Crystal Structures - Fundamental concept

• A crystalline material is one in which the atoms are situated in a repeating or periodic
array over large atomic distances; that is, long-range order exists, such that upon
solidification.
• Periodicity is one of the most important properties of crystals.
• Crystals are highly symmetrical arrays of atoms which substantially simplifies their
analysis
• Some of the properties of crystalline solids depend on the crystal structure of the
material, the manner in which atoms, ions, or molecules are spatially arranged.
Crystal Lattice
• Crystal lattice is the periodic and systematic arrangement of atoms that are found in
crystals with the exception of amorphous solids and gases.

• In the simplest of terms, the crystal lattice can be considered as the points of intersection
between straight lines in a three-dimensional network.

• The physical properties of crystals like cleavage, electronic band structure and optical
transparency are predominantly governed by the crystal lattice.

• Lattice – Arrangement of atoms/ions

• Motif/Basis – A group of one /more atoms located in a particular way with respect to each
other and associated with lattice point

• Crystal Structure = Lattice + Motif/Basis

Crystal Lattices
• The concept of a lattice is directly related to the idea of translational symmetry. A lattice
is a network or array composed of single motif which has been translated and
repeated at fixed intervals throughout space. For example, a square which is
translated and repeated many times across the plane will produce a planar square lattice.
• The unit cell of a lattice is the smallest unit which can be repeated in three dimensions in
order to construct the lattice. In a crystal, the unit cell consists of a specific group of atoms
which are bonded to one another in a set geometrical arrangement. This unit and its
constituent atoms are then repeated over and over in order to construct the crystal lattice.
The surroundings in any given direction of one corner of a unit cell must be identical to the
surroundings in the same direction of all the other corners.
• The corners of the unit cell therefore serve as points which are repeated to form a lattice
array; these points are termed lattice points.
• The vectors which connect a straight line of equivalent lattice points and delineate the
edges of the unit cell are known as the crystallographic axes.
 Unit Cell
• represent the symmetry of the crystal structure
• the basic structural unit or building block of the crystal structure and
defines the crystal structure by virtue of its geometry and the atom
positions within.
• The unit cell is characterized by its lattice parameters which consist
of the length of the cell edges and the angles between them
• Unit cell is the subdivision of the lattice that still retains the overall
characteristics of the entire lattice
• By stacking identical unit cells, the entire lattice can be constructed
• Primitive unit cells contain only one lattice point, which is made up
from the lattice points at each of the corners.
• Non-primitive unit cells contain additional lattice points, either on a
face of the unit cell or within the unit cell, and so have more than one
lattice point per unit cell. Non-Primitive Primitive

Symmetry restricts the unit cells to certain shapes so that the entire space is covered without gaps and overlaps
Crystal Symmetries
• Crystals possess a regular, repetitive internal structure.
• The concept of symmetry describes the repetition of structural features. Crystals therefore
possess symmetry, and much of the discipline of crystallography is concerned with
describing and cataloging different types of symmetry.
• Two general types of symmetry exist.
– Translational symmetry describes the periodic repetition of a structural feature
across a length or through an area or volume.
– Point symmetry, on the other hand, describes the periodic repetition of a structural
feature around a point. Reflection, rotation, and inversion are all point symmetries.

• Symmetries are most frequently used to classify the different crystal structures.
• In general one can generate 14 basic crystal structures through symmetries. These are
called Bravais lattices. Any crystal structures can be reduced to one of these 14 Bravias
lattices.
Ideal Crystals → Real Crystals → Microstructures → Material → Component
Ideal Crystal Ideal Mathematical Crystal

Consider only the Geometrical Entity

or
only the Physical Property
Crystal* Consider only the Orientational
or
Positional Order
Crystal**
Put in Crystalline defects
& Free Surface
& Thermal Vibration
‘Real Crystal’
Put in Multiple Crystals (Phases)
giving rise to interfacial defects
~Microconstituents
Put multiple ~microconstituents
Add additional residual stress 
Real materials are
Microstructure usually complex and we
start with ideal
descriptions
Material Material or Hybrid

Component
 Ideal Crystals → Real Crystals → Microstructures → Material → Component
Geometrical entity

Physical Property
Ideal Crystal Ideal Mathematical Crystal

Consider only the Geometrical Entity Part of the infinite crystal

or
only the Physical Property

Crystal*
Part of the infinite crystal
Consider only the Orientational
or
Positional Order

Crystal**
Part of the infinite crystal

Put in Crystalline defects

& Free Surface
& Thermal Vibration

‘Real Crystal’
 Crystal =
Lattice (Where to repeat)
+
Motif (What to repeat)
Crysta 

l
a
=
Lattic 

e
a
+
Motif Note: all parts of the motif do not sit on the lattice point
a
2

Motifs are associated with lattice points

 they need NOT sit physically at the lattice point
Making a 1D Crystal
 Some of the concepts are best illustrated in lower dimensions  hence we shall
construct some 1D and 2D crystals before jumping into 3D
 A strict 1D crystal = 1D lattice + 1D motif
 The only kind of 1D motif is a line segment
 An unit cell is a representative unit of the structure (finite part of an infinite
structure)
 which when translationally repeated gives the whole structure.

Lattic 

+
Motif
=
Crysta 

l
 Lattice

 Motif

 + 


b



Continued
Crystal 
| b | b
The 2D crystal (& lattice) is


specified using 3 lattice
      | a | a parameters: ‘a’, ‘b’ and α.

      
As before there are many
      
= ways of associating the
motif with a lattice point
        
(one of these is shown)
      
      
      
      


Note:
Each motif is identically oriented (orientationally ordered)
and
is associated exactly at the same position with each lattice point (positionally ordered)
 Motif is associated with the lattice point and need not ‘sit’ on the lattice point. In any case
the full motif cannot ‘sit’ on the lattice point (just one point, maybe the centroid of an object,
can ‘sit’ on the lattice point).
 Motif can be associated with a lattice point in many ways, as in the examples below.

