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Introduction and Crystallography

This document provides an introduction and overview of electrical and electronic materials. It acknowledges the contributions of various sources including class presentation slides and NPTEL lecture series. It discusses how the development of materials like silicon drove the electronics revolution and led to advances like integrated circuits and smaller computers. Flexible electronics are described as using substrates like polyimide and PEEK to assemble circuits on flexible surfaces, providing advantages like flexibility, light weight, and cost benefits. The document also provides an introduction to materials science and engineering, describing how structure relates to properties at various levels. Important material properties and classifications like metals, ceramics, polymers, and composites are outlined.

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Pritam Deb Roy
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0% found this document useful (0 votes)
148 views36 pages

Introduction and Crystallography

This document provides an introduction and overview of electrical and electronic materials. It acknowledges the contributions of various sources including class presentation slides and NPTEL lecture series. It discusses how the development of materials like silicon drove the electronics revolution and led to advances like integrated circuits and smaller computers. Flexible electronics are described as using substrates like polyimide and PEEK to assemble circuits on flexible surfaces, providing advantages like flexibility, light weight, and cost benefits. The document also provides an introduction to materials science and engineering, describing how structure relates to properties at various levels. Important material properties and classifications like metals, ceramics, polymers, and composites are outlined.

Uploaded by

Pritam Deb Roy
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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You are on page 1/ 36

National Institute of Technology Silchar

Silchar, Cachar, Assam 788010

ELECTRICAL AND ELECTRONIC


MATERIALS
(EC 208)

Mr. Anupal Deka


ACKNOWLEDGEMENT

I would like to express my sincere gratitude to Dr. Bijit Choudhuri, Faculty, NIT Silchar, sir
for his class presentation slides and NPTEL lecture series on “Introduction to Materials Science
and Engineering” by Prof. Rajesh Prasad which forms the majority of the contents of the 1st
chapter. Also minor contribution from the reference books of our institute syllabus and some
random internet sources are incorporated.

Mr. Anupal Deka


Introduction
 Development and advancement of Human societies are closely related with materials
 Transportation, housing, clothing, communication, recreation, and food production—
virtually every segment of our everyday lives is influenced to one degree or another by
materials.
 Human Civilizations have been named based on the level of their materials
development – Stone age, Bronze age etc.

Material Driven Electronics Revolution:


 Before invention of the Si chip Electro-mechanical computers were developed resulting
large structures like Harvard Mark I Electro-mechanical computer, 1940 – 5 tons, 8 x
51 feet and 500 miles of wire.
 Initial Germanium based electronic chips suffered from reliability issues.
 Invention of a metallurgical process, Zone refining, that can produce high purity Si led
to the development of semiconductor chips.
 Invention of a metallurgical process for stable and defect free silicon dioxide growth
over Si surface made MOSFET a reality and hence CMOS circuits.
 Development of smaller and smaller Si chips helped miniaturization that led to today’s
computers.
 Slowly electronics have started to move into the flexible and wearable device domain.
Ref. Hammock et al, 2013, Adv. Mater. 25, 5997–6038

 Flexible electronics, also known as flex circuits, is a technology for assembling


electronic circuits by mounting electronic devices on flexible plastic substrates, such as
polyimide, PEEK(Polyether ether ketone) or transparent conductive polyester.
 Flexible electronic circuits offer the following advantages:
1. Flexibility
2. Light and thin
3. Unbreakable
4. Cost advantage
5. Innovation
 Flexible electronic circuits are implemented to realize of electronic skin, organic light
emitting diodes (OLED), satellites, flexible interconnect, flexible healthcare devices
etc.

Ref. Ha et al, “Wearable and flexible sensors for user-interactive health-monitoring devices” J. Mater. Chem. B, 2018, 6, 4043

Material Science and Engineering:


 Materials science involves investigating the relationships that exist between the
structures and properties of materials.
 Materials engineering is, on the basis of these structure–property correlations,
designing or engineering the structure of a material to produce a predetermined set of
properties.
 The structure of the materials can broadly be viewed in four levels:
1. Subatomic structure involves electrons within the individual atoms and interactions
with their nuclei.
2. Atomic level structure encompasses the organization of atoms or molecules relative
to one another.
3. Microscopic structure involves structure which is subject to direct observation using
some type of microscope which contains large groups of atoms that are normally
agglomerated together.
4. Macroscopic structural elements are those that may be viewed with the naked eye.
Important Properties of Materials:
 The properties of the materials can broadly be classified into six main categories:

Engineering
requirements

Mechanical Thermal Electrical Chemical Magnetic Optical


Properties Properties Properties Properties Properties Properties

Tensile atomic Refractive


Specific Heat Resistivity Hysteresis
strength weight index

Thermal dielectric molecular Reflective


Hardness Coercivity
Conductivity strength weight index

Thermal atomic Magnetic Absorption


Ductility
Expansion number Permeability coefficient

Impact Thermal
Valency
Strength Resistance

Wear Thermal chemical


Resistance Fatigue composition

Corrosion Thermal
Acidity
Resistance Diffusivity

Density alkalinity

 Why do we need to study materials? In any field of applied science or engineering to


implement something physically we need some material object.
 Mostly a materials problem in engineering is one of selecting the right material from
the thousands that are available based on several criteria like i) properties required of
the material as per in-service conditions, ii) any deterioration of material properties that
may occur during service operation and iii) finally, probably the overriding
consideration is that of economics: What will the finished product cost?
Important Classification of Materials:

