CHAPTER I: CRYSTAL STRUCTURE

Content:

I. Introduction
II. Structure of cubic crystals (SC, BCC, FCC)
III. Ligancy and critical radius ratio in ionic crystal
IV. Miller indices, planes and direction
V. Crystal structure Analysis
VI. Imperfections: point, line, surface & volume (introductory)

I. Introduction

1.1 SHORT AND LONG RANGE ORDER

Order: Presence of some symmetry or correlation in a many-particle system.
Short-range order: It exists till the first or second-nearest neighbors of an atom. It implies non
dense, random packing (fig.1).

Figure 1: Short-range order of materials. Figure 2: Long-range order of materials.

Long-range order: It exists over long distances. It implies dense, regular packing (fig.2).
Dense, regular-packed structures having long-range tend to have lower energy.

1.1.1 Classification Of Matter On The Basis Of Order

Materials can be classified on the basis of order. Gases do not have any order. This is followed by
amorphous materials which has only short-range order. Next in line are liquid crystals which have
short and long range order in small volumes.
Finally, long range order is observed in crystalline materials.
They are of two types: single crystal and polycrystalline.
.

Figure 3:
Classification
of materials
on the basis
of order.

1.1.2 Difference Between Single And Poly-Crystals

Single crystal: A single crystal or monocrystalline solid is a material in which
the crystal lattice of the entire sample is continuous and unbroken to the edges of the sample,
with no grain boundaries (fig.4a).
The properties of a single crystal vary with direction. This is termed as anisotropy. For eg. the
modulus of elasticity (E) in BCC iron (fig.4b). The values of modulus of elasticity in BCC iron
is different along the edge of the cube and along the body diagonal of the cube giving rise to
anisotropy.

(b)
(a)
Figure 4: (a) Pictorial representation of a single crystal. (b) Modulus of elasticity (E) in BCC
iron.
Poly-crystal: It is comprised of many small randomly oriented crystals or grains. The properties
of a polycrystalline material may/may not vary with direction, depending on degree of texture
(orientation). If the grains are randomly oriented, then the properties are same along all directions
i.e., isotropic. For eg. the bulk modulus of randomly oriented polycrystalline iron is 210 GPa along
all directions (fig.5). However, if all the grains are oriented in a single direction, then the properties
will be anisotropic.

Figure 5:
Polycrystalline sample of non-oriented iron.

1.2 LATTICE, BASIS, CRYSTAL STRUCTURE

Space Lattice: A translational periodic arrangement of lattice points. Each lattice point in a lattice
has identical neighborhood of other lattice points.
Bravais Lattice: Bravais lattice, studied by Auguste Bravais (1850), is an infinite array of discrete
points in three dimensional space generated by a set of discrete translation operations described
by:
R = n1a1 + n2a2+n3a3
where ni are any integers and ai are known as the primitive vectors which lie in different directions
and span the lattice. For any choice of position vector R, the lattice looks exactly the same.
Motif or Basis: An atom or a group of atoms associated with each lattice point.
Crystal: A translational periodic arrangement of atoms. It is made up of lattice and basis.
Types of crystals

1.2.1 Unit Cell and Primitive Cell

Unit Cell
The smallest building block of a crystal, consisting of atoms, ions, or molecules, whose
geometric arrangement defines the symmetry and structure of the entire crystal lattice and whose
repetitive translation in space produces the crystal lattice is called the unit cell.
The unit cell is characterized by three lattice
constants a, b, c (the lengths of the basis vectors or
edges of the unit cell) and by the three angles α, β, γ
which separate these vectors from one another. α is
the angle between the basis vectors b and c, β
between a and c, and γ between a and b (fig. 6).
The lattice constants and the angles between them are
called lattice parameters.
The volume of a unit cell is given by
V = |𝒂. ( 𝒃 𝒙 𝒄 ) |
Figure 6: Pictorial representation of unit cell.
Primitive Cell
Primitive cell is a unit cell constructed so that it contains
only one lattice point. The primitive cell has lattice points
only at corners. It does not define the full symmetry of the
entire space lattice. There are multiple ways to select a
primitive cell (fig.7).

Figure 7: Multiple ways to

select a primitive cell.
Non-primitive unit cell: It has lattice Point at corners as well as at other points.

