Carbon Nanomaterials

and Technology
EE 6909

Dr. Md. Sherajul Islam

Assistant Professor

Department of Electrical and Electronics Engineering

Khulna University of Engineering & Technology
Khulna, Bangladesh
 LECTURE - 2
Basics: Crystal Structure
 The (Common) Phases of Matter

This doesn’t include Plasmas, but

these are the “common” phases!!

“Condensed Matter” includes both of

these. We’ll focus on Solids!
 Solids

• Solids consist of atoms or molecules undergoing

thermal motion about their equilibrium positions,
which are at fixed points in space.
• Solids can be crystalline, polycrystalline, or
amorphous.
• Solids (at a given temperature, pressure, volume)
have stronger interatomic bonds than liquids.
• So, Solids require more energy to break the
interatomic bonds than liquids.
 Crystal Structure
Topics
1. Periodic Arrays of Atoms
2. Fundamental Types of Lattices
3. Index System for Crystal Planes
4. Simple Crystal Structures
5. Direct Imaging of Crystal Structure
6. Non-ideal Crystal Structures
7. Crystal Structure Data
 Periodic Arrays of Atoms
Experimental Evidence of periodic
structures.
(See Kittel, Fig. 1.)
The external appearance of crystals gives some clues to this.
Fig. 1 shows that when a crystal is cleaved, we can see that it
is built up of identical “building blocks”. Further, the early
crystallographers noted that the index numbers that define plane
orientations are exact integers.

Cleaving a
Crystal
Elementary Crystallography
 The Three General Types of
Solids
Single Crystal
Polycrystalline
Amorphous
• Each type is characterized by the size of the
ordered region within the material.
An ordered region is a spatial volume in
which atoms or molecules have a regular
geometric arrangement or periodicity.
 Crystalline Solids

• A Crystalline Solid is the solid form of a substance in

which the atoms or molecules are arranged in a definite,
repeating pattern in three dimensions.
• Single Crystals, ideally have a high degree of order, or regular
geometric periodicity, throughout the entire volume of the
material.
• A Single Crystal has an atomic structure that
repeats periodically across its whole volume. Even
at infinite length scales, each atom is related to
every other equivalent atom in the structure by
translational symmetry.

Single Pyrite Crystal Amorphous Solid

Single Crystals
 Polycrystalline Solids
• A Polycrystalline Solid is made up of an aggregate of
many small single crystals (crystallites or grains).
Polycrystalline materials have a high degree of order over
many atomic or molecular dimensions. These ordered
regions, or single crystal regions, vary in size & orientation
with respect to one another. These regions are called grains (or
domains) & are separated from one another by grain
boundaries.
• The atomic order can vary from one domain to the next.
The grains are usually 100 nm - 100 microns in diameter.
Polycrystals with grains that are < 10 nm in diameter are called
nanocrystallites.
Polycrystalline
Pyrite Grain
 Amorphous Solids
• Amorphous (Non-crystalline) Solids are
composed of
randomly orientated atoms, ions, or molecules
that do not form defined patterns or lattice
structures. Amorphous materials have order only
within a few atomic or molecular dimensions. They
do not have any long-range order, but they have
varying degrees of short-range order. Examples of
amorphous material include amorphous silicon,
plastics, & glasses.
 Departures From the “Perfect Crystal”

• A “Perfect Crystal” is an idealization that does not

exist in nature. In some ways, even a crystal surface
is an imperfection, because the periodicity is
interrupted there.
• Each atom undergoes thermal vibrations around their
equilibrium positions for temperatures T > 0K. These
can also be viewed as “imperfections”.
• Real Crystals always have foreign
atoms (impurities), missing atoms
(vacancies), & atoms in between
lattice sites (interstitials) where
they should not be. Each of these
spoils the perfect crystal structure.
 Crystallography