Materials

Advanced
Metals Ceramics Polymers Composites
materials

Semiconductors

Biomaterials

Smart Materials

Nanomaterials

 Materials in this group are composed of one or more metallic elements and often also
nonmetallic elements (e.g., carbon, nitrogen, and oxygen) in relatively small amounts.
e.g., iron, aluminum, copper, titanium, gold, and nickel. Atoms in metals and their
alloys are arranged in a very orderly manner and in comparison to the ceramics and
polymers, are relatively dense. Metallic materials have large numbers of nonlocalized
electrons; that is, these electrons are not bound to particular atoms. Many properties of
metals are directly attributable to these electrons. For example, metals are extremely
good conductors of electricity and heat, and are not transparent to visible light; a
polished metal surface has a lustrous appearance. In addition, some of the metals (i.e.,
Fe, Co, and Ni) have desirable magnetic properties. metal alloy refers to a metallic
substance that is composed of two or more elements.
 Ceramics are compounds between metallic and nonmetallic elements; they are most
frequently oxides, nitrides, and carbides. E.g. aluminum oxide (or alumina, Al2O3),
silicon dioxide (or silica, SiO2), silicon carbide (SiC), silicon nitride (Si3N4), and, the
traditional ceramics— composed of clay minerals (i.e., porcelain), as well as cement
and glass. Ceramic materials are typically insulative to the passage of heat and
electricity (i.e., have low electrical conductivities), and are more resistant to high
temperatures and harsh environments than metals and polymers. With regard to optical
characteristics, ceramics may be transparent, translucent, or opaque and some of the
oxide ceramics (e.g., Fe3O4) exhibit magnetic behavior.
 Polymers include the familiar plastic and rubber materials. Many of them are organic
compounds that are chemically based on carbon, hydrogen, and other non-metallic
elements (i.e., O, N, and Si). E.g. polyethylene (PE), nylon, poly(vinyl chloride) (PVC),
polycarbonate (PC), polystyrene (PS), and silicone rubber. Furthermore, they have very
large molecular structures, often chainlike in nature, that often have a backbone of
carbon atoms. They have low electrical conductivities and are nonmagnetic.
 A composite is composed of two (or more) individual materials, which come from the
categories previously discussed—metals, ceramics, and polymers. E.g. fiberglass,
carbon fiber–reinforced polymer(CFRP) The design goal of a composite is to achieve
a combination of properties that is not displayed by any single material, and also to
incorporate the best characteristics of each of the component materials. A large number
of composite types are represented by different combinations of metals, ceramics, and
polymers. Furthermore, some naturally occurring materials are composites—for
example, wood and bone.
 Materials that are utilized in high-technology (or high-tech) applications are sometimes
termed advanced materials. By high technology we mean a device or product that
operates or functions using relatively intricate and sophisticated principles; examples
include electronic equipment, computers, fiber-optic systems, spacecraft, aircraft, and
military rocketry. These advanced materials are typically traditional materials whose
properties have been enhanced, and also newly developed, high-performance materials.
Furthermore, they may be of all material types (e.g., metals, ceramics, polymers), and
are normally expensive.
 Semiconductors have electrical properties that are intermediate between the electrical
conductors (i.e., metals and metal alloys) and insulators (i.e., ceramics and polymers).
Furthermore, the electrical characteristics of these materials are extremely sensitive to
the presence of minute concentrations of impurity atoms, for which the concentrations
may be controlled over very small spatial regions. Semiconductors have made possible
the advent of integrated circuitry that has totally revolutionized the electronics and
computer industries (not to mention our lives) over the past three decades.
 Biomaterials are employed in components implanted into the human body to replace
diseased or damaged body parts. These materials must not produce toxic substances
and must be compatible with body tissues (i.e., must not cause adverse biological
reactions). All of the preceding materials—metals, ceramics, polymers, composites,
and semiconductors—may be used as biomaterials.
 Smart (or intelligent) materials are a group of new and state-of-the-art materials now
being developed that will have a significant influence on many of our technologies. The
adjective smart implies that these materials are able to sense changes in their
environment and then respond to these changes in predetermined manners—traits that
are also found in living organisms. In addition, this “smart” concept is being extended
to rather sophisticated systems that consist of both smart and traditional materials.
 One new material class that has fascinating properties and tremendous technological
promise is the nanomaterials. Nanomaterials may be any one of the four basic types—
metals, ceramics, polymers, and composites. However, unlike these other materials,
they are not distinguished on the basis of their chemistry, but rather, size; the nano-
prefix denotes that the dimensions of these structural entities are on the order of a
nanometer (10–9 m)—as a rule, less than 100 nanometers (equivalent to approximately
500 atom diameters). E.g. Graphene, Carbon nanotube, quantum dot etc.
Crystal Structure:
 In terms of atomic arrangement solids can be classified into mainly two categories: i)
Crystalline and ii) Amorphous.
 Crystalline materials exhibit periodic arrangement of atoms. A definite repetitive
pattern is observed.
 Amorphous materials have random arrangement of atoms.
 Crystalline solids can be further classified into two categories: i) Monocrystalline and
ii) Polycrystalline
 Monocrystalline materials exhibit single periodic arrangement of atoms throughout.
 Polycrystalline materials exhibit a periodic arrangement of atoms for some region
another periodic arrangement of atoms for some different region and/or so on.

 When viewed through naked eye any crystalline material appears to be featureless but
upon viewed through optical microscope it starts showing certain features.
 These regions are called grains and the lines are called grain boundaries.
 As they are observed when viewed through microscope they are known as
microstructures also.

Optical microscope view Zoomed view of pearlite


 In certain grains, there are some dark patches also which is called pearlite, and the
lighter regions remaining of the grains were called ferrite then.
 Pearlite, when zoomed, itself is combination of alternate bands of dark (cementite) and
white (ferrite) regions.
 In order to identify the crystal structure, X-ray diffraction technique is used.
Crystallography:
 A 3 dimensional periodic arrangement of atoms in space will be called crystal.
 A lattice is a 3 dimensional periodic arrangement of points in space.
 A crystal is a physical object whereas lattice is a geometrical concept.
 The relationship between crystal and lattice is expressed by an equation:
Crystal = Lattice + Motif (or Basis)
 An atom or a group of atoms associated with each lattice point in a crystal is called a
basis of that crystal.
 In crystal, lattice tells us how to repeat and basis tells us what to repeat.

