1

CRYSTAL STRUCTURE

Solid state physics is largely concerned with crystals and electrons in the crystals and
their effect on the material characteristics.

An ideal crystal is an infinite repetition of identical structure or UNIT CELL in a certain

array of points known as LATTICE.

A lattice consists of group of atoms, known as BASIS arranged in each point.

Consider the following 2dimensional crystal consisting of 2 atoms.

u1
O a1

u2

a2
Crystal structure Basis Lattice

A lattice is typically represented by lattice vectors.

v v v v v
r ' = r + u1 a1 + u 2 a 2 + u 3 a3

v v v v v v
Where; { a1 , a 2 , a3 } are the fundamental lattice vectors and { u1 , u 2 , u 3 } are integers that
defines the dimensions of the lattice.

Here the relative position of the jth atom relative to the lattice points can be defined as:

O a1
v v v v
r j = x j a1 + y j a 2 + z j a3

rj xj
v v v
Where; { a1 , a 2 , a3 } are the fundamental
translation vectors and { x j , y j , z j } are
yj
integers that defines the coordinates of the
jth atom. a2
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Unit cells are also known as primitive cells. They are defined as the smallest possible
v v v
parallelepiped defined by primitive vectors { a1 , a 2 , a3 } . There should only be one
lattice point in every unit cell.

Consider the following 2dimensional lattice points. Only cells {A, C, D} are valid unit
cells, since they contain only one lattice point.
B

A a1
a1
a2 a2

C D
a1 a1

a2 a2
E
a1
a2
A primitive cell can be constructed by bisecting the lines joining one atom to its nearest
(and second nearest) neighbors. The enclosed volume (area) is also known as Wigner-
Seitz cell.

The area (2D) and the volume (3D) for a parallelepiped are given by:

Area = | a1 a 2 | and Volume = | a1 a 2 a3 |

2D lattice groups: 120o

90o 90o
90o

A. Square lattice B. Rectangular C. Centered Rectangular D. Hexagonal

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3D Crystal systems
b
1. Cubic a=b=c = = = 90o
a 2. Tetragonal a=bc = = = 90o
3. Orthorhombic a b c = = = 90o
4. Rhombohedral a=b=c = = 90o
c 5. Hexagonal a=bc = = 90o; = 120o

6. Monoclinic a b c = = 90o
7. Triclinic a b c 90o

14 Bravais Lattices

1. Cubic

Simple body centered face centered

a. Volume, conventional cell a3 a3 a3

b. Lattice points per cell 1 2 4
c. Volume, primitive cell a3 a3 a3
d. Lattice point per unit volume 1/ a3 2/ a3 4/ a3
e. Number of nearest neighbors 6 8 12
f. Nearest neighbor distance a 3 a/2 2 a/2
g. Number of second neighbor 12 6 6
h. Second neighbor distance 2a a a
i. Packing fraction 1/6 1/8 3 1/6 2

a. Volume, conventional cell = L x W x T = a3

b. Lattice points per cell

SCubic = { 8 lattice points / 8 cells } = 1
BCC = { 8 lattice points / 8 cells } + { 1 center lattice point / 1 cell } = 2
FCC = { 8 lattice points / 8 cells } + { 6 center lattice point / 2 cells } = 4
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c. Volume, primitive cell = | a1 a2 a3 |

Simple cubic primitive vectors:

a3
a1 = a x z
a 2 = a y a2 y
x
a 3 = a z a1
volume = | a x (a y a z ) |
= | a x (a 2 x ) | = a3

Body Centered Cubic primitive vectors:

v
a1 = 1
2 a ( x + y z )
v
a2 = 1
2 a ( x + y + z)
v a2
a3 = a ( x y + z )
1
2
v a3
volume = | a1 { 12 a ( x + y + z ) 12 a ( x y + z) } |
v
= | a1 14 a 2 {(0 + z + y ) + ( z 0 + x )
a1
+ (+ y + x + 0)}
= | 12 a ( x + y z ) 14 a 2 {2 y + 2 x} |
= | 14 a 3 ( x + y z ) { y + x} | = 1
4 a 3 ( 2)
= 1
2 a3

Face Centered Cubic primitive vectors:

v
a1 = 1
2 a ( x + y )
v
a2 = 1
2 a ( y + z )
v a2
a3 = a ( x + z )
1
2
v
volume = | a1 { 12 a ( y + z ) 12 a ( x + z ) } | a3
v
= | a1 14 a 2 {( z + x ) + ( y + 0)}
a1
= | a ( x + y ) 14 a 2 { z + x + y} |
1
2

