Crystal Structure Continued!

NOTE!!
Again, much discussion & many figures in
what follows was constructed from lectures
posted on the web by Prof. Beire GNL
(Turkey). She has done an excellent job
covering many details of crystallography &
she illustrates with many very nice pictures
of lattice structures. Her lectures are posted Here:
http://www1.gantep.edu.tr/~bgonul/dersnotlari/.
Her homepage is Here:
http://www1.gantep.edu.tr/~bgonul/.

The Wigner-Seitz Method

to Construct a Primitive Cell
A simple, geometric method to construct a Primitive Cell is
called the Wigner-Seitz Method. The procedure is:

1. Choose a starting lattice point.

2. Draw lines to connect that point
to its nearest neighbors.
3. At the mid-point & normal to
these lines, draw new lines.

4. The volume enclosed is called

a Wigner-Seitz cell.
Illustration for the 2 dimensional
parallelogram lattice.

3 Dimensional Wigner-Seitz Cells

Face Centered Cubic

Wigner-Seitz Cell

Body Centered Cubic

Wigner-Seitz Cell
3

Lattice Sites in a Cubic Unit Cell

The standard notation is shown in the figure.

It is understood that all distances are in units of
the cubic lattice constant a, which is the length
of a cube edge for the material of interest.

Directions in a Crystal: Standard Notation

See Figure Choose an origin, O. This

choice is arbitrary, because every lattice
point has identical symmetry. Then,
consider the lattice vector joining O to
any point in space, say point T in the figure.
As weve seen, this vector can be written

T = n1a1 + n2a2 + n3a3

[111] direction

In order to distinguish a Lattice Direction from a

Lattice Point, (n1n2n3), the 3 integers are enclosed in
square brackets [ ...] instead of parentheses (...), which
are reserved to indicate a Lattice Point. In direction
[n1n2n3], n1n2n3 are the smallest integers possible for
the relative ratios.

Examples

210

X = 1, Y = , Z = 0
[1 0]
[2 1 0]

X= ,Y=,Z=1
[ 1]
[1 1 2]

Negative Directions
When we write the direction
[n1n2n3] depending on the
origin, negative directions
are written as

Z direction

R = n1a1 + n2a2 + n3a3

To specify the direction, the
smallest possible integers (origin) O
must be used. - Y direction

- X direction
Y direction
[n1n2 n3 ]

X direction
- Z direction

Examples of Crystal Directions

X = 1, Y = 0, Z = 0
[1 0 0]

X = -1, Y = -1, Z = 0
[110]

Examples
A vector can be moved to the origin.

X = -1, Y = 1, Z = -1/6
[-1 1 -1/6]
[6 6 1]

Crystal Planes
Within a crystal lattice it is possible to identify
sets of equally spaced parallel planes.

These are called lattice planes.

In the figure, the density of lattice points on each
plane of a set is the same & all lattice points are
contained on each set of planes.
The set of
planes for a
2D lattice.

b
a

Miller Indices
Miller Indices are a symbolic vector representation for
the orientation of an atomic plane in a crystal lattice &
are defined as the reciprocals of the fractional intercepts
which the plane makes with the crystallographic axes.
To find the Miller indices of a plane, take the following steps:

1. Determine the intercepts of the plane along

each of the three crystallographic directions.
2. Take the reciprocals of the intercepts.
3. If fractions result, multiply each by the
denominator of the smallest fraction.
11

Example 1

Axis

Intercept
points

Reciprocals

Smallest
Ratio

(1,0,0)

1/1 1/ 1/
1

Miller ndices

0
(100)

12

Example 2

(0,1,0)
(1,0,0)

Axis

Intercept
points

Reciprocals

1/1

Smallest
Ratio

1/ 1 1/

Miller ndices

0
(110)
13

Example 3

(0,0,1)

(0,1,0)

(1,0,0)

Axis

Intercept
points

Reciprocals

1/1

1/ 1

1/ 1

Smallest
Ratio

Miller ndices

(111)
14

Example 4

Axis

Intercept
points

1/2

Reciprocals
(0,1,0)
(1/2, 0, 0)

Smallest
Ratio

1/() 1/ 1 1/
2

Miller ndices

(210)
15

Example 5

Axis

Intercept
points

Reciprocals

1/1

Smallest
Ratio

1/ 1/()

Miller ndices (102)

16

Example 6
Axis

Intercept
points

-1

Reciprocals

1/-1

Smallest
Ratio

-1

1/ 1/()

