Lecture 4: X-ray diffraction

Contents
1 Introduction to diffraction

2 Braggs law

3 Braggs law example

4 X-ray spectrometer

Introduction to diffraction

In Lecture 2, we looked at interaction of X-rays with matter - specifically

X-ray absorption. Absorption is a continuous process wrt X-ray wavelength
due to the scattering of the radiation. Along with this background there are
sharp absorption peaks when the energy of the X-rays couples with certain
electronic transitions in the material. In lecture 3, we looked at crystalline
solids and their properties. In X-ray diffraction we focus on a combination on
both, how X-rays interact with crystalline solids, specifically the phenomenon
of diffraction.
Diffraction by light waves is a well known phenomenon. The theory was put
forward by Dutch physicist Christian Huygens and refined by French physicist Augustin-Jean Fresnel. If we have a ruled grating with the spacing of
the order of the wavelength of light (400-700 nm) each point on the grating can be considered to be a source of secondary waves. These secondary
waves can interfere forming alternate maxima and minima i.e. diffraction
pattern. X-rays have wavelength of the order of 01 - 10
A. Crystals have
lattice constants and hence interplanar spacing around 2 - 6
A. Thus a crystalline material naturally serves as a ruled grating with the ability to scatter
X-rays producing maxima and minima i.e. diffraction. Diffraction using Xrays was first shown by German physicist von Laue in 1912 where he used a
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Figure 1: Diffraction of X-rays from a set of planes. For constructive interference the path difference must be a integral multiple of the wavelength.
Taken from http://en.wikipedia.org/wiki/Braggs law
copper sulphate crystal (CuSO4 with a triclinic structure) to get diffraction
patterns from X-rays. This work was carried forward by a father-son scientist
team W.H. Bragg and W.L. Bragg who managed to express the condition for
diffraction in a mathematical form. this was called Braggs law. They were
also able to solve the structure of sodium chloride (with 2 interpenetrating
fcc structures) using X-rays thus proving the power of X-ray diffraction to
solve crystal structures.

Braggs law

Braggs law in the simplest sense gives the condition for constructive interference for X-rays incident on a set of lattice planes. Constructive interference
occurs when the intensities of the waves add to each other while the opposite
is destructive interference where the intensities cancel each other. Braggs
law can be derived from the general set of diffraction conditions derived by
von Laue, which we shall see in the context of electron diffraction. Consider a
set of planes as shown in figure 1 The interplanar spacing between the planes
is denoted by d. If the Miller indices of the plane is (hkl) and the system is
cubic then d is related to a by
h2
k2
l2
1
=
+
+
d2
a2
a2
a2
a
d=
2
h + k 2 + l2

(1)

For a tetragonal system with two lattice parameters a and c the equation is
modified as
1
h2
k2
l2
= 2 + 2 + 2
(2)
d2
a
a
c
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For a hexagonal system where = 120 the relation between d-spacing and
lattice parameters are
1
4 h2 + hk + k 2
l2
(
=
)
+
(3)
d2
3
a2
c2
From figure 1 x-rays are incident at an angle on 2 planes with spacing d. Xrays reflected from the bottom plane have to travel an extra distance, which
is given by 2dsin (from geometry). This is the then the path difference
between the x-rays reflected from the material. For constructive interference
this path length has to be an integral multiple (n)of the wavelength. Thus,
Braggs law can be stated as
2dsin = n

(4)

Here, n is an integer and can take values 1, 2, 3 and so on. This represents
the order of reflection. Braggs law is the most important law in diffraction.
It is not only used for XRD but also when we look at diffraction in an electron microscope. For a given set of planes there are reflected waves in all
possible directions but these are not reinforced (the waves are not in phase)
and hence the intensity is weak. The strongest reflected intensity is when
the angle is equal to the Bragg angle i.e. the diffracted wave. The incident
beam, diffracted beam, and the reflecting planes are coplanar.

Braggs law example

Let us use an example to understand Braggs law. Consider a metal with

fcc crystal structure, Nickel (Ni) with lattice constant a of 3.52
A. Cu K
radiation of wavelength 1.54
A is incident on Ni. Considering only first order
reflection (n=1) equation 4 can be written as
2dsin =

sin =
2d

(5)

The first criteria is that sin cannot be greater than 1 so that 2d or

d 2 . Thus, using Braggs law only those d-spacings greater than half
the wavelength of X-rays used will produce diffraction. This sets a lower
limit on the measurable d-spacing and dictates the choice of X-rays used for
diffraction. On the other hand, if we use too low a wavelength the angles ()
will be very small and hence it will be hard to differentiate one line from the
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Figure 2: Ni XRD pattern taken from a Canadian 5 cents coin. Taken from
http://chemistry.beloit.edu/Edetc/nanolab/nickel2/index.html

other. Typically, for metals Cu K is used as the X-ray source.

If we consider the 100 family of planes for Cu, the d-spacing is the same
A and
as a and using equation 4 = 12.64 . For 110 d = a2 = 2.49
a

= 18.21 . For 111 d = 3 = 2.03

A and = 22.27 . Thus as d-spacing
reduces the diffraction angle increases. The experimental XRD pattern from
Nickel is shown in figure 2 The experimental pattern does not contain all the
d-spacings and actually starts from the 111 family with each line having different intensity. We will see the reason for this when dealing with structure
factors and intensity. Also the the plot is intensity vs. 2. This is the angle between the incident X-ray (source) and the diffracted X-ray (detector).
Thus, if we know the X-ray wavelength and the crystal structure and lattice
constant of the material under investigation we can calculate the positions
(2) of all the lines.
Apart from Cu K another commonly used X-ray source is Mo K with
a wavelength of 0.71
A. Since the wavelength is smaller the angles will also
be smaller, for the same d-spacing. Thus, if we use Mo for the above Ni
example the 111 line will fall at = 10.07 instead of 22.27 . Mo sources

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Figure 3: Schematic of X-ray spectrometer. Taken from Elements of X-ray

diffraction - B.D. Cullity.
are normally used for small molecules where the d-spacing is smaller and we
need a smaller wavelength to obtain diffraction, see equation 5.

X-ray spectrometer

Experimentally Braggs law can be used in 2 ways:

1. Use X-rays of single (monochromatic) and known wavelength () and
measure the diffraction angle () and use that to calculate the d-spacing
and hence the crystal structure. This is called structure analysis.
2. Alternate is to use planes of known spacing (d), measure and from
this calculate . This technique is called X-ray spectrometry and is a
way of doing chemical analysis with X-rays. We can also use this to
get a true line source for structure analysis.
A schematic of the X-ray spectrometer is shown in figure 3 The source is an
X-ray tube which emits a continuous spectrum of X-rays with some characteristic sharp peaks (depending on the tube voltage being above the threshold).
The X-rays fall on a crystal with known d-spacing. Thus, different X-rays are
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diffracted at different angles which are measured by the detector that is rotated. Thus, we can get a plot of I vs. or I vs. Energy of the X-ray source.
This can be used for calibrating new X-ray sources and chemical analysis. If
instead of the detector we had a narrow exit slit that only the wavelength corresponding to the slit angle will be emitted while the others will be stopped.
Thus using the X-ray spectrometer a very narrow monochromatic source can
be obtained especially for use in high precision X-ray diffractometers.