= | 18 a 3 ( x + y ) { z + x + y} | = 1
8 a 3 (2)
= 1
4 a3

d. Lattice point per volume = Lattice points per cell / Conventional cell volume
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e. Number of nearest neighbors

Simple body centered face centered

f. Nearest neighbor distance : d 2 = x 2 + y 2 + z 2

Simple Cubic

d 2 = a2

Body centered cubic

2 2 2 2
a a a a
d 2 = + + = 3
2 2 2 2
3
d = a
2

Face centered cubic

2 2 2
a a a
d 2
= + = 2
2 2 2
2
d = a
2
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i. Packing fraction

Simple cubic
a
r =
2
1 4 3
volume spheres = 8 r
8 3
4 a 4 a 3
3

= =
3 2 3 8

= a3
6

Body centered cubic

4r = 3a
4 3 1 4 3
volume spheres = 1 r + 8 r
3 8 3
3
4 3 8 3 3 3
= 2 a = a
3 4 3 4 16

3
= a3
8

Face centered cubic

4r = 2a
1 4 3 1 4 3
volume spheres = 6 r + 8 r
2 3 8 3
3
4 2 16 2 2 3
= 4 a = a
3 4 3 4 16

2
= a3
6

Question:

Construct the 3D Wigner-Seitz cells for SC, BCC and FCC.

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2. Tetragonal

simple body
centered
3. Orthorhombic

simple body base face

centered centered centered

4. Rhombohedral 5. Triclinic

6. Monoclinic

Questions:

Show that a rhombohedral crystal can be constructed within a face-centered cubic.

Identify their respective lattice parameters and primitive vectors. Also compute for
their respective volumes.

Show that a base-centered orthorhombic crystal can be reduced to tetragonal crystal.

Identify their respective lattice parameters and primitive vectors. Also compute for
their respective volumes.
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7. Simple Hexagonal
z

a3
a1 x

a1 x a2
a2 120o

Hexagonal primitive vectors:

v
a1 = a x
v 1 3
a2 = a x + a y
2 2
v
a3 = c z

Question:
Solve for the volume for the unit hexagonal crystal from the given primitive vectors.

Show that the close packing fraction for HCP is the same as that of FCC.
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Common Metal structures:

1. Body centered cubic : common for metals like V, Cr, Mo and W and their alloys.

1 1 1
basis atoms : ( 0, 0, 0 ) and ( , , )
2 2 2

2. Face centered cubic : common for metals like Al, Ni, Cu, Ag, Au and Pt.

1 1 1 1 1 1
basis atoms : ( 0, 0, 0 ), ( , , 0 ), ( , 0 , ), and (0, , )
2 2 2 2 2 2

3. Hexagonal closed pack: common for metals like Be, Mg, Zn and Zr.
z

a3

a1 x
a2
120o

Show that the basis atoms for a hexagonal closed pack (HCP) have coordinates;
a 1 3
( 0, 0, 0 ) and ( x , a x + a y , c z )
3 2 2
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Common Semiconductor Structures:

1. Diamond (FCC) usual for silicon, germanium and diamond

tetrahedron

Lattice : FCC
1 1 1
Basis atoms : ( 0, 0, 0 ) and ( , , )
4 4 4

Lattice : SC

Basis atoms :

origin ( 0, 0, 0 ) and
1 1 1 1 1 1
face ( , , 0 ), ( , 0 , ), ( 0 , , ) and
2 2 2 2 2 2
1 1 1 3 3 1 1 3 3 3 1 3
tetra ( , , ), ( , , ), ( , , ), ( , , )
4 4 4 4 4 4 4 4 4 4 4 4
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2. Zinc Sulfide (FCC), zincblende, usual in GaAs and GaN

Gallium
Arsenic

tetrahedron

Lattice : FCC
1 1 1
Basis atoms : Gallium ( 0, 0, 0 ) and Arsenic ( , , )
4 4 4

3. Wurtzite (HCP), usual in GaAs and GaN

Gallium
Arsenic

tetrahedra

Questions:

Identify the basis atoms of Wurtzite for the simple hexagonal lattice.
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Common Ceramic Structures:

*unit cells must be electrically neutral.

M=metal and X=non metal.

