M.No: 2.

2
Experimental Techniques of X-ray Diffraction

Introduction
Knowledge about the interaction between the X-rays and materials is necessary to
obtain valuable information about the materials. Crystal structures can be determined
using X-ray, electron and neutron diffractions. Composition of the materials can be
investigated from the studies like Auger spectrometry, X-ray photoelectron
spectrometry, electron spectrometry for chemical analysis, electron energy loss
spectrometry, Rutherford backscattering spectrometry, etc. The topographic
information of the crystals can be obtained using Scanning probe microscope,optical
microscope, scanning electron microscope and light scattering techniques.

EXPERIMENTAL METHODS OF X-RAY DIFFRACTION

Diffraction can occur whenever Bragg's law is satisfied. With monochromatic
radiation, an arbitrary setting of a single crystal in an x-ray beam will not generally
produce any diffracted beams. There would be very little information in a single
crystal diffraction pattern from using monochromatic radiation. To satisfy the Bragg
law λ and θ have to be varied. Practically this is done by:
• using a range of x-ray wavelengths (i.e. white radiation) or
• by rotating the crystal or using a powder or polycrystalline specimen.
The ways in which these quantities are varied distinguish the three main diffraction
methods:

Diffraction λ θ
method (Wavelength) (Braggangle)

Laue Method Variable Fixed

Rotating Fixed Partly
crystal Method variable

Powder Fixed Variable

Method

LAUE METHOD
The Laue method is mainly used to determine the orientation of large single crystals.
In this method a single crystal is held stationary in a beam of collimated and
continuous x-ray radiation. A source that produces x-rays over a wide range of wave
lengths, preferably, less than an Angstram to few angstrams is used. The
dimensions of the crystal used should be of the order of 1 x 1 x 1 mm3 . A pin hole
arrangement produces a well collimated beam. A flat camera is used to record the
diffraction pattern on a flat film. The diffraction pattern consists of series of spots.
There are two practical variants of the Laue method, the back-reflection and the
transmission Laue method.
Back-reflection Laue method
In back-reflection method, the film is placed between the x-ray source and the crystal.
The beams which are diffracted in a backward direction are recorded.
One side of the cone of Laue reflections is defined by the transmitted beam. The film
intersects the cone, such that the diffraction spots generally lying on an hyperbola
( see fig-1).

Figure-1: Back-reflection Laue diffraction

Transmission Laue Method

In the transmission Laue method, the film is placed behind the crystal to receive
beams which are transmitted through the crystal. One side of the cone of Laue
reflections is defined by the transmitted beam. The film intersects the cone, such that
the diffraction spots generally lying on an ellipse (see fig-2)

Figure-2: Transmission Laue diffraction

Formation of Laue spots
The reflection of x-rays occurs satisfying the equation λ = 2(dhkl )sinθ. For a given
set of planes (i.e. for given values of h,k,l) the spacing ‘d’ is constant and since the
crystal is stationary in this method, the angle θ is fixed by the setting of the specimen.
Here the wavelength for which the given set of planes can reflect is also fixed. The
reflection corresponding to various planes are each produced by their appropriate
wave-length, and hence a Laue photograph requires a range of wave-lengths in the
incident beam. If a set of planes of indices hkl reflects a wave-length λ with a
particular setting of the crystal, then the set of planes of (2h 2k 2l) will reflect in the
same direction a wave-length λ/2 and so on for the other multiples of (hkl). The
reflections must occur in the same direction from all orders of (hkl), because the
planes (hkl), (2h 2k 2l) etc., are all parallel. The experimental arrangement of this
method is shown in fig-3

Figure- 3: Laue arrangement

CHARACTERISTIC FEATURES OF LAUE PHOTOGRAPH

One of the characteristic features of the Laue photograph is the arrangement of spots
on a series of conic sections; ellipses in case of transmission method and hyperbolae
in case of back reflection method. Each of these is the locus of reflections from lattice
planes which intersect in a common axis i.e. lie in the same zone. Laue reflections
from planes of the same zone all lie on the surface of an imaginary cone whose axis
is the zone axis.
 A feature of many transmission Laue photographs is a region near the centre
which is devoid of spots(fig-3). This effect is due to both the finite size of the
unit cell of the crystal and also to the existence of a minimum wave-length in the
x-ray spectrum.
 As we traverse a Laue photograph from outside towards the centre, the
corresponding value of dhkl decrease. A limit is set up by the minimum value of
the wave-length in the x-ray spectrum and consequently spots cannot occur
with in a certain distance from the centre of the photograph.
 The Laue photograph as a whole becomes richer and richer in spots and these
appear closer and closer to the centre if λmin is progressively reduced by
increasing the potential applied on the x-ray tube.
Laue photograph can be indexed using the concepts of Gnomonic projection and
Reciprocal lattice.