Ref. NPTEL lecture


Lattice translation:
 Lattice translation can be defined as
any vector from one lattice point to
another lattice point.
 In 2D, ruv =ua+vb and in 3D, ruvw
=ua+vb+wc respectively denote lattice
translation where u, v and w are integers
and a, b and c are lattice constants.
Unit cell:
 Unit cell can be defined as a region of
space, which can generate the entire lattice (or crystal) by repetition in all possible
direction through lattice translations.
 The unit cell term can be used for either of the lattice or of the crystal.
 A parallelogram in 2D or a parallelepiped in 3D with corners at the lattice points is very
common example of unit cell.
 A given lattice can have many, in fact,
infinitely many unit cells i.e. unit cells are
not unique for a lattice.
 Primitive unit cell are those which have
lattice points only at the corners of the unit
cell while non-primitive unit cell have
lattice points at corners as well as points
other than the corners of the cell also.
Crystal coordinate system:
 By selecting a corner as origin, the vectors
from that corner along the edges of the unit
cell define the basis vectors of the lattice.
 Basis vectors of the lattice need not to be
orthogonal i.e. crystal coordinate system
can be non cartesian.
Fig. Different types of unit cell for the same lattice(NPTEL)
 The lengths of 3 edges (a, b and c) of the unit cell (or the 3 basis vectors), and the 3
inter-axial angles between them (α, β and γ) are
called the lattice parameters. By convention, α is
angle between b and c, β is angle between a and
c, and γ is angle between a and b.
 If we are given the lattice parameters, we can
construct the unit cell and hence lattice of the
crystal, but not the entire crystal without knowing
the motif.
 All lattices can be classified into 7 crystal systems
namely cubic, tetragonal, orthorhombic, hexagonal, trigonal (or rhombohedral)
monoclinic and triclinic.
 Further, in each crystal system, there are 1 to 4 Bravais lattices namely primitive(P),
body-centred or volume-centred(I or B), Face-centred(F) and end-centred or base-
centred (C).
 Primitive means lattice points are only at the corners of the unit cell.
 Body-centred or volume-centred means lattice points are at corners as well as the body
centre.
 Face-centred means lattice points are at corners plus all face centres.
 End-centred or base-centred means lattice points are at corners and not on all faces, but
only on one pair of parallel faces.
 We in crystal space can have 7 P, 3 I, 2 F and 2 C which constitute the 14 Bravais
lattices possible.
 7 systems, 4 types, 7×4=28 lattices were theoretically possible, but we have only 14
Bravais lattices practically. Why?
 For other theoretically possible ways either the unit cell is not unique i.e. it can be
reduced to any of these 14 lattices and/or symmetry of the crystal system is lost.
 A. Bravais(Scientist) in 1848 showed that these 14 lattices represent the only ways to
arrange points periodically in space while preserving lattice point surroundings,
symmetry and uniqueness.(Earlier it was supposed to be 15 as one monoclinic was
double counted ).
 A single lattice or crystal can be represented by (infinitely) many different unit cells so
lattices cannot be classified on the basis of its unit cell shape.
 What is the real basis for such classification of lattices? Answer is symmetry actually.
Crystal Symmetry:
 An object is said to be symmetric with respect to a geometric operation, if it can be
brought into self-coincidence by that operation.
 All lattices possess translational symmetry as lattice can be defined as a set of points
possessing translational symmetry i.e. translational symmetry is a defining symmetry
of any lattice.
 A lattice may possess other non-translational symmetries also.
 The non-translational symmetries are also called point symmetry, because in contrast
to translational symmetry which move all the point, point symmetry leaves atleast some
points unchanged.
 One of the important point symmetry operation is the rotation about an axis, by some
angle θ provided it brings the object into self-coincidence; obviously, rotation moves
all points except the points on the axis.
 Another point symmetry is-reflection. The reflection is w.r.t. an imaginary mirror plane.
The points will be imaged at equal distance on the other side of the mirror plane
bringing the object into self-coincidence. Here, the points on the mirror plane remain
invariant.
 Final point symmetry is-inversion. The inversion is w.r.t. an imaginary point called
centre of inversion. The points will be imaged at equal distance on the other side of the
centre of inversion bringing the object into self-coincidence. Here, centre of inversion
point only remain invariant.
 An object is said to possess an n-fold axis of rotation if it can be brought into self-
coincidence by rotation through the minimum angle θmin= 360°/n.
 For n=1, θmin= 360° which is
equivalent to no symmetry.
 A regular(isoscale sides and
angles) n-sided polygon will
have an n-fold axis of rotation.
 For crystal lattice, as we
already know that
translational symmetry is
inherent so it puts some
restrictions on n-fold rotation
symmetry to be allowed in
lattice. So as per this, only
n=1,2,3,4 and 6-fold rotation
are allowed, others are
prohibited. (Proof of this
statement is out of scope)