In all the cases the

conventional unit cell is
marked in orange. This UC
has lattice points as vertices.
 Lattice Parameters
• The physical properties of solids depend entirely upon the arrangement of the atoms that
make up the solid and the distances between them.
• The arrangement of the atoms in a crystal structure is a combination of the size and shape of
the unit-cell and the arrangement of atoms inside the unit-cell.
• The shape of the unit cells is described by the lattice symmetry. Unit cell = 3-dimensional unit
that repeats in space
• The size of the unit-cell is described in terms of its unit-cell parameters. These are the
edge lengths and the angles of the unit-cell.

• The unit cell geometry is defined in terms of six parameters: the three
edge lengths a, b, and c, and the three inter-axial angles α, β, and γ
indicated in Figure 3.4, and are termed the lattice parameters or
lattice constants of a crystal structure
• Seven possible combinations of a, b, c & α, β, γ resulting in seven
crystal systems
Bravais Lattice
• By assigning specific values for axial lengths and inter-axial angles, unit cells of different
types can be constructed
• Crystallographers have shown that only 7 different types of crystal systems are necessary
to create and construct all the lattices
• Bravais showed that there are 14 possible ways of constructing the crystal lattice from
seven crystal systems.
• Seven different crystal Systems
• Cubic – 3

• Hexagonal – 1
• 0rthorhombic – 4

• Tetragonal – 2
• Rhombohedral – 1

• Monoclinic – 2
• Triclinic - 1
Crystal Structures - The 14 Bravais Lattices

In 1850, Auguste Bravais showed that crystals

could be divided into 14 unit cells, which meet the
following criteria.
•The unit cell is the simplest repeating unit in the
crystal.
•Opposite faces of a unit cell are parallel.
•The edge of the unit cell connects equivalent
points.
Crystal Structures - The 14 Bravais Lattices
A Bravais lattice is an infinite array of discrete points with an arrangement and
orientation that appears exactly the same viewed from any point of the array. A three
dimensional Bravais lattice consists of all points with position vectors R of the form:

R = n1a1 + n2a2 + n3a3,

where the three primitive lattice vectors ai are not all in the same plane, and the n's are
integers.

one lattice point per unit cell since the points at the eight corners are shared by eight
adjacent unit cells.

Crystallographers often describe a crystal in terms of a non-primitive unit cell which is larger
than the primitive cell. For instance, a body-centered cubic crystal has a non-cubic primitive
cell, but it is often described in terms of a cubic conventional cell which is twice the size of the
primitive cell.
Crystal Systems - Seven

3
Crystal Systems - Seven
4

7
Crystal Structures – Metallic Crystals
• tend to be densely packed.
• have several reasons for dense packing
– Typically, made of heavy element.

– Metallic bonding is not directional; i.e., no restrictions as to the number and position of
nearest-neighbor atoms
– Nearest neighbour distances tend to be small in order to lower potential energy.

• have the simplest crystal structures

• Metallic Crystal Structures

– Three relatively simple crystal structures are found for most of the common metals:

• body-centered cubic,

• face-centered cubic, and

• hexagonal close-packed.
Notations
• Atomic radius – It is defined as half the distance between the centres of the neighboring
atoms
• Coordination Number – The no. of atoms which are directly surrounding the particular atom;
it is also defined as the no. of nearest neighbors for that particular atom
• Atomic Packing fraction – Close packing of atoms in a unit cell of the crystal structure is
known as APF
Volume of atoms per unit cell
APF  No. of effective atoms in the unit cell 
Volume of unit cell
Face-centered cubic (FCC)
• Some of the familiar metals having this crystal structure are
copper, aluminum, silver, and gold
• spheres or ion cores touch one another across a face diagonal;
the cube edge length a and the atomic radius R

face-diagonal the length = 4R

• each corner atom is shared among eight unit cells, whereas a
face-centered atom belongs to only two
• Two other important characteristics of a crystal structure
– coordination number , and

– the atomic packing factor (APF).

FCC - Coordination number
• each atom has the same number of nearest-neighbor or touching
atoms, which is the coordination number.
• For face-centered cubics, the coordination number is 12.
– the front face atom has four corner nearest-neighbor atoms
surrounding it,
– four face atoms that are in contact from behind, and

– four other equivalent face atoms residing in the next unit cell
to the front
 FCC - Atomic packing factor (APF)
• The APF is the sum of the sphere volumes of all atoms within a
unit cell (assuming the atomic hard-sphere model) divided by
the unit cell volume

• Both the total atom and unit cell volumes may be calculated in
terms of the atomic radius R face-diagonal the length = 4R

atoms per
unit cell
Volume = a3

• the atomic packing factor is 0.74.

Comparison of crystal structures

Crystal structure coordination # packing factor close packed directions

Simple Cubic (SC) 6 0.52 cube edges

Body Centered Cubic

8 0.68 body diagonal
(BCC)

Face Centered Cubic

12 0.74 face diagonal
(FCC)

Hexagonal Close Pack

12 0.74 hexagonal side
(HCP)
Crystal Structures
• The Body-Centered Cubic Crystal Structure

• The Hexagonal Close-Packed Crystal Structure

Body Centered Cubic Crystal Structure (BCC Structure)

• The hard spheres touch one another along cube diagonal

• Eight nearest neighbors surround the central atom hence CN = 8
• Effective Number of atoms per unit cell, n = 2
• Center atom (1) shared by no other cells: 1 x 1 = 1 and 8 corner
atoms shared by eight cells: 8 x 1/8 = 1

