EPH 304

Atomic Arrangement in Solids

2 units

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 COURSE OUTLINES

❑Theory of atomic arrangements

❑Crystallography
❑Crystalline and non-crystalline materials
❑Crystalline defects
❑X-ray diffraction (Half of the semester)

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 Theory of Atomic Arrangements
• Bonding: attraction between atoms, ions or molecules that enables the
formation of chemical compounds.
• The bond may result from the electrostatic force of attraction between
oppositely charged ions as in ionic bonds; or through the sharing of
electrons as in covalent bonds.
• Types of Bonding
(i) Ionic: compounds of metallic and non-metallic elements (oxides,
carbides, nitrides, sulphides e.g. ceramic, NaCl, MgO/
(ii) Covalent: formed from non-metallic elements. The bonded atoms
shared pair electron between themselves or each other (sharing of
electrons). Most semiconductors are covalent e.g. Si, polymer/plastic,
diamond, C etc
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 Ionic Bonding
• Occurs between +ve and -ve ions.
• Requires electron transfer.
• Large difference in electronegativity required.
• Example: NaCl

Na (metal) Cl (nonmetal)
unstable unstable
electron

Na (cation) + - Cl (anion)
stable Coulombic stable
Attraction 4
 Ionic bond – metal + nonmetal

donates accepts
electrons electrons

Dissimilar electronegativities: Mg = 1.3, O = 3.5

ex: MgO Mg 1s2 2s2 2p6 3s2 O 1s2 2s2 2p4

[Ne] 3s2

Mg2+ 1s2 2s2 2p6 O2- 1s2 2s2 2p6

[Ne] [Ne]

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 NOTE: it is difficult to
Examples: Ionic Bonding deform ionic solids
• Predominant bonding in Ceramics
because of the strong
NaCl
electrostatic force between
MgO
the ions. Ceramic
CaF 2
materials are very brittle
CsCl
and cannot be deformed
easily (to deform, we have
to break the bond which is
not easy to break).
Properties of Ionic bonding
Hard
Give up electrons Acquire electrons High melting point
Soluble in polar liquids
Electrical insulators (conductors in solution6
 Covalent Bonding
formed from non-metallic elements. The bonded atoms shared pair electron between
themselves or each other (sharing of electrons). Most semiconductors are covalent e.g.
Si, polymers/plastics, diamond, C etc.

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 Properties of
Covalent bonding

• Very hard
• High melting points
• Insoluble in nearly all
liquids

• Semiconductors (Except
diamond)
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 Metallic Bonding
In metals, bond is isotropic and spherical.
It occurs among a large aggregate of atoms such as crystal. Most metals have fcc,
bcc, hcp, which provides the densest packed of atoms thus the highest of solids. e.g.
various metals and alloy, Na

Properties of Metallic Bond

• Ductile
• Metallic luster
• High electrical and thermal conductivity

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 Crystallography
& Crystal
Structures

Crystallography: it is the study of the geometric form and other physical properties of
crystalline solids by using X-rays.
It is branch of science that examines crystals, or
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It is the experimental science that determine the arrangement of atoms in the crystalline solids
•Matter
✓Any substance which has mass and occupies space
✓All physical objects are composed of matter.

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• Solids
• Objects with definite size & shape are solids
• Incompressible, rigid and mechanically strong
• Atoms are closely packed

• Liquids and Gases

✓ Atoms or molecules are not fixed and cannot form any shape and size
✓ They gain the shape and size of the container
✓ Atoms are loosely packed.

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• Crystalline Solids
• The solids in which atoms or molecules are arranged in a
regular and orderly manner in 3-D
• Examples – (a) metallic: Gold, Silver, Aluminium
• (b) Non-metallic: Diamond, silicon, Quartz, graphite

• Amorphous Solids
• The solids in which atoms or molecules are
not arranged in a regular and orderly
manner in 3-D Amorphous Si02
• Example: Glass, Plastic, rubber (Glass) 16
Differences between Crystalline & Amorphous Solids

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 Crystal
• Crystals are made of matter, atoms, molecules and/or ions that fit together in
repeating patterns, called unit cells.
• What is a crystal?
• A crystal is a 3-dimensional translationally periodic arrangement of atoms in space.
Or it is a substance in which the atoms or molecules are arranged in a definite,
repeating pattern in three dimension.
• It may also be defined as a solid composed of atoms, ions or molecules arranged
in a pattern periodic in three-dimensions and has long range order. There is no
distortion.