Crystallography ≡ The branch of science that deals with the

geometric description of crystals & their internal arrangements.
It is the science of crystals & the math used to describe them.
It is a VERY OLD field which pre-dates Solid State Physics
by about a century! So (unfortunately, in some ways) much of
the terminology (& theory notation) of Solid State Physics
originated in crystallography.
 Crystallography

A Basic Knowledge of Elementary

Crystallography is Essential
for Solid State Physicists!!!
• A crystal’s symmetry has a profound influence on many of
its properties.
• A crystal structure should be specified completely,
concisely & unambiguously.
• Structures are classified into different types according to
the symmetries they possess.
• In this course, we only consider solids with “simple”
structures.
 Crystal Lattice

Crystallography focuses on the geometric properties of crystals. So, we

imagine each atom replaced by a mathematical point at the equilibrium
position of that atom. A Crystal Lattice (or a Crystal) ≡ An idealized
description of the geometry of a crystalline material. A Crystal ≡ A 3-
dimensional periodic array of atoms. Usually, we’ll only consider ideal
crystals. “Ideal” means one with no defects, as already mentioned. That is,
no missing atoms, no atoms off of the lattice sites where we expect them to
be, no impurities,…Clearly, such an ideal crystal never occurs in nature.
Yet, 85-90% of experimental observations on crystalline materials is
accounted for by considering only ideal crystals!

Platinum Surface Crystal Lattice

(Scanning Tunneling
Platinum Microscope) Structure of Platinum
 Crystal Lattice

Mathematically 2 Dimensional Example


A Lattice is Defined as 

an Infinite Array of y

Points in Space
B C
in which each point has b α
D E

identical surroundings
to all others. The points O a A x

are arranged exactly

in a periodic manner.
 Ideal Crystal ≡ An infinite periodic repetition
of identical structural units in space.

• The simplest structural unit we can imagine

is a Single Atom. This corresponds to a
solid made up of only one kind of atom ≡
An Elemental Solid.
• However, this structural unit could also be a
group of several atoms or even molecules.
The simplest structural unit for a given
solid is called the BASIS
• The structure of an Ideal Crystal can
be described in terms of a mathematical
construction called a Lattice.
A Lattice ≡
• A 3-dimensional periodic array of points in space. For a
particular solid, the smallest structural unit, which when
repeated for every point in the lattice is called the Basis.
• The Crystal Structure is defined once both the lattice & the
basis are specified. That is

Crystal Structure ≡ Lattice +

Basis
 Crystalline Periodicity

• In a crystalline material, the equilibrium

positions of all the atoms form a crystal
Crystal Structure ≡ Lattice + Basis

Lattice 

2 Atom Basis 

Crystal 
Structure
 Crystalline Periodicity

Crystal Structure ≡ Lattice + Basis

For another example, see the figure.
Crystal
Structure
Lattice
 Basis


 Crystalline Periodicity

Crystal Structure ≡ Lattice + Basis

For another example, see the figure.

Basis Crystal
 Structure

Lattice 
A Two-Dimensional (Bravais) Lattice
with Different Choices for the Basis
 2 Dimensional Lattice
Lattice with atoms at the corners
of regular hexagons
y

y B C D E
b α
B C D
E O x
b F G a A
x H
O a A
 The atoms do not necessarily lie at lattice
points!!
Crystal Structure = Lattice + Basis

Basis


Crystal 
Structure
 Bravais Lattice
• An infinite array of discrete points with an
arrangement and orientation that appears
exactly the same, from any of the points
the array is viewed from.
• A three dimensional Bravais lattice
consists of all points with position vectors
R that can be written as a linear
combination of primitive vectors. The
expansion coefficients must be integers.
Honeycomb net: Bravais lattice with
two point basis
 Translation Vector T

