small grain35 size..etc.

Advantages & Disadvantages of XRD

Compared to Other Methods

Advantages
X-Rays are the least expensive, the most
convenient & the most widely used method to
determine crystal structures.
X-Rays are not absorbed very much by air, so the
sample need not be in an evacuated chamber.

Disadvantages
X-Rays do not interact very strongly with lighter
elements.
36

Diffraction Methods

Neutrons

Electrons

~1
E ~ 0.08 eV
interact with
nuclei, highly
penetrating

~1
E ~ 150 eV
interact with
electrons, less
penetrating
37