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• Single crystal
✓It has an atomic structure that repeats
periodically across its whole volume.
Even at infinite length scales, each atom
is related to every other equivalent
atom in the structure by translational
symmetry.

• Polycrystal: is a material made up of

an aggregate of many small single
crystals. It is also called crystallites or
grains
• The grains are usually 100 nm – 100
microns in diameter.
• Polycrystals with grains that are less
than 10 nm in diameter are called nano-
crystalline
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• Many solids are crystalline (if they are not single-crystals, they consist of
many connecting crystals called Polycrystalline.
• Not all solids are crystalline, some are amorphous (i.e. not have any regular
interior arrangement of atoms, ions or molecules such as glass.
• The ideal crystal has an infinite 3D repetition of identical units, which may be
atoms or molecules.
• All ionic solids and most covalent solids are crystalline.
• All solid metals, under normal circumstances, are crystalline.

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Crystal structure composed of :
• set of atoms (motif) or basis
• lattice
• Unit cell 21
 For better understanding of crystal structure, we must know the following technical
terms of crystals like......
Lattice OR
Space lattice
• Unit cell
• Lattice parameters • Fill in the gap
• Lattice constant at home
• Atomic packing factor
• Co-ordination number
• Basis etc
The crystal structure is formed by associating every lattice point with an assembly of
atoms or molecules or ions, which are identical in composition, arrangement and
orientation, is called as the basis. The atomic arrangement in a crystal is called crystal
structure.
If the basis is substituted for the lattice points, then the resulting structure is called
crystal structure. 24
 Space Lattice or Crystal Lattice
• A 3-D transitional periodic arrangement of points in space is called a Lattice.
• An infinite array of points in 3-D in which every point has an identical
environment to all others is called Space Lattice
• Or it is geometric arrangement of matters (atoms, ions or molecules)

Basis or Motif
• The fundamental part of a symmetric design that, when repeated, creates the
whole pattern
• Simply, an atom or a group of atoms associated with each lattice point is called
Basis or Motif.
• In 3-D, translation defines operations which “move” the motif into infinitely
repeating patterns.
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What is the relationship between the lattice and the crystal?
Crystal = Space Lattice + Motif (basis)

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• A cell is a finite representation of the infinite lattice.
• It is a parallelogram (2D) or a parallelopiped (3D) with lattice point points at their
corners.
• The crystal is then represented as a lattice (its arrangement of points is called lattice
not the line which are joining them).
• Lattice point is a 3-D arrays of points. Each point has identical surrounding. Lattice
are infinite in extent but crystals are not.
Three dimensional lattice

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SPACE LATTICE AND UNIT CELL
The smallest possible portion or geometrical
figure of crystal lattice and which buildup by
repetition in 3-D is called Unit cell.
It is basic structural unit or building blocks of the
crystal structure.

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 Space lattice and Unit cells

1-D 3-D
2-D

Criteria used for the selection of unit cells:

✓ The smallest sized unit that retains the
characteristics of the space lattice.
✓ Edges of the cell should coincide with
symmetry axes.
✓ Edges of the cell related to each other by the
symmetry of the lattice
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 Space lattice and Unit cells

✓ Each unit cell requires two vectors a and b for its description
✓ A 3-D can similarly divided into unit cells described 3 vectors (a, b & c)
✓ Exact location of particles in a unit cell can be obtained by X-ray diffraction.
✓ The unit cell is described by the lengths of its edges, a, b, c (which are
related to the spacing between layers) and the angles between the edges, α,
β and γ.
✓ The 3 lengths a, b, c and 3 interaxial angles α, β and γ are called the LATTICE
PARAMETERS 34
• Differentiate between Space lattice and Unit cells?
✓A space lattice is an array of points showing how particles (atoms, ions or
molecules) are arranged at different sites in 3-dimensional spaces.
✓every point has identical surrounding.
✓Whereas unit cell is the smallest repeating motif or pattern, or
✓the smallest repeating unit in space lattice which, when repeated over
again, results in a crystal of the given substance.

