CHAPTER 2: CRYSTAL STRUCTURES SPACE LATTICE is an imaginary network of

lines with atoms at lines intersection that

SHORT-RANGE ORDER (SRO) is the regular
representing the arrangement of atoms
and predictable arrangement of the atoms
over a short distance, usually one or two UNIT CELL is a convenient repeating unit of
atom spacings. a space lattice. The axial lengths and axial
angles are the lattice constants of the unit
LONG-RANGE ORDER (LRO) is a regular
cell
repetitive arrangement of atoms in a solid
which extends over a very large distance. LATTICE PARAMETER is the length of each
unit cell axis. In cubic systems, all three
SOLID MATERIALS
orthogonal lattice parameters are equal
1. CRYSTALLINE STRUCTURE refers to the
BASIC TYPES OF UNIT CELLS: Simple, Body
atoms or ions of solid arranged in a pattern
Centered, Face Centered, Base Centered
that repeats itself in three dimensions,
forming a solid that has long-range order TYPES OF UNIT CELLS:
(LRO) and is referred to as a crystalline
1. CUBIC:
solid or crystalline material.

→ Examples of crystalline materials are

metals, alloys and some ceramic materials:
Celestite (SrSo4), Pyrite (FeS2), Halite
(NaCl)

2. NON-CRYSTALLINE STRUCTURE
(Amorphous) refers to some materials
whose atoms and ions are not arranged in
a long-range, periodic and repeatable 2. TETRAGONAL
manner and possess only short-range
order (SRO). Materials with only short-
range order are classified as amorphous
(without form) or non-crystalline.

→ Example: Liquid water (H2O)

SINGLE CRYSTAL is the regular periodic

arrangement of atoms extends over the
entire volume of solids and it possesses
long range order.

POLYCRYSTALLINE SOLID is made up of an

aggregate of a large number of tiny single
crystals oriented in different directions and
separated by well-defined boundaries.
3. ORTHORHOMBIC 7. TRICLINIC

4. RHOMBOHEDRAL

COORDINATION NUMBER (CN) is the

number of closest neighbours to which an
atom is bonded (possible number of
anions touching a central cation)

RADIUS RATIO is the ratio of the radius of

the central cation to that of the
surrounding anions. CN is predicted from
the radius ratio
5. HEXAGONAL
CRITICAL RADIUS RATIO is the radius ratio
when the anions just touch each other
and contact the central cation

6. MONOCLINIC
PRINCIPAL METALLIC CRYSTAL
STRUCTURE

• 90% of the metals have either Body

Centered Cubic (BCC), Face Centered
Cubic (FCC) or Hexagonal Close Packed
(HCP) crystal structure.
Simple • The simple cubic unit cell has
Cubic (SC) one atom at each corner
Structure • Contains one atom, 1/8 of each
of eight atoms
• l = 2r

Body • Represented as one atom at

Centered each corner of cube and one at
Cubic the center of cube
(BCC) • Each atom has 8 nearest
Structure neighbours
• Coordination number is 8
• Atomic Packing Factor is 0.68
• Examples: Chromium (a = 0.289 Atoms contact each other at cube
nm), Iron (a = 0.287 nm), diagonal. Therefore, the relationship
Sodium (a = 0.429 nm) between the length of the cube side, a
• Each unit cell has eight 1/8 and the atomic radius, R is
atom at corners, 1 full atom at 𝟒𝐑
𝐚=
the center, therefore each unit √𝟑
cell has (8 x 1/8) + 1 = 2 atoms

Face • Represented as one atom each

Centered at the corner of cube and at the
Cubic center of each cube face
(FCC) • Structure is packed as close
Structure together as possible
• Coordination number is 12
• Atomic Packing Factor is 0.74
• Examples: Aluminum Atoms contact each other across cubic
(a = 0.405nm), Gold (a =0.408nm) face diagonal. Therefore, the relationship
• Each unit cell has eight 1/8 between the length of the cube side, a
atom at corners and six 1/2 and the atomic radius, R is
atoms at the center of six faces 𝟒𝐑
𝐚=
• Therefore, each unit cell has (8 √𝟐
x 1/8) + (6 x 1/2) = 4 atoms
 Hexagonal • Represented as an atom at
Close- each of 12 corners of a hexagonal
Packed prism, 2 atoms at top and bottom
(HCP) face and 3 atoms in between top
Structure and bottom face
• Atoms attain higher APF by
attaining HCP structure than
simple hexagonal structure
• Coordination number is 12
• Atomic Packing Factor is 0.74
• Examples: Zinc (a = 0.2665 nm,
c/a = 1.85), Cobalt (a = 0.2507
nm, c/a = 1.62)
• Ideal c/a ratio is 1.633
• Each atom has six 1/6 atoms at
each of top and bottom layer,
two 1/2 atoms at top and bottom
layer and 3 full atoms at the
middle layer, therefore, each HCP
unit cell has (2 x 6 x 1/6) + (2 x
1/2) + 3 = 6 atoms

