Chapter 2 Determination of Crystal Structure

2
DETERMINATION OF
CRYSTAL
STRUCTURE

2.1 METHODS OF DETERMINING CRYSTAL STRUCTURE

Studying the structure of crystals is very useful in theoretical and practical applications.
We mean by crystal structure that corresponding to relationship between atomic planes in
the crystal and determination of the lattice parameters. The following methods are widely
used for determining crystal structure
(i) X-ray diffraction: This includes the following methods
(a) Bragg’s spectrometer method
(b) Laue’s method
(c) Powder method
(ii) Electron diffraction and
(iii) Neutron diffraction

2.2 X-RAY DIFFRACTION

X-rays provide a powerful tool for the study of crystal structure. X-rays, being
electromagnetic radiations, also undergo the phenomenon of diffraction as observed for
visible light. The ordered arrangement of atoms in a crystal with interatomic spacing of the
order of few angstroms behaves like a three-dimensional diffraction grating for X-rays.
One can easily verify this. Let us consider sodium metal whose density equals 1.013 ×
103 kg/m3 and molecular weight, M is 23 respectively. The structure of sodium is BCC and
hence the number of atoms/unit volume = 2. The crystal density , accordingly the

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Chapter 2 Determination of Crystal Structure

cell constant is ( ) So, we have

where NA is Avogadro’s number (= 6.023 × 1026 atom/kmol).

Thus the wavelength of the radiation required for diffraction by sodium metal is of the
order of a few angstroms which is clearly in the range of X-rays.

BRAGG’S LAW
In 1912, Laue suggested that a crystal which consisted of a three-dimensional array of
regularly spaced atoms could serve as a grating. On the suggestion of Laue, his associates
succeeded in diffracting X-rays by passing them through a thin crystal of Zinc blende. The
diffraction pattern obtained by them consists of a central spot and a series of spots
arranged in a definite pattern around the central spot. This symmetrical pattern of spots is
known as Laue pattern.
The explanation for this was given by Bragg. According to Bragg, the spots are produced
due to the reflection of some of the incident X-rays from the various sets of parallel crystal
planes (called as Bragg’s planes), which contain a large number of atoms.
Consider a ray PA reflected at atom A in the direction AR from plane I and another ray QB
reflected at another atom B in the direction BS (Fig. 2.1).
The two reflected rays AR and BS will be in phase or out of phase depending on the path
difference.
When the path difference, CB + BD is a whole wavelength , or multiple of whole
wavelength (n ), then the two rays will reinforce each other and produce an intense spot
due to constructive interference.

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Chapter 2 Determination of Crystal Structure

Fig. 2.1 Reflection of X-rays from lattice planes in a crystal

Obviously, the condition of reinforcement, i.e. constructive interference is:

CB + BD = n
CB = BD = d sin
where is the angle between the incident ray and the planes of reflection and called as
glancing angle. Therefore, we have
2d sin =n
where d is the interplanar spacing of planes, i.e. distance between the same set of planes
and n = 1, 2, 3,. . . stand for first order, second order, third order maxima respectively.
This equation is known as Bragg’s law. We must note that the Bragg’s reflection can
occur only for ≤ 2d.
The directions along which the maxima are observed can be obtained from Bragg’s law,
by giving different values of ; i.e.,

As the order of spectrum increases, the intensity goes on decreasing.

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Chapter 2 Determination of Crystal Structure

We must note that the Bragg equation is not limited to atomic planes parallel to the crystal
surface; it is applied to all planes in the crystal.

BRAGG’S X-RAY SPECTROMETER

The apparatus used in X-ray crystal diffraction is denoted by diffractometer as shown in
Fig. 2.2.
The X-rays from the target T of an X-ray tube pass through two slits S1 and S2 in thick
lead sheets. They then fall on the single crystal D mounted on a turn table. The crystal is
rotated by means of the turn-table so as to increase the glancing angle at which X-rays
are incident at the exposed face of the crystal. The position of the crystal can be read with
the help of the vernier v and a circular scale. An ionisation chamber I is mounted on an
arm which can rotate about the same axis as that of the crystal table. The ionisation
chamber or photographic plate is used for measuring the intensities of reflected rays.

Fig. 2.2 Bragg’s X-ray spectrometer

By measuring glancing angles ( ) at which reflection occurs, one can determine the
interplanar spacings knowing the wavelength of X-rays according to Bragg equation: 2d
sin =n .
As an example, consider X-ray diffraction from rock salt (NaCl) cubic crystal, the

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Chapter 2 Determination of Crystal Structure

variation of ionization current against glancing angle is shown in Fig. 2.3.