• Atomic Radius R = 3 a/4

• APF = 0.68
• Packing Efficiency = 68%
• Some of the materials that
possess BCC structure include
lithium, sodium, potassium,
barium, vanadium, alpha-iron and
tungsten
Hexagonal Close Pack Structure
• Metals don’t crystallize into simple hexagonal structure since the APF is too low
• The atoms in the hcp structure are also packed along close-packed planes.
• It should also be noted that both the FCC and HCP structures are known as close-packed
structures with crystallographic planes having the same arrangement of atoms;
• However, the order of stacking the planes is different. Atoms in the hexagonal close-
packed planes (called the basal planes) have the same arrangement as those in the FCC
close-packed planes
Hexagonal Close Pack Structure
• The coordination number, CN = 12 (same
as in FCC)
• Atomic radius = a/2
• Number of atoms per unit cell, n = 6.
– 3 mid-plane atoms shared by no other
cells: 3 x 1 = 3
– 12 hexagonal corner atoms shared by 6
cells: 12 x 1/6 = 2
– 2 top/bottom plane center atoms
shared by 2 cells: 2 x 1/2 = 1
Expression for ideal c/a ratio - HCP

• The atom at point M is midway between the top and

bottom faces of the unit cell that is MH= c/2.
• And, since atoms at points J, K, and M, all touch one
another
Expression for ideal c/a ratio - HCP
HCP Structure - Atomic packing factor
Crystal Structures - Density computations
Theoretical density (ρ) for metals
mass(m)
Density (  ) 
volume(v)

mass = (number of atoms per unit cell) x (mass of each atom)

mass of each atom = atomic weight/Avogadro’s number

n = number of atoms associated with each unit cell

A = atomic weight (g/mol)
VC = volume of the unit cell (cm3 per unit cell)

NA = Avogadro’s number (6.022 x 1023 atoms/mol)

Theoretical Density Computation for Copper
Question: Copper has an atomic radius of 0.128 nm, an FCC crystal structure, and an
atomic weight of 63.5 g/mol. Compute its theoretical density and compare the answer with its
measured density.

Solution : the crystal structure is FCC, n, the number of atoms per unit cell, is 4.
Furthermore, the atomic weight ACu is given as 63.5 g/mol.
3
• The unit cell volume VC for FCC is 16R 2 where R, the atomic radius, is 0.128 nm.
Polymorphism and Allotropy

• Polymorphism
– Same compound occurring in more than one crystal structure
– depends on both the temperature and the external pressure
– Eg. calcite, aragonite and vaterite minerals , different forms of calcium
carbonate

• Allotropy
– Polymorphism in elemental solids (e.g., carbon)
Crystallographic Points, Directions, and Planes
• When dealing with crystalline materials, it often becomes necessary to specify a particular
point within a unit cell, a crystallographic direction, or some crystallographic plane of
atoms.

• Labeling conventions have been established in which three

numbers or indices are used to designate point locations,
directions, and planes.
• The basis for determining index values is the unit cell, with a
right-handed coordinate system consisting of three (x, y, and z)
axes situated at one of the corners and coinciding with the unit
cell edges, as shown in Figure.
• For some crystal systems—namely, hexagonal, rhombohedral,
monoclinic, and triclinic-

-the three axes are not mutually perpendicular.

Point Coordinates
• The position of any point located within a unit cell may be specified in terms of its
coordinates as fractional multiples of the unit cell edge lengths (i.e., in terms of a, b, and c
• The position of any point located within a unit cell may be specified in terms of its
coordinates as fractional multiples of the unit cell edge lengths (i.e., in terms of a, b, and c).
• To illustrate, consider the unit cell and the point P
situated therein as shown in Figure.
• We specify the position of P in terms of the generalized
coordinates q, r, and s
where q is some fractional length of a along the x axis,
r is some fractional length of b along the y axis, and
s is some fractional length of c along the z axis.

• Thus, the position of P is designated using coordinates q r s with values that are less than or
equal to unity. Furthermore, we have chosen not to separate these coordinates by commas
or any other punctuation marks (which is the normal convention).
 Another 2D example
Miller Indices for directions in 2D

This direction is  [4 2]
Normally, we ‘take out’ the common factor
Miller Indices with magnitude  2[2 1]

Miller indices → [53] And then omit it! Miller Indices  [2 1]

We will see an example
STEPS in the determination of Miller indices for directions soon
 Position the vector, such that start (S: (x1, y1)) and end points (E: (x2, y2)) are lattice points and note the
value of the coordinates. Subtract to obtain: ((x2x1), (y2y1)).
 Write these number in square brackets, without the ‘comma’: [* *].
 ‘Remove’ the common factors. (Note: keep the common factor, preferably outside the bracket, if the length has to be preserved in
further computations).
 Set of directions represented
by the Miller index

[42]  2[2 1]

Miller Indices  2[2 1]

This
This Miller
Miller index
index represents
represents aa set
set (an
(an infinite set) of
infinite set) of all
all such
such parallel
parallel vectors
vectors (and
(and not
not just
just one
one vector)
vector)
originating at a lattice point and ending at a lattice point
How to find the Miller Indices for an arbitrary direction?  Procedure
 Consider the example below.
 Subtract the coordinates of the end point from the starting point of the vector denoting the direction 
If the starting point is A(1,3) and the final point is B(5,1)  the difference (BA) would be (4, 4).

 Enclose in square brackets, remove comma and write

negative numbers with a bar  [4 4]

 Factor out the common factor  4[11]

 If we are worried about the direction and magnitude

then we write  4[11]
 If we consider only the direction then we
write  [11]
 Needless to say the first vector is 4 times in
length
[11]  [11]
 The magnitude of the vector
is (1) 2  (1) 2  2
For the crystal in the figure below, what are the member(s) of the family of directions
<01>?

 The family <01> has only one member  [01] !!!

 This crystal has m symmetry and belongs to the rectangle 2D crystal system. (Not a square
crystal, though the unit cell is a square).
 The mirrors are vertical and pass through lattice points and between them.