Ref. NPTEL Lectures

 A lattice can have several (infinitely many) translations, a collection of all these
translational symmetries is called the translational group of the lattice. Translational
group contains all lattice translations.
 A lattice can have several non-translational symmetry, a collection of all these point
symmetry operations is called the point group of the lattice.
 A collection of all symmetry operations (translational + point) is together called the
space group of the lattice.
 Any 3D lattice can have only one of the 7 different kinds of rotational and reflection
symmetry or point groups which accounts for 7 crystal systems.
 Similarly, any 3D lattice can have only one of the 14 different kinds of translational,
rotational and reflection i.e. complete symmetry or space groups which accounts for 14
Bravais lattices.
 If it has only one-fold point symmetry
which means no special symmetry
then the crystal system (the least
symmetric crystal system) is called
triclinic.
 If it has a single 2-fold point
symmetry (w.r.t. the axis joining the
face centres of the parallel faces
having sides a and c) then the crystal
system is called monoclinic.
 If it has a single 3-fold point
symmetry (w.r.t. the axis along
lengthiest body diagonal) then the
system is called trigonal or
rhombohedral.
Ref. https://msestudent.com/
 If it has a single 6-fold point symmetry (w.r.t. the axis joining the face centers of the
hexagonal faces) then the system will be called a hexagonal crystal system.
 If we have three 2-fold point symmetry (3 mutually orthogonal 2-fold axes formed by
joining the centres of opposite faces) then it is called orthorhombic.
 If it has a single 4-fold point symmetry (axes formed by joining the centres of both
square size opposite faces) then we call it tetragonal.
 Finally, the most symmetric one is the cubic crystal system. It is characterized by four
3-fold point symmetry (along all the body diagonals although it has other point
symmetries like 4-fold, 2-fold and mirror planes etc.)
 Why cubic C was absent from the Bravais list?
 So, if rotated by 120° along body diagonal, it is not coming to self-coincidence and
hence the three-fold symmetry is lost and this confirms that it is not a cubic lattice.
 Further, if we observe, it actually have a
single 4-fold axes of symmetry which
indicates it to be a tetragonal lattice rather
than a cubic.
 Similarly if we observe any other structure
that are absent from Bravais lattice list,
they will in fact turn out to be a different
lattice already defined in the list in terms of
symmetry. There, sometime the edge
length may not be exactly as per
requirement of a crystal system but still we
will put them in that system giving priority
to symmetry.
Crystal Directions and Planes:
 In crystallography, we need to specify or name different directions and planes in a
crystal. Miller indexing of directions and planes are standard methods which are being
used for this purpose.
 Steps of Miller indexing of directions :
1. The first step in Miller in indexing is to choose an origin on the direction as in the
crystallographic coordinate system, we are free to choose the origin. The origin
always has to be on the direction or vice versa, the direction should pass through
the origin.
2. The next step is to choose a crystallographic coordinate system with axis parallel to
the unit cell edges (even if they are not orthonormal in a non-cubic crystal) as this
is what is called the crystallographic coordinate system. Also, if already some
crystallographic axes were defined w.r.t. an origin, then for a new origin in that
same crystal system, the new axes must be parallel to the earlier axes also.
3. The next step is to find the coordinates of another convenient point on the direction
itself in terms of the lattice parameters ‘a’, ‘b’ and ‘c’ and hence take these
coefficients of ‘a’, ‘b’ and ‘c’ to represent this direction.
4. The next step is to reduce those coefficients to smallest integers and this can be
done either by dividing all by their highest common factor (if we have all integer
values) or multiplying by the lowest common multiplier of their denominator (if we
have any fractional value among them). For negative no, put a bar above.
5. The final step is to just put these three numbers in a square bracket [ ] as it is an
internationally agreed upon convention for Miller indices of any direction. Also
unless and until we have a 2 digit Miller indices for one of the components, we
should not use any comma to separate them.
 Unlike vectors, Miller indices of a direction represents only the orientation of the line,
not its particular position in the crystal space. So, all parallel directions have the same
Miller indices.
 To find Miller indices of directions,
OA and PQ:
 Considering O to be origin and
defining crystal edges passing
through O as X,Y and Z axis, OA is
a/2 + b/2 + c
→ ½ ½ 1
→ [112]
 Again now considering P to be
origin and defining crystal edges
passing through P and parallel to
previous axes as X,Y and Z axis, PQ
is – 1a – 1b + 1c
→ –1 –1 1
→ [ 1̅ 1̅ 1 ]

 AG = [1 1 1] ; BI = [2 1̅ 1] ; CF = [1̅ 0 1] ̅̅̅̅ 11 20 ]
IJ = [20

 Sometime we are not interested in just one direction because crystals can have
symmetry and symmetry relates many directions. So many directions become
equivalent. For example, if you take a cubic crystal, all the edges of the cube are
equivalent by the cubic symmetry. If we index the edge along x axis it will be [100] or
[1̅00], if we index along the y axis [010] or [01̅0] and indexed along z axis, [001] or
[001̅]. But if one is not interested in a specific direction, just want to talk about the cube
edges for all directions along the cube edges which are equivalent by symmetry then
<100> should be used as <uvw> means the specific direction [uvw] and all other
direction related to [uvw] by the symmetry of the crystal.
 It is important that when we are using < > notation we have to know which crystal
system we are talking about because different crystals will have different symmetries
and the same symbol may mean different things. For example, <100> in cubic crystal
(a=b=c) mean any of [100], [1̅00], [010], [01̅0], [001] or [001̅] but in tetragonal
(a=b≠c) it means any of [100], [1̅00], [010] or [01̅0] only.
 Steps of Miller indexing of planes :
1. The first step in Miller in indexing is to choose an origin not on the plane as in the
crystallographic coordinate system, we are free to choose the origin.
2. The next step is to choose a crystallographic coordinate system with axis parallel to
the unit cell edges (even if they are not orthonormal in a non-cubic crystal) as this
is what is called the crystallographic coordinate system. Also, if already some
crystallographic axes were defined w.r.t. an origin, then for a new origin in that
same crystal system, the new axes must be parallel to the earlier axes also.
3. The next step is to find the intercepts along axis in terms of the lattice parameters
‘a’, ‘b’ and ‘c’ and hence take these coefficients of ‘a’, ‘b’ and ‘c’ to represent this
plane.
4. Take reciprocal of intercepts.
5. The next step is to reduce those coefficients to smallest integers if and only if the
plane is passing through any of the corner points and this can be done either by
dividing all by their highest common factor (if we have all integer values) or
multiplying by the lowest common multiplier of their denominator (if we have any
fractional value among them). If the plane is not passing through any of the corner
points then no need to do this reduction. For negative no, put a bar above.
6. The final step is to just put these three numbers in a round bracket i.e. parentheses
( ) as it is an internationally agreed upon convention for Miller indices of any plane.
Also unless and until we have a 2 digit Miller indices for one of the components,
we should not use any comma to separate them.
 To find Miller indices of the triangular plane,
considering O to be origin and defining crystal
edges passing through O as X,Y and Z axis,
intercepts of the given plane are: 1a, 1b, 1c
→111
→111
→111
→(1 1 1)
 To find Miller indices of ABCD plane, considering
O to be origin and defining crystal edges passing
through O as X,Y and Z axis, intercepts of the given
plane are: 1a, ∞b, ∞c
→1∞∞
→100
→100
→(1 0 0)
 To find Miller indices of EBCO plane, shifting
origin to O* and defining crystal edges passing
through O as X,Y and Z axis, intercepts of the given
plane are: 1a, -1b, ∞c
→ 1 -1 ∞
→ 1 -1 0
→ 1 -1 0
→ (1 1̅ 0)
 Intercepts: 1a, 3b, 2c
→132
→ 1 1/3 1/2
→623
→ (6 2 3)
z

