Crystalline Solid State

The Crystalline Solid State
Chapter 7
Monday, October 19, 2015

Types of Solids
Amorphous Solids are solids that lack a regular three-dimensional
arrangement of atoms. They lack long-range structural order.
Crystalline solids have atoms/ions/molecules arranged in regular,

repeating patterns. They possess long-range periodicity.
• minimizes free energy of the atoms/ions/molecules
• the unit cell is the smallest repeating structural unit that has the full crystal
symmetry
SiO2 glass
SiO2 crystal (α-quartz)

Types of Solids
Amorphous Solids are solids that lack a regular three-dimensional
arrangement of atoms. They lack long-range structural order.
Crystalline solids have atoms/ions/molecules arranged in regular,

repeating patterns. They possess long-range periodicity.
• minimizes free energy of the atoms/ions/molecules
• the unit cell is the smallest repeating structural unit that has the full crystal
symmetry
Types of crystalline solids:

• Ionic Crystals
• Covalent or Network Crystals
• Molecular Crystals
• Metallic Crystals
• Group VIII Crystals (frozen Noble Gases)
The 7 Crystal Systems
All 3D crystals belong to one of 7 crystal systems.
Cubic
The 14 Bravais Lattices
All 3D crystals belong to one of 14 Bravais lattices.
Bravais lattice: An infinite array of points with an arrangement and
orientation that looks exactly the same from any lattice point.
Types of Cubic Lattices
There are three cubic Bravais lattices:
b a
Simple Cubic Body-Centered Cubic Face-Centered Cubic
• The lengths of the unit cell edges (a,b,c) are called lattice constants.
• For cubic crystals, a = b = c, so there is only one lattice constant (a).
Contents of a Unit Cell
An important feature of the unit cell is the number of lattice points it
contains. Atoms/ions/molecules are often located at lattice points.
1
8  atoms  8 
+ occupancy
1 atom  1
occupancy
22 atoms
atoms in
in aa
Body-Centered
Cubic cell
1 1
8  atoms  8  8  atoms  8 
occupancy occupancy
1 atom in a 1
Simple Cubic cell + 6  atoms  2  occupancy
44 atoms
atoms in
in aa
Face-Centered
Cubic cell
An important feature of the unit cell is the number of lattice points it
contains. Atoms/ions/molecules are often located at lattice points.
Atoms Shared Between: Each atom counts:

corner 8 cells 1/8
face center 2 cells 1/2
body center 1 cell 1
edge center 4 cells 1/4
8 × 1/8 = 1 8 × 1/8 8 × 1/8 8 × 1/8

+1×1=2 + 2 × 1/2 = 2 + 4 × 1/2 = 4
Consider
sodium chloride:
rock salt
(not Bravais)
Cl at corners: (8  1/8) = 1 Cl at face centres (6  1/2) = 3

Na at edge centers (12  1/4) = 3 Na at body centre = 1
Unit cell contents: 4(Na+Cl-)

Types of Cubic Cells
Different cubic cells result from different packing of atoms.
r
r r
Simple Cubic Body-Centered Cubic Face-Centered Cubic
Atoms per Coordination

Unit Cell Lattice Constant Packing Fraction
cell Number
Simple Cubic 1 6 2r 52%
4r
Body-Centered Cubic 2 8 68%
3
Face-Centered Cubic 4 12 2r 2 74%

Close-Packed Structures
The Hexagonal Close-Packed Structure
An HCP crystal is a close-packed structure with the stacking
sequence …ABABAB…
To construct:
1st layer: 2D HCP array (layer A)
2nd layer: HCP layer with each sphere placed in alternate interstices in 1st layer (B)
3rd layer: HCP layer positioned directly above 1st layer (repeat of layer A)
…ABAB…
A B
B A
HCP is two interpenetrating simple hexagonal

lattices displaced by a1/3 + a2/3 + a3/2
The Cubic Close-Packed Structure
A CCP crystal is a close-packed structure with the stacking
sequence …ABCABC…
To construct:
1st layer: 2D HCP array (layer A)
2nd layer: HCP layer with each sphere placed in alternate interstices in 1st
layer (B)
3rd layer: HCP layer placed in the other set of interstitial depressions (squares, C)
4th layer: repeats the 1st layer (A)
…ABCABC…
stacking
of HCP layers
along
A body diagonal
B C
It turns out that the CCP structure is

just the FCC Bravais lattice!
Close-Packed Structures
Most common are HCP and CCP, but an infinite number of stacking
sequences are possible.
silicon carbide
Example: silicon carbide has over 250 polytypes

e.g., 6H-SiC stacking sequence …ABCACB…
Metallic Solids
• Most metals crystallize in ccp, hcp, or bcc structures
• Metallic bonding is stronger than London dispersion forces, but
weaker than covalent bonding
Solid M / g mol–1 Melting Point / °C
Kr 83.80 –157
Cu 63.55 1083
C (diamond) 12.01 3500

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The Crystalline Solid State

Monday, October 19, 2015

Crystalline solids have atoms/ions/molecules arranged in regular,

SiO2 crystal (α-quartz)

Crystalline solids have atoms/ions/molecules arranged in regular,

Types of crystalline solids:

Atoms Shared Between: Each atom counts:

8 × 1/8 = 1 8 × 1/8 8 × 1/8 8 × 1/8

Cl at corners: (8  1/8) = 1 Cl at face centres (6  1/2) = 3

Unit cell contents: 4(Na+Cl-)

Simple Cubic Body-Centered Cubic Face-Centered Cubic

Atoms per Coordination

Simple Cubic 1 6 2r 52%

Face-Centered Cubic 4 12 2r 2 74%

HCP is two interpenetrating simple hexagonal

It turns out that the CCP structure is

Example: silicon carbide has over 250 polytypes

C (diamond) 12.01 3500

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