1.

9 THE CRYSTALLINE STATE 55

2R a

a a
FCC unit cell
(a) (b) (c)

Figure 1.32 (a) The crystal structure of copper which is face-centered cubic (FCC). The atoms are positioned at well-
defined sites arranged periodically, and there is a long-range order in the crystal. (b) An FCC unit cell with close-packed
spheres. (c) Reduced-sphere representation of the FCC unit cell. Examples: Ag, Al, Au, Ca, Cu, γ-Fe (>912 °C), Ni, Pd, Pt,
and Rh.

1.9 THE CRYSTALLINE STATE

1.9.1 TYPES OF CRYSTALS
A crystalline solid is a solid in which the atoms bond with each other in a regular
pattern to form a periodic collection (or array) of atoms, as shown for the copper
crystal in Figure 1.32. The most important property of a crystal is periodicity,
which leads to what is termed long-range order. In a crystal, the local bonding
geometry is repeated many times at regular intervals, to produce a periodic array
of atoms that constitutes the crystal structure. The location of each atom is well
known by virtue of periodicity. There is therefore a long-range order, since we can
always predict the atomic arrangement anywhere in the crystal. Nearly all metals,
many ceramics and semiconductors, and various polymers are crystalline solids in
the sense that the atoms or molecules are positioned on a periodic array of points
in space.
All crystals can be described in terms of a lattice and a basis.15 A lattice is an
infinite periodic array of geometric points in space, without any atoms. When we
place an identical group of atoms (or molecules), called a basis, at each lattice
point, we obtain the actual crystal structure. The crystal is thus a lattice plus a
basis at each lattice point. In the copper crystal in Figure 1.32a, each lattice point
has one Cu atom and the basis is a single Cu atom. As apparent from Figure 1.32a,
the lattice of the copper crystal has cubic symmetry and is one of many possi-
ble lattices.
Since the crystal is essentially a periodic repetition of a small volume (or cell)
of atoms in three dimensions, it is useful to identify the repeating unit so that the

15
Lattice is a purely imaginary geometric concept whose only requirement is that the infinite array of points has
periodicity. In many informal discussions, the term lattice or crystal lattice is used to mean the crystal structure
itself. These concepts are further developed in Section 1.14 under Additional Topics.
56 CHAPTER 1 ∙ ELEMENTARY MATERIALS SCIENCE CONCEPTS

crystal properties can be described through this unit. The unit cell is the most con-
venient small cell in the crystal structure that carries the properties of the crystal.
The repetition of the unit cell in three dimensions generates the whole crystal struc-
ture, as is apparent in Figure 1.32a for the copper crystal.
The unit cell of the copper crystal is cubic with Cu atoms at its corners and one
Cu atom at the center of each face, as indicated in Figure 1.32b. The unit cell of Cu
is thus said to have a face-centered cubic (FCC) structure. The Cu atoms are shared
with neighboring unit cells. Effectively, then, only one-eighth of a corner atom is in
the unit cell and one-half of the face-centered atom belongs to the unit cell, as shown
in Figure 1.32b. This means there are effectively four atoms in the unit cell. The
length of the cubic unit cell is termed the lattice parameter a of the crystal struc-
ture. For Cu, for example, a is 0.362 nm, whereas the radius R of the Cu atom in
the crystal is 0.128 nm. Assuming the Cu atoms are spheres that touch each other,
we can geometrically relate a and R. For clarity, it is often more convenient to draw
the unit cell with the spheres reduced, as in Figure 1.32c.
The FCC crystal structure of Cu is known as a close-packed crystal structure
because the Cu atoms are packed as closely as possible, as is apparent in Figure 1.32a
and b. The volume of the FCC unit cell is 74 percent full of atoms, which is the
maximum packing possible with identical spheres. By comparison, iron has a body-
centered cubic (BCC) crystal structure, and its unit cell is shown in Figure 1.33.
The BCC unit cell has Fe atoms at its corners and one Fe atom at the center of the
cell. The volume of the BCC unit cell is 68 percent full of atoms, which is lower
than the maximum possible packing.
The FCC crystal structure is only one way to pack the atoms as closely as pos-
sible. For example, in zinc, the atoms are arranged as closely as possible in a hex-
agonal symmetry, to form the hexagonal close-packed (HCP) structure shown in
Figure 1.34a. This structure corresponds to packing spheres as closely as possible
first as one layer A, as shown in Figure 1.34b. You can visualize this by arranging
six pennies as closely as possible on a table top. On top of layer A we can place an
identical layer B, with the spheres taking up the voids on layer A, as depicted in
Figure 1.34b. The third layer can be placed on top of B and lined up with layer A.
The stacking sequence is therefore ABAB. . . . A unit cell for the HCP structure is
shown in Figure 1.34c, which shows that this is not a cubic structure. The unit cell

