.

Various crystals with cubic structures • Each atom has four nearest neighbours thus coordination number = 4.
• The lattice constant 𝑎=3.50 Å in carbon structure
NaCl structure • The entire diamond structure may be constructed by tetrahedral units. The
• The NaCl crystal has a 𝑓𝑐𝑐 structure number of atoms per unit cell is 2.
with 𝑁𝑎+ and 𝐶𝑙− ions as the basis.
• The packing fraction of diamond is 0.34 in comparison to other fcc
• The 𝑁𝑎+ ions are situated at the structures having 0.74 as the packing fraction and thus the diamond’s
corners as well as at the centers of the lattice is relatively empty.
faces of the cube and 𝐶𝑙− ions are
relatively displaced half the edge of
the unit cell along each axis.
• Thus, 𝑁𝑎𝐶𝑙 crystal can be thought of
as composed of superposed 𝑓𝑐𝑐 𝑁𝑎+
and 𝐶𝑙− sub-lattices. 𝐾𝐶𝑙 has similar structure as 𝑁𝑎𝐶𝑙

𝑪𝒔𝑪𝒍 Structure Zinc Blende (ZnS) structure

• CsCl an ionic crystal, is a good • The structure lies in close resemblance to that of diamond with an
example of simple cubic. exception of having two fcc lattices occupied by different elements.
• The lattice constant being a = b = c = • The structure represents two types of atoms: the darker circles
4.11 Å. representing Zn atoms and the lighter ones S atoms.
• At all the eight corners of the cube, the • We can say that ZnS has equal number of Zn and S atoms distributed
Cs+ ions are situated and Cl- ions are on a diamond lattice so that each has four of the opposite kind as
situated at the body centre of each unit nearest neighbours.
cell and vice-versa.
• There is one ion per unit cell of Cs+
and one ion of Cl- and hence one
molecule per unit cell.

Diamond Structure Calculation of Lattice Constant

• Consider a cubic lattice of lattice constant a. If 𝜌 is the density of the
• The diamond structure can be observed in Carbon (C), grey tin and crystal under consideration, then
semi-conductors like Ge, Si that basically crystallises in this form. • Volume of unit cell V = 𝑎3,  Mass in each unit cell = 𝑎3𝜌
• It has 𝑓𝑐𝑐 lattice with a basis consisting of two carbon atoms • If 𝑀 is the molecular weight and 𝑁 the Avogadro number, then
associated with each lattice point, one atom is at (0,0,0) and the
Mass of each molecule = .
other at ( , , ) of the main diagonal of cube or we can say that at a
distance of one quarter of the body diagonal from the lattice point • Further if n is the number of molecules (lattice points) per unit cell, then
along the body diagonal. the mass in each unit cell = 𝑛.
• The diamond lattice is composed of two superposed 𝑓𝑐𝑐 sub-
lattices, one displaced relative to the other by one-fourth of a body
diagonal.
• From this relation, the value of the lattice constant ‘𝑎’ can be calculated.

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Crystal Planes and Miller Indices: • Crystal planes are defined as some imaginary planes inside
a crystal in which large concentration of atoms are present.
• Inside the crystal, there exists certain directions along which
• A crystal may be thought of as being made up of many large concentration of atoms exists.
different sets of parallel and equidistant planes passing • These directions are called crystal directions.
through the lattice points.
• These are called lattice planes.
• Many properties of the crystal can be understood in terms of
the spatial geometry of these planes.
• Miller indices (hkl) is a set of three numbers h, k and l used
to designate these different sets of planes.

How to obtain the Miller indices? Steps to determine the Miller Indices of a plane.
• Any plane in the crystal can be thought of as making
intercepts on the crystallographic axes a, b and c which may
i. Determine the intercepts by the given lattice plane on the
be primitive or non-primitive.
three coordinate axes say x, y and z axes .
• Express the intercepts in terms of multiples of unit lattice
ii. Note the reciprocal of the intercepts.
constants (a, b, c).
iii. Simplify by reducing the reciprocals into whole numbers.
• Find the reciprocal of the numbers.
iv. For this multiply each reciprocal by a number obtained after
• Reduce the reciprocals to smallest integers by multiplying
taking L.C.M. of denominator.
them with the least common multiple (LCM) of their
denominators. v. Enclose the numbers so obtained in parentheses.
• Enclose the integers in a parentheses: (hkl).

