The Structure of Crystalline Solids

Mahfodzah Md Padzi
 Fundamental Concepts
• Crystalline : the atoms
are situated in a
repeating or periodic
array over large atomic
distances - that is, long-
range order exists, such
that upon solidification,
the atoms will position
themselves in a
repetitive three-
dimensional pattern.
 Long-Range-Order (LRO)
• Most metals and alloys,
semiconductors, ceramics and
some polymers have a crystalline
structure (where the atoms or ions
display in a long-range-order (LRO).
• The atoms or ions in these material
form a regular repetitive, grid like
pattern in three dimension.
• These materials are referred as a
crystalline structure.
 Fundamental Concepts
• crystal structure : Some of the properties of
crystalline solids depend on the crystal structure
of the material, the manner in which atoms,
ions, or molecules are spatially arranged.
 Fundamental Concepts
Space lattice Unit cells
An IMAGINARY NETWORK Unit cell is that block of atoms
of lines with atoms at lines which REPEATS itself to form
intersection that representing space lattice.
the arrangement of atoms is
called space lattice. Space Lattice

Unit Cell
Fundamental Concept
 Crystal Systems and Bravais
Lattice
• Only SEVEN different types of unit cells are necessary to
create all point lattices which:

1. Cubic
2. Tetragonal
3. Orthorhombic
4. Rhombohedral
5. Hexagonal
6. Monoclinic
7. Triclinic
Crystal Systems and Bravais
Lattice
• According to Bravais (1811-1863), fourteen standard
unit cells can describe all possible lattice networks
based on FOUR basic types of unit cells which are:

• Simple

• Body Centered

• Face Centered

• Base Centered
i. Cubic Unit Cell
a=b=c
α = β = γ = 900

Simple Body Centered Face centered

 ii. Tetragonal
a =b ≠ c
α = β = γ = 900

Simple Body Centered

10
 iii. Orthorhombic
a≠ b≠ c
α = β = γ = 900

Simple Body Centered Face Centered Base Centered

iv. Rhombohedral v. Hexagonal
a= b≠ c
a =b = c α = β = 900
α = β = γ ≠ 900 γ = 1200

Simple Simple
vi.Monoclinic vii. Triclinic
a≠ b≠ c a≠ b≠ c
α = γ = 900 ≠ β α ≠ β ≠ γ ≠ 900

Base
Simple Centered Simple
 Metallic CrystalStructures
90% of the metals have either Body Centered Cubic (BCC),
Face Centered Cubic (FCC) or Hexagonal Close Packed (HCP)
crystal structure.

HCP is denser version of simple hexagonal crystal structure.

BCC Structure FCC Structure HCP Structure

 Body Centered Cubic (BCC)
BCC crystal structure
Represented as:

• one atom at each corner of cube

• one at the center of cube.

• Examples :-
(a) Atomic-site unit cell
➢ Chromium (a=0.289 nm)

➢ Iron (a=0.287 nm)

➢ Sodium (a=0.429 nm)

(b) Hard-sphere unit cell (c) Isolated unit cell

 BCC
Each unit cell has:
• eight 1/8 atom at corners
• 1 full atom at the center.
Therefore each unit cell has;

(8 x 1/8) + 1 = 2 atoms
Atoms contact each other at cube
diagonal. Therefore;

a = 4R
3
 Face Centered Cubic (FCC)
Crystal Structure
FCC structure is represented as
one atom each
at the corner of cube
at the center of each cube
face. (a) Atomic-site unit cell

Examples :-
a) Aluminum (a = 0.405)
b) Gold(a = 0.408)

15
(b) Hard-sphere unit cell (c) Isolated unit cell
 FCC
Each unit cell has:
a) eight 1/8 atom at corners
b) six ½ atoms at the center of six faces

Therefore each unit cell has (8 x 1/8) + (6 x ½) = 4 atoms

Atoms contact each other across cubic face diagonal.
Therefore;
a =4R
2
 Hexagonal Close-Packed Structure
(HCP)
The HCP structure is represented as
1. atom at each of 12 corners of a hexagonal prism
2. atoms at top and bottom face
3. atoms in between top and bottom face.