(111) (2̅ 2̅ 2 ) and (2 0 2̅)


 A zero in the Miller indices correspond to infinity in terms of the intercept and infinity
in terms of intercept means the plane is parallel to that axis.
 Miller indices of a plane specifies only its orientation in space and not its position.
 Miller indices of a given plane passing through any corner atoms, actually not only
represents that plane, but all such parallel planes passing through any corner atoms as
all such parallel planes have same Miller indices.
 Any plane having Miller indices (nh nk nl) is also parallel to planes having Miller
indices (h k l) but they are not passing through any corner points.
 If all of the indices (h k l) if we take the negatives of them, −h −k and −l or (ℎ̅ 𝑘̅ ̅l )
then they represent the same plane. This is true because any plane will give divide the
space into two halves. We are not allowed to choose the origin on the plane. We can
only choose the origin on one half of the plane or the other half of the plane. So, when
we choose the origin on one half space, we will get one set of indices and if we choose
origin on the other side, we will get the negative indices.
 For a set of symmetry related planes, we put one of the indices in curly brackets { }.
So, if you use this curly bracket {h k l}, it represents not only the (hkl) plane, but all
other planes related to (hkl) by the symmetry of the crystal.
 {100}cubic = (1 0 0), (0 1 0), (0 0 1), (1̅ 0 0), (0 1̅ 0), (0 0 1̅ ) and {100}tetragonal = (1
0 0), (0 1 0), (1̅ 0 0) and (0 1̅ 0).
 Miller Indices of a plane and its normal direction are identical for cubic crystals i.e.
(hkl) ┴ [hkl]
 Weiss Zone law states that the condition for a direction [u v w] to lie in (or equivalently
in crystallography is parallel to) a plane (h k l) is hu + kv + lw = 0.
Inter-planar Spacing:
 Inter-planar spacing is the distance between successive (h k l) planes passing through
the corners of the unit cell. It has a universal symbol dhkl.
 It is also the same distance equal to the distance between the origin and the nearest (h k
l) plane.
 The geometry becomes very complicated for calculation of dhkl for crystals which are
not having axes which are orthogonal i.e. except for cubic, tetragonal and orthorhombic

Note: Miller indices are the reciprocal of the intercepts in terms of the corresponding lattice
parameters.
𝑑ℎ𝑘𝑙
 Inter planar spacing of two parallel consecutive (h k l) and (nh nk nl) plane is = 𝑛

Angle Between Two Planes or Directions:


 Angle between two planes ( h1 k1 l1 ) and ( h2 k2 l2 ) or two directions [ h1 k1 l1 ] and [ h2
ℎ1 ℎ2 +𝑘1 𝑘2 +𝑙1 𝑙2
k2 l2 ] is given by cos 𝛳 =
√(ℎ12 +𝑘12 +𝑙12 )(ℎ22 +𝑘22 +𝑙22 )
Diamond Crystal structure: http://lampx.tugraz.at/~hadley/ss1/crystalstructure/structures/diamond/diamond.php
 Diamond is a crystal structure with a face centered cubic Bravais lattice and two atoms
𝑎 𝑏 𝑐
in the basis resulting an FCC crystal with an extra atom placed at 4 + 4 + 4 from each
of the FCC atoms.
 Si, Ge, C and α-Sn form this crystal
structure.
 Atomic packing factor (APF) or packing
efficiency 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 i.e. 𝐴𝑃𝐹 =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎𝑛 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
 In diamond lattice, the distance between
two nearest atoms is
2 2 2
𝑎 𝑏 𝑐
√( − 0) + ( − 0) + ( − 0) = √3𝑎
4 4 4 4
as for cubic systems, a = b = c.
 If the radius of an atom is R, the distance between the
centers of two atoms is = 2R.
 Now, √3𝑎
2𝑅 =
4
 So 𝑎 = 4.61𝑅
1 1 4
(8×8+6×2+4)×3𝜋𝑅 3
 Atomic Packing Factor =
𝑎3
= 0.34
 Planar density (PD) refers to density of atomic packing on a
particular plane and is given by the ratio of no of atoms on a
𝑁𝑜 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑎 𝑝𝑙𝑎𝑛𝑒
plane and area of the plane i.e. 𝑃𝐷 = 𝐴𝑟𝑒𝑎 𝑜𝑓 𝑡ℎ𝑒 𝑝𝑙𝑎𝑛𝑒