For cubic structure:

a=b=c
• The interplanar spacing for a given set of parallel planes is Intercepts along x axis
fixed but for different set of planes, the interplanar spacing = ∞
varies and so the density of lattice points too. Intercepts along y axis
= 𝑎
Intercepts along z axis
(010) = ∞
Miller Indices
Along x = = 0
Along y =
Along x = =0
(hkl) = (0 0) = (010)

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For cubic structure:

a=b=c Intercepts along x axis
=𝑎
Intercepts along x axis Intercepts along y axis
=𝑎 =𝑎
Intercepts along y axis Intercepts along z axis
=∞ =𝑎
Intercepts along z axis Miller Indices
=∞
(111)
Along x =
(100) Miller Indices
Along y =
Along x =
Along x =
Along y = =0
(hkl) = ( ) = (111)
Along x = =0
(hkl) = ( 0 0) = (100)

Intercepts along x axis The different kinds of bracket have different

=𝑎
Intercepts along y axis meaning:
=𝑎
(110) Intercepts along z axis (hkl) represents plane
=∞
Miller Indices [hkl] represents a direction
Along x =
{hkl} represents family of planes
Along y =
Along x = =0 <hkl> represents family of directions
(hkl) = ( 0) = (110)

Intercepts along x axis

Spacing between Lattice
= 𝑎/2 Planes
Intercepts along y axis • The spacing between any two
=∞ consecutive planes in a given unit
Intercepts along z axis cell can be easily derived.
(200) =∞
• Let us consider three mutually
Miller Indices
perpendicular coordinate axis
Along x =
OA, OB and OC.
Along y = =0 • Assume that a plane (hkl)
Along x = =0 parallel to the plane passing
(hkl) = ( 0 0) = (200) through the origin makes
intercepts a/h, b/k and c/l
along the three orthogonal axes

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• Let the line ON be the normal to the plane passing through Diffraction of X-rays, electrons and Neutron’s by Crystals
the origin,
• the length d of which represents the inter planer spacing • The crystal diffraction is explored through the diffraction of
between two consecutive planes. waves of wavelength comparable with the interatomic spacing
which is of the order of 1Å
• ON makes angle a, b, g with the three axes.
• Radiation of longer wavelength cannot resolve the details of
• Thus, OA = a/h, OB = b/k, OC = c/l and ON = d. crystal structure,
• We can calculate the values of d in terms of a, b and c. • while the radiation of much shorter wavelength is diffracted
• From triangles ONA, ONB, ONC we have: through very small angle which are inconvenient to measure.
• X-rays have wavelength of the order of 1Å.
• According to de-Broglie, material particles in motion also
behave as waves.

Diffraction of X-rays, electrons and Neutron’s by

Crystals
From cosine theorem: • Calculations show that the electrons and neutrons also possess
wavelength  ≈1Å.
• Therefore, the crystal structure may be studied by the
Substituting values of cos a, cos b 𝑎𝑛𝑑 cos g diffraction of neutral X-rays and neutrons and less often by
electrons,
• because electron beam being charged, is also diffracted by
atomic electrons.

X-ray Diffraction
It is to be noted that the formula is applicable only to primitive
• X-ray diffraction was first conceived by Von Laue in 1912, and subsequently
lattices of cubic, orthorhombic and tetragonal systems. tested by Freidrich and Knipping.
• The two very well demonstrated that whenever an X-ray beam is made to
i) For a cubic lattice, 𝑎 = 𝑏 = 𝑐, therefore the equation becomes pass through a single crystal it gets broken up into a collection of diffracted
beams.
• With the use of diffraction technique, one can realise the direct exploration
of the interior of the crystals.
ii) For a tetragonal crystal 𝑎 = 𝑏 ≠ 𝑐, so the equation becomes • The measurement of distance between the atoms and the associated internal
symmetry can be well studied using diffraction technique.
• The technique gives the possibility of knowing the intensities of the
diffracted beams and their directions which depends on the atomic
arrangements in crystal.
• The complete information about the crystals thus can be obtained by
measurement of their intensities and directions.