Miller ndices (102)

17

Examples of Miller Indices

Plane intercepts axes at 3a , 2b , 2c
[2,3,3]

Reciprocal numbers are:

1 1 1
, ,
3 2 2

Miller Indices of the plane: (2,3,3)

b
2

Indices of the direction: [2,3,3]

(200)

(111)
(110)

(100)

(100)

Crystal Structure

19

Indices of a Family of Planes

Sometimes. when the unit cell has rotational
symmetry, several nonparallel planes may be
equivalent by virtue of this symmetry, in which
case it is convenient to lump all these planes in
the same Miller Indices, but with curly
brackets.
{100} (100), (010), (001), (0 1 0), (00 1 ), ( 1 00)
{111} (111), (11 1 ), (1 1 1), ( 1 11), ( 1 1 1 ), ( 1 1 1), ( 1 1 1 ), (1 1 1 )

Thus indices {h,k,l} represent all the planes

equivalent to the plane (hkl) through rotational
symmetry.
20

Classification of Crystal Structures

Crystallographers showed a long time ago that, in 3
Dimensions, there are 14 BRAVAIS LATTICES

+ 7 CRYSTAL SYSTEMS
This results in the fact that, in 3 dimensions, there are only 7
different shapes of unit cell which can be stacked together to
completely fill all space without overlapping. This gives the 7
crystal systems, in which all crystal structures can be classified.
These are:
The Cubic Crystal System (SC, BCC, FCC)
The Hexagonal Crystal System (S)
The Triclinic Crystal System (S)
The Monoclinic Crystal System (S, Base-C)
The Orthorhombic Crystal System (S, Base-C, BC, FC)
The Tetragonal Crystal System (S, BC)
The Trigonal (or Rhombohedral) Crystal System (S)
21

22

Coordination Number
For a Bravais Lattice,

The Coordinaton Number

The number of lattice points closest to a given point
(the number of nearest-neighbors of each point).
Because of lattice periodicity, all points have the same
number of nearest neighbors or coordination number.
(That is, the coordination number is intrinsic to the lattice.)

Examples
Simple Cubic (SC) coordination number = 6
Body-Centered Cubic coordination number = 8
Face-Centered Cubic coordination number = 12

Atomic Packing Factor

(or Atomic Packing Fraction)

For a Bravais Lattice,

The Atomic Packing Factor (APF)

the volume of the atoms within the unit cell

divided by the volume of the unit cell.

When calculating the APF, the volume of the atoms in

the unit cell is calculated AS IF each atom was a hard
sphere, centered on the lattice point & large enough to
just touch the nearest-neighbor sphere.
Of course, from Quantum Mechanics, we know that this
is very unrealistic for any atom!!

1- CUBIC CRYSTAL SYSTEMS

3 Common Unit Cells with Cubic Symmetry

Simple Cubic
(SC)

Body Centered Cubic

(BCC)

Face Centered Cubic

(FCC)

3 Common Unit Cells with Cubic Symmetry

a- The Simple Cubic (SC) Lattice

The SC Lattice has one lattice point in its unit cell, so
its unit cell is a primitive cell.
In the unit cell shown 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.

The Coordinatination Number of the SC Lattice = 6.

c
a

Simple Cubic (SC) Lattice

Atomic Packing Factor

b- The Body Centered Cubic

(BCC) Lattice
The BCC Lattice has two lattice
points per unit cell so the BCC unit
cell is a non-primitive cell.
Every BCC lattice point has 8
nearest- neighbors. So (in the hard
sphere model) each atom is in
contact with its neighbors only
along the body-diagonal directions.
Many metals (Fe,Li,Na..etc),
including the alkalis and several
transition elements have the BCC
structure.

c
a
29

BCC Structure

Body Centered Cubic (BCC) Lattice

Atomic Packing Factor
4R
a=
3

V atoms
=
= 0.68
V unit cell

APF BCC

(0.433a)

31

Elements with the BCC Structure

c- The Face Centered Cubic

(FCC) Lattice
In the FCC Lattice there are atoms at the corners of
the unit cell and at the center of each face.
The FCC unit cell has 4 atoms so it is a non-primitive cell.

Every FCC Lattice point has 12 nearest-neighbors.

Many common metals (Cu,Ni,Pb..etc) crystallize in
the FCC structure.

