Module 2: Crystalline Properties of Solids

Prepared by: Mark Jeffry D. De Leon

1 CONTENTS
2 Introduction ................................................................................................................................................... - 1 -
3 Crystal and Lattice......................................................................................................................................... - 1 -
4 Crystal Systems, Unit Cells and Bravais Lattice ............................................................................................ - 3 -
4.1 Crystal Systems ..................................................................................................................................... - 3 -
4.2 Unit Cell ................................................................................................................................................. - 3 -
4.3 Wigner-Seitz Cell .................................................................................................................................... - 5 -
4.4 Bravais Lattice ....................................................................................................................................... - 5 -
5 Miller Index Notation ..................................................................................................................................... - 6 -
6 Real Crystal Structures of Semiconductors................................................................................................... - 7 -
6.1 Common Crystal Structures of Semiconductors .................................................................................... - 7 -
6.2 Atomic Packing Factor ........................................................................................................................... - 9 -
6.3 Density Calculation ................................................................................................................................ - 9 -
7 References .................................................................................................................................................. - 10 -

2 INTRODUCTION
This module would give a brief introduction to the crystallography. By the end of this module, the learner should
be able to:
1. Define what a crystal, lattice and unit cell are.
2. Identify the 7 crystal systems and the 14 Bravais lattices.
3. Identify the unit cells of different crystals.
4. Use the Miller Index notation to name crystallographic directions and planes.
5. Illustrate some common crystal structures for semiconductor materials.
6. Identify the basis, lattice, and coordination number of real crystal structures.
7. Calculate the atomic packing factor (APF) and density of different crystalline materials.

3 CRYSTAL AND LATTICE

Matter can be found in different states. From our earlier science classes, we can broadly classify matter into solid,
liquid, gas, and plasma. Matter transitions between these different phases by adding or removing energy from
body. An example of this is the removal of heat from water (via the lowering of temperature) turns it into ice.

Figure 1 Different States of Matter

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Looking at solids specifically, the distribution of molecules or atoms, when a liquid or gas cools determine the type
of solid formed. Depending on how ordered the resulting structure is, we can end up with either crystalline or
amorphous solids.

Figure 2 Different Forms of Solids

For the rest of this module, we will be focusing on crystals. A crystal can be defined as a solid consisting of a
pattern (basis) arranged periodically in three dimensions. The basis can consist of a single atom, group of atoms
or other compounds. The lattice, meanwhile, is the periodic arrangement of our basis in a crystal.

Figure 3 Visual Representation of Lattice, Basis and Crystal Structure

Specifically, a lattice is a mathematical object which consists of a periodic arrangement of points in space. We can
represent it using the vector:

𝑅⃗ = 𝑛1 𝑎 + 𝑛2 𝑏⃗ + 𝑛3 𝑐
where:

{𝑎, 𝑏⃗, 𝑐 } are the translation vectors

{𝑛1 , 𝑛2 , 𝑛3 } are integer coefficients
An important property of a lattice is that it is invariant after translation with integer multiples of the translation
vector (i.e. translating by integer multiples of the translation vector would yield the same looking lattice). Another
thing to note is that when an origin point is chosen at a lattice point, the position of all other lattice points can be
determined by substituting integer values into the coefficients of the translation vectors.

Figure 4 Example of a three-dimensional lattice

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4 CRYSTAL SYSTEMS, UNIT CELLS AND BRAVAIS LATTICE

4.1 CRYSTAL SYSTEMS

All possible three-dimensional lattices belong into one of seven possible crystal systems. Crystal systems are
grouped depending on the orientation and the length of the translation vectors. (Note: no crystal may have a
structure other than one of the seven crystal systems.)

Figure 5 Seven crystal systems

Table 1 Seven Crystal Systems

4.2 UNIT CELL

A lattice can be regarded as a periodic arrangement of unit cells offset by translation vectors. These cells fill the
entire space with no voids. The choice of unit cells to be repeated in a lattice is arbitrary, and as such, not all
choices of unit cells would have the same volume.

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 Figure 6 Examples of possible unit cells for a 2D lattice.

A unit cell with the smallest volume is called the primitive unit cell (PUC). Translation vectors defining the PUC are
then called the basis lattice vectors. The choice of a PUC is not unique, but all possible PUCs have identical
properties:
1. All PUCs contain only one lattice point.
2. All PUCs have the same volume.

Figure 7 3D lattice of primitive unit cells

From vector algebra, the volume of a PUC is:

𝑉 = |𝑎 ∙ (𝑏⃗ × 𝑐 )|

For a lot of real crystals, the PUC of is shaped like a parallelepiped, which makes it a tad difficult to visualize. It is
just easier for human brains to visualize structures that are orthogonal (ex. cubes, boxes) so in most real crystals,
we tend to represent the unit cell as a cube or a box. This is termed as the conventional unit cell representation
and it may contain more than one lattice point.
As an example, we can look at the conventional face-centered cubic unit cell:

Figure 8 Conventional face-centered cubic unit cell

The number of lattice points in an orthogonal unit cell nu can be calculated by:
𝑛𝑓 𝑛𝑐
𝑛𝑢 = 𝑛𝑖 + +
2 8
where:

• ni - # of interior points

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 • nf - # of face points
• nc - # of corner points
Applying the above formula, we get that the conventional unit cell for the FCC lattice contains 4 lattice points.

Practice: Determine the number of lattice points in the simple cubic and body centered cubic lattices.

