Crystal Structures

and
Crystallography

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 Classification of matter

Matter

LIQUIDS
GASES SOLIDS

Amorphous Quasicrystals Crystals

Single
Polycrystals
Crystals
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 Crystalline Solids Amorphous Solids
• Regular arrangement of • No regular arrangement
atoms along the 3 D. of atoms.
• Have long range order. • Have short range order.
• Sharp melting point. • No sharp melting point.
• They are anisotropic. • They are isotropic.
• They are most stable. • They are most unstable.
• They have a regular cut. • They have irregular cut.
• They show all • They don’t show all
characteristic of solids. characteristics of solids.
• Ex: Diamond, NaCl, KCl, • Ex: Glasses, Plastic,
Copper, Iron, etc. Rubber.

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 Basic Definitions
a

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 Crystal Lattice: An infinite array of imaginary points in
which every point has environment as that of the other and
hence one lattice point cannot be distinguished from the other.
 Space lattice: An infinite array of points in a three
dimensional space such that every point has identical
surrounding.

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 Basis
A group of atoms (or ions) which when attached
to every lattice points produces the crystal structure.

Basis

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Lattice + Basis = Crystal structure 9
 Crystal Structure
 Crystal structure can be obtained by attaching atoms, groups of
atoms or molecules which are called basis (motif) to the lattice
sides of the lattice point.
Crystal Structure = Crystal Lattice + Basis

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 A two-dimensional Bravais lattice with different
choices for the basis

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 Unit Cell: The building block of the crystal which when translated
along the three axes gives the actual crystal structure.
It should occupy a minimum volume.
Smallest repeatable unit in a point lattice
Choice of the Unit Cell is not unique

S S

S S S
b
S

a S S S S

S
S S S S S

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 The choice of unit cell
is not unique.

b S S

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 Types of Lattice

Simple Lattice or Primitive Lattice (P)

Base Centered Lattice ©

Body Centered Lattice (I)

Face Centered Lattice (F)

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 Type Description Symbol
Primitive Lattice points on corners only. P
Body-Centered Lattice points on corners as well I
as in the center of the unit cell
body.
Face Centered Lattice points on corners as well F
as in the centers of all faces.
Base Centered Lattice points on corners as well C
as on the center of top &
bottom face.

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Simple Cubic (SC) Lattice + Sphere Motif

Unit cell of the SC lattice Simple Cubic Crystal

 If these spheres were ‘spherical atoms’ then the atoms would be touching each other
 The kind of model shown is known as the ‘Ball and Stick Model’
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 Body Centered Cubic (BCC) Lattice + Sphere Motif

Atom at (½, ½, ½)

Body Centred Cubic Crystal

Atom at (0, 0, 0)
=
Unit cell of the BCC lattice

Space filling
model

So when one usually talks about a BCC crystal what is meant is a BCC
Central atom is coloured differently for better visibility lattice decorated with a mono-atomic motif
Note: BCC is a lattice and not a
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 Base Centered Lattice (C )

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 All atoms are identical- coloured differently for better visibility

Face Centered Cubic (FCC) Lattice + Sphere Motif

Cubic Close Packed Crystal

(Sometimes casually called the FCC crystal)

=
Unit cell of the FCC lattice

Space filling
model

So when one talks about a FCC crystal what is meant is a FCC lattice
decorated with a mono-atomic motif

Note: FCC is a lattice and not a Video:

Video:FCC
FCCcrystal
crystal
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Face Centered Cubic (FCC) Lattice + Two Ion Motif

NaCl Crystal

Note: This is not a close packed

Has a packing fraction of ~0.67 (using rigid sphere model)
crystal
Note that the two ion motif leads to crystal which is not close packed  unlike the mono-
atomic (sphere) packing case
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 Face Centred Cubic (FCC) Lattice + Two Carbon atom Motif
(0,0,0) & (¼, ¼, ¼)

Diamond Cubic Crystal

=

It requires a little thinking to convince yourself that

the two atom motif actually sits at all lattice points!
Note: This is not a close packed Video:
Video:Diamond
Diamondcrystal
crystal
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There are no close packed directions in this crystal either!
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 Primitive unit cells: Contains only one lattice point, in
the unit cell. Example Simple Cubic (SC)

 Non-primitive unit cells: Contains more than one

lattice point in the unit cell. Example Body Centered Cubic
(BCC), Face Centered Cubic (FCC)

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 1

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 Crystallographic axes & Lattice
parameters

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 Crystal systems

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 Crystal systems
Cubic

Tetragonal

Orthorhombic

Monoclinic

Triclinic

Hexagonal

Trigonal (Rhombohedral)

http://www.materials.ac.uk/elearning/matter/Crystallography/3dCrystallograp
hy/7crystalsystems.html