 Planar density of {100} planes of diamond structure =


1
(4×4+1) 2
=
𝑎2 𝑎2

 Planar density of {110} planes of diamond structure =


1 1
(4×4+2×2+2×1) 2√2
=
√2𝑎2 𝑎2
 Planar density of {111} planes of diamond structure =
1 1
(3×6+3×2) 4
=
√3 2
𝑎 √3𝑎2
2
Bragg's Law:
 Diffraction occurred whenever wave motion encountered a set of regularly spaced
scattering objects, provided that the wavelength of the wave motion was of the same
order of magnitude as the repeat distance between the scattering centers.
 The wavelength of X ray and interatomic distances of most materials are in the same
range so X ray diffraction is very common in crystals.
 The experimental validation of crystallography is due to X ray diffraction technique
e.g. that there are 7 crystal system, 14 Bravais lattice or a particular material is which
type among them etc.
 Laue’s postulate: “If crystals are periodic arrangement of atoms and if X rays are waves
then crystals should act as a 3D diffraction grating for X rays”. After the experiment as
diffraction pattern was observed so it established both.
 Bragg used X ray diffraction technique as a tool to study a crystal and is mainly about
analysis of two things i) peak positions and ii) peak intensities.
 Peak positions tells us about its lattice and peak intensities about its motif or basis.
 If an incident beam is falling on a sample
and if all of the X-rays is not absorbed
then we expect a transmitted beam which
is in the same direction as the incident
beam. But if the sample is crystalline then
we may get diffracted beams other than
the transmitted beam, i.e., beams in
directions other than the transmitted beam
direction. We can have more than one
such diffracted beams from the same
crystal under the same condition.
 If these diffracted beams from the sample are analysed properly then it can be used to
solve the structure of the crystal because the directions and intensities of these beams
depend upon the crystal structure.
 Bragg's law part I: “For every diffracted beam there exists a set of crystal lattice planes
such that the diffracted beam appears to be specularly reflected i.e. reflected from
mirror”.
 Bragg simplified the analysis of crystal
structure by visualizing the diffraction as
reflection. Although actually atoms are
interacting with the incoming X-rays and
create a diffracted beam, Bragg simplified
the analysis of crystal structure by
visualizing the end result as a reflection from
a crystal lattice plane.
 If the X-ray beam falls on crystal atoms from
an incident direction, and once the atoms
interact with this incoming X-ray beam, they
will get diffracted in all directions.
 If we then pick up a given direction, let us say the blue direction and see how the waves
coming from different atoms in this direction add up, they may either constructively
interfere or they may destructively interfere.
 If there is a constructive interference in this blue direction, we will get a strong beam
and that will be called the diffracted beam from the crystal.
 So, the incoming beam falls on all the atoms of a crystal and they interact with the
incoming beam and create scattered radiations in all possible directions, then only in
some specific direction, they constructively interfere and those specific directions are
the directions of the diffracted beam.
 In order to interpret this blue diffracted beam as
a reflection, Bragg introduced a parallel set of
planes containing the atoms and the diffracted
beam and incoming beam are inclined at equal
angles to this plane so that the diffracted beam
appears simply a reflection from this blue set of
plane.
 If there is another direction, the red direction, in
which also there is a constructive interference
then Bragg's law assures that we will be able to
find another set of planes from which this red
diffracted beam also will appear to be reflected.
This is the first part of Bragg's law.
 In X-ray reflection or X-ray diffraction, the
incident or reflected angle is measured from the
plane instead of plane normal.
 The second part of Bragg's law states that for an
incoming X ray the necessary condition for its
scattered waves to interfere constructively is
when the difference between the path lengths of
the two waves reflected from two consecutive
parallel atomic planes passing through the corner
points is equal to an integer multiple of the
wavelength i.e. 𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 where λ is the
wavelength of the incoming X-ray, n is a number
which is the order of diffraction, 𝑑ℎ𝑘𝑙 is the inter-
planar spacing and θ is the angle with the plane.
Proof:
The 1st incoming X-ray wave is reflected or diffracted with the incident angle θ is equal
to the reflection angle θ. The 2nd X-ray wave will also go onto the second plane at a
distance 𝑑ℎ𝑘𝑙 and get reflected. We drop perpendicular from O on the second beam OP
and again on second reflected beam OR. The incoming X-rays before OP are parallel
and they are covering equal distance. Similarly, after OR again they are traveling equal
distance. So, the extra distance which the bottom beam goes through is the distance
PQR. So, if we find the distance PQ+QR that will be the path difference.
Now by looking at the right-angle triangle OPQ or ORQ, OQ is the inter-planar spacing
𝑑ℎ𝑘𝑙 . So, PQ is nothing but 𝑑ℎ𝑘𝑙 sin 𝜃 and similarly QR is also 𝑑ℎ𝑘𝑙 sin 𝜃. So, the total
path difference as shown here is 2𝑑ℎ𝑘𝑙 sin 𝜃 .
We know that the path difference for constructive interference should be an integral
multiple of the wavelength i.e. 𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃. Hence proved.
 For fixed values of λ and 𝑑ℎ𝑘𝑙 , there may be several angles of incidence 𝜃 1, 𝜃 2, 𝜃 3 . . . at
which diffraction may occur, corresponding to n = 1, 2, 3,. . . .
2𝑑ℎ𝑘𝑙 sin 𝜃 𝑑ℎ𝑘𝑙
 Also 𝑛λ = 2𝑑ℎ𝑘𝑙 sin 𝜃 → λ = → λ = 2𝑑𝑛ℎ 𝑛𝑘 𝑛𝑙 sin 𝜃 where 𝑑𝑛ℎ 𝑛𝑘 𝑛𝑙 = 𝑛
=
𝑛
𝑎
i.e. nth order reflection from (h k l) plane is equivalent to 1 st order
√(𝑛ℎ)2 +(𝑛𝑘)2 +(𝑛𝑙)2
reflection from (nh nk nl) plane and there cannot be any distinction between them in the
experiment.
 So while solving problems we will always treat the reflections to be of 1st order reflection
only from (nh nk nl) plane to make it easier and uniform.
 Bragg's law is necessary but not
sufficient condition as it
involves 𝑑ℎ𝑘𝑙 term which is valid
for only atomic planes passing
through corner points. If the
crystal have non corner points
like in FCC or BCC then extra
parallel atomic planes not passing
through the corner points are also
there in between two consecutive
parallel atomic planes passing
through the corner points.
 The Bragg law can be applied in two ways. By using x-rays of known wavelength λ and
measuring 𝜃, we can determine the spacing 𝑑ℎ𝑘𝑙 of various planes in a crystal: this is
structure analysis in crystallography.
 Alternatively, we can use a crystal with planes of known spacing 𝑑ℎ𝑘𝑙 , measure 𝜃, and thus
determine the wavelength λ of the radiation used : this is x-ray spectroscopy.
 Different possible experimental setup for structure analysis using x ray diffraction: i)
Variable λ and fixed 𝜃 (Laue’s method), ii) Fixed λ and variable 𝜃 (Rotating crystal
method) and iii) Fixed λ and variable 𝜃 (Powder method, most common).