Fig. 2.3 Variation of ionization current with glancing angle

This curve is obtained when X-rays from a tube containing a platinum target were
reflected by the crystal. The experimental results have shown that the first order reflection
maxima occurred at 5.9°, 8.4° and 5.2° for (100), (110) and (111) planes respectively.
For first order reflection, n = 1 and hence

One can follow this procedure for other crystals.

Bragg’s equation can be used to calculate the lattice constant. Figure 2.4 shows the
diffraction pattern of tungsten metal. The numbers on the peak are the Miller indices of the
planes which produce that peak. One can compute the interplanar spacings by measuring
the value of and using Bragg’s law

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Chapter 2 Determination of Crystal Structure

In cubic lattice

√
Then
√

The wavelength of the X-ray value is known, for first order diffraction n = 1, and from
the X-ray diffraction chart (indicated from Fig. 2.4) we can determine the angle at
layer (h k l).
Therefore the lattice constant a for the investigated sample can be determined.

Fig. 2.4 Diffraction pattern intensity at various angle

LAUE’S METHOD
This is one of the principal methods to study X-ray diffraction and to determine crystal
structure. Fig. 2.4 shows Lau apparatus. In this method, a single crystal is placed in the
path of X-rays beam and the glancing angle is kept constant. Continuous spectra of X-
ray, having wide range of wavelengths, are allowed to fall on the crystal at 90°on the plane
of the crystal. Each set of crystal plane d selects appropriate value of wavelength and
produces a spot which fulfills Bragg’s law:
2d sin =n
When primary rays are allowed to pass through the crystal, they produce a black spot at B

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Chapter 2 Determination of Crystal Structure

(Fig. 2.5) on photographic plate PP. Different Wavelengths are included in the primary X-
rays and hence they will produce spots around this central spot, which are less
pronounced as depicted in Fig. 2.6.

Fig. 2.5 Laue’s Method

Let ab represent the position of one of the possible Bragg’s plane, the corresponding
angle and A any spot (other than central spot) on PP. From the triangle OAOB, one finds
AB = R tan 2 . Knowing AB and R, one can find for the corresponding plane.

Fig. 2.6 Laue pattern for a crystal

POWDER METHOD
This method is quite useful when single crystals of large size are not available. The sample
used is in the form of a fine powder containing a large number of tiny crystallites with
random orientations. The powder is placed in a capillary tube. This powder specimen is

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Chapter 2 Determination of Crystal Structure

mounted at the centre around which a strip of circular photographic film is positioned (Fig.
2.7).
A collimated beam of monochromatic X-rays strikes the specimen through a small hole.
Let us consider that the incident beam make an angle with a set of parallel crystal plane.

Fig. 2.7 Powder method

If Bragg condition is satisfied, then there will be reflection. Since there are a large number
of randomly oriented crystals in the powder sample and hence there are several possible
orientations of this set of planes of same angle . The reflected rays will not be in the form
of parallel beam but they will lie on the surface of a cone with its apex at the sample and
the semivertical angle 2 (Fig. 2.8). Different cones are observed for different sets of d
and for a particular value of n, and also for different combinations of and n for a
particular value of d (Fig. 2.9).

Fig. 2.8 A cone produced by reflection of X-rays in powder method

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Chapter 2 Determination of Crystal Structure

Fig. 2.9 The X-ray powder diffraction pattern for cubic crystal

2.3 ELECTRON AND NEUTRON DIFFRACTION

Since waves are diffracted by a crystal, we can also use electrons and neutrons instead of
X-rays, provided the wavelengths of matter waves associates with these particles are in the
range of 1 to 10 Å.
Wavelength for neutron

Where is in Angstroms and E in eV. Thus the energy of a neutron of wavelength of 1 Å

is = 0.08 eV. The thermal neutrons in a atomic reactor have the energy = 0.08 eV and
hence can be used for the study of crystal diffraction.
We must note that there are many differences between neutron diffraction X-ray
diffraction. X-rays are scattered by electrons, whereas neutrons are scattered by nuclei.
Using this property of neutrons, one can study many low atomic weight elements by
neutron diffraction where X-rays are incapable of giving precise results.

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Chapter 2 Determination of Crystal Structure

Wavelength for electron

where is in Angstroms and E is in kilo eV.

Like X-rays or neutrons, electrons can also be used. However, the electrons are much
more easily scattered and hence the penetration depth is small. This is why electron
diffraction method is used in surface studies-bonds, defects, energy states, etc.