[01]
Family of directions
Let us consider a square lattice:
 [10] and [01] belong to the same family  related by a 4-fold rotation
 [11] and [11] belong to the same family  related by a 4-fold rotation
 [01] and[0 1] belong to the same family  related by a 2-fold rotation
(or double action of 4-fold)

 hk   [hk ],[hk ],[hk ],[h k ],[ kh],[kh],[ kh ],[k h ]

 10   [10],[01],[10],[0 1]
 11   [11],[11],[1 1],[1 1]

Essentially the 1st and 2nd index can

be interchanged and be made
negative (due to high symmetry)

4mm
Let us consider a Rectangle lattice:
 [10] and [01] do NOT belong to the same family
 [11] and[11] belong to the same family  related by a mirror
 [01] and[0 1] belong to the same family  related by a 2-fold rotation
 [21] and [12] do NOT belong to the same family
Writing down all the members of the family
 hk   [hk ],[hk ],[hk ],[ h k ]
 10   [10],[10]
 11   [11],[11],[1 1],[1 1]
Same family (related by
horizontal mirror)
 12   [12],[12],[12],[12]
The 1st and 2nd index can NOT be
interchanged, but can be made
negative
Same family (related by
vertical mirror)

Different directions as no 4-
fold
2mm
Let us consider a square lattice decorated with a rotated square to give a
SQUARE CRYSTAL (as 4-fold still present):
 [10] and [01] belong to the same family  related by a 4-fold
 [11] and [11] belong to the same family  related by a 4-fold
 [01] and [0 1] belong to the same family  related by a 4-fold (twice)
[12]
 [12] and do NOT belong to the same family
Writing down all the members of the family
 hk   [hk ],[h k ],[kh],[kh ]
 10  [10],[10],[01],[0 1]
 11  [11],[11],[1 1],[1 1]
 12  [12],[21],[1 2],[2 1]
 21   [21],[12],[2 1],[12]

4
Point Coordinates
Point Coordinates
Specification of Point Coordinates
• Specify point coordinates for all atom positions for a BCC unit cell
 Crystallographic Directions
• A crystallographic direction is defined as a line between two points, or a vector.

Steps used to determine the three directional indices:

1. A vector of convenient length is positioned such that it passes through the origin of the
coordinate system. Any vector may be translated throughout the crystal lattice without
alteration, if parallelism is maintained.

2. The length of the vector projection on each of the three axes is determined; these are
measured in terms of the unit cell dimensions a, b, and c.

3. These three numbers are multiplied or divided by a common

factor to reduce them to the smallest integer values.

4. The three indices, not separated by commas, are enclosed in

square brackets, thus: [uvw]. The u, v, and w integers correspond
to the reduced projections along the x, y, and z axes, respectively.
For each of the three axes, there will exist both positive and negative coordinates. Thus
The [100], [110], and [111]
negative indices_are also possible, which are represented by a bar over the appropriate
directions within a unit cell.
index. Eg. the [111 ]
Crystallographic Directions
Crystallographic Directions
Crystallographic Directions - Family
• For some crystal structures, several nonparallel directions with different indices are
crystallographically equivalent; this means that the spacing of atoms along each direction
is the same.
• The directions in a crystal are given by specifying the coordinates (u, v, w) of a point on a
vector passing through the origin. It is indicated as [uvw]. For example, the direction [110]
lies on a vector whose projection lengths on x and y axes are one unit.
• Directions of a form or family like [110], [101], [011] are written as <110>

<100> and <110> family <111> family

Further points
 General Miller indices for a direction in 3D is written as [u v w].
 The length of the vector represented by the Miller indices is: u 2  v 2  w2

Important directions in 3D represented by Miller Indices (cubic lattice)

Z  Three important set of directions related to the

[011] cube are:
(i) cell edge ([001] type),
[001]
(ii) face diagonal ([011] type),
(iii) body diagonal ([111] type).
Memorize
these
[101] Body diagonal

[010]
Y
[111]
[100] Face diagonal

[110]
X [110]
Procedure as before
 (Coordinates of the final point  coordinates of the initial point).
 Reduce to smallest integer values.
Family of directions

Index Members in family for cubic lattices Number

(True for cubic crystals in holohedral class, but not true for all cubic crystals)

<100> [100],[100],[010],[0 10],[001],[00 1] 32=6

<110> [110],[110],[1 10],[1 10],[101],[101],[10 1],[10 1],[011],[0 11],[01 1],[0 1 1] 6  2 = 12

<111> [111],[111],[1 11],[11 1],[1 11],[11 1],[1 1 1],[1 1 1] 42=8

the ‘negatives’ (opposite direction)

Alternate
Symbol
symbol
[] → Particular direction
<> [[ ]] → Family of directions
Hexagonal Crystals
• Problem – In crystals having hexagonal symmetry, some crystallographic equivalent
directions will not have the same set of indices.
• This is circumvented by utilizing a four-axis, or Miller–Bravais, coordinate system as
shown in Figure.

• The three a1, a2, and a3 axes are all contained within a single
plane (called the basal plane) and are at 120° angles to one
another.
• The z axis is perpendicular to this basal plane.
• Directional indices, will be denoted by four indices, as [uvtw]; by
convention, the first three indices pertain to projections along
the respective a1, a2, and a3 axes in the basal plane

Coordinate axis system for a

hexagonal unit cell
(Miller–Bravais scheme).
 Related to ‘l’ index

Related to ‘k’ index

Related to ‘i’ index Related to ‘h’ index

Directions Drawing the [1120] direction

a1 a2 a3
Projections a/2 a/2 −a

Normalized wrt LP 1/2 1/2 −1

Factorization 1 1 −2

Indices [1 1 2 0]
We do similar exercises to draw other directions as well

Drawing the [101 0] direction

a1 a2 a3
Projections 3a/2 0 –3a/2
Normalized wrt
3/2 0 – 3/2
LP
Factorization 1 0 −1
Indices [1 0 –1 0]
Conversion of Directional Indices for a Hexagonal Unit Cell
Convert the [111] direction into the four-index system for hexagonal crystals