X-ray diffractometer and powdered crystal


technique:
 In powder technique, a powdered crystal, or a
polycrystalline sample, is irradiated with a
collimated X-ray beam of known wavelength
(monochromatic).
 Powdering the crystal enables a given set of
(hkl) planes to receive the X-rays at many
different angles θ and at many different
orientations, or tilts. It allows the angle θ
to be scanned for differently oriented
crystals.
 All directions from the crystal that are at
an angle 2θ to the transmitted beam
define a cone called a diffraction cone as
the diffracted beam is along one
particular direction on the diffraction
cone for a set of diffraction planes (hkl)
with a particular orientation to the
transmitted beam.
 Since all possible crystal orientations are
present by virtue of powdering, the diffracted rays form diffraction cones and the
diffraction pattern developed on a photographic plate has diffraction rings.
 Each diffraction ring in the powder technique in Figure represents diffraction from a given
set of (hkl) planes.
 Whenever the angle θ satisfies the Bragg law for a given set of atomic planes, with Miller
indices (hkl) and with an interplanar separation dhkl, there is a diffracted beam.

 An X-ray detector placed at an angle 2θ with respect to the transmitted beam will register
a peak in the detected X-ray intensity.

 The instrument that allows this type of X-ray diffraction study is called a diffractometer.
The variation of the detected intensity with the diffraction angle 2θ represents the
diffraction pattern of the crystal.
 We use 2θ i.e. angle of detector with respect to the transmitted beam for plotting the
diffraction pattern as θ is not directly available during expriment as we don’t know the
position or orientation of the crystal planes inside the crystal.
 The diffraction pattern intensity analysis gives clearer understanding regarding the crystal
i.e. relative atomic density of the corresponding atomic planes although position of the
peaks already gives idea regarding the crystal i.e. regarding available atomic planes.
#
= 3.75 cm
Crystal imperfections or defects:
 Real crystals show deviations from ideality and are termed as defects or imperfections.
 They are very important topic in material science because these defects or imperfections
control the properties of material.
 Defects can be classified based on dimensionality into three categories:
a) Zero dimensional or point defects e.g. vacancy, interstitial and substitutional
defects,
b) One dimensional or line defects e.g. edge and screw dislocation defects,
c) Two dimensional or surface defects e.g. free surface, grain boundary, twin
boundary, stacking fault defects.
Vacancy defects:
 In an ideal single-crystal lattice, the atoms are arranged in
a perfect periodic arrangement. However, in a real crystal,
an atom may be missing from a particular lattice site. This
defect is referred to as a vacancy.
 It is found that at any temperature other than absolute
zero, under thermodynamic equilibrium i.e. at constant
temperature and pressure, there must be certain fraction
of vacant sites in a crystal as it minimizes the Gibbs free
energy of the system.
 If the number of atoms per unit volume in the crystal is N and Ev is the average energy
required to create a vacancy, then the vacancy concentration nv is given by
𝐸
𝑛𝑣 = 𝑁 exp( 𝑘𝑇𝑣 )

where k is Boltzmann’s constant and T absolute temperature.


Interstitial defects:
 If any atom is located not in lattice point but between
lattice sites then such defect is referred to as an
interstitial defect.
 In the case of vacancy and interstitial defects, not only is
the perfect geometric arrangement of atoms broken but
also the ideal chemical bonding between atoms is
disrupted, which tends to change the electrical properties
of the material.
Substitutional defect:
 If any lattice point is
occupied by some foreign
atom instead of original
atom then such defect is
called substitutional defect.
 The new atom may have
dimension larger or smaller
than the original atom and
therefore will alter the
geometric arrangement in the surrounding and hence can change electrical properties.
 In semiconductor we do doping which means adding impurity to an intrinsic
semiconductor in order to obtained desired electrical conductivity.
 So doping is two-step process of creating a vacancy defect by removing the original
semiconductor atom from its lattice site and then filling that vacancy by the dopant
atom as a substitutional defect.
 Doping can severely disturb the geometric arrangement if there is mismatch in physical
size of the original atom and dopant atom and is called lattice mismatch. This may lead
to poor electrical property. This is one of the reasons why not all group 3 or group 5
elements are used as dopant for the doping of silicon but only few dopants like Al or B
and P or As which have acceptable size similar to Si are only used practically.
 Also the doping process is practically realised through diffusion of dopant atoms
through vacancy or interstitial locations as at room temperature there is abundant
vacancy as well as interstitial sites in Si diamond structure crystal.
Schottky and Frenkel defects:
 In ionic crystals, we have two more varieties of
point defects.
 The defect which is created if a cation is moved
from its normal location to some other interstitial
site in the crystal is called Frenkel defect. So, we
have a pair of defects simultaneously i.e. there is a
cation vacancy as well as a cation interstitial.
 If the whole pair of a cation anion pair is missing
from the regular site then this kind of defect is called Schottky defect.
 A simple cation vacancy or a simple anion vacancy is not possible because that will
lead to charge imbalance in the crystal and thus the Gibbs free energy of such crystal
will be much higher because of that charge imbalance.
Edge dislocation defects:
 An edge dislocation defect is formed in a crystal when an atomic plane terminates
within the crystal instead of passing all the way to the end of the crystal.
 If we look from top it appears that the
crystal have one extra half plane and
from bottom if we look then it appears
a half plane is missing. So it is not any
defect in top or bottom portion of the
crystal but the defect is concentrated
only around the region where the so
called extra half plane has suddenly or
abruptly ended.
 A line going from the front of the
crystal into inside parallel to the
bottom edge of the extra half plane is called the edge dislocation line.
 The energy required to create a dislocation is typically 100 eV per nm of dislocation
line. On the other hand, it takes only a few eV to form a point defect which is a few nm
in dimension.
 Apart from the half plane approach, there is another way of looking at dislocations
which is slip approach.
 In a regular crystal if we make a horizontal cut upto a certain number of vertical planes
and try to push the upper half of the crystal w.r.t. the lower half and make it stabilised
when it is pushed by lattice constant (i.e. inter planar spacing) along that direction then
a few pushed planes from top will align perfectly with next plane of bottom half and
form bonds with it. Then a few other planes might not align perfectly and will form a
loose bond and with one plane left hanging in between them without any bonds with
bottom half. So now hanging plane looks similar to extra half plane discussed earlier
i.e. now if we name the plane along the entire crystal containing the cut plane as slip
plane then the edge of the hanging plane will lie on it and will denote edge dislocation
line.
 In this thought experiment, although the crystal is both above and below the slip plane
but if we look only at the slip plane then edge dislocation line now appears to be as the
boundary between slip and no slip region where slip region means the region where the
crystal above the slip plane is slipping with respect to the crystal below the slip plane
(which is only happening in the left side).
 Every dislocation or line defect is associated with two characteristic vectors i) Tangent
vector or Line vector ( 𝑡̂ ), and ii) Burger’s vector ( 𝑏⃗ )
 The unit vector parallel or
tangent to the dislocation line is
called tangent or line vector. It
represents the orientation of the
dislocation line.
 The magnitude and direction of
slip undergone while creating the
dislocation is known as Burger’s
vector.
 Classification of various
dislocation is done based on the
angular relation between the
burgers vector and the tangent
vector.
 When Burger’s vector is perpendicular to
the tangent vector of any dislocation then
it is called edge dislocation.
 In the 3D view of the crystal having edge
dislocation shown in the figure if X axis is
along right side and Y axis is along up in the plane of the paper and Z axis is coming
out of the plane of paper then we can write Burger’s vector, 𝑏⃗ = a 𝑥̂ and tangent vector
= + 𝑧̂ or - 𝑧̂ (+ or – does not matter much here).
Screw dislocation defects:
 When Burger’s vector is parallel to the
tangent vector, screw dislocation is formed.
 In screw dislocation, the parallel planes
perpendicular to the dislocation line, join to
form a continuous spiral ramp or more
accurately a helicoidal surface, (as spiral is a
2D curve while helix is a 3D curve) and the
screw dislocation line is the axis of this helicoidal surface.

