NANOTECHNOLOGY

ENMT800020
 Lecture #03
Physics of Solids: Crystal Structures

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Introduction
❑ Most solids are crystalline with their atoms
arranged in a regular manner.
❑ They have what is called long-range order
because the regularity can extend throughout the
crystal.
❑ In contrast, amorphous materials lack of long
range order, but they have what is called short-
range order so the local environment of each atom
is similar to that of other equivalent atoms, but this
regularity does not persist over appreciable
distances.
Size dependence
❑ Many properties of solids depend on the size
range over which they are measured.
❑ Microscopic details become averaged when
investigating bulk materials.
❑ At the macro- or large-scale range ordinarily studied
in traditional fields of physics such as mechanics,
electricity and magnetism, and optics, the sizes of the
objects under study range from millimeters to
kilometers.
❑ The properties associated with these materials are
averaged properties, such as the density and elastic
moduli in mechanics, the resistivity and magnetization
in electricity and magnetism, and the dielectric
constant in optics.
❑ When measurements are made in the micrometer
or nanometer range, many properties of materials
change, such as mechanical, ferroelectric, and
ferromagnetic properties.
❑ The characteristics of solids at the nanoscale
level, can be considered to be 1 to l00 nm.
❑ Below this there is the atomic scale near 0.1
nm, followed by the nuclear scale near a
femtometer (10-6 nm).
❑ A lattice consisting of a repeating unit (“the
unit cell”) arranged such that identical
surroundings exist everywhere one looks.
 Lattice points The repeating unit
containing one or or “unit cell”
more atoms

A lattice consisting of a regularly repeated array of points

(have translational symmetry)
 Lattice or not?

❑ Thisis a lattice
❑ Why?
❑ Each point has
identical surroundings
 Lattice or not?

❑ Thisis not a lattice

❑ Why?
❑ Surroundings of all
points are not
identical
❑ There are only a finite number of lattices that
satisfy the periodicity requirement for a crystalline
material
❑ But the number of crystal structures far exceeds the
number of lattices that exist
❑ How? Due to differences in what is located at each
lattice point (could b one or many but will be the
same for all points)
 Motif

One atom per lattice points Two atoms per lattice points

These two examples have the same 2D lattice, but a

different crystal structure
Basic questions:
Q: How does a crystal lattice differ from a crystal
structure?
A: A crystal structure is built of atoms, whereas a crystal
lattice is an infinite pattern of points, each of which
must have the same surroundings in the same
orientation. A lattice is a mathematical concept: there
are only 5 different two-dimensional (planar) lattices
and 14 different three-dimensional (Bravais) lattices.
❑ All the unit cells shown describe the lattice
❑ The lattice is not affected by the choice of unit cell
Unit cell and lattice
❑ The choice of unit cell is arbitrary so long a unit
cell can be repeated
❑ What we usually do is to use the simplest, most
symmetrical unit cell that will describe the lattice
Two-dimensional lattices
❑ There are only five two-dimensional lattices

Square Rectangular Oblique Diamond Hexagonal

Three-dimensional lattices
❑ There are only 14 possible three-dimensional lattices
called Bravais lattices
❑ Could we produces others? No, other lattices can be
described by one of the 14 unit cells in the Bravais
lattice set
❑ Could we use more than one unit cell from amongst the
14? Often, yes we could, but as with 2-D we use the
simplest most symmetrical as a convenience
Basic crystallography
Crystal system Lattice symbol Lattice parameters
1. Triclinic aP a  b  c,   90o,   90,   90o
2. Monoclinic primitive mP a  b  c,  = 90o,   90,  = 90o
Monoclinic centered mC
3. Orthorhombic primitive oP a  b  c,  =  =  = 90o
Orthorhombic C-face-centered oC
Orthorhombic body-centered oI
Orthorhombic face-centered oF
Crystal system Lattice symbol Lattice parameters
4. Tetragonal primitive tP a = b  c,  =  =  = 90o
Tetragonal body-
centered tI
5. Trigonal a = b = c,  =  =  (primitive
(Rhombohedral) hR cell);
a' = b’  c’, ’ = ’ = 90o, ’ = 120o
(hexagonal cell)
6. Hexagonal primitive hP a = b  c,  =  = 90o,  = 120o
7. Cubic primitive cP a = b = c,  =  =  = 90o
Cubic body-centered cI
Cubic face-centered cF
 c b b