1.3 SYMMETRY
Symmetry: A body is said to be symmetrical when it can be divided into parts that are related to
each other in certain ways.
Symmetry Operation: An operation that leads to superimposition of an object on itself.
Symmetry operators: translation, rotation, reflection, inversion.
Symmetry Element: An imaginary geometric entity (line, point, plane) about which a symmetry
operation takes place.
Symmetry elements: point, line, plane.
Rotation: An n-fold rotation symmetry means rotation through an angle of 2π/n will repeat the
object or motif n times in a full 360⁰ rotation. n =1 means no symmetry. In a crystal, only 2, 3, 4
and 6-folds of rotation are possible.
Reflection: An object with a reflection symmetry will be a mirror image of itself across a plane
called mirror plane (m).
Inversion: In this operation, every part of the object is reflected through an inversion center called
center of symmetry which is denoted as i. The object is reproduced inverted from its original
position.
Combined Operations:
1. Screw Axis: A screw axis (helical axis or twist axis) is a line that is simultaneously
the axis of rotation and the line along which translation of a body occurs.
2. Glide plane: A glide plane (or transflection) is a symmetry operation describing how a
reflection in a plane, followed by a translation parallel with that plane, may leave the
crystal unchanged.
3. Roto-inversion: A rotoinversion axis combines rotation about an axis of rotation with
inversion.
4.
1.4 SEVEN DIFFERENT CRYSTAL SYSTEMS AND FOURTEEN DIFFERENT
BRAVAIS LATTICES:
Crystals are divided into 7 crystal systems according to their geometric symmetries and into 7
lattice systems according to their Bravais lattices.
A lattice system is generally identified as a set of lattices with the same shape according to the
relative lengths of the cell edges (a, b, c) and the angles between them (α, β, γ).
Each lattice is assigned to one of the following classifications (lattice types) based on the positions
of the lattice points within the cell: primitive (P), body-centered (I), face-centered (F), base-
centered (A, B, or C), and rhombohedral (R).
The 14 unique combinations of lattice systems and lattice types are collectively known as
the Bravais lattices.
Thus, solids are classified into 7 crystal systems and 14 Bravais lattices as represented in table 1
and 2.
Table 1: Classification of solids into 7 crystal systems on the basis of geometric symmetries.

Table 2: Classification of solids into 7 crystal systems and 14 Bravais lattices.

II. STRUCTURE OF CUBIC CRYSTALS

2.1 CUBIC CRYSTAL STRUCTURES

2.1.1 Parameters of crystal structure:
• Number of atoms per unit cell or Effective number: It is the total number of atoms per
unit cell.
• Co-ordination number: It is the number of nearest neighboring atoms to a particular atom
in the crystal.
• Atomic radius: It is defined as half of the distance between two nearest neighbors in a
crystal of a pure element since any two nearest neighboring atoms touch each other. It is
usually expressed in terms of the edge of the unit cell ‘a’.
• Atomic packing factor (Packing density) (APF): Atomic packing factor (APF) or
packing density indicates how closely atoms are packed in a unit cell and is given by the
ratio of volume of atoms in the unit cell and volume of the unit cell.

2.1.2 Simple Cubic Structure

• Number of atoms per unit cell or Effective number:
There are 8 atoms at the eight corners of the unit cell. Each of
these atoms are shared by eight unit cells.
Therefore, effective number of atoms in simple cubic unit cell
is equal to
8 (corner atoms) x 1/8 = 1 atom / unit cell.
• Co-ordination number:
Each corner atom is in contact with two other atoms along the
edges of the cube.
Hence, the co-ordination number of simple cubic structure is 6.

• Atomic radius: a
In a simple cubic structure, the atoms touch each other along
the edge of the cube.
Hence, the atomic radius 'R' in terms of the length of the edge R
of the unit cell 'a' is a = 2R
Figure 8: Simple Cubic
Structure
• Atomic Packing Factor

• Co-ordinates of atoms in simple cubic structure.

2.1.3 Body-centered Cubic Structure

Figure 9: Body-centered cubic structure

• Number of atoms per unit cell or Effective number:

There are 8 atoms at the eight corners and 1 atom at the center of the unit cell.
Each of the corner atoms are shared by eight unit cells while the center atom entirely belongs
to the unit cell.
Hence, the effective number of atoms per unit cell is
8 (corner atoms) x 1/8 + 1 centre atom = 2 atoms / unit cell.