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• If 𝑂𝑀 and 𝑂𝑁 are perpendiculars drawn from 𝑂 on 𝑂’𝐴’ and 𝑂’𝐵’, then

path difference between the beam reflected at two consecutive planes will
be an integral multiple of the wavelength 
• i.e the beams will show constructive interference giving maximum
intensity.
• Thus, for a given path difference of , 2, 3 .... etc a strong reflection
will be observed at an angle  and hence we get,
2𝑑sin  = 𝑛 
• where n is an integer and represents order.
• This result is the famous Bragg’s equation.
• It is obvious from this equation that for given values on 𝑛,  𝑎𝑛𝑑 𝑑, there
will be strong reflection.

Bragg’s Law
• It is now obvious that there are only certain directions 𝑠, in
• In 1912, W.H. Bragg and W.L. Bragg, father & son, suggested a model
which could explain diffraction in crystals. which the reflection of a given wavelength  from all parallel
• They pointed that a crystal can be divided into sets of parallel planes.
planes add up in phase to give a strong reflected (diffracted)
beam.
• X rays can diffract or reflect by these set of parallel planes and the
constructive interference can occur in between the resulted reflected rays.
• Bragg derived a simple mathematical relationship which explains the
condition for Bragg reflection.
• This is known as Bragg’s law.
• In a given crystal, let us think a set of parallel atomic planes having
spacing d between them.
• Now, consider a narrow beam of X-rays of wavelength  incident on
the planes at glancing angle .
• The angle which the reflected beam makes with the plane is .

Bragg’s reflection Determination of Crystal Structure

• Consider the rays reflected at two consecutive planes 𝑃𝑄 and 𝑅𝑆. Laue Method
• Thus the rays 𝐴𝑂 and 𝐴’𝑂’ are reflected at 𝑂 and 𝑂’ respectively • In 1912, Max Von Laue suggested for the very first time the use
along 𝑂𝐵 and 𝑂’𝐵’ such that 𝐵𝑂𝑄=  𝐵′𝑂′𝑆= . of a crystal as a three dimensional diffraction grating.
• Probably, it can be considered as one of the oldest method of
X-ray diffraction.
• This method is used for the determination of crystal structure.
• Experimental Arrangement consists of a continuous, well-
collimated X-ray beam obtained from a collimator with a fine
hole.
1. A single crystal held stationary on a goniometer which can
change the orientation relative to incident X-ray beam.

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2. Two flat photographic films are used: one to receive the

transmitted and the other for reflected diffraction beams.

Working Principle
• When X-ray beam falls on the single crystal which is held stationary
in the path of X-rays with wavelengths ranging from 0.2 to 2Å, the
beam is diffracted.
• The beam after diffraction forms a series of spots on the screen
called Laue spots which are characteristics of crystal structure.
• This is due to the fact that a crystal consists of a set of parallel
planes with different interplanar spacing and for certain values of 
and d, diffraction becomes possible as the Bragg’s condition is
satisfied.
• We can change the orientation of the crystal with respect to the
incident incoming beam of X-rays with the help of goniometer.

• Again we get a different type of pattern on the photographic

plate as Bragg’s condition is satisfied and diffraction takes
place for a new set of atomic planes.
• Each spot in the Laue diffraction pattern corresponds to an
interference maximum for a set of crystal planes satisfying the
Bragg equation 2𝑑sin = 𝑛 for a particular wavelength
selected from the continuous incident beam.
• i) From the position and intensities of these spots, one can
determine crystal structure 𝑖.𝑒., the values of primitives 𝑎,𝑏,𝑐
and the details of unit cell of the solid and not the structure
of the crystal.
• ii) Crystal imperfections can be determined by observing
Laue’s patterns.