a a
 α b
c c
 
a 

Triclinic Primitive monoclinic Base-centered monoclinic

c
c c

b c
120o b b b
a a
α α a a
α

Rhombohedral Primitive hexagonal Primitive tetragonal Body-centered tetragonal

 c c
c c

b b
b b a a
a a

Primitive Body-centered Base-centered Face-centered

orthorhombic orthorhombic orthorhombic orthorhombic

c c c

b b b
a a a

Primitive cubic Body-centered cubic Face-centered cubic

Do we need only 14 Bravais?

At first sight this lattice seems to

be “base centered tetragonal”,
i.e. not a Bravais lattices
However, the lattice is actually
simple (or primitive) tetragonal
More than one Bravais?

FCC crystal lattice

Body centered tetragonal (BCT)
lattice
❑ The FCC crystal shown could equally be described
by a body centered tetragonal (BCT) lattice
❑ However, we usually find the use of FCC as a
description far more convenient than BCT
 ❑ Howcan we stack metal atoms to minimize empty
space?

vs.

2-dimensions
28
 Metals tend to be densely packed because:
❑ Typically, only one element is present, so all atomic
radii are the same.
❑ Metallic bonding is not directional.
❑ Nearest neighbor distances tend to be small in
order to lower bond energy.
❑ The “electron cloud” shields cores from each other

29
Linear atomic density
❑ Directions and planes are related to the degree of
atomic spacing or atomic packing.
❑ Linear density corresponds to the fraction of line
length in particular crystallographic direction that
passes through atom centers (total radius/total
length).
Planar atomic density
❑ Planar density is simply the fraction of total
crystallographic plane area that is occupied by
atoms; the plane must pass through an atom’s
center for the particular atom to be included (unit
cell areas/plane area).
Atomic packing factor
❑ Atomic packing factor (APF) is defined as the
fraction of solid sphere volume in a unit cell, or

total sphere volume VS

𝐴𝑃𝐹 = =
total unit cell volume VC
Density calculation
The theoretical density of a crystalline material is:
𝑛 σ 𝐴𝐶 + σ 𝐴𝐴
𝜌=
𝑉𝐶 𝑁𝐴
where n is the number of formula units within unit
cell, AC is the sum of the atomic weights of all
cations, AA is the sum of the atomic weights of all
anions, VC is volume of the unit cell, and NA is
Avogadro’s number (6.023 x 1023 atoms/mol)
 Simple Cubic Structure (SC)
34

❑ Rare due to low

packing density (only
Po has this structure)
❑ Close-packed
directions are cube
edges.
 Simple Cubic Structure (SC)
35

❑ Rare due to low

packing density (only
Po has this structure)
❑ Close-packed
directions are cube
edges.
 Simple Cubic Structure (SC)
36

Coordination # = 6
❑ Rare due to low (# nearest neighbors)

packing density (only

Po has this structure)
❑ Close-packed
directions are cube
edges.
Atomic Packing Factor (APF)
Volume of atoms in unit cell*
APF =
Volume of unit cell
*assume hard spheres
• APF for a simple cubic structure = 0.52
volume
atoms atom
a 4
unit cell 1 p (0.5a) 3
3
R=0.5a APF =
a3 volume
close-packed directions
unit cell
contains 8 x 1/8 =
1 atom/unit cell
 Body Centered Cubic Structure (BCC)
38

❑Atoms touch each other along cube diagonals.