INFORMATION OBTAINABLE FROM LAUE PHOTOGRAPH

Thus the Laue method enables us to investigate the symmetry of the crystal lattice
and to determine the orientation of planes. For example if the crystal possesses a
four- fold axis of symmetry parallel to the beam, the Laue photograph will also show
four-fold symmetry. This method is widely used to orient crystals for solid state
experiments.
The Laue method, is however, not a convenient method for the determination of
crystal structure, why because, out of the wide range of wavelengths present in the
continuous x-ray source it is possible for the several wavelengths to reflect in different
orders from a single plane so that different orders of reflection may superpose a
single Laue spot. Thereby the measurement of the reflection intensity of individual
spots becomes difficult and hence that of the missing reflections. In fact the missing
reflections would have been an important step in the determination of the crystal
structure. However, the shape of the unit cell can be established from the symmetry
of the pattern.
This method can also be used to assess crystal perfection from the size and shape of
the spots. If the crystal has been bent or twisted in anyway, the spots become
distorted and smeared out.

ROTATING CRYSTAL METHOD

In this method, a monochromatic beam of x-rays is incident on a single crystal
mounted on a rotating spindle such that one of its crystallographic axes coincides
with the axis of rotation and kept perpendicular to the direction of the incident
beam(see fig-4(a)). The single crystal having dimensions of the order of 1mm is
positioned at the centre of a cylindrical holder concentric with the rotating spindle as
shown in Fig-4. A photographic film is attached at the inner circular surface of the
cylinder.

Figure-4
The diffraction takes place from those planes which satisfy the Bragg’s condition for a
particular angle of rotation. The planes parallel to the axis of rotation diffract the
incident rays in a horizontal plane. However, reflections cannot be observed for those
planes which always contain the incident beam. The planes inclined to the rotation
axis produce reflections above or below the horizontal plane depending upon the
angle of inclination. The horizontal lines produced by diffraction spots on the
photographic film are called layer lines. If the crystal is positioned such that its c-axis
coincides with the axis of rotation, all the planes with Miller indices of the type (hko)
will produce the central layer line. Likewise, the planes having Miller indices of the
type (hk1) and (hk-1) will produce the layer lines above and below the central line
respectively, and so on.. These layer lines are shown in Fig-4(c). The vertical spacing
between the layer lines depends on the distance between the lattice points along the
c-axis. Hence the distance c can be measured from the photographic film. Similarly,
one can determine the translation vectors a and b on mounting the crystal along a
and b axes respectively. Thus the dimensions of the unit cell can be easily
determined.

POWDER METHOD
This is the most widely used diffraction method to determine the structure of
crystalline solids. The sample used is in the form of a fine powder containing a large
number of tiny crystallites, with random orientations. It is prepared by crushing the
commonly available polycrystalline material, thus eliminating the tedious process of
growing the single crystals.
The experimental arrangement used to produce diffraction is shown in Fig-5 below. It
consists of a cylindrical camera, called the Debye-Scherrer camera, whose length is
small as compared to the diameter.
 Figure-5

The finely powdered sample is filled in a thin capillary tube, or it is simply pasted on a
wire, by means of a binder and mounted at the centre of the camera. The capillary
tube or wire and the binder should be of a non-diffracting material. A collimated beam
of monochromatic x-rays is produced by passing the x-rays through a filter and a
collimator. The x-rays enter the camera through the collimator and strike the
powdered sample. Since the specimen contains a large number of small crystallites
(~1012 in 1mm3 of powder sample) with random orientations, almost all the possible θ
and d values are available. The diffraction takes place for those values of d and θ
which satisfy the Bragg’s condition. i.e. 2d sin θ = nλ, λ being a constant in this
case. Also, since for a particular value of the angle of incidence θ, numerous
orientations of a particular set of planes are possible, the diffracted rays
corresponding to fixed values of θ and d lie on the surface of a cone with its apex at
the sample and the semi vertical angle equal to 2 θ. Different cones are observed for
different sets of d and θ for a particular value of n, and also for different combinations
of θ and n for a particular value of d. The transmitted x-rays move out of the camera
through an exit hole located diametrically opposite to the entrance hole. A
photographic film is attached to the inner side of the curved surface 0f the camera.
Each cone of the reflected beam leaves two impressions on the film which are in the
form of arcs on either side of the exit hole with their centres coinciding with the hole.
Similarly, cones produced by back-reflected x-rays produce arcs on either side of the
entrance hole. If the sample consists of coarse grains rather than fine particles, a
spotty diffraction pattern may be obtained. This is because a sufficient number of
crystallites with all possible orientations may not be available in a coarse-grained
sample. In such a case, the sample has to be rotated to obtain almost continuous
diffraction arcs. The film is exposed for a long time a few hours in order to obtain
reflected lines of sufficiently high intensity. It is then removed from the camera and
developed. The arcs produced by reflected rays appear dark on the developed film.
The angle θ corresponding to a particular pair of arcs is related to the distance S
between the arcs as
4 θ(radians) = S/R ------ (1)
where R is the radius of the camera.
If θ is measured in, degrees, the above equation is modified as
4 θ(degrees) = (57.296)S/R -----(2)
The calculations can be made simpler by taking the radius of the camera in multiples
of 57.296. For example, taking R = 57.296 mm,
we get θ(degrees) = S(mm)/4 ---- (3)
Thus one-fourth of the distance between the corresponding arcs of a particular pair in
mm is a measure of the angle θ in degrees. Knowing all the possible θ values and
considering only the first order reflections from all the possible planes, the interplanar
spacing (d) for various sets of parallel planes contributing to these reflections can be
calculated from equation
d = λ/2(Sinθ) ------ (4)
These d values are used to determine the space lattice of the crystal structure.