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 Primitive

Non-Primitive
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Crystal System
• Lengths & angles that defined the
unit cells are called lattice constant
or parameter of unit cell.
• Dividing space by 3 sets of planes, we
can produce unit cell of various
shapes
✓ Depending on we arrange the planes
✓ E.g. if a = b = c and α = β = γ = 90° i.e.
equally spaced and perpendicular, the
unit cell is Cubic
✓ if the axial length and angles are
different, it produces unit cells of
various shapes and kinds of point
lattices
• 7 different kinds of cells are
necessary to include all the possible
point lattices.
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 Crystal System
• 7 different kinds of cells are necessary to include all the possible point lattices
• These correspond to the 7 crystal systems into which all crystals can be classified.
• In summary, the crystal classes are grouped into 7 crystal structures/systems based on the
following criteria:
✓ Relative length of the crystallographic axes
✓ Number of crystallographic axes
✓ Values of the interaxial angles
✓ Some essential element of symmetry.
• Crystal faces: The regular internal structure of a solid is manifested by the development of
surfaces that define the shape of the crystal, and which may be related to one another by
certain elements of symmetry.
• Bravais law: crystal faces are most likely to develop (fully) along those planes with the
highest density of lattice points.
• It therefore states that the frequency by which a face is observed in a crystal is directly
proportional to the number of “points” or “nodes” it intersects in a lattice.
• It demonstrated in 1850 that there are 14 possible point lattices and no more.
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 Crystal System

•Homework: Sketch 7 crystal structures

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Crystal System

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Crystal System

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 Crystal System
• Some unit cells are simple, or primitive, cells (P or R)
• And some are non-primitive cells (i.e. any other symbols).
• Primitive cell is any cell that containing lattice points on the corners only per unit cell e.g.
simple cubic.
• Non-primitive: any cell containing lattice points on the corners and additional lattice points in
the interior or on the faces
✓Have more than one or additional lattice point per cell e.g. FCC
• NOTE
✓A lattice point in the interior of a cell “belongs” to that cell
✓while one in a cell face is shared by two cells, and
✓one at a corner is shared by eight.
𝑵𝒇 𝑵𝒄
𝑵𝒖 = 𝑵𝒊 + +
𝟐 𝟖
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 Crystal System
• Examples:

• Simple cubic has Nu =8/8 = 1 for simple cubic, each atom contributes 1/8 atom
• Class work
✓ Calculate Nu for BCC
✓ And Nu for FCC
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 Crystal System
•FCC

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Crystal System

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 Crystal System
• Answer for BCC BCC has Nu = 1 + 0 + 8/8 = 2
Nu =no of atoms per unit cell

• Answer for FCC

FCC has Nu = 0 + 6/2 + 8/8 = 545

Lattice directions and Planes

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 Lattice directions and Planes
• Miller indices are used to specify directions and planes.
• These directions and planes could be in lattices or in crystals.
• The number of indices will match with the dimension of the lattice or the
crystal.
• For example:
✓in 1D there will be 1 index, and
✓In 2D there will be two indices etc.
• Important notations
✓(h, k, l) represents a point – note the exclusive use of commas
✓Negative numbers/directions are denoted with a bar on top of the number
✓[h k l] represents a direction
✓<h k l> represents a family of directions
✓(h k l) represents a plane
✓{h k l} represents a family of planes
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 Crystal Planes
• Miller indices specify orientation without
position in space
• It based on the intercepts of plane with
the 3-crystal axis (i.e. 3 edges of the unit
cell)
• The intercept of the plane is measured in
terms of edge length or dimension of the
unit cell
• It the unit distance from the origin = ½ x-
dimension of the cell
• i.e. it has x-intercept to be ½
• Also cuts y and z at ½ .
• NOTE: If a plane is parallel to an axis, it
will meet at infinity.
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 Crystal Planes

The reciprocal procedure avoids the intercept

of infinity for a plane parallel to an oxis
by making it to zero. 60
Crystal Planes

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Crystal Planes

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 Crystal Planes
• Procedures to determine the miller indices are:
✓ Identify the plane intercepts on the x, y and z-axes.
✓ Specify the intercepts in the fractional coordinates
✓ Take the reciprocals of the fractional intercepts
• In another way,
✓ Find the intercepts on the 3-axes in multiples or fractions of the edge length i.e. , ,
✓ Take the reciprocal of these numbers
✓ Reduce the numbers to three smallest integers having the same ratio as the reciprocal
✓ Enclose the three-integer numbers in parenthesis i.e. (h k l)
• Apply the procedure to the above figure
111
✓ Step 1.
222
✓ Step 2. 2 2 2
✓ Step 3. 2 2 2
✓ Step 4. (2 2 2)
• NOTE: {h k l} are the (h k l) types of planes which are crystallographic equivalent 63
 Crystal Planes - examples
1. 2.