All atoms are identical. ex: Cr, W, Fe (), Tantalum, Molybdenum

2 atoms/unit cell: 1 center + 8 corners x 1/8. Coordination # = 8

 Atomic Packing Factor: BCC
39

3a

2a
R Close-packed directions:
a
length = 4R = 3 a
atoms volume
4
unit cell 2 p ( 3a/4) 3 APF for a body-centered cubic
3 atom
APF = structure = 0.68
volume
a3
unit cell
 Face Centered Cubic Structure (FCC)
40

❑ Atoms touch each other

along face diagonals.
❑ All atoms are identical; the
face-centered atoms are
shaded differently only for
ease of viewing. Ex: Al, Cu,
Au, Pb, Ni, Pt, Ag
 Face Centered Cubic Structure (FCC)
41

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8. Coordination # = 12

 Atomic Packing Factor: FCC
42

Close-packed directions: Unit cell contains:

length = 4R = 2 a 6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
2a

atoms volume
4
unit cell 4 p ( 2a/4) 3
a 3 atom
APF =
volume
a3
unit cell

APF for a face-centered cubic structure = 0.74; maximum achievable APF

 Hexagonal Close-Packed (HCP)
43
 • ABAB... Stacking Sequence
46

• 3D Projection • 2D Projection

A sites Top layer

c
B sites Middle layer

A sites Bottom layer

a

• Coordination # = 12 6 atoms/unit cell

• APF = 0.74 ex: Cd, Mg, Ti, Zn
• c/a = 1.633
 (a) (b)
Unit cells (a) of the simple hexagonal and
(b) hcp structures
 A

C
A Layer B Layer C Layer
A B

A-B-C close-packing of the FCC structure A-B-C close-packing of the FCC structure
 b
a
a
c
b
b
a
a
b
c a
b b
A Layer B Layer A Layer
a a

A-B-A close-packing of the HCP structure Cubic close Hexagonal close

packing packing
❑ Construction of the cubic
unit cell of the ccp
structure: (a) shows three
close-packed layers A, B
and C which are stacked
in (b) in the ‘ABC …’
sequence from which
emerges the cubic unit
cell which is shown in (c)
in the conventional
orientation.
❑ Construction of the
rhombohedral unit cell of
the ccp structure: the close-
packed layers (a) are
again stacked (b) in the
‘ABC …’ sequence but the
resulting rhombohedral
cell (c) does not reveal the
cubic symmetry.
Directions
z

c ❑ Direction [u v w] travels u
along a, v along b, w
along c
b
a y ❑ This direction travels 0
along a, 1 along b, and ½
x along c
 z
❑ Axis x y z
c
❑ Intercept 0 1 ½
❑ Clear fraction 0 2 1
(multiply through by 2)
b
a y ❑ With directions [u v w] denotes
a specific direction, <u v w>
x denotes a direction type
Directions, hexagonal
Direction in a hexagonal
lattice uses four-index
system, [u’v’tw’] called
Weber indices.
[uvw] → [u’v’tw’]
u‘ = (2u – v)/3
v‘ = (2v – u)/3
t = - (u’ + v’)
w‘= w
 Planes
z
❑ Planes are represented by
c
Miller indices (h k l)
❑ If plane does not cut axes
b
y intercept = 
a ❑ Axis x y z
x
❑ Intercept 1 2/3 
❑ Intercept 1 2/3 
❑ Invert 1 3/2 0
❑ Clear fraction 2 3 0 (multiply through
by 2)
❑ Here we have (2 3 0)
❑ (h k l) = plane; and {h k l} = plane type
Hexagonal planes and Miller indices

Hexagonal lattices and

Miller-Bravais indices
uses h, k, i, and l in
which h + k + i = 0; or
i = - (h + k)
Interstitial Sites
120o

O
O O T T
O T T T T T
T O
O O T
T T
O T
T T T T
O O
T OT
O T
O O
O
60o

Octahedral sites (O) in FCC. The Tetrahedral site (T) in FCC. Location of tetrahedral site (T)
body-centered site and one edge There is one within each corner, and octahedral sites (O) in HCP.
site are outlined. and together they form a Dotted lines show one of each
simple cubic array. type.
Exercise 1
Index the lattice planes
drawn in the figure. The c-
axis in all lattices is normal
to the plane of the page
and hence the index l is 0
in all cases.
Exercise 2
Index the lattice planes
drawn in the figure using
Miller – Bravais (hkil) and
Miller indices (hkl). The lattice
is hexagonal with the c-axis
is normal to the plane of the
page and hence the index l
is 0 in all cases.
Exercise 3
Give the indices of
the directions
e
marked on the b
figure below. In all a b
cases the axis not
shown is d c a
perpendicular to the
plane of the paper
and hence the index
w is 0 in all cases.
Exercise 4
❑ Index the following planes and directions:
c c c
b b b
1/2 1/2
a a a 2/3
1/2 1/4