1. Cesium Chloride (BCC), MX

Lattice : SC
Basis ions :
Cl ( 0, 0, 0 ) and Cl-
1 1 1
Cs + ( , , )
2 2 2
Cs+
Electrically neutral :
1
1 Cs + + 8 Cl
8

2. Sodium Chloride (FCC), MX - usual in MgO, CaO, FeO and NiO

Cl-

Na+
Lattice : FCC
Basis ions :
Cl ( 0, 0, 0 ) and
1
Na + ( 0 , 0 , )
2

Electrically neutral :
1 1 1
8 Cl (corner ) + 6 Cl ( face) + 12 Na + (edge) + 1 Na + (center )
8 2 4

Question:

Identify the 7 basis ions for the Sodium Chloride structure in a SC lattice. Check
for electrical neutrality.
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3. Calcium Flourite (FCC) MX2 usual for UO2, ThO2, TeO2

Ca2+

F-

Top view Side view

Lattice : FCC
Basis ions :
1 1
Ca 2+ (, , 0 ) and
2 2
1 1 1 3 1 1
F ( , , ) and F ( , , )
4 4 4 4 4 4

Electrically neutral :
1 1
8 Ca 2+ (corner ) + 6 Ca 2+ ( face) + 8 F (inner cube)
8 2

Question:

Identify the 12 basis ions for the Calcium Flouride structure in a SC lattice. Check
for electrical neutrality.
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4. Silicon Dioxide (FCC) MX2

Si 4+

O 2-

tetrahedron Top view

Lattice : FCC
Basis atoms :

1 1 1
Si 4+ ( 0, 0, 0 ) and ( , , )
4 4 4

2 2 2
O 2 ( , , ) and
4 4 4
3 2 3 2 2 3 2 2 3 2 2 3 2 3 2
( , , ), ( , , ), ( , , )
4 4 4 4 4 4 4 4 4

Electrically neutral :
1 4+ 1
8 Si (corner ) + 6 Si 4+ ( face) + 4 Si 4+ (tetra )
8 2
2
+ 16 O (inner tetra )
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Crystal Lattice directions:

Coordinates are denoted by (u, v, w); we use parentheses and the numbers u, v and w are
separated by commas.

Directions are denoted by [u v w]; where u, v and w are the smallest integers proportional
to the components of a certain lattice vector T.
*Note the square brackets and absence of commas.
v
T = u x + v y + w z

Bond lengths are usually computed from the distance between two lattice points.
It is more convenient to use vectors in our computations.

As an example, what is the bond length between atoms located at the origin O:(0,0,0) and
the body diagonal P:(1,1,1) for a cubic.

We can define a certain vector T from the coordinates of the two given points. The
distance is then determined by taking the dot product of the vector with itself.
z

Q : ( 0, 0, 0 ) (q1 , q 2 , q3 )
P : ( 1, 1, 1 ) ( p1 , p 2 , p 3 ) P:(1,1,1)

v
T = ( p1 q1 ) a1 + ( p 2 q 2 ) a 2 + ( p3 q3 ) a 3 Q
v v
d 2 = | T T |
x
= | {( p1 q1 ) a1 + ( p 2 q 2 ) a 2 + ( p3 q 3 ) a 3 }
{( p1 q1 ) a1 + ( p 2 q 2 ) a 2 + ( p3 q3 ) a 3 } |

= | {(1 0) a1 + (1 0) a 2 + (1 0) a 3 } {(1 0) a1 + (1 0) a 2 + (1 0) a 3 } |
= | { a1 + a 2 + a 3 } { a1 + a 2 + a 3 } |
= | { a1 a1 + a 2 a 2 + a 3 a 3 } |
= 1+1+1 = 3

d = 3
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The technique may seem trivial when the unit vectors are 90o with each other, but they
may prove to be cumbersome otherwise. Thus we introduce matrix representation to
generalize our solution.