Solution

u   1; v  1; w  1

Multiplication of the preceding indices by 3 reduces them to the lowest set, which yields values
for u, v, t, and w of 1, 1, 2 and 3, respectively.
_
Hence, the [111] direction becomes [1123].
Crystallographic Planes
• The orientations of planes for a crystal structure are
represented in a similar manner.
• Again, the unit cell is the basis, with the three-axis
coordinate system as represented in Figure. In all but
the hexagonal crystal system, crystallographic planes
are specified by three Miller indices as (hkl).
• Any two planes parallel to each other are equivalent
and have identical indices.
Crystallographic Planes
The procedure used to determine the h, k, and l index numbers is as follows:

1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.

2. At this point the crystallographic plane either intersects or parallels each of the three axes;
the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
3. The reciprocals of these numbers are taken. A plane that parallels an axis may be
considered to have an infinite intercept, and, therefore, a zero index.

4. If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.3

5. Finally, the integer indices, not separated by commas, are enclosed within parentheses,
thus: (hkl).
Miller Indices for PLANES
Miller indices for planes is not as intuitive as that for directions and special care must be taken
in understanding them

Illustrated here for the cubic lattice

 Find intercepts along axes → 2 3 1 1 1

 Take reciprocal → 1/2 1/3 1* 1
2 3
 Convert to smallest integers in the same ratio → 3 2 6
 Enclose in parenthesis → (326) Note the type of brackets
 Note: (326) does NOT represent one plane but an infinite set of parallel planes
passing through lattice points.
 Set of planes should not be confused with a family of planes- which we shall consider next.
* As we shall see later reciprocals are taken to avoid infinities in the ‘defining indices’ of planes
  Why do need Miller indices (say for planes)?
 Can’t we just use intercepts to designate planes?
Thus we see that Miller indices does the following:
 Avoids infinities in the indices (intercepts of (1, , ) becomes (100) index).
 Avoids dimensioned numbers
 Instead we have multiples of lattice parameters along the a, b, c directions (this implies
that 1a could be 10.2Å, while 2b could be 8.2Å).

 How to know if a given atom/lattice point is ‘sitting’ on a plane?

 Use the intercept form of the equation of a plane. If (a,0,0), (0,b,0) & (0,0,c) are the intercepts
along x, y & z, then the equation is as below.
 Substitute the coordinates of the atom to check if equation is satisfied [done for the (½, ½, ½)
atom of BCC as below ( for the (112) plane).

x y z The (112) plane  x  y  2 z  1

This (½, ½, ½) atom sits on the on (110) plane
  1 The (110) plane  x  y  1
a b c
Check for the ( 2 , 2 , 2 ) atom   2  2  2. 2  1  0
1 1 1 1 1 1 Check   1
2  2  1  0
1

This implies that the atom at (½,½,½) does not sit on this plane.
Let us consider a cubic lattice and important (low index) planes therein). Cubic lattice
These planes are {100}, {110} & {111}. Note: Do NOT pass plane through
origin. Shift it by one unit in x,y,z or a
Z combination.

Y Intercepts → 1 1 
(reciprocal  1 1 0)
Plane → (110)
X Family → {110} → 12 members
For the orange plane
Intercepts → 1   (reciprocal  1 0 0)
 
Members :(110),(101),(011),(1 10),(10 1),(0 1 1),
Plane → (100)
Family → {100} → 6 members 
(110),(1 10),(01 1),(10 1),(0 11),(101)
 
Members :(100),(010),(001),(100),(0 10),(00 1)
Obtained by using the point group symmetry: 4/m 3 2/m

Note: (100) and (100) are identical in terms of Miller indices, as the common factor 1 can be ‘removed’.
Also, the infinite set of (100) planes includes the (100) plane. However, often we retain both these while
writing out the members of the family. Intercepts → 1 1 1
(reciprocal  1 1 1)
The purpose of using Plane → (111)
reciprocal of intercepts and Family → {111} → 8
not intercepts themselves in (Octahedral plane) 
Members : (111),(1 1 1),(11 1),(1 11),(111),
Miller indices becomes clear 
(1 11),(11 1),(1 1 1)
Points about planes and directions
 Typical representation of an unknown/general direction → [uvw].
Corresponding family of directions → <uvw>.
 Unknown/general plane → (hkl).
Corresponding family of planes → {hkl}.
 Double digit indices should be separated by commas or spaces
→ (12,22,3) or (12 22 3).
 In cubic lattices/crystals the (hkl) plane is perpendicular to the [hkl] direction
(specific plane perpendicular to a specific direction)
 [hkl]  (hkl). E.g. [111]  (111). Note: the correct way is to put a ‘bar’.

However, this cannot be generalized to all crystals/lattices (though there are other
specific examples).

 The inter-planar spacing can be computed knowing the Miller indices for the planes (hkl) and
the kind of lattice involved. The formula to be used depends on the kind of lattice and the
formula for cubic lattices is given below.

a
d cubic lattice

Interplanar spacing (d(hkl)) in cubic lattice (& crystals) ( hkl )
h2  k 2  l 2
 What does the ‘symbol’ (111) mean/represent?
The symbol (111) represents Miller indices for an infinite set of parallel planes, with
intercepts 1, 1 & 1 along the three crystallographic axis (unit lattice parameter along these),
which pass through lattice points.
 (111) is the Miller indices for a plane (?) (to reiterate)
 It is usually for an infinite set of parallel planes, with a specific ‘d’ spacing. Hence, (100) plane
is no different from a (–100) plane (i.e. a set consists of planes related by translational
symmetry).
However, the outward normals for these two planes are different.
Sometimes, it is also used for a specific plane.
 Are the members of the family of {100} planes: (100), (010), (001), (–100), (0–10), (00–1)?
 This is a meaningless question without specifying the symmetry of the crystal. The above is
4 2
true if one is referring to a crystal with (say) 3
m m
symmetry. A ‘family’ is a symmetrically
related set (except for translational symmetry– which is anyhow part of the symbol (100)).
  What about the plane passing through the origin?