FCC Structure

Face Centered Cubic (FCC) Lattice

Atomic Packing Factor
4R
a=
3

APF FCC
BCC

Crystal Structure

V atoms
=
= 0.74
0.68
V unit cell

(0.353a)

35

Elements That Have the

FCC Structure

FCC & BCC:

Conventional Cells With a Basis

Alternatively, the FCC Lattice can

be viewed in terms of a Conventional
Unit Cell with a 4-point basis.
Similarly, the BCC lattice can be
viewed in terms of a Conventional
Unit Cell with a 2- point basis.

Example: Atomic Packing Factor

2- HEXAGONAL CRYSTAL SYSTEMS

In a Hexagonal Crystal System, three equal
coplanar axes intersect at an angle of 60,
and another axis is perpendicular to the
others and of a different length.

The atoms are all the same.

Simple Hexagonal Bravais Lattice

Hexagonal Close Packed

(HCP) Lattice
This is another structure that
is common, particularly in
metals. In addition to the two
layers of atoms which form
the base and the upper face
of the hexagon, there is also
an intervening layer of atoms
arranged such that each of
these atoms rest over a
depression between three
atoms in the base.

Hexagonal Close Packed

(HCP) Lattice

The HCP lattice is not a Bravais lattice, because orientation of the

environment of a point varies from layer to layer along the c-axis.

Hexagonal Close Packing

HCP Lattice
Hexagonal Bravais Lattice with a 2 Atom Basis

Comments on Close Packing

Close-Packed Structures

ABCABC fcc
ABABAB hcp

THE MOST IMPORTANT

CRYSTAL STRUCTURES
Sodium Chloride Structure Na+Cl Cesium Chloride Structure Cs+Cl-

Hexagonal Closed-Packed Structure

Diamond Structure

Zinc Blende

48

1 Sodium Chloride Structure

Sodium chloride also
crystallizes in a cubic lattice,
but with a different unit cell.
The sodium chloride
structure consists of equal
numbers of sodium &
chlorine ions placed at
alternate points of a simple
cubic lattice.
Each ion has six of the other
kind of ions as its nearest
neighbors.

NaCl Structure

 This structure can also be

considered as a face-centered-cubic
Bravais lattice with a basis
consisting of a sodium ion at 0 and
a chlorine ion at the center of the
conventional cell, at position

a / 2( x y z )
LiF, NaBr, KCl, LiI, have
this structure.
The lattice constants are of the
order of 4-7 Angstroms.

NaCl Type Crystals

2 - CsCl Structure

2 - CsCl Structure
Cesium Chloride, CsCl,
crystallizes in a cubic
lattice. The unit cell may be
depicted as shown.
(Cs+ is teal, Cl- is gold)
Cesium Chloride consists
of equal numbers of Cs and
Cl ions, placed at the points
of a body-centered cubic
lattice so that each ion has
eight of the other kind as its
nearest neighbors.

CsCl Structure
The translational symmetry of this structure
is that of the simple cubic Bravais lattice, and
is described as a simple cubic lattice with a
basis consisting of a Cs ion at the origin 0
and a Cl ion at the cube center

a / 2( x y z )
CsBr & CsI crystallize in this structure.The
lattice constants are of the order of 4 angstroms.

CsCl Structure

8 cells

CsCl Crystals

The Ancient Periodic Table

4 - Diamond Structure
The Diamond Lattice consists of 2
interpenetrating FCC Lattices.
There are 8 atoms in the unit cell. Each atom bonds
covalently to 4 others equally spaced about a given atom.

The Coordination Number = 4.

The diamond lattice is not a Bravais lattice.

C, Si, Ge & Sn crystallize in the Diamond structure.

Diamond Lattice

Diamond Lattice
The Cubic Unit Cell

 Diamonds are made up exclusively of carbon atoms.

Each carbon atom shares an electron with 4 other carbon atoms
forming 4 single bonds and each of those 4 carbons share 3 electrons
with 3 carbons this continues in a 3D plane where the diamond is to
the size that you require. they are hard to draw accurately with out a
program to assist you, the program allows you to see the structure in
space to see what carbons are likely to bind to already drawn carbons.

5 Zinc Blende or ZnS Structure

The Zincblende Structure has equal
numbers of zinc and sulfur ions
distributed on a diamond lattice, so that

Each has 4 of the opposite kind as

nearest-neighbors.
This structure is an example of a lattice with a
basis, both because of the geometrical position of
the atoms & because two types of atoms occur.

Some compounds with this structure are:

AgI, GaAs, GaSb, InAs, ....