• Co-ordination number:
The body-centered atom is in contact with all the 8
corner atoms.
Hence, co-ordination number of body-
centered cubic structure is 8.

• Atomic radius: In a body-centered cubic structure, 4

the atoms touch each other along the body diagonal of R
the cube. Hence, the atomic radius 'R' in terms of the
length of the edge of the unit cell 'a' is

√𝟑a = 4R (fig.10).

Figure 10
 • Co-ordinates of atoms in Body center cubic structure

• Atomic Packing Factor

Calculation of APF:

2.1.4 Face-centered Cubic Structure (FCC)

• Number of atoms per unit cell or Effective number:
There are 8 atoms at the eight corners and 6 atom at the centre of each face of the unit cell.
Each of the corner atoms are shared by eight unit cells while the face-centered atoms are shared
by 2 unit cells.
Hence, the effective number of atoms per unit cell is
8 (corner atoms) x 1/8 + 6 (face-centered atoms) x 1/2 = 4 atoms / unit cell.

• Co-ordination number:
The face centered atom in the front face is in contact with four corner atoms and four other face-
centered atoms behind it (two sides, top and bottom) and is also touching four face-centered
atoms of the unit cell in front of it.
Hence, co-ordination number of FCC is 12.
 Figure 11: Face-centered
cubic structure.

• Atomic radius:
In a face-centered cubic structure, the atoms touch each
other along the face diagonal of the cube. Hence, the
atomic radius 'R' in terms of the length of the edge of
the unit cell 'a' is

√𝟐a = 4R (fig.12).

Figure 12
• Atomic Packing Factor:

Calculation of APF:
Co-ordinates of atoms in FCC.

Fractional Co-ordinates: 000,100, 010, 001, 110,101,

011,111, ½ ½ 0, ½ 0 ½, 0 ½ ½ ,½1 ½ , 1 ½ ½ , ½ ½ 1
Unique Positions: (0,0,0), (1/2,1/2,0), (1/2,0,1/2),
(0,1/2,1/2)

2.2 CLOSEST PACKED STRUCTURES

The term "closest packed structures" refers to the most tightly packed or space-efficient
composition of crystal structures (lattices). Atoms, ions or molecules which lie on the lattice points
are assumed to be spherical to explain the bonding and structures of crystals. Unfilled space will
always exist in the packing of spheres. In closest packed structures, the arrangement of the spheres
are densely packed in order to maximize the efficiency of packing and minimize the volume of
unfilled space.

2.2.1 Types of Holes from Close-Packing of Spheres

Gaps are left uncovered by a single layer of spheres arranged in the shape of a hexagon. This is a
trigonal hole.

Figure 17: Pictorial representation of a trigonal hole.

The stacking of two close packed layers of atoms produces 2 types of voids or holes.
1. Tetrahedral holes (voids)
Tetrahedral voids (holes) exist where four atoms come together (atom from layer b lie on top of
trigonal hole from layer a) (fig.18). There are 2 tetrahedral holes per atom.
 Figure 18: Pictorial representation
of a tetrahedral hole.

2. Octahedral hole
Octahedral spaces (holes) occur where six atoms come together (three atoms from layer b surround
a hole from layer a) (fig.19). Octahedral holes are larger than tetrahedral ones. There is 1 octahedral
voids per atom.

Figure 19: Pictorial

representation of an octahedral
hole.

2.2.2 FCC and HCP close-packed structures

FCC and HCP are the closest packed structures. Both FCC and HCP crystal structures have atomic
packing factors of 0.74 (maximum possible value). Both FCC and HCP crystal structures have co-
ordination number 12. The difference between the two structures is in the stacking sequence.

Figure 20: Voids left in a single layer of atoms.

Hexagonal Close Packed (HCP) Structure:
In HCP structure, the atoms in the second layer (B) lies above the
holes in the first layer (A). The third layer has the same arrangement
of atoms as the first layer (fig. 21). Since the structure repeats itself
after every two layers, the stacking sequence for HCP is A-B-A-B-
A-B…… The HCP structure covers all the tetrahedral holes. A

Figure 21: Hexagonal close-packed structure.

