Introduction to Solid State Physics

▪ Crystal Structure

Glass (SiO2) Quartz (SiO2) Silicon (Si)

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 Crystal Structure
▪ Periodic arrays of atoms
▪ Fundamental types of lattices
▪ Index system for crystal planes
▪ Simple crystal structures
▪ Direct image of atomic structure
▪ Non-ideal crystal structures
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 Introduction
Solid State physics is largely concerned with crystals and electrons in crystals. The
study of solid state physics began in the early years of this century following the discovery
of x-ray diffraction by crystals.
When a crystal grows in a constant environment, the form develops as of identical
building blocks were added continuously (figures below). The building blocks are atoms or
group of atoms, so that a crystal is a three-dimensional periodic array of atoms.

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 In 1895, a German physicist, W. C. Roentgen discovered x-ray.

In 1912 Laue developed an elementary theory of the diffraction of x-rays

by a periodic array. In the second part, Friedrich and Knipping reported the first
experimental observations of x-ray diffraction by crystals.

The work proved decisively that crystals are composed of a periodic

array of atoms. The studies have been extended to include amorphous or
noncrystalline solids, glasses, and liquids. The wider field is known as
condensed matter physics.

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 Periodic Arrays of Atoms
An ideal crystal is constructed by the infinite repetition of identical structural
units in space. The structural unit is a single atom, comprise many atoms or
molecules.

The concepts of Lattice & Basis

The structure of all crystals can be described in terms of a lattice, with a
group of atoms attached to every lattice point. The group of atoms is called the basis.

crystal structure = lattice + basis

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 Lattice Translation Vectors
The lattice is defined by three fundamental translation vectors 𝐚1 , 𝐚2 , 𝐚3 such that the
atomic arrangement looks the same in every respect when viewed from the point 𝐫 as
when viewed from the point of (1)
𝐫 ′ = 𝐫 + 𝑢1 𝐚1 + 𝑢2 𝐚2 + 𝑢3 𝐚3
where 𝑢1 , 𝑢2 , 𝑢3 are arbitrary integers. The set of points 𝐫 ′ defined by (1) for all
defines 𝑢1 , 𝑢2 , 𝑢3 a lattice.

➢ A lattice is a regular periodic array of points in space.

crystal structure = lattice + basis

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 crystal structure = lattice + basis

✓ The lattice and the translation vectors 𝐚1 , 𝐚2 , 𝐚3 are said to be primitive

if any two points 𝐫, 𝐫 ′ from which the atomic arrangement looks the
same always satisfy (1) with a suitable choice of the integers 𝑢1 , 𝑢2 , 𝑢3 .
✓ The primitive translation vectors, there is no cell of smaller volume 𝐚1 ∙
𝐚2 × 𝐚3 that can serve as a building block for the crystal structure.

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Figure 2 The crystal structure is formed by the
addition of the basis (b) to every lattice point of
the space lattice (a). By looking at (c), one can
recognize the basis and then one can abstract the
space lattice. It does not matter where the basis is
put in relation to a lattice point.

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 Basic and the Crystal Structure
A basic of atoms is attached to every lattice point, with every basis
identical in composition, arrangement, and orientation.
The number of atoms in the basis may be one, or it may be more
than one. The position of the center of an atom j of the basis relative to
the associated lattice point:
𝑟𝑗 = 𝑥𝑗 𝐚1 + 𝑦𝑗 𝐚2 + 𝑧𝑗 𝐚3

We may arrange the origin, which we have called the associated

lattice point, so that 0 ≤ 𝑥𝑗 , 𝑦𝑗 , 𝑧𝑗 ≤ 1.