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 Crystal systems
1. Cubic Crystal System

Ex: Polonium

Other Cubic :Diamond,

ZnS,Au,Cu,Ag,NaCl

a=b=c  =  =  = 90°
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2.Tetragonal system

Ex: White Tin, SnO4,TiO2

a=bc  =  =  = 90°
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3. Orthorhombic system

Ex: Mg2SiO4, SnSO4,

KCl Mg Cl2.H2O

abc  =  =  = 90°
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4. Monoclinic system


Ex: Na3AlF6,BaVO4
Na2B4O7.10 H2O

abc  =  = 90°,   90°

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5. Triclinic system

Ex: K2Cr2O7,H3BO3 


abc       90°
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6. Rhombohedral (Trigonal) system

Ex: Calcite(CaCO3),
As, Sb, Bi ,

a=b=c  =  =   90°
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 7. Hexagonal system

Ex: Quartz (SiO2), AgI,

ZnO

 =  = 90°,  = 120°
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 Crystals Systems

Nacl &CaF2 NiSO4 &SnO2 KNO3,BaSO4 Quartz,Calcite

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Na2SO4,FeSO4 CuSO4,K2Cr2O7 SiO2,AgI
 Summary: Fourteen Bravais
Lattices in Three Dimensions

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Fourteen Bravais Lattices …

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 14 Bravais lattices
Body Face Base
Primitive
Crystal system centered centered centered
(P)
(I) (F) (C)

Cubic    
Tetragonal    
Orthorhombic    
Monoclinic    
Triclinic    
Rhombohedral    
Hexagonal    
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 Parameters Determining the
Crystal Structure of the
Materials

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 CHARACTERISTICS OF UNIT CELL

 Number of atoms per unit cell or effective number of atoms:

The total number of atoms present in a unit cell.
Ex: SC: 1, BCC: 2, FCC: 3

 Nearest Neighboring distance (2r):

The distance between the ceters of two nearest neighboring atoms is
called nearest neighboring distance.
It is expressed in terms of the length of the edge of the unit cell and it is given by 2r

 Atomic Radius: It is the half the distance between any two nearest
neighbor atoms which have direct contact with each other.
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 Coordination Number (N): It is the number of
nearest neighboring and equidistance atoms to a
particular atom.

 Atomic Packing Factor or Packing Fraction : It

is the ratio of volume occupied by the atoms in a unit cell
to the total volume of the unit cell.

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 Body Centred Cubic
Simple Cubic FCC
Or
Primitive

Face Centred Cubic

FCC

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 Simple Cubic or Primitive

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• It is a primitive cell.
• Atoms are present only at the corners of the unit cell.
• Corner atoms touch along the lattice constant.
• Number of atoms per unit cell is Z = 1.
• Atomic radius a = 2r or r = a/2.
• Coordination Number or Number of nearest
neighboring atoms N = 6.
• Packing Factor 52%.
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 1
n  8  1
8

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 Body Centered Cubic (BCC)

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• It is a non primitive cell.
• Atoms are present not only at the corners of the unit
cell but also an atom at the center of the unit cell.
• Corner atoms touch along the body diagonal.
• Number of atoms per unit cell is Z = 2.
• Atomic radius 𝑎 √3
𝑟 =
4
• Coordination Number or Number of nearest
neighboring atoms N = 8.
• Packing Factor 68%.

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  1
n   8    1  2
 8

CN = 8

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 Face Centered Cubic (FCC)

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• It is a non primitive cell.
• Atoms are present not only at the corners of the unit
cell but at the center of each face.
• Corner atoms touch along the face diagonal.
• Number of atoms per unit cell is Z = 4.
• 𝑎 √2
Atomic
𝑟 radius
=
4
• Coordination Number or Number of nearest
neighboring atoms N = 12.
• Packing Factor 74%.

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  1  1
n  8    6   4
 8  2

CN = 12

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 Number of Lattice points

Primitive Body centered Face centered Base centered

(P) (I) (F) (C)

1  1
n   8    1  2 n   8     6    4 n   8     2    2
1 1 1 1
n  8  1
8  8  8  2  8  2

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 Co-Ordination Number
SC BCC

CN = 8
CN = 6

FCC

CN = 12

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 Relation between atomic radius and edge length

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 SC FCC
BCC

r  3a / 4 Z=2 r a/2 2 Z=4

r a/2 Z=1
4 3 4 3 4 3
r r r
PF = 3 3  Z PF = 3 3  Z PF = 3 3  Z
a a a

PF = 52% PF = 68% PF = 74%

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 COMPARISON OF CRYSTAL STRUCTURES

Crystal structure coordination # packing factor close

packed directions

• Simple Cubic (SC) 6 0.52

cube edges

• Body Centered Cubic (BCC) 8 0.68

body diagonal

• Face Centered Cubic (FCC) 12 0.74

face diagonal

• Hexagonal Close Pack (HCP) 12 0.74

hexagonal side
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 It is a non primitive cell.
1. It is a primitive cell.

