Lecture - 3
CRYSTAL STRUCTURE
• Solids consist of atoms or molecules executing thermal
motion about an equilibrium position fixed at a point in
space.
• Solids can take the form of crystalline ,
Polycrystalline , or amorphous materials.
• Solids (at a given temperature, pressure, and volume)
have stronger bonds between molecules and atoms
than liquids.
• Solids require more energy to break the bonds.
• Crystalline Solid is the solid form of a substance in which the
atoms or molecules are arranged in a definite, repeating pattern in
three dimension.
• Single crystals, ideally have a high degree of order, or regular
geometric periodicity.
Single crystal 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.
Examples: quartz, salt, diamond
Single Crystal
Amorphous Solid
Single Crystal
Polycrystal is a material made up of an aggregate of
many small single crystals (also called crystallites or
grains).
Polycrystalline material have a high degree of order
over many atomic or molecular dimensions.
Polycrystalline
1
0
These ordered regions, or single crytal
regions, vary in size and orientate one another.
These regions are called as grains (domain)
and are separated from one another by grain
boundaries. The atomic order can vary from
one domain to the next.
The grains are usually 100 nm - 100 microns in
diameter. Polycrystals with grains that are <10 nm in
diameter are called nanocrystalline
Crystal Lattice
• An infinite array of points in space
y
• Each point has
B C
identical surroundings b α
D E
to all others. O a A x
• Arrays are arranged exactly in a periodic manner
13
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
Crystal Lattice
Bravais Lattice (BL) Non-Bravais Lattice (non-BL)
Atoms can be of different kind
All atoms are of the same kind
Some lattice points are not
All lattice points are equivalent
equivalent
A combination of two or more BL
Crystal Structure
1
Translational Lattice Vectors – 2D
A space lattice is a set of points such
P
that a translation from any point in the
lattice by a vector;
Rn = n1 a + n2 b
locates an exactly equivalent point, i.e.
a point with the same environment as
P.
This is translational symmetry.
The vectors a, b are known as lattice
Point D(n1, n2) = (0,2)
vectors and (n1, n2) is a pair of integers
whose values depend on the lattice
Point F (n1, n2) = (0,-1) point.
An ideal three dimensional crystal is described by 3 fundamental
translation vectors a, b and c. If there is a lattice point represented by the
position vector R, there is then also a lattice point represented by the
position vector where u, v and w are arbitrary integers.
R=ua+vb+wc
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• The smallest component of the crystal (group of
atoms, ions or molecules), which when stacked
together with translational repetition reproduces the
whole crystal.
S S
b S
S S S
a
S S S S
S S S S S
12
2D Unit Cell example -(NaCl)
We define lattice points ; these are points with identical environments
Choice of origin is arbitrary - lattice points need not be
atoms - but unit cell size should always be the same.
This is also a unit cell -
it doesn’t matter if you start from Na or Cl
15
This is NOT a unit cell even though they are all the same
- empty space is not allowed!
16
Unit Cell in 3D
17
Unit Cell in 3D
18
Lecture - 4
CRYSTAL STRUCTURE –Part 2
Unit cell contents
Counting the number of atoms within the unit cell
Atoms Shared Between: Each atom counts:
corner 8 cells 1/8
face centre 2 cells 1/2
body centre 1 cell 1
lattice type cell contents
P 1 [=8 x 1/8]
I 2 [=(8 x 1/8) + (1 x 1)]
F 4 [=(8 x 1/8) + (6 x 1/2)]
Unit Cell
• The unit cell and, consequently, the entire
lattice, is determined by the six lattice
constants:
• a, b, c, α, β and γ.
• Only 1/8 of each lattice point in a unit cell
can actually be assigned to that cell.
• Each unit cell in the figure can be
associated with 8 x 1/8 = 1 lattice point.
TYPICAL CRYSTAL STRUCTURES
In 3D dimension:
1 4 B R AVA I S L AT T I C E S &
7 C R Y S TA L S Y S T E M
• There are only seven different shapes of unit cell which
can be stacked together to completely fill all space (in 3
dimensions) without overlapping.
• This gives the seven crystal systems, in which all
crystal structures can be classified.