1/4

1/3

1/4
Exercise 5
❑ Sketch the following planes and directions:
(402ത )[3ത 4ത 4] (2ത 26ത )[665] (63ത 2)[3ത 23ത ]
c c c
b b b
a a a
 Exercise 6

❑ Calculate the linear density of the [100] direction

for BCC.
❑ Calculate the atomic packing factor for SC, BCC,
and FCC and then calculate FCC planar density in
the (110).
 Atomic/ionic positions
65

❑ The more complicated the crystal structure and the

larger the unit cell, the more difficult it is to visualize
the atom or ion positions from diagrams or
photographs of models—atoms or ions may be hidden
behind others and therefore not seen.
❑ Another form of representation, the crystal plan or
crystal projection, is needed, which shows precisely
the atomic or ionic positions in the unit cell.
 ❑ The first step is to specify axes x, y and z from a
common origin and along the sides of the cell.
66

❑ By convention the ‘back left-hand corner’ is chosen

as the origin, the z-axis ‘upwards’, the y-axis to the
right and the x-axis ‘forwards’, out of the page.
❑ The atomic/ionic positions or coordinates in the unit
cell are specified as fractions of the cell edge
lengths in the order x, y, z.
 ❑ Thus in the bcc structure the atomic/ionic coordinates
67
are (000) (the atom/ion at the origin) and (½ ½ ½)
(the atom/ion at the center of the cube).
❑ As all eight corners of the cube are equivalent positions
(i.e. any of the eight corners can be chosen as the
origin), there is no need to write down atomic/ionic
coordinates (100), (110), etc.; (000) specifies all the
corner atoms, and the two-coordinates (000) and (½
½ ½) represent the two atoms/ions in the bcc unit cell.
 ❑ Inthe fcc structure, with four atoms/ions per unit
cell, the coordinates are (000), (½ ½ 0), (½ 0
68

½), (0 ½ ½).
69

Plans of (a) bcc structure, (b)

ccp or fcc structure, (c) Li2O
(antifluorite) structure, (d)
CaF2 (fluorite) structure.
Exercise 7
Cassiterite, tin dioxide, SnO2, adopts the rutile structure,
with a tetragonal unit cell, lattice parameters, a = 0.4738
nm, c = 0.3187 nm, with Sn atoms at: 0, 0, 0; ½, ½, ½;
and O atoms at: 3/10, 3/10, 0; 4/5, 1/5, ½; 7/10,
7/10, 0; 1/5, 4/5, ½. Taking one corner of the unit cell as
origin, determine the atom positions in nm and calculate the
unit cell volume in nm3. Draw a projection of the structure
down the c-axis, with a scale of 1 cm = 0.1 nm. Determine
its theoretical density.
Exercise 8
The structure of SrTiO3, is cubic, with a lattice parameter a
= 0.3905 nm. The atoms are at the positions: Sr: ½, ½, ½;
Ti: 0, 0, 0; O: ½, 0, 0; 0, ½, 0; 0, 0, ½. Sketch the unit
cell. What is the number of formula units in the unit cell?
What is the theoretical density of this material?

Note: This structure type is an important one, and belongs

to the perovskite family.
References
❑ B.D. Cullity: Elements of X-ray Diffraction, 2nd ed., Addison-
Wesley Publishing Company Inc., Reading, Massachusetts,
1978
❑ C. Hammond: The Basics of Crystallography and Diffraction,
3rd ed., Oxford University Press Inc., New York, 2009.
❑ R.J.D. Tilley: Crystals and Crystal Structures, John Wiley &
Sons Ltd., Chichester, West Sussex, England, 2006
❑ W.D. Callister, Jr.. Fundamentals of Materials Science and
Engineering, John Wiley & Sons, Inc., New York, 2001