2. Atoms are present only at

Atoms are present not only at
It is a non primitive cell.
the corners of the unit cell. the corners of the unit cell but
Atoms are present not only at the
also an atom at the center of
3. Corner atoms touch along corners of the unit cell but at the
the unit cell. center of each face.
the lattice constant.
Corner atoms touch along the face
4. Number of atoms per unit Corner atoms touch along the diagonal.
body diagonal.
cell is Z = 1. Number of atoms per unit cell is Z
= 4.
5. Atomic radius a = 2r or r =
Number of atoms per unit cell
a/2. is Z = 2. 𝑟 =
Atomic radius 𝑎 √
4
Coordination Number or Number
6. Coordination Number or of nearest neighboring atoms N =

𝑟 =
Atomic radius 𝑎 √ 12. 3
Number of nearest
4Packing Factor 74%.
neighboring atoms N = 6. Coordination Number or
Number of nearest neighboring
7. Packing Factor 52%.
atoms N = 8.

Packing Factor 68%.

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 Density Computations
• Relation between lattice constant and Density
Lattice constant is “a”
Number of atoms per unit cell is “n”
Atomic weight of the substance is “A”
Density of the unit cell “ρ”
The Avagadro’s Number = N = 6.023 x 1023 atoms/ mole
𝐴
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑒𝑎𝑐h 𝑀𝑜𝑙𝑒𝑐𝑢𝑙𝑒=
𝑁
𝐴
𝑀𝑎𝑠𝑠 𝑜𝑓 n 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 = 𝑛
𝑁
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝜌=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑈𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝑛𝐴 𝑛𝐴
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑡h𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 𝜌 = =
𝑁𝑎
3
𝑁 𝑉𝑐
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 Problems

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If the atomic radius of lead (fcc) is 0.175 nm,
calculate the volume of its unit cell in cubic
meters

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Molybdenum has a BCC crystal structure, an atomic
radius of 0.1363 nm, and an atomic weight of 95.94
g/mol. Compute its density.

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Calculate the radius of a palladium atom, given that
Pd has an FCC crystal structure, a density of 12.0
g/cm3, and an atomic weight of 106.4 g/mol.

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Calculate the radius of a tantalum atom, given that Ta has
a BCC crystal structure, a density of 16.6 g/cm3, and an
atomic weight of 180.9 g/mol.

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Some hypothetical metal has the simple cubic crystal
structure shown in Figure. If its atomic weight is 74.5
g/mol and the atomic radius is 0.145 nm, compute its
density

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Determine the atomic radius of Mo. Given that
atomic weight is 95.94 g/mol and density of Mo
is 10.2 g/cm3.

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A metal is found to have BCC structure, a
lattice constant of 3.31 Angstroms, and a
density of 16.6 g/cm3. Determine the atomic
weight of the element

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 Crystallographic
Points, Directions
and Planes
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 Crystal planes
Crystal planes are defined as some imaginary planes inside a crystal in which large
concentration of atoms are present. Inside the crystal, there exists certain directions along
which large concentration of atoms exists. These directions are called crystal directions.
Figure 1.18 shows a two-dimensional lattice with different orientations of crystal planes.

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 Miller Indices
• The crystal lattice may be regarded as made up
of infinite set of parallel equidistant planes
passing through the lattice points which are
known as Lattice planes.

• In simple terms, the planes passing through

lattice points are called lattice planes.

• For a given lattice, the lattice planes can be

chosen in a different number of ways.

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 Miller Indices
Different lattice planes in a crystal

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 The orientation of planes or faces in a crystal can
be described in terms of their intercepts on the three
axes.
 Miller introduced a system to designate a plane in
a crystal.
 He introduced a set of three numbers to specify a
plane in a crystal.
 This set of three numbers is known as ‘Miller
Indices’ of the concerned plane.
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MILLER INDICES FOR CRYSTALLOGRAPHIC PLANES

Miller Indices are the reciprocals of the intercepts (with fractions

cleared) made by the plane with the crystallographic x, y, z axes which
are reduced to smallest whole numbers.