Cubic Close Packed (CCP) Structure:

In CCP structure, the atoms in the second layer (B) lies above the holes in
the first layer (A). The third layer is completely different than that first two
layers and is stacked in the depressions of the second layer (fig. 22). The A
stacking sequence for CCP is A-B-C-A-B-C….. The octahedral holes are
covered in CCP structure.

B
A

Figure 22: Cubic Close Packed (CCP) Structure.

III. LIGANCY AND CRITICAL RADIUS RATIO

3.1 CRITICAL IONIC RADIUS RATIO

Radius Ratio Rule
In ideal ionic crystals, coordination numbers are determined largely by electrostatic considerations.
Cations surround themselves with as many anions as possible and vice-versa. This can be related
to the relative sizes of the ions which gives the radius ratio rule.
The number of anions surrounding a central cation is called the Ligancy.

The radius ratio rule states that as the size (ionic radius rC) of a cation increases, more anions of a
particular size can pack around it. Thus, knowing the size of the ions, we should be able to predict
a priori which type of crystal packing will be observed. We can account for the relative size of
both ions by using the ratio of the ionic radii (ρ):
ρ = rC/rA
where rC is the ionic radius of the cation and rA is the ionic radius of the anion.

Limiting Radius Ratios (Critical Radius Ratio).

For a specific structure, we can calculate the limiting radius ratio, which is the minimum
allowable value for the ratio of ionic radii (rC/rA) for the structure to be stable (fig.23).

Cation is
too small
Figure 23: The stability limit for the ratio of ionic radii.
Limiting radius ratio for coordination number (ligancy) 3 (trigonal planar):
AB is an ionic compound having coordination number 3. All the three B are in contact with A but
not to each other (fig.24-1).

Figure 24: [1] Stable limit of AB ionic compound. [2] Stability limit (or limiting radius ratio) of
AB ionic compound.
A limiting case arises when all the three are also come in contact with each other (fig.24-2).

Assume that the radius of cation is r + and anion is r –. Red circle represents cation and blue circles
represent anion, respectively.
Therefore, cos 30 ° = DC/DE
or, DE = DC / cos 30 °
or, r + + r − = r − / 0.866 [ ∴ cos 30 ° = 0.866]
or, r + + r − = 1.155 × r −
or, r + / r − = 1.115-1.000 = 0.155
Limiting radius ratio for coordination number 3 is 0.155.

Limiting radius ratio for coordination number (ligancy) 4 (tetrahedral):

The distance from the centre of the tetrahedron to the corner, d, is (fig. 25).
d = r+ + r-
To get as close to the cation as possible, the anions must touch along the edge of the tetrahedron.
This distance, a, is
a = r- + r- = 2r-
The tetrahedral angle, θ, is 109.5°
sin(θ /2) = r- / (r+ + r-)
So, sin(54.7°) = r- / (r+ + r-)
r+ / r- = 0.225
Figure 25: Limiting radius ratio for tetrahedral.

Limiting radius ratio for coordination number (ligancy) 6 (octahedral):

Along the cube edge, the cation is touching two anions so its length, a, is:
a = r- + 2r+ + r- = 2r+ + 2r-
To get as close to the cation as possible, the anions must touch along the face diagonal of the
cube (fig. 26). The diagonal has length, d, where:
d = r- + 2r- + r- = 4r-
Using Pythagoras’ theorem, the length of the side and face diagonal of a cube are related:

d2 = a2 + a2 = 2a2

d = (2)1/2a
So, 4r- = (2)1/2(2r+ + 2r-)

r+ / r- = (2)1/2 – 1 = 0.414

Figure 26: Limiting radius ratio for octahedral.

IV MILLER INDICES, PLANES AND DIRECTIONS

4.1 Miller Indices

Miller indices are used to specify directions and planes in crystals.
To find the Miller Indices of a plane, follow these steps
1. First draw the cube.
2. Identify the intercepts on the x- , y- and z- axes.
3. Specify the intercepts in fractional co-ordinates. Co-ordinates are converted to fractional
co-ordinates by dividing by the respective cell-dimension.
4. Take the reciprocals of the fractional intercepts.
5. Clear fractions by multiplying or dividing by a common factor.
6. Reduce to lowest terms. This final manipulation generates the miller indices (hkl) which
(by convention) should then be specified without being separated by any commas or
other symbols. The miller indices are also enclosed within standard brackets (….).
7. Planes can also have negative intercept e.g. 1, -1/2, 1 Hence, h k l = 1 -2 1. This is
denoted as ( 1 20 1 ).