 The Miller indices refer to a whole set of parallel planes passing through lattice points. This
implies that on of the planes of the infinite set actually passes through the origin.
 As shown below, usually we do not take that particular plane for the determination of Miller
indices; but a parallel one, which does not pass through the origin.

Plane passing through origin

Plane passing through origin
Intercepts →  0  Hence use this plane Intercepts → 0 0 
Plane → (0  0)
Plane → (  0)
We want to avoid infinities in Miller indices
In such cases the plane is translated by a unit distance along the non zero axis/axes
and the Miller
Intercepts → indices
1  are computed Intercepts → 1 1 
Plane → (0 1 0) Plane → (1 1 0)
  In the crystal below what does the (10) plane contain? Using an 2D example of a crystal.
 The ‘Crystal’ plane (10) can be thought of consisting of ‘Lattice’ plane (10) + ‘Motif’ plane (10). I.e.
the (10) crystal plane consists of two atomic planes associated with each lattice plane. The green plane and the
maroon plane.
 This concept can be found not only in the superlattice example give below, but also in other crystals.
E.g. in the CCP Cu crystal (110) crystal plane consists of two atomic planes of Cu.
Note that this is a super-crystal (superlattice) with
two interpenetrating sub-crystals (sublattices) one
with green circle and origin at (0,0) & other with
maroon circle and origin at (½, ½)

Crystal plane = lattice plane (01)

+ motif plane (two atomic rows: one green circles and
one maroon circles)

Crystal plane consists of two atomic

planes (green plane and maroon plane)
  Why do we need 3 indices (say for direction) in 3-dimensions?

 A direction in 3D can be specified by three angles- or the three direction cosines.

 There is one equation connecting the three direction cosines:
Cos   Cos   Cos   1
2 2 2

 This implies that we required only two independent parameters to describe a direction.
Then why do we need three Miller indices?
 The Miller indices prescribe the direction as a vector having a particular length (i.e. this
prescription of length requires the additional index)
 Similarly three Miller indices are used for a plane (hkl) as this has additional information
regarding interplanar spacing. E.g.: a
cubic lattice
d hkl 
h2  k 2  l 2

d100  a

d110  a / 2  a 2 / 2

d111  a / 3  a 3 / 3
 1) What happens to dhkl with increasing hkl?
2) Can planes have spacing less than inter-atomic spacings?
3) What happens to lattice density (no. of lattice points per unit area of plane)?
4) What is meant by the phrase: ‘planes are imaginary’?
1) As h,k,l increases, ‘d’ decreases  we could have planes with infinitesimal spacing.
2) The above implies that inter-planar spacing could be much less than inter-atomic spacing.

3) With increasing indices (h,k,l) the lattice

2D lattice has been considered for easy
visualization. density (or even motif density) decreases.
Hence, planes look like lines! (in 2D lattice density is measured as no. of lattice points per
a a a unit length).
d 34  
d13  25 5  E.g. the (10) plane has 1 lattice point for
10
length ‘a’, while the (11) plane has 1 lattice
point for length a2 (i.e. lower density).
With increasing indices the 4) Since we can draw any number of planes
interplanar spacing decreases
a
through the same lattice (as in the figure),
d10  a clearly the concept of a lattice plane (or
1
for that matter a crystal plane or a lattice
direction) is a ‘mental’ construct
a (imaginary).
a d11 
d12  2
5
1 more view with more planes and unit cell overlaid In an upcoming slide we will see
how a (hkl) plane will divide the
edge, face diagonal and body
diagonal of the unit cell
In this 2D version you can already
note that diagonal is divided into
(h + k) parts

Note
Note the
the axis
axis is
is changing
changing locally!
locally!
  Do planes and directions have to pass through lattice points?

 In the figure below a direction and plane are marked.

 In principle d1 and d1' are identical vectorally- but they are positioned differently w.r.t to the origin.
 Similarly planes p1 and p1' are identical except that they are positioned differently w.r.t to the
coordinate axes.
 In crystallography we usually use d1 and p1 (those which pass through lattice points) and do not
allow any parallel translations (which leads to a situation where these do not pass through lattice
points) .
 We have noted earlier that Miller indices (say for planes) contains information about the interplanar
spacing and hence the convention.

 Sometimes it may seem to us that a given plane

or direction is not passing through lattice points,
if we consider the part within the unit cell only.
E.g. the green planes (13) considered previously.
 In such cases (where actually an intersection
occurs, but not seen) we should extend the planes
Extend to see the
to see
Seems thegreen
like this intersection. intersection
plane is not intersecting a
lattice point
  For a plane (11) what are the units of the intercepts?

 Here we illustrate the concept involved using the (11) plane, but can be applied equally well to
directions as well.
 The (11) plane has intercepts along the crystallographic axis at (1,0) and (0,1).
 In a given lattice/crystal the ‘a’ and ‘b’ axis need not be of equal length (further they may be inclined
to each other). This implies that thought the intercepts are one unit along ‘a’ and ‘b’, their physical
lengths may be very different (as in the figure below).

b (11)

a
 (111)
Further points about (111) planes

Family of {111} planes within the cubic unit cell

Orange
(Light green triangle and light blue triangle are
plane
NOT part (111) planes within the unit cell).
of (111)
The Orange hexagon is parallel to these planes.
set (does
not pass a a 3 Body diagonal length
through
cubic
d (111)   a 
lattice 12  12  12 3 3 3
points- also
see next
slide)

Blue and green The (111) plane(s) {the blue and the orange ones} trisects the body diagonal
planes are (111)
The Orange hexagon Plane cuts the cube into
two polyhedra of equal volumes
 Further points about (111) planes

The central (111) plane (orange colour) is not a ‘space filling’ plane!