2.4 RECIPROCAL LATTICE

We have seen that the diffraction of X-rays occurs from various sets of parallel planes
having different orientations (slopes) and interplanar spacings. In certain situations
involving the presence of a number of sets of parallel planes with different orientations, it
becomes difficult to visualize all such planes because of their two-dimensional nature. To
solve the problem, Ewald introduced a new type of lattice known as the reciprocal lattice.
The idea underlying the development was that each set of parallel planes could be
represented by a normal to these planes having length equal to the reciprocal of the
interplanar spacing. Thus the direction of each normal represents the orientation of the
corresponding set of parallel planes and its length is proportional to the reciprocal of the
interplanar spacing. These points form a regular arrangement which is called a reciprocal
lattice. One can construct a reciprocal lattice to a direct lattice using the following
procedure:
(i) Take origin at some arbitrary point and draw normals to every set of parallel planes of
the direct lattice
(ii) Take length of each normal equal to the reciprocal of the interplanar spacing for the
corresponding set of planes. The terminal points of these normals form the

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Chapter 2 Determination of Crystal Structure

reciprocal lattice
Let us consider, as an example for the construction of reciprocal lattice, the unit cell of a
monoclinic crystal looking along its unique axis, i.e. c-axis.

For simplicity, we may consider planes belonging to a single zone. This makes the
normal to all parallel planes belonging to the zone axis, i.e., normal to the c-axis.

Fig. 2.10 Graphical construction of two dimensional reciprocal lattice

In Fig. 2.10, we can see that the zone axis lies perpendicular to the plane of the diagram
and hence all normals to the parallel planes of the family of the zone will lie in the plane
of the diagram. Figure 2.10 also shows the edge views of four (h k l) planes, viz., (100),
(110), (120) and (010) all belonging to [001] zone. We must note that the normals to the
family of planes (100), (200), (300) etc. are parallel. Further d100 = 2d200 = 3dS00 =
4d400 etc.
Obviously, while

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Chapter 2 Determination of Crystal Structure

where K is a scale factor chosen for the construction of the reciprocal lattice. Clearly, the
distance of the reciprocal lattice point representing the set of parallel planes (nh 0 0) from
the origin will be n times greater than the distance of the reciprocal lattice point from the
origin representing the set of parallel planes (300) will be at a distance from the origin
equal to three times the distance of the reciprocal lattice point representing the set of
parallel planes (100).
In reciprocal lattice, it is the convention to represent the reciprocal lattice point
representing the set of parallel planes with Miller indices (h, k l) by the same Miller
indices without the parenthesis. We can see in Fig. 2.10 that the reciprocal lattice points
representing the set of parallel planes (100), (200), (300) etc . . ., are indicated by 100,
200, 300 etc . . . .
We have taken the planes belonging to [001] zone and after plotting the reciprocal lattice
points of all the (h k o) planes, we obtained a two dimensional lattice (Fig. 2.10). A
reciprocal lattice vector, , is defined as a vector having magnitude equal to the
reciprocal of the interplanar spacing and direction coinciding with normal to (h k l)
planes. Thus, we have

where nˆ is the unit vector normal to the (h k l) planes.

Denoting the fundamental reciprocal vectors , and by a*, b* and c*
respectively, one obtains
⃑
⃑⃑⃑⃑
⃑

⃑⃑⃑⃑
⃑

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Chapter 2 Determination of Crystal Structure

⃑
⃑⃑⃑
⃑
where ⃑ is the volume of the direct cell.

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Chapter 2 Determination of Crystal Structure

2.5 PROBLEMS
Problem 2.1 Determine the interplanar spacing when a beam of X-ray of wavelength 1.54
Å is directed towards the crystal at angle 20.3° to the atomic plane.

Problem 2.2 X-rays with wavelength of 0.58 Å are used for calculating d200 in nickel. The
reflection angle is 9.5°. What is the size of unit cell?

Problem 2.3 Calculate the Bragg angle if (111) planes of a cube (a = 3.57 Å) crystal are
exposed to X-rays (wavelength = 1.54 Å)

Problem 2.4 For a certain BCC crystal, the (110) plane has a separation of 1.181 Å. These
planes are indicated with X-ray of wavelength 1.540 Å. Show that the maximum order of
the Bragg’s reflection that can be observed is n = 1.

Problem 2.5 The glancing angle of 10° is observed in first order Bragg’s reflection. Show
that the angle for 3rd order reflection is 31.S9°.

Problem 2.6 A diffraction pattern of a cubic crystal of lattice parameter a = 3.16 Å is

obtained with a monochromatic X-ray beam of wavelength 1.54 Å. The first line on this
pattern was observed to have = 20.3°. Obtain the interplanar spacing and Miller
indices of the reflecting plane.

Problem 2.7 Determine interatomic spacing when glancing angle of 30° is observed
during first order reflection in a crystal having Miller indices as (111). The Wavelength of
X-rays is 2 Å.

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