Seven Crystal System:
ﻣﻛﻌب.1
1. Cubic Crystal System (SC, BCC,FCC)
ﺳداﺳﻲ اﻟﺷﻛل.2
2. Hexagonal Crystal System (S)
ﺛﻼﺛﻲ اﻟﻣﯾل.3
3. Triclinic Crystal System (S)
أﺣﺎدي اﻟﻣﯾل.4
4. Monoclinic Crystal System (S, Base-C)
ﻣﻌﯾﻧﻲ ﻣﺗﻌﺎﻣد اﻟﻣﺣﺎور.5
5. Orthorhombic Crystal System (S, Base-C, BC, FC) رﺑﺎﻋﻲ اﻟزواﯾﺎ.6
6. Tetragonal Crystal System (S, BC) ( ﺛﻼﺛﻲ اﻟزواﯾﺎ )ﻣﻧﺷور ﺳداﺳﻲ ﻣﻧﺗظم.7
7. Trigonal (Rhombohedral) Crystal System (S)
Seven Crystal System:
1. Cubic Crystal System (SC,
BCC,FCC)
2. Tetragonal Crystal System
(S, BC)
3. Orthorhombic Crystal System
(S, Base-C, BC, FC)
4. Hexagonal Crystal System
(S)
5. Monoclinic Crystal System
(S, Base-C)
6. Triclinic Crystal System (S)
7. Trigonal (Rhombohedral)
Crystal System (S)
• Coordinatıon Number (CN) : The Bravais lattice points closest
to a given point are the nearest neighbours.
• Because the Bravais lattice is periodic, all points have
the same number of nearest neighbours or
coordination number. It is a property of the lattice.
A simple cubic has coordination number, 6
A body-centered cubic lattice, 8
A face-centered cubic lattice,12
• Atomic Packing Factor (APF) is defined as the volume of
atoms within the unit cell divided by the volume of the unit
cell.
a- Simple Cubic (SC)
Simple Cubic has one lattice point so its primitive cell.
In the unit cell on the left, the atoms at the corners are cut because
only a portion (in this case 1/8) belongs to that cell. The rest of the
atom belongs to neighboring cells.
Coordinatination number of simple cubic is 6.
b
c
a
Atomic Radius for SC:
• It is half the distance between any two
nearest neighbors in the given crystal
structure.
• It is expressed in terms of cube edge a
a = 2r, r = a/2
Atomic Radius, r = 0.5a a
Atomic Packing Factor of SC:
• APF = 0.52
• That means that the percentage of packing is 52%
• Thus, 52% of the volume of the simple cubic unit cell is occupied by atoms
and the remaining 48% volume of unit cell is vacant or void space.
b-Body Centered Cubic (BCC)
BCC structure has 8 corner atoms and 1 body
center atom.
Each corner atom is shared by 8 unit cells.
The center atom is not shared by any of the unit
cells.
So the Number of atoms per unit cell:
n = (1/8)x8 +1 = 2
b c
a
b-Body Centered Cubic (BCC)
BCC has two lattice points so BCC
is a non-primitive cell.
BCC has eight nearest neighbors.
Each atom is in contact with its
neighbors only along the body-
diagonal directions.
Hence, the coordination no.
for BCC unit cell is 8
Many metals (Fe,Li,Na..etc), b c
including the alkalis and several
transition elements choose the a
BCC structure.
Atomic Radius for BCC unit cell
r =a x (3)1/2/4 r = (0.43) a
Atomic Packing Factor of BCC
(0,433a)
2
The percentage of packing for BCC structure is 68%
Thus , 68% of the volume of body centered cubic cell
is occupied by atoms and the remaining 32% of the
volume is vacant or void space
c- Face Centered Cubic (FCC)
FCC structure has 8 corner
atoms and 6 face centre atoms.
Each corner atom is shared by 8
unit cells.
Each face centered atom is
shared by 2 unit cells.
So the
Number of atoms present in unit
cell is
n = (1/8 x8) + (1/2 x 6)
=1+3
=4
• Co ordination Number
• The corner atom in its own plane touches 4 face centred
atoms.
• In the plane just above, the corner atom has another 4
face centered atoms as its nearest neighbours
• Similarly, in the plane just below it has 4 more face
centered atoms as its nearest neighbours
• Therefore the no. of nearest neighbours are :
4+4+4 = 12
Many of common metals (Cu,Ni,Pb..etc) crystallize in FCC
structure.
Atomic Radius for FCC
r = a x (2)1/2/4
Atomic Packing Factor of FCC
FCC
0.74
4 (0.353a)