Portion of the (111)

plane not included
within the unit cell

Suppose we want to make a calculation of areal density

(area fraction occupied by atoms) of atoms on the (111)
plane- e.g. for a BCC crystal.
Q) Can any of these (111) planes be used for the
calculation?
A) If the calculation is being done within the unit cell then
The portion of the central (111) plane as intersected
the central orange plane cannot be used as it (the hexagonal
by the various unit cells
portion) is not space filling → as shown in the figure on
the right.
Members of a family of planes in cubic crystal/lattice

Index n*
Tetrahedron inscribed inside a
{100} 6 cube with bounding planes
The (110) plane
belonging to the {111}cubic lattice
{110} 12 bisects the face
diagonal
family (subset of the full family)
The (111) plane
{111} 8 trisects the body
diagonal

{210} 24
{211} 24
{221} 24
{310} 24
{311} 24
{320} 24 8 planes of {111}cubic lattice family
{321} 48 forming a regular octahedron

n* is the No. of members in a cubic lattice

Summary of notations A family is also referred to as a symmetrical set
Alternate
Symbol
symbols
[] [uvw] Particular direction
Direction
<> <uvw> [[ ]] Family of directions
() (hkl) Particular plane
Plane
{} {hkl} (( )) Family of planes
.. .xyz. [[ ]] Particular point
Point
:: :xyz: Family of points
Points about (hkl) planes
For a set of translationally equivalent lattice planes will divide:
Entity being divided
Direction Number of parts
(Dimension containing the entity)
Cell edge (1D) a [100] h
b [010] k
c [001] l
This implies that the
Diagonal of cell face (2D) (100) [011] (k + l)
(111) planes will
(010) [101] (l + h) divide the face
(001) [110] (h + k) diagonals into two
Body diagonal (3D) [111] (h + k + l) parts and the body
diagonal into 3 parts.
Some general points
Condition (hkl) will pass through
h even midpoint of ‘a’
face centre (001)
(k + l) even
midpoint of face diagonal (001)
(h + k + l) body centre
even midpoint of body diagonal
 Q&A Write down the members of the family of planes {110} for the tetragonal lattice.
 Let the ‘c’ axis be the unique axis for the tetragonal lattice. The tetragonal lattice has the
highest symmetry possible for the tetragonal system (4/m 2/m 2/m).
 The family of planes can be written as {1 1 0}. The first two indices can be permuted, while
the third one cannot.
 Hence, {1 1 0}  (110), (110), (110), (110).
 As we know (110)  (110)  (110). I.e. all these planes belong to the same set.
Crystallographic Planes
Crystallographic Planes
Crystallographic Planes
 Related to ‘l’ index

Related to ‘k’ index

Miller-Bravais Indices for the Basal Plane

Related to ‘i’ index Related to ‘h’ index

Intercepts →    1
Plane → (0 0 0 1)

Basal
 Intercepts → 1 1 - ½  (h k i l)
Plane → (1 12 0) i = (h + k)

a3

a2
Planes which have  intercept along c-
axis (i.e. vertical planes) are called
Prism planes
a1

The use of the 4 index notation is to bring out the equivalence between crystallographically
equivalent planes and directions (as will become clear in coming slides)
Examples to show the utility of the 4 index notation Obviously (related by 3-fold symmetry), the ‘green’
and ‘blue’ planes belong to the same
family and first three indices have the
same set of numbers (as brought out by the
a3 Miller-Bravais system)

a2

a1

Planes which have  intercept along c-

axis (i.e. vertical planes) are called Prism
Intercepts → 1 –1   Intercepts →  1 –1  planes

Miller (3 index) → (1 1 _ 0 ) Miller (3 index) → (0 1 _ 0)

Miller-Bravais → (1 1 0 0 ) Miller-Bravais → (0 11 0)
Examples to show the utility of the 4 index notation

a3

Intercepts → 1 1 – ½ 
Plane → (1 12 0)

a2

a1
Intercepts → 1 –2 –2 
Plane → (2 11 0 )
 Inclined planes which have finite intercept
along c-axis are called Pyramidal planes

Intercepts → 1 1 - ½ 1
Plane → (1 12 1)

Intercepts → 1   1 1
Plane → (1 01 1)
Hexagonal Crystals
Conversion from the three-index system to the four-index system,

 uvw   uvtw
is accomplished by the following formulas: Several different directions are indicated
in the hexagonal unit cell
1
u   2u   v
3
1
v   2v   u  
3
t   u  v 
w  w
_ _
Eg. the [010] direction becomes [1210].
Crystallographic Planes
 The concept of a family of planes
 A set of planes related by symmetry operations of the lattice or the crystal is called a family
of planes (the translation symmetry operator is excluded→ the translational symmetry is
included in the definition of a plane itself*).
 All the points which one should keep in mind while dealing with directions to get the
members of a family, should also be kept in mind when dealing with planes.
 Members of a family (of planes or directions) of a lattice or crystal, as they are related by
the symmetry of the crystal, are identical (in all respects).
 The family of planes is enclosed in { } brackets,
while an individual member is enclosed in ( ) brackets.

* As the Miller index for a plane line (100) implies a infinite parallel set of planes.
Weiss Zone Law

 If the Miller plane (hkl) contains (or is parallel to) the direction [uvw] then:

h.u  k .v  l.w  0
 This relation is valid for all crystal systems (referring to the standard unit cell).