Examples:-
Zinc (a = 0.2665 nm, c/a= 1.85)
Cobalt (a = 0.2507 nm, c/a= 1.62)

HCP crystal structure:

(a) Schematic of the crystal structure (larger cell)
(b) Hard-sphere model
 HCP
Each atom has:
 six 1/6 atoms at each of top and bottom
layer
 two ½ atoms at top and bottom layer
 3 full atoms at the middle layer

Therefore each HCP unit cell has:

(2 x 6 x 1/6) + (2 x ½) + 3 = 6 atoms
Ideal HCP c/a ratio is 1.633.
 HCP
Isolated HCP unit cell also called the primitive cell.
The atoms at locationsmarked:
‘1’ contribute 1/6 of anatom
‘2’ contribute 1/12 of anatom
‘3’ contribute 1 atom

Therefore each HCP unit cell (primitive cell) has

(4 x1/6) + (4 x 1/12) + 1 = 2 atoms

HCP crystalstructure:
(c) Isolated unit cell schematic
Crystal Structures
 Atomic Packing Factor(APF)
The APF is the sum of the sphere volumes of all atoms
within a unit cell (assuming
the atomic hard-sphere model) divided by the unit cell
volume—that is,

Formula:

Volume of atoms in unit cell

APF =
Volume of unit cell
APF for BCC structure
Volume of atoms in unit cell
APF =
Volume of unit cell

But;

8.723 R 3
Therefore; APF = 3 = 0.68
12.32 R
Atom Positions in Cubic UnitCells
Cartesian coordinate system is use 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.
 z axis is the direction towards top.
 Negative directions are to the opposite of positive
directions.

Atom positions are located using unit distances along the

axes.
Figure3.9 Atomic position in a BCC unit cell.
 Direction
In cubic crystals, direction indices are vector components of
directions resolved along each axes, resolved to smallest
integers.
Direction indices are position coordinates of unit cell where
the direction vector emerges from cell surface, after converted
to integers.

30
Fig 3.1: Some directions in cubic unit cells
 PROCEDURE TO FIND DIRECTION INDICES
Produce the direction vector till it
emerges from surface of cubic cell z
(1,1/2,1)
(1,1/2,1) - (0,0,0)
Determine the coordinates of point of = (1,1/2,1)
emergence and origin y
(0,0,0) 2 x (1,1/2,1)
Subtract coordinates of point of x = (2,1,2)
Emergence by that of origin
The direction indices are [212]
Are all are NO Convert them to
integers? smallest possible
YES integer by multiplying
Are any of the direction by an integer.
vectors negative?
YES
NO
Represent the indices in a square Represent the indices in a square
bracket without comas with a bracket without comas (Eg: [212] )
over negative index (Eg: [121])
31
 Exercise
i. Draw the following direction vectors in cubic unit
cells:
a. [100] and [110]
b. [112]
c. [1 1 0]
d. [3 2 1]

ii. Determine the direction indices of the cubic direction

between the position coordinates (3/4 , 0 , ¼) and (1/4 ,
½ , ½)
33
 Latticeplane
Miller Indices are 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.

z Miller Indices = (111)

y
x
 MILLER INDICES - PROCEDURE
Choose a plane that does not pass z
Miller Indices = (111)
through origin

Determine the x,y and z intercepts y

of the plane x

Find the reciprocals of the intercepts

Fractions? Clear fractions by

Yes multiplying by an integer to
determine smallest set of
Place a ‘bar’ over the whole numbers
Negative indices

Enclose in parenthesis (hkl)where h,k,l are

miller indicesof cubic crystal plane forx,y and z
axes. Eg: (111)
 Miller Indices -Examples
z
 Intercepts of the plane at x,y & z
(100) axes are 1, ∞ and ∞
y  Taking reciprocals we get (1,0,0).
 Miller indices are (100).
x
x

 Intercepts are 1/3, 2/3 & 1.

 taking reciprocals we get (3, 3/2,
1).
 Multiplying by 2 to clear fractions,
we get (6,3,2).
 Miller indices are (632).
 Plot the plane (101)
 Taking reciprocals of the indices we get (1
∞ 1).
 The intercepts of the plane are x=1, y= ∞
(parallel to y) and z=1.

Figure EP3.7 a

Plot the plane (2 2 1)

 Taking reciprocals of the indices we get (1/2
1/2 1).
 The intercepts of the plane are x=1/2, y= 1/2
and z=1.