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 SUMMARY OF MEANINGS OF PARENTHESES
(q,r,s) represents a point – note the exclusive use of
commas
[hkl] represents a direction
<hkl> represents a family of directions

(hkl) represents a plane

{hkl} represents a family of planes

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 Procedure for finding Miller Indices
1. Determine the coordinates of the intercepts made
by the plane along the three crystallographic axis.
2. Divide the intercepts with unit cell cube edge
(lattice constants).
3. Determine the reciprocals of these number.
4. Reduce these reciprocals into the smallest whole
numbers by multiplying each with their L.C.M to
get the smallest whole number.
5. Enclose the smallest whole numbers in ( )
 This give the Miller indices (h k l) of the plane.
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 Important Features
of Miller Indices

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• If a plane is parallel to any of the coordinate
axis, then its intercepts will be infinity.
• A plane passing through origin has non zero
intercepts.
• All the parallel equidistant planes have the
same Miller Indices.
• Miller Indices define a set of equidistant parallel
planes.
• If the Miller Indices of two planes have the same
ratio then the planes are parallel to each other.
• If (hkl) are the Miller Indices of a plane, then the
plane
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cuts the axis into h, k and l equal parts.
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 Crystal planes

http://www.doitpoms.ac.uk/tlplib/miller_indices/lattice_draw.php

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 Crystallographic
z Planes
z
c
c

y
a b y
a b
x z
x
c


 y

a b
x

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 Inter-planar spacing in
Crystals

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107
 Inter-planar spacing in different crystal systems

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108
 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)

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 Locate the points having coordinates 1/4, 1, 1/2

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 Locate the points having coordinates 1/4, 1, 1/2

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 Directions and Planes
• Used to understand the concept of
crystallography.
• In crystal there exists directions and planes
which contain large concentration of atoms.
• A crystallographic direction is defined as a line
between two points, or a vector.

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 Determine the indices

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Reciprocal lattice:
It is easy to think a set of parallel crystal planes in
terms of their normals, since as the planes are two
dimensional, their normals will be one dimensional in
nature.

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Geometrical construction of reciprocal lattice:
1. Fix up some point in the direct lattice as a common
origin.
2. From this common origin draw normals to each and
every set of parallel planes in the direct lattice.
3. Fix the length of each normal equal to the reciprocal
of the inter-planar spacing (1/dhkl) of the set of parallel

planes (h k l) it represents.
4. Put a point at the end of each normal.

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 Q3: Determine the miller indices for the planes shown in
the following unit cell

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Q4: What are Miller Indices? Draw (111) and (110) planes in a cubic
lattice.

Q5: Sketch the following planes of a cubic unit cell (001), (120), (211)

Q6: Obtain the Miller indices of a plane which intercepts at a, b/2 and 3c in
simple cubic unit cell. Draw a neat diagram showing the plane

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 Problems on inter-planar spacing

1. Explain how the X-ray diffraction can be employed to determine the crystal
structure. Give the ratio of inter-planar distances of (100), (110) and (111)
planes for a simple cubic structure.

2. The distance between (110) planes in a body centered cubic structure is

0.203 nm. What is the size of the unit cell? What is the radius of the atom?

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 Problem on Bragg’s law
1. A beam of X-rays of wavelength 0.071 nm is diffracted by (110) plane of rock salt with
lattice constant of 0.28 nm. Find the glancing angle for the second-order diffraction.
2. A beam of X-rays is incident on a NaCl crystal with lattice plane spacing 0.282 nm. Calculate
the wavelength of X-rays if the first-order Bragg reflection takes place at a glancing angle of
8 °35′. Also calculate the maximum order of diffraction possible.
3. Monochromatic X-rays of λ = 1.5 A.U are incident on a crystal face having an inter-planar
spacing of 1.6 A.U. Find the highest order for which Bragg’s reflection maximum can be
seen.
4. For BCC iron, compute (a) the inter-planar spacing, and (b) the diffraction angle for the (220)
set of planes. The lattice parameter for Fe is 0.2866 nm. Also, assume that monochromatic
radiation having a wavelength of 0.1790 nm is used, and the order of reflection is 1.
5. The metal niobium has a BCC crystal structure. If the angle of diffraction for the (211) set of
planes occurs at 75.99o (first order reflection) when monochromatic X-radiation having a
wavelength 0.1659 nm is used. Compute (a) the inter-planar spacing for this set of planes and
(b) the atomic radius for the niobium atom.

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 Problems
1. Chromium has BCC structure. Its atomic radius is 0.1249 nm . Calculate the
free volume / unit cell.
2. Lithium crystallizes in BCC structure. Calculate the lattice constant, given
that the atomic weight and density for lithium are 6.94 and 530 kg/m 3
respectively.
3. Iron crystallizes in BCC structure. Calculate the lattice constant, given that
the atomic weight and density of iron are 55.85 and 7860 kg/m 3
respectively.
4. If the edge of the unit cell of a cube in the diamond structure is 0.356 nm,
calculate the number of atoms/m3.
5. A metal in BCC structure has a lattice constant 3.5A o. Calculate the number
of atoms per sq. mm area in the (200) plane.
6. Germanium crystallizes in diamond (from) structures with 8 atoms per unit
cell. If the lattice constant is 5.62 Ao, calculate its density.

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