Intercepts : ½ a , a ,∞
Fractional intercepts : ½ , 1 , ∞
Miller Indices : (210)

Intercepts : ½ a , ∞ ,∞
Fractional intercepts : ½ , ∞, ∞
Miller Indices : (200)
 Intercepts : a , a , ∞
Fractional intercepts : 1 , 1 ,∞
Miller Indices : (110)

Intercepts : a , a , a
Fractional intercepts : 1 , 1 , 1
Miller Indices : (111)

Planes having similar indices are equivalent, e.g. faces of the cube (100), (010) and (001). This is
termed as a family of planes and denoted as {100} which includes all the (100) combinations
including negative indices (fig. 27).
 Figure 27: Families of planes {100}, {110} and {111}.

4.1.1 Interplanar Spacing

To find the interplanar spacing for the set of planes with Miller indices (hkl), take the origin on
any one plane of this set and erect axes in the directions of crystal axes a, b and c.
The interplanar spacing d for the planes of indices (hkl) is equal to the distance from origin to the
nearest plane of the set under question.
The distance d is measured along the normal drawn from origin to the plane (hkl). Let the normal
to the plane make angles a, b and g with x-axis, y-axis and z-axis respectively.
The intercept of the plane on the three axes are
OA = a/h, OB = a/k, OC = a/l
where a is the length of the cube edge.
Figure 28: Intercepts made by the plane with miller indices (hkl) along a, b and c axes.
cos a = d/OA = dh/a,
cos b = d/OB = dk/a
cos g = d/OC = dl/a
For orthogonal axes,
cos2 a + cos2 b + cos2 g = 1
Therefore,
2 48 58 68
𝑑456 7 8 + 8 + 8 ==1
9 ; <

1
or 𝑑456 =
48 58 68
@ + ;8 + < 8
98

For cubic system, a = b = c. Hence, we get,

𝑎
𝑑456 =
√ℎ2 + 𝑘 2 + 𝑙 2

4.1.2 Crystal Directions

The directions in a crystal are given by specifying the coordinates (u, v, w) of a point on a vector
(ruvw) passing through the origin.
ruvw = ua + vb + wc.
It is indicated as [uvw]. For example, the direction [110] lies on a vector r110 whose projection
lengths on x and y axes are one unit (in terms of unit vectors a and b).
Directions of a form or family like [110], [101], [011] are written as <110>. Families of
directions <100>, <110> and <111> are given in figures 29 and 30.

Figure 29: <100> and <110> family.

Figure 30: <111> family.

To determine a direction of a line in the crystal:

1. Find the coordinates of the two ends of the line and subtract the coordinates (Head – Tail)
OR draw a line from the origin parallel to the line and find its projection lengths on x, y
and z axis in terms of the unit vectors a, b and c.
2. Convert fractions, if any, in to integers and reduce to lowest term.
3. Enclose in square brackets [uvw].
4. The line which passes through uvw will also pass through 2u2v2w and ½ u ½ v ½ w.
Hence [uvw], [2u2v2w] and [½ u ½ v ½ w] are same and written as [uvw].
V CRYSTAL STRUCTURE ANALYSIS

5.1 Bragg Diffraction

• Bragg diffraction was first proposed by William Lawrence Bragg and his father William
Henry Bragg in 1913.
• They found that crystals, at certain specific wavelengths and incident angles, produced
intense peaks of reflected radiation.
• Both neutron and X-ray wavelengths are comparable with inter-atomic distances
(~150 pm) and thus are an excellent probe for this length scale.
• Bragg's law confirmed the existence of real particles at the atomic scale, as well as
providing a powerful new tool for studying crystals in the form of X-ray and neutron
diffraction.
• W. L. Bragg and W. H. Bragg were awarded the Nobel Prize in physics in 1915 for their
work in determining crystal structures beginning with NaCl, ZnS, and diamond.
5.1.1 Bragg Condition
• Bragg diffraction occurs when radiation, with wavelength comparable to atomic spacings,
is scattered in a specular fashion by the atoms of a crystalline system, and undergoes
constructive interference.
• Specular reflection implies that all light is reflected at the same angle.
• The crystal is modelled as a set of discrete parallel planes (Bragg planes) separated by a
constant parameter d.
• When waves scattered from Bragg planes interfere constructively, they remain in phase
since the difference between the path lengths of the two waves is equal to
an integer multiple of the wavelength.
• The path difference between two waves undergoing interference is given by 2dsinq,
where q is the scattering angle.
• The effect of the constructive or destructive interference intensifies because of the
cumulative effect of reflection in successive crystallographic planes of the crystalline
lattice.
• This leads to Bragg's law, which describes the condition on q