Figure 1.33 Body-centered

cubic (BCC) crystal structure.
(a) A BCC unit cell with close-
packed hard spheres representing
the Fe atoms. (b) A reduced-
sphere unit cell.

a
 1.9 THE CRYSTALLINE STATE 57

Layer B

c
Layer A
Layer B
Layer A
Layer A Layer A
a
(a) (b) (c) (d)
Figure 1.34 The hexagonal close-packed (HCP) crystal structure. (a) The hexagonal close-packed (HCP) structure.
A collection of many Zn atoms. Color difference distinguishes layers (stacks). (b) The stacking sequence of closely
packed layers is ABAB. (c) A unit cell with reduced spheres. (d) The smallest unit cell with reduced spheres.

shown, although convenient, is not the smallest unit cell. The smallest unit cell for
the HCP structure is shown in Figure 1.34d and is called the hexagonal unit cell.
The repetition of this unit cell will generate the whole HCP structure. The atomic
packing density in the HCP crystal structure is 74 percent, which is the same as that
in the FCC structure.
Covalently bonded solids, such as silicon and germanium, have a diamond crys-
tal structure brought about by the directional nature of the covalent bond, as shown
in Figure 1.35 (see also Figure 1.6). The rigid local bonding geometry of four Si–Si
bonds in the tetrahedral configuration forces the atoms to form what is called the
diamond cubic crystal structure. The unit cell in this case can be identified with
the cubic structure. Although there are atoms at each corner and at the center of
each face, indicating an FCC-like structure, there are four atoms within the cell as
well. Thus, there are eight atoms in the unit cell. The diamond unit cell can actually
be described in terms of an FCC lattice (a geometric arrangement of points) with
each lattice point having a basis of two Si atoms. If we place the two Si atoms at
each site appropriately, for example, one right at the lattice point, and the other
displaced from it by a quarter lattice distance a∕4 along the cube edges, we can
easily generate the diamond unit cell. In the copper crystal, each FCC lattice point
has one Cu atom, whereas in the Si crystal each lattice point has two Si atoms; thus
there are 4 × 2 = 8 atoms in the diamond unit cell.
In the GaAs crystal, as in the silicon crystal, each atom forms four directional
bonds with its neighbors. The unit cell looks like a diamond cubic, as indicated in
Figure 1.36 but with the Ga and As atoms alternating positions. This unit cell is
termed the zinc blende structure after ZnS, which has this type of unit cell. Many
important compound semiconductors have this crystal structure, GaAs being the
most commonly known. The zinc blende unit cell can also be described in terms of
a fundamental FCC lattice and a basis that has two atoms, Zn and S (or Ga and As).
For example, we can place one S at each lattice point and one Zn atom displaced
from the Zn by a∕4 along the cube edges.
58 CHAPTER 1 ∙ ELEMENTARY MATERIALS SCIENCE CONCEPTS

C
S

a
a
Zn

a a
a a

Figure 1.35 The diamond unit cell Figure 1.36 The zinc blende (ZnS)
which is cubic. The cell has eight cubic crystal structure.
atoms. Many important compound crystals
Gray Sn (α-Sn) and the elemental have the zinc blende structure.
semiconductors Ge and Si have this Examples: AlAs, GaAs, GaP, GaSb,
crystal structure. InAs, InP, InSb, ZnS, ZnTe.