POWDER DIFFRACTOMETER
Modern X-ray techniques give a series of peaks instead of diffraction intensities as in
Debye Scherrer method. In this method a detector is used instead of the film. A
convergent incident ray is used to give a good peak resolution. The powder is filled in
the hole of a sample holder. The set up requires that if reflection is obtained when the
beam is incident at an angle θ with the lattice plane, the reflected beam is recorded at
an angle of 2θ in what is referred to as θ-2θ scan. The peak positions and the
intensities are readily obtained from the chart. The powder diffractometer uses an x-
ray detector like a Proportional or Scintillation Counter to measure the positions of the
diffracted beams. Diffractometry is a widely used method because it measures the
intensities directly. A typical Powder diffraction pattern for NiZn is shown
in fig-6.

Figure-6: Powder diffraction pattern for

NiZn (four different samples)

Table-2: Information obtainable from diffractogram

 Feature
Peak positions (2θ values)
Non –indexable lines
Width of peaks
Peak intensities
Peak Shapes
(other than widths)
Information obtained
Unit cell dimensions and symmetry.
Presence of a crystalline impurity
Particle Size/Strain.
Unit Cell contents (Basis Vectors) and
thermal vibrations
Stacking faults, Layer defects

The positions of the peaks are directly related to the dimensions of the unit cell. The
intensities are related to the contents of the unit cell. The d-spacings are taken
because they are independent of the wavelength of the light used . Normally relative
intensities are used in order to normalize the intensities . The normalization of
intensities is done by taking a reference for the strongest peak and other intensities
are scaled accordingly.
The x-ray powder diffraction pattern of a mixture containing two or more compounds
is the weighted sum of the individual patterns. Although a powder diffraction pattern is
used as a finger print for identifying a material, other important information is obtained
in it.

APPLICATIONS OF POWDER DIFFRACTION

X-ray powder diffraction has opened up new avenues in the studies of structures. It
has a number of applications as described below.

(i) Qualitative analysis:

From the pattern, the d-spacings are recorded and the relative intensities of the 10
strongest lines are measured and are compared with the patterns of the known
compounds. This comparison is done with the help of a powder diffraction file that
contains the patterns of some standard compounds divided into subdivisions like
minerals, inorganic, organic.
(ii) Quantitative Analysis:
For a two-component mixture the relative concentration of each of the components
can be obtained by measuring the relative intensities of the strong non overlapping
lines each belonging to the two components.
(iii) Structure of alloys:
An alloy is a mixture of two or more elements. If the composition is uniform it
produces a typical powder diffraction pattern. If one of the components precipitates, it
produces separate lines on the powder pattern corresponding to the component.
(iv) Stress Determination in metals:
If there is a stress in a metal then the angle of the diffraction cone changes because
of a change in the d-spacing due to stress. By measuring the changes in the cone
angle accurate measurements of stress can be made. In addition, stress invariably
broadens diffraction peaks unless it is absolutely uniform on an atomic scale.
(v) Determination of particle size:
As the size of the crystallite decreases, the angular spread of the reflection increases.
The half height width can be used a measure of the mean particle size of the sample.
(vi) Identification and raw material evaluation:
For some complex materials, it is difficult to analyze the pattern. But since similar
materials exhibit similar patterns, we can for example determine the structure of
different clays as a cement material by comparing with acceptable clay and thus
relate structure to properties.