2dsinq = nl
where n is a positive integer and l is wavelength of incident wave.
5.1.2 Derivation of Bragg’s Law
Suppose that a single monochromatic wave (of wavelength l ) is incident on aligned planes
of lattice points, with separation d, at angle θ. These planes are also termed as Bragg planes.
Points A and C are on one plane, and B is on the plane below (fig.31). Points ABCC' form a
quadrilateral.

Figure 31: Monochromatic wave incident on a set of Bragg planes.

There will be a path difference between the ray that gets reflected along AC' and the ray that gets
transmitted, then reflected, along AB and BC respectively. This path difference is
(AB + BC) – AC’
The two separate waves will arrive at a point with the same phase, and hence undergo constructive
interference, if and only if this path difference is equal to any integer value of the wavelength, i.e.
(AB + BC) – AC’ = nl where n is an integer. (1)

Now, AB = BC = d/sinθ (2)

AL = d/tanθ and AC = 2 AL. Therefore, AC = 2 d/tan θ
Also, AC’ = AC cos θ = (2 d/tanθ) cos θ = (2 d/sinθ ) cos2θ (3)
Therefore, from equation (1) and (3),
nl = (2 d/sinθ ) (1-cos2θ) = (2 d/sinθ ) sin2θ = 2 dsinθ
Hence, 2dsinq = nl which is Bragg’s law.
If only two planes of atoms were diffracting, then the transition from constructive to destructive
interference would be gradual as a function of angle, with gentle maxima at the Bragg angles.
However, since many atomic planes are interfering in real materials, very sharp peaks surrounded
by mostly destructive interference result.
The possible “d” spacing defined by the miller indices, h, k, l are determined by the shape of the
unit cell.
9
For cubic unit cell, d= , and 2dsinq = l for n =1.
√48 E5 8 E6 8
29 FGH I
Hence, l =
√48 E5 8 E68

5.2 Rules for determining the diffracting {hkl} planes in cubic crystals:

Crystal Reflection Present Reflection Absent

BCC (h+k+l) = even (h+k+l) = odd

FCC (h,k,l) all odd or all even (h,k,l) mixture of odd and
even

In order to be sure of satisfying Bragg’ law, either l or θ must be continuously varied during the
experiment. The ways in which these parameters are varied distinguish the three main diffraction
methods:
Ø Laue Method : l is varied and θ is fixed.
Ø Rotating Crystal method: l is fixed and θ is varied.
Ø Powder Method : l is fixed and θ is varied.

5.2.1 Laue Method

In this method, continuous radiation is used. This radiation falls on a stationary crystal. The crystal
diffracts the X-ray beam and produces a pattern of spots which conform exactly with the internal
symmetry of the crystal. The Laue method can be used in two ways:
Transmission method
Back-reflection method
depending on the relative position of the X-ray source, the crystal and the photographic film (to
detect the diffracted X-rays) (fig. 32).

Figure 32: Transmission method and back-reflection method of Laue method.

• In the Laue method, the crystal is fixed in a position relative to the X-ray beam,
• Thus, not only is the value for d fixed, but the value of θ is also fixed.
• The diffracted beam is produced by diffraction from the planes which belong to a particular
zone axis (ZA) of the crystal.
• The beam in each set all lie on the surface of an imaginary cone: the axis of this cone is the
zone axis.
• When this beam intersects with the plane of the photographic film it produces spots.
• The spots which lie on any one curve are reflections from planes which belong to one zone.
• Each diffracted beam in the Laue method has a different wavelength.
• The Laue method is used mainly for the determination of crystal orientation and assessment
of crystal quality because the positions of the spots on the film depend on the orientation
of the crystal with respect to the incident beam.
5.2.2 Rotating Crystal Method
• In the rotating crystal method, a single crystal is mounted with an axis normal to
a monochromatic x-ray beam (fig. 33).
• A cylindrical film is placed around it and 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, and at that point a diffracted beam will be formed.
• The reflected beams are located on the surface of imaginary cones. When the film is laid
out flat, the diffraction spots lie on horizontal lines.
• The chief use of the rotating crystal method is in the determination of unknown crystal
structures.