Ratio of radii = 1 Ratio of radii = 0.75 25¢

25¢ 1¢ Unit cell

1¢ 1¢

Nearest neighbors = 6 Nearest neighbors = 4 A two-dimensional crystal of

pennies and quarters

Figure 1.37 Packing of coins on a table top to build a two-dimensional crystal.

In ionic solids, the cations (e.g., Na+) and the anions (Cl−) attract each other
nondirectionally. The crystal structure depends on how closely the opposite ions can
be brought together and how the same ions can best avoid each other while maintain-
ing long-range order, or maintaining symmetry. These depend on the relative charge
and relative size per ion.
To demonstrate the importance of the size effect in two dimensions, consider
identical coins, say pennies (1-cent coins). At most, we can make six pennies
touch one penny, as shown in Figure 1.37. On the other hand, if we use quarters16

16
Although many are familiar with the United States coinage, any two coins with a size ratio of about 0.75 would
work out the same.
 1.9 THE CRYSTALLINE STATE 59

Cl–
Na+
Cl–

Cs+

Figure 1.38 A possible reduced- Figure 1.39 A possible reduced-sphere

sphere unit cell for the NaCl (rock unit cell for the CsCl crystal.
salt) crystal. An alternative unit cell may have Cs+ and
An alternative unit cell may have Cl− interchanged. Examples: CsCl, CsBr,
Na+ and Cl− interchanged. Examples: CsI, TlCl, TlBr, and TlI.
AgCl, CaO, CsF, LiF, LiCl, NaF, NaCl,
KF, KCl, and MgO.

(25-cent coins) to touch one penny, at most only five quarters can do so. However,
this arrangement cannot be extended to the construction of a two-dimensional
crystal with periodicity. To fulfill the long-range symmetry requirement for crys-
tals, we can only use four quarters to touch the penny and thereby build a two-
dimensional “penny–quarter” crystal, which is shown in the figure. In the
two-dimensional crystal, a penny has four quarters as nearest neighbors; similarly,
a quarter has four pennies as nearest neighbors. A convenient unit cell is a square
cell with one-quarter of a penny at each corner and a full penny at the center (as
shown in the figure).
The three-dimensional equivalent of the unit cell of the penny–quarter crystal is
the NaCl unit cell shown in Figure 1.38. The Na+ ion is about half the size of the
Cl− ion, which permits six nearest neighbors while maintaining long-range order.
The repetition of this unit cell in three dimensions generates the whole NaCl crystal,
which was depicted in Figure 1.9b.
A similar unit cell with Na+ and Cl− interchanged is also possible and equally
convenient. We can therefore describe the whole crystal with two interpenetrating
FCC unit cells, each having oppositely charged ions at the corners and face centers.
Many ionic solids have the rock salt (NaCl) crystal structure.
When the cation and anions have equal charges and are about the same size,
as in the CsCl crystal, the unit cell is called the CsCl unit cell, which is shown
in Figure 1.39. Each cation is surrounded by eight anions (and vice versa),
which are at the corners of a cube. This is not a true BCC unit cell because the
atoms at various BCC lattice points are different. (As discussed in Section 1.14,
CsCl has a simple cubic lattice with a basis that has one Cl− ion and one
Cs+ ion.)
Table 1.3 summarizes some of the important properties of the main crystal
structures considered in this section.
60 CHAPTER 1 ∙ ELEMENTARY MATERIALS SCIENCE CONCEPTS