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Figure 3a Lattice points of a space lattice in
two dimensions. All pairs of vectors a1, a2 are
translation vectors of the lattice. But a1’’’, a2’’’
are not primitive translation vectors because we
cannot form the lattice translation T from
integral combinations of a1’’’ and a2’’’. The
other pairs shown of a1 and a2 may be taken as
the primitive translation vectors of the lattice.
The parallelograms 1, 2, 3 are equal in area and
any of them could be taken as the primitive cell.
The parallelogram 4 has twice the area of a
primitive cell.
Figure 3b Primitive cell of a space lattice in
three dimensions.
Figure 3c Suppose these points are identical
atoms: Sketch in on the figure a set of lattice
points, a choice of primitive axes, a primitive
cell, and the basis of atoms associated with a
lattice point.

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 Primitive Lattice Cell
The parallelepiped defined by primitive axes a1, a2, a3 is called a primitive
cell. A primitive cell is a type of cell or unit cell. A cell will fill all space by the
repetition of suitable crystal translation operations. A primitive cell is a minimum-
volume cell.
There is always one lattice point per primitive cell. If the primitive cell is a
parallelepided with lattice points at each of the eight corners, point is shared among
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eight cells, so that the total number of lattice points in the cell is one: 8 × = 1. The
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volume of a parallelepided with axes a1, a2, a3 is
𝑉𝑐 = 𝐚1 ∙ 𝐚2 × 𝐚3
The basis associated with a primitive cell is called a primitive basis. No basis contains
fewer atoms than a primitive basis contains.
Another way of choosing a primitive cell called Wigner-Seitz cell.
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Wigner-Seitz Primitive Cell
Figure 4 A primitive cell may also be chosen
following this procedure: (1) draw lines to
connect a given lattice point to all nearby lattice
points; (2) at the midpoint and normal to these
lines, draw new lines or planes. The smallest
volume enclosed in this way is the Wigner-Seitz
primitive cell. All space may be filled by these
cells, just as by the cells of Fig. 3.

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Primitive Unit Cell

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 Unit Cell

The unit cell is a structural unit or building

block that can describe the crystal structure.
Repetition of the unit cell generates the
entire crystal.

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Fundamental Types of Lattices

Figure 5 A fivefold axis of symmetry cannot

exist in a periodic lattice because it is not
possible to fill the area of a plane with a
connected array of pentagons. We can,
however, fill all the area of a plane with just
two distinct designs of “tiles” or elementary
polygons.

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Figure 6 (a) A plane of symmetry parallel to the faces of a cube. (b) A diagonal
plane of symmetry in a cube. (c) The three tetrad axes of a cube. (d) The four triad
axes of a cube. (e) The six diad axes of a cube.
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Two-Dimensional Lattice Types

Figure 7 Four special lattices in

two dimensions.

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Three-Dimensional Lattice Types

The point symmetry

groups in three dimensions
require the 14 different
lattice types listed in Table
1. The general lattice is
triclinic, and there are 13
special lattices. These are
grouped for convenience
into systems classified
according to seven types of
cells

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7 crystal systems: divided into
14 Bravias lattice (lattice
illustration).

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7 crystal systems: divided
into 14 Bravias lattice
(angle illustration).

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 Common Cubic Lattice Structure

➢ Atomic (hard sphere) radius, R, defined by ion core radius - typically 0.1 -
0.2 nm.
➢ There are three lattices in the cubic system: simple cubic (sc), body-centered
cubic (bcc), and face-centered cubic (fcc).
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 Table 2: Characteristics of Cubic Lattice
Cubic Structure Simple BCC FCC
Volume of conventional cell 𝑎3 𝑎3 𝑎3
Lattice points per cell 1 2 4
Volume of primitive cell 𝑎3 𝑎 3 Τ2 𝑎 3 Τ4
Lattice points per unit volume 1Τ𝑎3 2Τ𝑎3 4Τ𝑎3
No. of nearest neighbour 6 8 12
Nearest neighbour distance 𝑎 0.886𝑎 0.707𝑎
No. of second nearest neighbour 12 6 6
Second nearest neighbour distance 𝑎 2 𝑎 𝑎
Atomic packing factor 1 1 1
𝜋= 𝜋 3= 𝜋 2=
6 8 6
0.524 0.680 0.740
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Simple Cubic Crystal Structure

c z

a
b

a, b, and c are known as the lattice constant

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❑ The coordination number, CN
➢ the number of closest neighbors to which an atom is bonded = number of touching atoms