Figure 33: Rotating crystal method.

5.2.3 Powder Method (Debye-Scherrer Method)
• The “Debye–Scherrer” method, uses monochromatic radiation, but uses a distribution of
crystallographic planes as provided by a polycrystalline sample.
• Since there are millions of crystals in the powder material, there will be many crystals in
that powder which will be in a position to diffract the incident beam and there will be
enough of them to get the effect of a continuous point reflections which will be lying along
the arc of the cone.
• A separate cone is formed for each set of differently spaced lattice planes.
• Diffraction from polycrystalline materials, or “powder diffraction” with monochromatic
radiation, requires the Debye–Scherrer diffractometer to provide only one degree of
freedom in changing the diffraction conditions, corresponding to changing the 2θ angle
(fig. 34).
• The sample in the Debye–Scherrer diffractometer is rotated by an angle θ while the detector
is rotated by an angle 2θ.

Figure 34: Schematic diagram of a Debye-Scherrer diffractometer.

VI IMPERFECTIONS: Point, Line, Surface and Volume

6.1 CRYSTAL DEFECTS

A perfect crystal is an idealization; there is no such thing in nature. It is useful to classify crystal
lattice defects by their dimension.
• The 0-dimensional defects affect isolated sites in the crystal structure, and are hence called
point defects. An example is a solute or impurity atom, which alters the crystal pattern at
a single point.
• The 1-dimensional defects are called dislocations. They are lines along which the crystal
pattern is broken.
• The 2-dimensional defects are surfaces, such as the external surface and the grain
boundaries along which distinct crystallites are joined together.
• The 3-dimensional defects change the crystal pattern over a finite volume. They include
precipitates, which are small volumes of different crystal structure, and also include large
voids or inclusions of second-phase particles.

6.1.1 Point Defects:

A point defect disturbs the crystal pattern at an isolated site. It is useful to distinguish intrinsic
defects, which can appear in a pure material, from extrinsic defects, which are caused by solute or
impurity atoms.

Intrinsic defects
An intrinsic defect is formed when an atom is missing from a position that ought to be filled in the
crystal, creating a vacancy,
or when an atom occupies an interstitial site where no atom would ordinarily appear, causing an
interstitialcy.
The two types of intrinsic point defects are shown in fig. 35.

Figure 35: Illustration of a vacancy and interstitial in a hexagonal lattice.

Because the interstitial sites in most crystalline solids are small (or have an unfavorable bonding
configuration, as, for example, in the diamond lattice) interstitialcies are high-energy defects that
are relatively uncommon.
Vacancies, on the other hand, are present in a significant concentration in all crystalline materials.
Their most pronounced effect is to govern the migration of atoms on the crystal lattice (solid state
diffusion). In order for an atom to move easily from one crystal lattice site to another the target
site must be vacant.

Ordered compounds can have more complex intrinsic defects. In most compounds the different
species are charged to at least some degree.
An intrinsic defect destroys the local charge balance, which must be restored in some way. The
compound defects that preserve charge are easiest to visualize in binary ionic solids like NaCl. An
isolated vacancy in an ionic solid creates an excess charge. The excess charge can be compensated
by a paired vacancy on the sublattice of the other specie; for example, the excess charge associated
with a Na vacancy is balanced if there is a Cl vacancy nearby.
A neutral defect that involves paired vacancies on the cation and anion sublattices is called a
Schottky defect. The concentration of Schottky defects decreases the density of the crystal.
Alternatively, the charge imbalance caused by the vacancy can be corrected by adding an
interstitial of the same specie; a Na vacancy is compensated by a Na interstitial.
A neutral defect that is made up of a paired vacancy and interstitial is called a Frenkel defect. The
concentration of Frenkel defects does not change the density of the crystal.
In compounds whose atoms are less strongly ionized it is energetically possible for species to
exchange sites, so that an A-atom appears on the B sublattice or vice versa.
This type of point defect is called an anti-site defect, and is fairly common in semiconducting
compounds such as GaAs.