The distance between two points defined by the vectors p and q (in terms of the unit
vectors ai) can be compactly represented as;

N N
pq = ( p i ai ) (q j a j ) =
i , j =1
p
i , j =1
i g ij q j

Where N is the number of space dimension and the gij is the metric tensor that is unique
for each crystal system.

a 2 0 0 a2 a 2 cos a 2 cos

g ijcubic =0 a2 0 ; g ijr hom bohedral = a 2 cos a2 a 2 cos
0 0 a 2 a 2 cos a 2 cos a 2

a 2 0 0 a2 12 a 2 0

g ijtetragonal =0 a2 0 ; g ijhexagonal = 12 a 2 a2 0
0 0 c 2 0 0 c 2

a 2 0 0 a2 0 ac cos

g orthr hom bic
ij =0 b2
0 ; g monoclinic
ij = 0 b 2
0
0 0 c 2 ac cos 0 c 2

a2 ab cos ac cos

g triclinic
ij = ab cos b2 bc cos
ac cos bc cos c 2

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The main body diagonal of a monoclinic crystal with lattice parameters

(a, b, c, , , ) = (3, 4, 6, 90o, 120o, 90o) is computed below;

P:(1,1,1)
c

O
z
a
b

N N
pq = ( p a ) (q a
i , j =1
i i j j )= p
i , j =1
i g ij q j

p = q = [ 111 ]
N
p p = p
i , j =1
i g ij p j

a2 0 ac cos 32 0 3 6 cos120 o

g ijmonoclinic = 0 b2 0 = 0 42 0
ac cos 0
3 6 cos 120
2 o
c 0 62
9 0 9
g ijmonoclinic = 0 16 0
9 0 36
a2 0 ac cos p1
N
p
d = | p p | =
2
p i g ij p j = [ p1 p 2 p3 ] 0 b2 0 2
i , j =1
ac cos 0 c 2 p3

9 0 9 1 0

d = [1 1 1] 0 16
2
0 1 = [1 1 1] 16 = 43

9 0 36 1 27
d = 43

Draw and compute for the lengths from the origin of the directions [110] and
[311] for (a) cubic crystal with lattice parameter a=4 (b) orthorhombic crystal
with lattice parameters (a, b, c, , , ) = (2, 3, 4 90o, 90o, 90o).

Draw and compute for the body and basal diagonal for a hexagonal crystal with
lattice parameter (a, b, c, , , ) = (2, 2, 6, 90o, 90o, 120o).
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The angle between chemical bonds also represent the angle between directions (vectors)
defined by the position of the atoms. As an exercise, we will use the tensor already
presented in the computation.

Consider a monoclinic crystal having lattice parameters (a, b, c, , , ) = (4, 6, 5, 90o,

120o, 90o). We can compute for the angle between directions [101] and [-201].

First we setup the metric tensor for the given monoclinic crystal;

a2 0 ac cos 42 0 4 5 cos120 o

g ijmonoclinic = 0 b2 0 = 0 62 0
ac cos 0 c 2 4 5 cos120 o 0 52

16 0 10
g ijmonoclinic
= 0 36 0
10 0 25

We then compute for the lengths of the two directions provided;

16 0 101 6

d = [1 0 1] 0 36
2
0 0 = [1 0 1] 0 = 21
101
10 0 1
25 15
16 0 10 2 42
d 201 = [ 2 0 1] 0
2
36 0 0 = [ 2 0 1] 0 = 129

10 0 25 1 45

Using the definition of the dot product, we should be able to solve for the angle .
v v v v
p101 q 201 = | p101 || q 201 | cos = d101 d 201 cos
v v
1 p101 q 201
= cos

d d
101 201
16 0 10 2 42
p101 q 201 = [1 0 1] 0 36 0 0 = [1 0 1] 0 = 3

v v

10 0 25 1 45
3
= cos 1 86.69 o

21 129
Diamond FCC contains 4 tetrahedrons; find the lengths of the directions to the
tetrahedron center (, , ) from the (a) origin and (b) basal center (, , 0). Find
the angle between these two directions.
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Lattice planes are indexed according to the technique proposed by William Miller. First
the intercepts (s1, s2, s3) between the lattice plane and the lattice unit vectors (a1, a2, a3)
were determined. Second, take the inverse of the intercepts (1/s1, 1/s2, 1/s3). Lastly,
reduce the inverse into the lowest possible integers (h,k,l) using a common prime
multiple.

Planes are indexed by (h k l), these are all integers enclosed by parentheses and without
commas. Shown below are the shaded lattice planes with their corresponding indices.
Also shown are the perpendicular directions of each of the shaded lattice planes.

(021)
(110)

(111)
(100)

Family of directions is denoted as <hkl>. For instance, the family of directions <111> is a
collection of [111], [-111], [1-11], and [11-1]. Shown in the figure below.

The family of planes is denoted as {hkl}. For instance, the family of planes {110} is a
collection of (110), (1-10), (-1-10) etc. Shown in the figure below.
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Reading topics:
Crystal symmetry and coordination