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 Crystal Planes - examples
1. • The plane intersects the x-axis at point a. It runs parallel along y and z axes.
• Thus, this plane can be designated as (1,∞,∞)

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 Crystal Planes - examples
2. • Likewise, the yellow plane can be designated as (∞,1,∞)
• And the green plane can be written as (∞,∞,1)

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 Crystal Planes - examples
• Miller Indices are the reciprocals of the parameters of each crystal
• face. Thus:
• Pink Face
• = (1/1, 1/∞, 1/∞) = (100)
• Green Face
• = (1/∞, 1/∞, 1/1) = (001)
• Yellow Face
• = (1/∞, 1/1, 1/∞) = (010)

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 Crystal Planes - examples
3. What is the Miller index of the plane below?

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 Crystal Planes - examples
Answer
• The plane of interest cuts two
of the crystallographic axes.
• Intercepts: (1,1, ∞) → (110)

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 Crystal Planes - examples
4. What is the Miller index of the plane below?

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 Crystal Planes - examples
Answer

• This plane cuts all three

crystallographic axes.
• Intercepts = (1,1,1) → (111)

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 Crystal Planes - examples
5. What is the Miller index of the plane below?

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 Crystal Planes - examples
Answer:

• This plane cuts two of the

reference axes, but not
equidimensionally.
• Intercepts: (½, 1, 0) → (210)

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 Crystal Planes - examples
Homework:
What is the Miller index of the plane below?
1.
2.

3. Draw the following planes (101), (111), (202) and (112)

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 Crystal Direction
• Direction indices are defined in different manner
• The direction of any line in a lattice may be described by
✓ first drawing a line through the origin parallel to the given line and
✓ then giving the coordinates of any point on the line through the origin
• It is defined as the components of the direction resolved along each of the axes and
reduced to smallest integer.
• All parallel direction have the same direction indices
• Directions are crystallographic equivalent if the atom spacing along each direction the same
✓ Example cubic edge direction: [100], [010], [001], [01ത 0], [001ത ], [1ത 00] ≡ <100>
✓ Equivalent direction are called indices of a family
• The indices of the direction are taking as the smallest integer prop. to coordinates.
• For cubic cell, a = 1
• Get vector representation first, the tail origin first coordinate and then head origin
coordinate
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 Crystal Direction
• We start with coordinate of the axes
• Coordinates of selected points in the unit cell
• Number refers to distance from the origin in a
• Then determine coord. of 2 points that lie in the direct
on interest
• u1 v1 w1 and u2 v2 w2
• Very easy if the second corresponds with the origin of
coord system
• Subtract the coords i.e. u’ = u1-u2, v’ = v1-v2, w’ = w1-w2
• Clear the fractions from the differences to give the indices
in lowest integer value
• Write [ ] bracket and –ve indicate with bar over the integer
• [uvw] and [ത𝑢𝑣ҧ 𝑤]
ഥ are running in opposite directions
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 Crystal Direction
• Direction A
✓ Two points are 1, 0, 0, and 0, 0, 0
✓ 1, 0, 0, - (0, 0, 0) = 1, 0, 0
✓ No fractions to clear or integers to reduce
✓ [100]
• Direction B
✓ Two points are 1, 1, 1 and 0, 0, 0
✓ 1, 1, 1, - (0, 0, 0) = 1, 1, 1
✓ No fractions to clear or integers to reduce
✓ [111]
• Direction C
✓ Two points are 0, 0, 1 and 1/2, 1, 0
✓ 0, 0, 1 –(1/2, 1, 0) = -1/2, -1, 1
✓ 2 (-1/2, -1, 1) = -1,-2, 2
Home work: draw the crystal direction for [112],
✓ [1ത 2ത 2]
[110], [3ത 21ത ], [1ത 1 0], [1ത 1ത 0], [326]
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 Miller Indices of Directions
1. Choose a point on the direction as the origin.

z
2. Choose a coordinate system with axes parallel
to the unit cell edges.

y 3. Find the coordinates of another point on the

direction in terms of a, b and c

1a+0b+0c 1, 0, 0
x

4. Reduce the coordinates to smallest integers. 1, 0, 0

5. Put in square brackets [100]

 Miller Indices 3

z
Miller indices of a direction
represents only the
orientation of the line
corresponding to the
y
direction and not its position
or sense

x [100]

All parallel directions have the same Miller indices

Miller indices of a family of symmetry related directions

uvw = [uvw] and all other directions related to [uvw] by the symmetry of
the crystal

[001]
Tetragonal
Cubic

[010]

[010]
[100]
[100]

= [100], [010], = [100], [010]

100 100 tetragonal
cubic [001]