Extrinsic defects
The extrinsic point defects are foreign atoms, which are called solutes if they are intentionally
added to the material and are called impurities if they are not.
The foreign atom may occupy a lattice sites, in which case it is called a substitutional solute (or
impurity) or it may fill an interstitial site, in which case it is called an interstitial solute. Since, the
interstitial sites are relatively small, the type of the solute is largely determined by its size. Small
atoms, such as hydrogen, carbon and nitrogen are often found in interstitial sites. Larger atoms are
usually substitutional.

6.1.2 Line Defects - Dislocations

Dislocations are another type of defect in crystals. Dislocations are areas were the atoms are out
of position in the crystal structure. Dislocations are generated and move when a stress is applied.
It is responsible for the phenomenon of slip by which most metals deform plastically.
There are two basic types of dislocations, the edge dislocation and the screw dislocation (fig. 36).
Figure 36: Illustration of an edge and screw dislocation.

Edge Dislocation
In perfect crystal, atoms are arranged in both vertical and horizontal planes. If one of these vertical
planes does not extend to full length, but ends in between within the crystal, then it is called edge
dislocation.
Just above the edge of the complete plane the atoms are squeezed and are in a state of compression.
Just below the edge of the incomplete plane, the atoms are pulled apart and are in the state of
tension. The distorted configuration extends all along the edge into the crystal. The inter-atomic
bonds are significantly distorted only in the immediate vicinity of the dislocation line. Edge
dislocation are represented by Τ or ┴ depending on whether the incomplete plane starts from top
or from the bottom of the crystal, called as positive or negative edge dislocation. The magnitude
and the direction of the displacement are defined by a vector called Burgers vector. The Burgers
vector is perpendicular to the edge dislocation line.

Burgers vector
To describe the size and the direction of the main lattice distortion caused by a dislocation a so-
called Burgers vector b is introduced. To find the Burgers vector, a circuit from atom to atom
counting the same number of atomic distances in all directions is made. If the circuit encloses a
dislocation, it will not close. The vector that closes the loop is the Burgers vector (fig.37).
 Figure 37: The
Burgers circuit
for an edge
dislocation:
(A) Perfect
crystal and
(B) crystal with
distortion.

Screw Dislocations
There is a second basic type of dislocation, called screw dislocation. The motion of a screw
dislocation is also a result of shear stress, but the defect line movement is perpendicular to direction
of the stress and the atom displacement, rather than parallel. The Burgers vector is parallel to screw
dislocation line. The speed of movement of a screw dislocation is lesser compared to edge
dislocation.

6.1.3 Planar Defects

A disruption of the long-range stacking sequence can produce two other common types of crystal
defects: 1) a stacking fault and 2) a twin boundary.
Stacking fault: A change in the stacking sequence over a few atomic spacing produces a stacking
fault whereas a change over many atomic spacing produces a twin region. So, if the hcp structure
is going along as ABABAB and suddenly switches to ABABABCABAB, there is a stacking fault
present.
Twin boundary: Twin boundaries occur when two crystals of the same type intergrow, so that
only a slight misorientation exists between them. It is a highly symmetrical interface, often with
one crystal the mirror image of the other; also, atoms are shared by the two crystals at regular
intervals. This is also a much lower-energy interface than the grain boundaries that form when
crystals of arbitrary orientation grow together.
Twin boundaries occurs in pairs, such that the orientation change introduced by one boundary is
restored by other. The region between the pair of boundaries is called twin region.

Another type of planer defect is the grain boundary.

Grains can range in size from nanometers to millimeters across and their orientations are usually
rotated with respect to neighboring grains. Where one grain stops and another begins is known as
a grain boundary. Grain boundaries limit the lengths and motions of dislocations. Therefore,
having smaller grains (more grain boundary surface area) strengthens a material. The size of the
grains can be controlled by the cooling rate when the material cast or heat treated. Generally, rapid
cooling produces smaller grains whereas slow cooling result in larger grains.

6.1.4 Volume Defects

Volume defects occur on a much bigger scale than the rest of the crystal defects. Voids are regions
where there are a large number of atoms missing from the lattice.
Another type of bulk defect occurs when impurity atoms cluster together to form small regions of
a different phase. Other examples of bulk defects are pores, cracks and foreign particles.