Mixed dislocation defects:


 When Burger’s vector and tangent vector are neither parallel nor perpendicular to each
other rather at any other angle, then mixed dislocation is formed.
 This type of defect is more common in crystal compared to the two extreme cases.

Surface or interface defects:


 Interface or surface defects are 2D boundaries that have two normally separate regions
of two different materials (hetero phase) or have different crystal structures and/or
crystallographic orientations (homo phase).
 These imperfections include hetero phase (free or external surfaces, solid liquid phase
boundaries, interphase interface) and homo phase (grain boundaries, twin boundaries,
and stacking faults) defects.
Free surface defects:
 It is a defect which is present in any practical crystal even at absolute zero temperature.
 By definition a perfect crystal requires it to have infinite boundary but since it cannot
be infinite, there will obviously be an external boundary of the crystal and that external
boundary itself breaks the lattice periodicity at that position. So, this free surface or
external surface defect.
 Every external surface actually leads to
breaking of some regular bonds for all
atoms sitting at the surface and
breaking of bonds requires energy.
 Because of the breaking of these bonds,
extra energy is provided to the crystal
and that energy resides in those surface
atoms. So, integrated over the entire
surface that energy is called the surface
energy of the crystal or the surface energy of the surface.
 Commonly it is expressed as surface energy per unit area with the symbol gamma (γ)
for this quantity.
1
 Surface energy per unit area, 𝛾 = 2 𝑛𝐴 𝑛𝐵 𝜖 where 𝑛𝐴 is number of atoms per unit area,
𝑛𝐵 is number of bonds broken per atom and 𝜖 is the bond energy per bond.
Grain boundary defects:
 Single crystalline have only one orientation of the unit cells within the same sample but
they are very hard to form i.e. they are formed in a very controlled environment.
 Most of the naturally occurring crystals are of polycrystalline type.
 Polycrystalline materials have more than one orientation of the unit cells within the
same sample. So there will be different regions within the same sample with different
orientations. Each such regions are called grains. In each grain, the crystal structure and
the lattice parameter, everything is the same, only orientation is different.
 Grain boundary is a surface which separate regions with different orientations i.e. grains
within the crystal sample.
 Within the grain boundary region, there is some atomic mismatch in a transition from
one crystalline orientation to another adjacent one causing defect.
 A solid crystal is formed usually by solidification from its
liquid source. But when a liquid is cooled to below its freezing
temperature, solidification does not occur at every point in the
liquid simultaneously; rather, it occurs at some random sites
called nuclei, which are small crystal-like structures
containing perhaps only a few(50 to 100) atoms.
 Each such nuclei may have different orientations as the
process of nucleation is very random.
 The liquid atoms adjacent to a nucleus diffuse into the
nucleus, thereby causing it to grow in size to become a small
crystal, or a crystallite with a specific orientation, called a
grain.
 At the end of solidification, therefore, the whole structure has
grains with irregular shapes and orientations.
 As the liquid between the grains is consumed, some grains
meet and obstruct each other.
 The atoms at the grain boundaries obviously cannot follow
their natural bonding habits, because the crystal orientation
suddenly changes across the boundary.
 Therefore, there are both voids at the grain
boundary and stretched and broken bonds. In
addition, in this region, there are misplaced atoms
that do not follow the crystalline pattern on either
side of the boundary.
 Consequently, the grain boundary represents a
high-energy region per atom with respect to the
energy per atom within the bulk of the grains
themselves.
 The atoms can diffuse more easily along
a grain boundary because (a) less bonds
need to be broken due to the presence of
voids and (b) the bonds are strained and
easily broken anyway.
Atomic vibrations:
 A perfect single crystal contains atoms at particular lattice sites with constant
interatomic spacing.
 The atoms in a crystal at non zero temperature, however, have a certain thermal energy,
which is a function of its temperature.
 The thermal energy causes the atoms to vibrate in a random manner about an
equilibrium lattice point.
 In a sense, these atomic vibrations or also known as lattice vibrations, may be thought
of as imperfections or defects as it affects some electrical parameters.
 At any instant of time not all atoms vibrate at the same frequency and amplitude, nor
with the same energy. At a given temperature there will exist a distribution of energies
for the constituent atoms about an average energy.
 Over time the vibrational energy of any specific atom will also vary in a random
manner. With rising temperature, this average energy increases, and, in fact, the
temperature of a solid is really just a measure of the average vibrational activity of
atoms and molecules.
 At room temperature, a typical vibrational frequency is on the order of 1013 vibrations
per second, whereas the amplitude is a few thousandths of a nanometer.

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