For simple cubic ,

CN = 6

❑ Number of atoms per unit cell

➢ For an atom that is shared with m adjacent unit cells, we only count a fraction of the atom, 1/m

1/8
Atoms in the corners are shared by 8
cells thus its contribution to one cell
unit is 1/8

Since there are 8 corner atoms in a cell

unit the number of atoms per cell unit
for simple cubic is
8 x 1/8 = 1 atom/cell unit

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❑ Relationship between r and a

a a = 2r
a
r=
2
r

❑ Sum of atomic volumes in simple cubic

✓ Volume of a sphere ❖ Sum of atomic volumes in simple cubic

= number of atoms per cell unit x
volume of a sphere
4 3
= 1x r
3
✓ number of atoms per cell
3
unit for simple cubic 4 a
= 8 x 1/8 = 1 atom/cell unit =  
3 2

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❑ Atomic packing factor for simple cubic

➢ Atomic packing factor, APF = fraction of volume occupied by hard spheres

For simple cubic

= 0.52 or 52 %

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 Face-Centered Cubic (FCC) Crystal Structure
➢ Atoms are located at each of the corners and on the centers of all the
faces of cubic unit cell.
➢ Cu, Al, Ag, Au have this crystal structure.
➢ Three representations of the FCC unit cell.

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➢ The hard spheres touch one another across a face diagonal -
the cube edge length, a= 2R√2

(4r )2 = a 2 + a 2
2a = 16r
2 2

a = 8r = 2r 2

➢ The coordination number, CN = 12

➢ Number of atoms per unit cell, n = 4
▪ 6 face atoms shared by two cells: 6 × 1/2 = 3
▪ 8 corner atoms shared by eight cells: 8 × 1/8 = 1
➢ Atomic packing factor, APF = fraction of volume occupied by hard spheres
= (Sum of atomic volumes)/(Volume of cell) = 0.74 (maximum possible).
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▪ Corner and face atoms in the unit
cell are equivalent
▪ FCC crystal has APF of 0.74, the
maximum packing for a system
equal-sized spheres - FCC is a
close-packed structure
▪ FCC can be represented by a
stack of close-packed planes
(planes with highest density of
atoms)

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 Body-Centered Cubic (BCC) Crystal Structure
➢ Atom at each corner and at center of cubic unit cell.
➢ Cr, α-Fe, Mo have this crystal structure.

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➢ The hard spheres touch one another along cube
diagonal
➢ The cube edge length, a= 4R/√3
➢ The coordination number, CN = 8
➢ Number of atoms per unit cell, n = 2
▪ Center atom (1) shared by no other cells: 1 × 1 = 1
▪ 8 corner atoms shared by eight cells: 8 × 1/8 = 1
➢ Atomic packing factor, APF = 0.68
➢ Corner and center atoms are equivalent
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 Hexagonal Close-Packed Crystal Structure
➢ HCP is one more common structure of metallic crystals.
➢ Six atoms form regular hexagon, surrounding one atom in center. Another
plane is situated halfway up unit cell (c-axis), with 3 additional atoms
situated at interstices of hexagonal (close-packed) planes.
➢ Cd, Mg, Zn, Ti have this crystal structure.

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➢ Unit cell has two lattice parameters a and c. Ideal ratio c/a = 1.633 (He)
➢ The coordination number, CN = 12 (same as in FCC)
➢ Number of atoms per unit cell, n = 6
▪ 3 mid-plane atoms shared by no other cells: 3 × 1 = 3
▪ 12 hexagonal corner atoms shared by 6 cells: 12 × 1/6 = 2
▪ 2 top/bottom plane center atoms shared by 2 cells: 2 × 1/2 = 1
➢ Atomic packing factor, APF = 0.74 (same as in FCC)
➢ All atoms are equivalent.
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 Diamond Crystal Structure
➢ A unique structure typically associated to a hybrid of carbon.
➢ Actually made up of two interpenetrating FCC.
➢ Many compound semiconductors such as gallium arsenide, β-silicon
carbide, and indium antimonide adopt the analogous zincblende
structure.