37 Figure EP3.7 c
 Plot the plane (110)
• The reciprocals are (1,-1, ∞)
• The intercepts are x=1, y=-1 and z= ∞ (parallel to z
axis)

Note:
To show this plane in a single unit cell, the origin is moved along the positive
direction of y axis by 1 unit.
38
 Exercise
1. Draw the following crystallographic planes in cubic unit cells:
a. (101)
b. (110)
c. (221)
d. (110)

2. Determine the miller index for the plane given cubic unit cell.

39 (a) (b)
 Miller Indices – Important
Relationship
• Direction indices of a direction perpendicular to a crystal
plane are same as miller indices of the plane.
• Example:-

• Interplanar spacing between parallel closest planes

with same miller indices is given by

d h kl
a
2 2 2
 Planes and Directions in
Hexagonal Unit Cells
• Four indices are used (hkil) called as Miller-Bravais
indices.
• Four axes are used (a1, a2, a3 and c).
• Reciprocal of the intercepts that a crystal plane
makes with the a1, a2, a3 and c axes give the h,k,i
and l indices respectively.
 Hexagonal Unit Cell -
• Basal Planes:-
Examples
Intercepts a1 = ∞
a2 = ∞
a3 = ∞ c = 1
(hkil) = (0001)
 Hexagonal Unit Cell -
Examples
• Prism Planes :-
For plane ABCD,
Intercepts a1 = 1
a2 = ∞ a3 = -1
c=∞
(hkil) = (10 1 0)
 Directions in HCP Unit
Cells
• Indicated by 4 indices [uvtw].
• u,v,t and w are lattice vectors in a1, a2, a3 and cdirections
respectively.
u + v = -t

• Example
•
 Volume Density
Mass/Unit cell
• Volume density of metal = v =
Volume/Unit cell
• Example:- Copper (FCC) has atomic mass of 63.54
g/mol and atomic radius of 0.1278 nm.
4R 4 0.1278nm
a= = = 0.361 nm
2 2
Volume of unit cell = V= a3 = (0.361nm)3 = 4.7 x 10-29 m3
FCC unit cell has 4 atoms.
(4atoms)(63.54g / mol) 10 6 Mg
Mass of unit cell = m = = 4.22 x 10-28 Mg
6.02 1023 atoms / mol g

m 4.22 10 28 Mg Mg g
v 29 3
8.98 8.98
10 m m3
V 4.7 cm3
 Planar AtomicDensity
Formula planar atomic density:

Equivalent number of atoms whose

p =
centers are intersected by selected area
Selected area
 Planar Atomic Density
Example:

In Iron (BCC, a=0.287 nm), the (110) plane intersects center of

5 atoms (four ¼ and 1 full atom). Calculate the planar atomic
density.
 Planar atomic density
- Equivalent number of atoms = (4 x ¼ ) + 1
= 2 atoms

- Area of 110 plane = 2a  a = 2a 2

Therefore;

 p
=
2
2 (0.287) 2

17.2atoms 1012 nm 2
=
nm 2 mm2

= 1.72 x 1013 atoms/mm2

 Linear AtomicDensity
Formula linear atomic density:


Number of atomic diameters intersected by
selected length of line in direction of interest
l =
Selected length of line
 Linear Atomic Density

Example:-

For a FCC copper crystal (a=0.361 nm), the [110] direction

intersects 2 half diameters and 1 full diameter.
Solution:

- The number of atomic diameters intersected by this length of line are:

½ + ½ + 1 = 2 atomic diameters

- The length of the line is:

2  0.361nm

Therefore;

 l
=
2atoms
=
3.92atoms
=
3.9210 6 atoms

2  0.361nm nm mm
 Crystalline and
Noncrystalline Materials

• Single Crystals

• Polycrystalline Materials

• Anisotropy

• Noncrystalline Solids
 Single Crystal
• when the periodic and
repeated arrangement of
atoms is perfect or
extends throughout the
entirety of the specimen
without interruption
 Polycrystalline
• crystalline
solids are
composed of a
collection of
many small
crystals or
grains (a) Small crystallite nuclei.
(b) Growth of the crystallites; the obstruction of some
grains that are adjacent to one another is also shown
(c) Upon completion of solidification, grains having
irregular shapes have formed.
(d) The grain structure as it would appear under the
microscope; dark lines are the grain boundaries
 Anisotropy
• The physical properties of single
crystals of some substances
depend on the crystallographic
direction in which
measurements are taken. For
example, the elastic modulus,
the electrical conductivity, and
the index of refraction may have
different values in the [100] and
[111] directions

• Isotropy?
 Noncrystalline
Solids/Amorphous

• lack a systematic and

regular arrangement of
atoms over relatively
large atomic distances

Two-dimensional schemes of the structure of

(a) crystalline silicon dioxide and (b)
noncrystalline silicon dioxide.
Comparison