ATOMIC PACKING FACTOR (APF) or packing fraction is the fraction of volume in a crystal
structure that is occupied by atoms. It is dimensionless and always less than unity.
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐚𝐭𝐨𝐦𝐬 𝐢𝐧 𝐮𝐧𝐢𝐭 𝐜𝐞𝐥𝐥
𝐀𝐏𝐅 =
𝐕𝐨𝐥𝐮𝐦𝐞 𝐨𝐟 𝐮𝐧𝐢𝐭 𝐜𝐞𝐥𝐥
FOR BCC STRUCTURE:
CARTESIAN COORDINATE SYSTEM is used
to locate atoms.
• In a cubic unit cell, y-axis is the direction
to the right, x-axis is the direction coming
out of the paper and z-axis is the direction
towards top.
DIRECTION INDICES
• Vector components of directions
resolved along each axes, resolved to
smallest integers
• Position coordinates of unit cell where
the direction vector emerges from cell
surface, after converted to integers
DIRECTIONS IN CUBIC UNIT CELLS is
defined as a line between two parts or a
vector component of the direction
resolved along each of the coordinate axis
and reduced to the smallest integers.
• Origin coordinate: (3/4 , 0 , 1/4)
• Emergence coordinates: (1/4, 1/2, 1/2)
• Emergence – Origin Coordinates
(1/4, 1/2, 1/2) - (3/4 , 0 , 1/4) = (-1/2, 1/2,
1/4)
• Multiply by 4 to convert all fractions to
integers 4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
• Therefore, the direction indices: [2 2 1]
X- RAY DIFFRACTION
• An adaptable non-destructive technique
that is very important to identify crystallite
phases and orientation of any solid
material
USES OF XRD TECHNIQUE
→ To determine the structure of crystalline
solid, phases that exist in the crystal and
dimension of the unit cell
• Structural properties includes: lattice
parameter, lattice strain, grain size, phase
composition, preferred orientation, and
stress and strain of the sample
→ To measure the thickness of thin films
and multi-layers thin film and to ensure
that some of the particle will be oriented
BRAGG’S LAW gives the relationship
among the angular positions of the
reinforced diffracted beams in terms of the
wavelength of the incoming X-ray radiation
and of the interplanar spacing dhkl of the
crystal planes.
𝐧𝛌 = 𝟐𝐝𝐡𝐤𝐥 𝐬𝐢𝐧 𝚹
INTERPLANAR SPACING (dhkl) is the
distance between two adjacent parallel
planes of atoms with the same Miller
indices
𝐚
𝐝𝐡𝐤𝐥 =
√𝐡𝟐 + 𝐤 𝟐 + 𝐥𝟐
MILLER INDICES are used to refer to
specific lattice planes of atoms. They are
reciprocals of the fractional intercepts
(with fractions cleared) that the plane
makes with the crystallographic x , y and z
axes of three nonparallel edges of the cubic
unit cell
 QUESTIONS

EXAMPLE 1 EXAMPLE 2

Draw a reduced-sphere unit cell for BCC, The atomic radius of a body centered cubic
FCC and HCP. What is the number of (BCC) is 0.143 nm. Calculate the volume of
atoms for each structure? its unit cell

1. Body-centered cubic (BCC) 𝟒𝐑 𝟑

𝐕𝐜 = 𝐚𝟑 =
Corners: 8 x 1/8 = 1 atom √𝟑

Center: 1 atom 4 (0.143 × 10 m)

V =
Total: 2 atoms per unit cell √3
V = 3.60 × 10 m

EXAMPLE 3

Determine the coordination number for

cesium chloride (CsCl) and sodium chloride
2. Face-centered cubic (FCC) (NaCl), given the ionic radius: Cs+ = 0.170
nm; Na+ = 0.102 nm; Cl- = 0.181 nm.
Corners: 8 x 1/8 = 1 atom
Center: 6 x 1/2 = 3 atoms
Total: 4 atoms per unit cell

radius of cation (Cs )

Radius ratio =
radius of anion (Cl )
0.170 × 10 m
3. Hexagonal close-packed (HCP) =
0.181 × 10 m
Top and bottom layer: = 0.939
2 x 6 x 1/6 = 2 atoms
֍ Therefore, coordination number for
2 x 1/2 = 1 atom
Cesium Chloride (CsCl) is 8.
Middle layer: 3 atoms
radius of cation (Na )
Total: 6 atoms per unit cell Radius ratio =
radius of anion (Cl )
0.102 × 10 m
=
0.181 × 10 m
= 0.564

֍ Therefore, coordination number for

Sodium Chloride (NaCl) is 6.
EXAMPLE 4

Molybdenum has a BCC crystal structure,

an atomic radius of 0.1465 nm and atomic
weight of 95.94 g/mol. Compute its
theoretical density.