Table 1.3 Properties of some important crystal structures

a and R Number of Atomic

Crystal (R is the Radius Coordination Atoms per Packing
Structure of the Atom) Number (CN) Unit Cell Factor Examples
Simple cubic a = 2R 6 1 0.52 No metals (Except Po)
4R
BCC a= √3
8 2 0.68 Many metals: α−Fe, Cr, Mo, W
4R
FCC a= √2
12 4 0.74 Many metals: Ag, Au, Cu, Pt
HCP a = 2R 12 2 0.74 Many metals: Co, Mg, Ti, Zn
c = 1.633a
8R
Diamond a= √3 4 8 0.34 Covalent solids:
Diamond, Ge, Si, α-Sn
Zinc blende 4 8 0.34 Many covalent and ionic solids.
Many compound semiconductors.
ZnS, GaAs, GaSb, InAs, InSb
NaCl 6 4 cations 0.67 Ionic solids such as NaCl, AgCl,
LiF, MgO, CaO
4 anions (NaCl) Ionic packing factor depends on
relative sizes of ions.
CsCl 8 1 cation Ionic solids such as CsCl, CsBr, CsI
1 anion

EXAMPLE 1.16 THE COPPER (FCC) CRYSTAL Consider the FCC unit cell of the copper crystal shown in
Figure 1.40.
a. How many atoms are there per unit cell?
b. If R is the radius of the Cu atom, show that the lattice parameter a is given by a = R2 √2.
c. Calculate the atomic packing factor (APF) defined by
Volume of atoms in unit cell
APF =
Volume of unit cell
d. Calculate the atomic concentration (number of atoms per unit volume) in Cu and the
density of the crystal given that the atomic mass of Cu is 63.55 g mol−1 and the radius
of the Cu atom is 0.128 nm.
SOLUTION

a. There are four atoms per unit cell. The Cu atom at each corner is shared with eight other
adjoining unit cells. Each Cu atom at the face center is shared with the neighboring unit
cell. Thus, the number of atoms in the unit cell = 8 corners (18 atom) + 6 faces (12 atom) =
4 atoms.
b. Consider the unit cell shown in Figure 1.40 and one of the cubic faces. The face is a
square of side a and the diagonal is √a2 + a2 or a √2. The diagonal has one atom at
the center of diameter 2R, which touches two atoms centered at the corners. The diago-
nal, going from corner to corner, is therefore R + 2R + R. Thus, 4R = a √2 and
a = 4R∕√2 = R2 √2. Therefore, a = 0.3620 nm.
 1.9 THE CRYSTALLINE STATE 61

1
8
th of an atom

R
Half of an atom
a 2R

a Figure 1.40 The FCC unit cell.

R
The atomic radius is R and the lattice
a parameter is a.

(Number of atoms in unit cell) × (Volume of atom)

c. APF =
Volume of unit cell
4 3 42 3
4× πR πR
3 3 42π
= = = = 0.74
a3 (R2 √2) 3 3(2 √2) 3
d. In general, if there are x atoms in the unit cell, the atomic concentration is
Number of atoms in unit cell x
nat = = 3
Volume of unit cell a
Thus, for Cu
4
nat = = 8.43 × 1022 cm−3
(0.3620 × 10−7 cm) 3
There are x atoms in the unit cell, and each atom has a mass of Mat∕NA grams. The
density ρ is

( NA )
Mat
x
Mass of all atoms in unit cell
ρ= =
Volume of unit cell a3
that is,
natMat (8.43 × 1022 cm−3 ) (63.55 g mol−1 )
ρ= = = 8.9 g cm−3
NA 6.022 × 1023 mol−1
Note that the expression ρ = (nat Mat)∕NA is particularly useful in finding the atomic
concentration nat from the density since the latter can be easily measured or available in
various data resources.

1.9.2 CRYSTAL DIRECTIONS AND PLANES

There can be a number of possibilities for choosing a unit cell for a given crystal
structure, as is apparent in Figure 1.34c and d for the HCP crystal. As a convention,
we generally represent the geometry of the unit cell as a parallelepiped with sides
a, b, and c and angles α, β, and γ, as depicted in Figure 1.41a. The sides a, b, and c
and angles α, β, and γ are referred to as the lattice parameters. To establish a ref-
erence frame and to apply three-dimensional geometry, we insert an xyz coordinate
system. The x, y, and z axes follow the edges of the parallelepiped and the origin is