5 Zinc Blende or ZnS Structure

Zincblende (ZnS) Lattice

Zincblende Lattice
The Cubic Unit Cell

Diamond & Zincblende Structures

A brief discussion of both of these structures & a comparison.

These two are technologically important structures

because many common semiconductors have

Diamond or Zincblende Crystal Structures

They obviously share the same geometry.

In both structures, the atoms are all tetrahedrally

coordinated. That is, atom has 4 nearest-neighbors.
In both structures, the basis set consists of 2 atoms.

In both structures, the primitive lattice

Face Centered Cubic (FCC).
In both the Diamond & the Zincblende lattice there are 2
atoms per fcc lattice point.

In Diamond: The 2 atoms are the same.

In Zincblende: The 2 atoms are different.

Diamond & Zincblende Lattices

Diamond Lattice

Zincblende Lattice

The Cubic Unit Cell

The Cubic Unit Cell

Other views of
the cubic unit cell

A view of the tetrahedral coordination

& the 2 atom basis
Zincblende &
Diamond Lattices
Face Centered Cubic
(FCC) lattices with a
2 atom basis

The Wurtzite Structure

A structure related to the Zincblende Structure is the

Wurtzite Structure
Many semiconductors also have this lattice structure.
In this structure there is also

Tetrahedral Coordination
Each atom has 4 nearest-neighbors. The Basis set is 2 atoms.

Primitive lattice hexagonal close packed (hcp).

2 atoms per hcp lattice point. A Unit Cell looks like

The Wurtzite Lattice

View of tetrahedral
coordination &
the 2 atom basis.

Wurtzite Lattice

Hexagonal Close
Packed (HCP)
Lattice + 2 atom basis

Diamond & Zincblende crystals

The primitive lattice is FCC. The FCC primitive
lattice is generated by r = n1a1 + n2a2 + n3a3.
The FCC primitive lattice vectors are:
a1 = ()a(0,1,0), a2 = ()a(1,0,1), a3 = ()a(1,1,0)

NOTE: The ais are NOT mutually orthogonal!

Primitive FCC Lattice
cubic unit cell

Diamond:
2 identical atoms per FCC point

Zincblende:
2 different atoms per FCC point

Wurtzite Crystals
The primitive lattice is HCP. The
HCP primitive lattice is generated by

Primitive Lattice
Points

r = n1a1 + n2a2 + n3a3.

The hcp primitive lattice vectors are:

a1 = c(0,0,1)
a2 = ()a[(1,0,0) + (3)(0,1,0)]
a3 = ()a[(-1,0,0) + (3)(0,1,0)]

NOTE!
These are NOT mutually orthogonal!

Wurtzite Crystals
2 atoms per HCP point

Primitive HCP
Lattice: Hexagonal
Unit Cell

ELEMENTS OF SYMMETRY
Each of the unit cells of the 14 Bravais lattices
has one or more types of symmetry properties,
such as inversion, reflection or rotation,etc.
SYMMETRY

INVERSION

REFLECTION

ROTATION

Typical symmetry properties of a lattice.

Some types of operations that can leave a lattice invariant.

Operation

Element

Inversion

Point

Reflection

Plane

Rotation

Axis

Rotoinversion

Axes

Inversion

A center of inversion: A point at the center of the molecule.

(x,y,z) --> (-x,-y,-z)

A center of inversion can only occur in a molecule. It is
not necessary to have an atom in the center (benzene,
ethane). Tetrahedral, triangles, pentagons don't have
centers of inversion symmetry. All Bravais lattices are
inversion symmetric.
Mo(CO)6

Rotational Invariance &

Invariance on Reflection Through a Plane

Invariance on Reflection
through a plane

Rotational Invariance
about more than one axis

A plane in a cell such that, when a mirror reflection

in this plane is performed, the cell remains invariant.

Examples

A triclinic lattice has no reflection plane.

A monoclinic lattice has one plane midway

between and parallel to the bases, and so forth.

Rotational Symmetry
There are always a finite number of
rotational symmetries for a lattice.
A single molecule can have any degree
of rotational symmetry, but an infinite
periodic lattice can not.

Rotational Symmetries
90

120

180

This is an axis such that, if the cell is rotated around

it through some angles, the cell remains invariant.
The axis is called n-fold if the angle of rotation is 2/n.

Examples
A Triclinic Lattice has no axis of rotation.
A Monoclinic Lattice has a 2-fold axis
( = [2/2] = ) normal to the base.
90

Examples