The red directions lie on the blue planes

(1  1 )  (1  1)  (1  0)  0

(1  1 )  (1  1)  (0  0)  0

1
2 (1  2 )  (1 1)  (1 1)  0
Zone Axis
 The direction common to a set of planes is called the zone axis of those planes.
 E.g. [001] lies on (110), (110), (100), (210) etc.
 If (h1 k1 l1) & (h2 k2 l2) are two planes having a common direction [uvw] then according to
Weiss zone law:
u.h1 + v.k1 + w.l1 = 0 & u.h2 + v.k2 + w.l2 = 0
 This concept is very useful in Selected Area Diffraction Patterns (SADP) in a TEM.

Note: Planes of a zone lie on a great circle in the stereographic projection

Linear Densities
Linear density (LD) is defined as the number of atoms per unit length whose centers lie on
the direction vector for a specific crystallographic direction;

number of atoms centered on direction vector

LD 
length of direction vector

Determine the linear density of the [110] direction for the FCC crystal structure

<110> directions in the FCC lattice have 2 atoms (1/2 x 2 corner atoms + 1 center atom) and
the length is 4R

2atoms 1 2
LD110   
4R 2R a
Planar Densities
Planar density (PD) is taken as the number of atoms per unit area that are centered on a
particular crystallographic plane

number of atoms centered on a plane

PD 
area of plane

For eg. Planar density of {110} planes in the FCC crystal

There are 2 atoms (1/4 x 4 corner atoms + 1/2 x 2 side atoms) in the {110} planes in the FCC
lattice.

2atoms 1 2
PD110  2
 2
 2
8R 2 4 R 2 a
Crystalline and Noncrystalline Materials
Single crystals
• For a crystalline solid, when the periodic and repeated arrangement of atoms is perfect or
extends throughout the entirety of the specimen without interruption, the result is a single
crystal.
• All unit cells interlock in the same way and have the same orientation.
• single crystals have become extremely important in many of our modern technologies, in
particular electronic microcircuits, which employ single crystals of silicon and other
semiconductors
Crystalline and Noncrystalline Materials
Polycrystalline materials
• Most crystalline solids are composed of a collection of many small crystals or grains; such
materials are termed polycrystalline.

Schematic diagrams of the various stages in the solidification of a polycrystalline material;

Small crystallite Growth of the crystallites; Upon completion of The grain structure as
nuclei. the obstruction of some solidification, grains it would appear under
grains that are adjacent having irregular shapes the microscope; dark
to one another. have formed. lines are the grain
boundaries.
Crystalline and Noncrystalline Materials
• Anisotropy
The physical properties of single crystals of some substances depend on the
crystallographic direction in which measurements are taken. This directionality of
properties is termed anisotropy, and it is associated with the variance of atomic or ionic
spacing with crystallographic direction

Eg., the elastic modulus, the electrical conductivity, and the index of refraction may have
different values in the [100] and [111] directions.

• Substances in which measured properties are independent of the direction of

measurement are isotropic.
Crystalline and Noncrystalline Materials
Noncrystalline Solids
lack a systematic and regular arrangement of atoms over relatively large atomic
distances. Sometimes such materials are also called amorphous

Two-dimensional schemes of the structure of silicon dioxide

each silicon ion bonds to three

oxygen ions for both states,
beyond this, the structure is
much more disordered and
irregular for the non-crystalline
structure.
crystalline Noncrystalline
Summary
Fundamental Concepts: Atoms in crystalline solids are positioned in orderly and repeated
patterns that are in contrast to the random and disordered atomic distribution found in
noncrystalline or amorphous materials.

Unit Cells: Crystal structures are specified in terms of parallelepiped unit cells, which are
characterized by geometry and atom positions within.

Metallic Crystal Structures: Most common metals exist in at least one of three relatively
simple crystal structures:
– Face-centered cubic (FCC), which has a cubic unit cell.
– Body-centered cubic (BCC), which also has a cubic unit cell.
– Hexagonal close-packed, which has a unit cell of hexagonal symmetry.

• Unit cell edge length (a) and atomic radius (R) are related (See Equations for face-
centered cubic, and body-centered cubic.
• Two features of a crystal structure are
– Coordination number—the number of nearest-neighbor atoms, and
– Atomic packing factor—the fraction of solid sphere volume in the unit cell.
Summary
Density Computations: The theoretical density of a metal (ρ) is a function of the number of
equivalent atoms per unit cell, the atomic weight, unit cell volume, and Avogadro’s
number.

Polymorphism and Allotropy

Polymorphism is when a specific material can have more than one crystal structure.

Allotropy is polymorphism for elemental solids.

Crystal Systems
The concept of crystal system is used to classify crystal structures on the basis of unit cell
geometry—that is, unit cell edge lengths and interaxial angles. There are seven crystal
systems: cubic, tetragonal, hexagonal, orthorhombic, rhombohedral, (trigonal),
monoclinic, and triclinic.
Summary
Point Coordinates, Crystallographic Directions, Crystallographic Planes

Crystallographic points, directions, and planes are specified in terms of indexing schemes.
The basis for the determination of each index is a coordinate axis system defined by the
unit cell for the particular crystal structure.
– The location of a point within a unit cell is specified using coordinates that are fractional multiples of the cell
edge lengths.
– Directional indices are computed in terms of the vector projection on each of the coordinate axes.
– Planar (or Miller) indices are determined from the reciprocals of axial intercepts.

For hexagonal unit cells, a four-index scheme for both directions and planes is found to be
more convenient.
Summary
Single Crystals, Polycrystalline Materials

Single crystals are materials in which the atomic order extends uninterrupted over the
entirety of the specimen; under some circumstances, single crystals may have flat faces
and regular geometric shapes.

The vast majority of crystalline solids, however, are polycrystalline, being composed of
many small crystals or grains having different crystallographic orientations.

A grain boundary is the boundary region separating two grains, wherein there is some
atomic mismatch.

Anisotropy

Anisotropy is the directionality dependence of properties. For isotropic materials,

properties are independent of the direction of measurement.