Known BCC unit has 2 atoms, therefore

𝐧𝐀
𝛒=
𝐕𝐜 𝐍𝐀
Equivalent number of atoms = (4 x ¼ ) + 1 =
n = number of atoms associated with
2 atoms
each unit cell
Area of 110 plane: √2a × a = √𝟐𝐚𝟐
A = Atomic weight (g/mol)
2 2
Vc = Volume of the unit cell (m3) ρ = =
√2a √2(0.287 × 10 m)
NA = Avogadro’s number, 6.023 x 1023
ρ = 1.72 × 10 atoms/m
atoms
EXAMPLE 6
4R
V=a =
√3 Copper (FCC) has atomic mass of 63.54
g/mol and atomic radius of 0.1278 nm.
4(0.1465 × 10 m)
V= Calculate the volume density.
√3
Known FCC unit has 4 atoms, therefore
V = 3.87 × 10 m
4R
nA V=a =
ρ= √2
VN
g 4(0.1278 × 10 m)
(2)(95.94 ) V=
mol
ρ= √2
(3.87 × 10 m )(6.023 × 10 )
V = 4.72 × 10 m
ρ = 8.23 × 10 g/m
nA
EXAMPLE 5 ρ=
VN
In Iron (BCC, a=0.287 nm), the (110) plane g
(4)(63.54 )
intersects center of 5 atoms (four ¼ and 1 ρ= mol
full atom). Calculate the planar atomic (4.72 × 10 m )(6.023 × 10 )
density. ρ = 8.93 × 10 g/m
no. of atoms whose centers
are intersected by selected area
ρ =
selected area
EXAMPLE 7 64.582˚
θ= = 32.291˚
2
For FCC copper crystal (a=0.361 nm), the
[110] direction intersects 2 half diameters nλ
sin θ =
and 1 full diameter. Calculate the linear 2d
atomic density. (sin θ)(2d )
λ=
n
no. of atomic diameter
intersected by selected length (sin 32.291˚)(2)(0.14421 nm)
λ=
ρ = of line in direction of intersect 1
selected length of line
λ = 0.154 nm

EXAMPLE 9

Tantalum is BCC and has density of 1.67 x

104 kgm-3 . The atomic mass of tantalum is
180.9 gmol-1 . Calculate its atomic radius.
Known BCC unit has 2 atoms, therefore
The number of atomic diameters
Mass of unit cell (m):
intersected by this length of line are:
g
2(180.9 )
1/2 + 1/2 + 1 = 2 atomic diameters m= mol
6.023 X 10 atoms/mol
The length of this line is: √2a
m = 6.01 × 10 g
√𝟐 × 𝟎. 𝟑𝟔𝟏𝐧𝐦 mass per unit cell (m)
ρ=
2 volume per unit cell (V)
ρ =
√2(0.361 × 10 m) m 6.01 × 10 g
V= =
ρ = 3.92 × 10 atoms/m ρ 1.67 × 10 g/m

EXAMPLE 8 V = 3.60 × 10 m

The 2θ angle was found to be 64.582˚ for 4R

V=a =
the (220) planes. Determine its wavelength √3
(Given the lattice constant for gold is √V √3
0.40788 nm, assume first order diffraction) R=
4
a
d = √3.60 × 10 m √3
√h + k + l =
4
0.40788 nm
d = = 1.43 × 10 m
√2 + 2 + 0
d = 0.14421 nm
2θ = 64.582˚
EXAMPLE 10
Sketch the following crystallographic planes:

p/s: please don’t forget to label the origin

(632) 1 2
Intercepts = , ,1
3 3
1 1 1
Reciprocals = , ,
1/3 2/3 1
3
= 3, , 1 × 2
2
Reduction = (6, 3, 2)
Miller indices = (6 3 2)

(634) 1 3
Intercepts = , 1,
2 4
1 1 1
Reciprocals = , ,
1/2 1 1/4
4
= 2, 1, ×3
3
Reduction = (6, 3, 4)
Miller indices = (6 3 4)

(110) Intercepts = (1, 1, ∞)

1 1 1
Reciprocals = , ,
1 1 ∞
= (1, 1, 0)
Reduction = (1, 1, 0)
Miller indices = (1 1 0)

(200) 1
Intercepts = , ∞, ∞
2
1 1 1
Reciprocals = , ,
1/2 ∞ ∞
= (2, 0, 0)
Reduction = (2, 0, 0)
Miller indices = (2 0 0)

(111) Intercepts = ( 1, −1, ∞)

1 1 1
Reciprocals = , ,
1 −1 ∞
= (1, −1, 0)
Reduction = (1, −1, 0)
Miller indices = (1 1 0)
EXAMPLE 11

Determine the atomic packing factor for the face centered cubic (FCC) structure.
Volume of atoms in unit cell
APF =
Volume of unit cell
4
4 πR
APF = 3
4R
√2

16πR √2
APF = ×
3 64R
142.172
APF = = 0.74
192
EXAMPLE 12

Sketch the following crystallographic directions in unit cells.