4.3 WIGNER-SEITZ CELL

A primitive unit cell that exhibits the full symmetry of the lattice is called the Wigner-Seitz cell. The construction of
the Wigner-Seitz cell is done by:
1. Drawing lines from a given Bravais lattice point to all nearby lattice points
2. Bisecting these lines with perpendicular planes
3. Constructing the smallest polyhedron that contains the selected lattice point

Sample construction of Wigner-Seitz cell for Simple Cubic and Body-centered cubic can be found here:

http://www.chembio.uoguelph.ca/educmat/chm729/wscells/construction.htm

Figure 9 Construction of a Wigner-Seitz cell in 2D

Figure 10 Wigner-Seitz Cells of BCC and SC

Practice: Construct the Wigner-Seitz cell of Face Centered Cubic.

4.4 BRAVAIS LATTICE

Bravais lattices refer to the different 3-D configurations into which lattice points can be arranged in a crystal. Since
crystals are required to translate their unit cells in the directions of their translation vectors without any voids, it
was found that there are only 14 possible Bravais Lattices. Like with crystal systems, no crystal can have a lattice
other than one of the 14 Bravais lattices.

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 Figure 11 The 14 Bravais Lattices in 3D

Concept Check: Why isn’t there a base-centered cubic Bravais lattice?

5 MILLER INDEX NOTATION

In this section, we will be reviewing the Miller index notation. Shown below is the convention used to label
directions and planes using Miller Index notation:
Table 2 Miller Index notation for directions and planes

How to name directions:

1. Draw vector, and find the coordinates of the head (h1, k1, l1) and the tail (h2, k2, l2).
2. Subtract coordinates of tail from coordinates of head.
3. Remove fractions by multiplying by smallest possible factor.
4. Enclose in square brackets.

Practice: Determine the direction of the vector below:

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How to name planes:
1. If the plane passes through the origin, select an equivalent plane, or move the origin
2. Determine the intersection of the plane with the lattice axes.
3. Take the reciprocal (1/∞ = 0).
4. Convert to smallest integers.
5. Enclose in parantheses.
For cubic systems, the Miller indices for directions and planes have the following properties:

• The direction [hkl] is perpendicular to the plane (hkl)

• Interplanar spacing is given by:
𝑎
𝑑ℎ𝑘𝑙 =
√ℎ 2
+ 𝑘2 + 𝑙2
• Angle θ between two directions [hkl] and [pqr] is given by the relation:
ℎ𝑝 + 𝑘𝑞 + 𝑙𝑟
cos 𝜃 =
√(ℎ 2 + 𝑘 2 + 𝑙 2 )(𝑝2 + 𝑞2 + 𝑟 2 )

Practice: Determine the miller index of planes PRS and PQR then determine the angle between the two planes.

6 REAL CRYSTAL STRUCTURES OF SEMICONDUCTORS

This section lists some of the more common crystal structures for semiconductor solids.

6.1 COMMON CRYSTAL STRUCTURES OF SEMICONDUCTORS

Table 3 Crystal Structures of Real Semiconductors

Coordination Bravais
Structure Conventional Unit Cell Basis Examples
Number Lattice
Sample
How many The Placed in the
Name of Shows the conventional unit cell for elements
atoms are lattice lattice points
structure the structure or
bonded to a followed to result to
compounds

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 particular by the the crystal
atom basis structure

2 atoms
Diamond
4 FCC 000 C, Ge, Si
Cubic
¼¼¼

Hexagonal 2 atoms
Hexa-
Close- 12 000 Zn, Mg
gonal
Packed 2/3 1/3 ½

2 atoms
Anion at 000
MgO, TiC,
Rock Salt Cation at
6 FCC PbS
(NaCl) ½00
(may be
interchanged)

2 atoms
Anion at 000
Cesium
Cation at
Chloride 8 SC TiCl, CsBr
½½½
(CsCl)
(may be
interchanged)

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 2 atoms
Anion at 000
Zinc
Cation at GaAs, BeO,
Blende / 4 FCC
¼¼¼ SiC
Sphalerite
(may be
interchanged)

2 atoms
Anion at
BeO, ZnO,
Wurtzite 4 HCP 1/3 2/3 0
SiC
Cation at
1/3 2/3 3/8

6.2 ATOMIC PACKING FACTOR

The atomic packing factor (APF), or the packing efficiency, is the proportion of the crystal occupied by the atoms
(assuming that they are hard spheres). The basic formula for getting APF is:
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑙𝑙 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛𝑠𝑖𝑑𝑒 𝑡ℎ𝑒 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙
𝐴𝑃𝐹 =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙

Practice: Calculate for the APF of magnesium oxide.

𝑟𝑀𝑔2+ = 0.072 𝑛𝑚

𝑟𝑂2− = 0.140 𝑛𝑚

6.3 DENSITY CALCULATION

The density of crystals could also be calculated if its structure is known. The generalized formula for the density of
a defect-free crystal is:
𝑚𝑎𝑠𝑠 𝑛(𝐹𝑊)
𝜌= =
𝑣𝑜𝑙𝑢𝑚𝑒 𝑉𝑐 𝑁𝐴
where:

• ρ is density
• n is # of formula units in the unit cell
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 • FW is the molecular mass of one formula unit
• Vc is the volume of the unit cell
• NA is Avogadro’s number (6.0221409 x 1023)

Practice: Calculate for the density of MgO.

𝐴𝑊𝑂 = 16 𝑔/𝑚𝑜𝑙

𝐴𝑊𝑀𝑔 = 24.31 𝑔/𝑚𝑜𝑙

7 REFERENCES
Callister, W. D., & Rethwisch, D. G. (2020). Materials science and engineering (10th ed.). Hoboken, NJ: Wiley.

Razeghi, M. (2006). Fundamentals of solid state engineering (3rd ed.). New York: Springer.

Malcolm, L. (1997). Retrieved July 30, 2020, from

http://www.chembio.uoguelph.ca/educmat/chm729/wscells/construction.htm

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