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➢ lattice is "decorated" with a motif of
two tetrahedrally bonded atoms in each primitive
cell, separated by 1/4 of the width of the unit
cell in each dimension.
➢ The coordination number, CN = 4
➢ Number of atoms per unit cell, n = 8
▪ 4 atoms shared by no other cells: 4 × 1 = 4
▪ 8 corner atoms shared by 8 cells: 8 × 1/8 = 1
▪ 6 face atoms shared by two cells: 6 × 1/2 = 3
➢ Atomic packing factor, APF = 0.34

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Diamond Crystal Structure
Two FCC

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 Summaries of Various Crystal Structures
Structure Radius Atoms / Unit Atomic Coordination
Cell Packing Number
Factor
Simple Cubic 𝑎 1 𝜋 6
= 52 %
2 6
Body Centered Cubic 3𝑎 2 𝜋 3 8
= 68 %
4 8
Face Centered Cubic 2𝑎 4 𝜋 2 12
= 74 %
4 6
Hexagonal Close-Packed 𝑎 𝑐 8 6 74 % 12
, =
2 𝑎 3
Diamond 3𝑎 8 𝜋 3 4
= 34 %
8 16
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Elemental Periodic Table

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Primitive Cell Body-Centered Cubic

Figure 9 Body-centered cubic lattice,

showing a primitive cell. The primitive
cell shown is a rhombohedron of edge
1
2𝑎, and the angle between adjacent
2

edges is 10928’.

111
The coordinates of BCC = 000 and
222
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 Body-Centered Cubic
Figure 10 Primitive translation vectors of the
body-centered cubic lattice; these vectors
connect the lattice point at the origin to lattice
points at the body centers. The primitive cell is
obtained on completing the rhombohedron.

In terms of the cube edge 𝑎, the primitive translation vectors are

1 1 1
𝐚1 = 𝑎 𝐱ො + 𝐲ො − 𝐳ො 𝐚2 = 𝑎 −ො𝐱 + 𝐲ො + 𝐳ො 𝐚3 = 𝑎 𝐱ො − 𝐲ො + 𝐳ො
2 2 2
Here 𝐱ො , 𝐲,
ො 𝐳ො are the Cartesian unit vectors.
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 Face-Centered Cubic
Figure 11 The rhombohedral primitive cell of
the face-centered cubic crystal. The primitive
translation vectors 𝐚1 , 𝐚𝟐 , 𝐚3 connect the lattice
point at the origin with lattice points at the face
centers.

As drawn, the primitive vectors are:

1
𝐚1 = 𝑎 𝐱ො + 𝐲ො
2
The coordinates of FCC = 1
11 11 1 1
𝐚2 = 𝑎 𝐲ො + 𝐳ො
000 , 0 , 0 , 0 2
22 22 2 2 1
𝐚3 = 𝑎 𝐳ො + 𝐱ො
2
The angles between the axes are 60. 41
 Hexagonal

Figure 12 Relation of the primitive cell in the

hexagonal system (heavy lines) to a prism of
hexagonal symmetry.

Here
𝑎1 = 𝑎2 ≠ 𝑎3

❑ In the hexagonal system the primitive cell is a right prism based on a

rhombus with an included angle of 120.
❑ Figure 12 shows the relationship of the rhombic cell to a hexagonal
prism.
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 Summaries of Primitive Lattice
➢ Primitive cells by definition contain only one lattice point, but
the conventional bcc cell contains two lattice points, and the fcc
cell contains four lattice points.
➢ Hexagonal closed-packed = 6 lattice points and diamond = 8
lattice points.

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Try out……
Show how to obtain the atomic packing factor of
hexagonal (74 %) and diamond (34 %) unit cells

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Glass (SiO2) Quartz (SiO2) Silicon (Si)

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