Translation(a1,a2), Nontranslation
Vectors(a1’’’,a2’’’)
 Primitive Unit Cell
• A primitive cell or primitive unit cell is a
volume of space that when translated through all
the vectors in a Bravais lattice just fills all of
space without either overlapping itself or leaving
voids.
• A primitive cell must contain precisely one lattice
point.
 Fundamental Types of Lattices
• Crystal lattices can be mapped into
themselves by the lattice translations T
and by various other symmetry operations.
• A typical symmetry operation is that of
rotation about an axis that passes through
a lattice point. Allowed rotations of : 2 π,
2π/2, 2π/3,2π/4, 2π/6
• (Note: lattices do not have rotation axes
for 1/5, 1/7 …) times 2π
Five fold axis of symmetry cannot
exist
 Two Dimensional Lattices
• There is an unlimited number of possible
lattices, since there is no restriction on the
lengths of the lattice translation vectors or
on the angle between them. An oblique
lattice has arbitrary a1 and a2 and is
invariant only under rotation of π and 2 π
about any lattice point.
 UNIT CELLS (UC)
 A unit cell (also sometimes causally referred to as a cell) is a representative unit of the
structure.
 which when translationally repeated (by the basis vector(s)) gives the whole structure.
 The term unit should not be confused with ‘having one’ lattice point or motif
(The term primitive or sometimes simple is reserved for that).
 If the structure is a lattice, the unit cell will be unit of that (hence will have points* only).
 If the structure under considerations is a crystal, then the unit cell will also contain atoms
(or ions or molecules etc.).
 Note: Instead of full atoms (or other units) only a part of the entity may be
present in the unit cell (a single unit cell)
 The dimension of the unit cell will match the dimension of the structure**:
 If the lattice is 1D  the unit cell will be 1D,
if the crystal is 3D  then the unit cell will be 3D,
if the lattice is nD  the unit cell will be nD.

Lattice Will contain lattice points only

Unit cell of a
Crystal Will contain entities which decorate the lattice
* Strangely in crystallography often we even ‘split a point’ (and say that 1/8 th belongs to the UC).
** One can envisage other possibilities– e.g. a 2D motif may be repeated only along one direction (i.e. the crystal is 3D but the repeat direction
is along 1D)
 Why Unit Cells?
Instead of drawing the whole structure I can draw a representative part and specify
the repetition pattern.

ADDITIONAL POINTS
 A cell is a finite representation of the infinite lattice/crystal
 A cell is a line segment (1D) or a parallelogram (2D) or a parallelopiped (3D) with lattice
points at their corners  This is the convention
 If the lattice points are only at the corners, the cell is primitive.
Hence, a primitive unit cell is one, wherein the lattice points are only at the corners of the
unit cell (or the ends of a line segment unit cell in 1D)
 If there are lattice points in the cell other than the corners, the cell is
non-primitive.


Consider an infinite pattern made of squares



This way the infinite information content of
a crystal can be reduced to the information
This can be thought of as
required to specify the contents of a unit


a single square repeated cell (along with the lattice translation

in x and y directions vectors).
In general the following types of unit cells can be defined:
 Primitive unit cell
 Non-primitive unit cells
 Voronoi cells
 Wigner-Seitz cells
 1D

 Unit cell of a 1D lattice is a line segment of length = the lattice parameter

 this is the PRIMITIVE UNIT CELL (i.e. has one lattice point per cell).

Each of these lattice points contributes half a lattice point to the unit cell

Primitive UC

Contributions to the unit cell: Left point = 0.5, Middle point = 1, Right point = 0.5. Total = 2

Doubly Non-
primitive UC

Triply Non-
primitive UC
  Unit cell of a 1D crystal will contain Motifs in addition to lattice
points
 NOTE:
 The only kind of motifs possible in 1D are line segments
 Hence in ‘reality’ 1D crystals are not possible as Motifs typically
have a finite dimension (however we shall call them 1D crystals and
use them for illustration of concepts)
 We could have 2D or 3D motifs repeated along 1D (hence
periodicity and ‘crystallinity’ is only along 1D)
Correct unit cell Though the whole lattice point is
shown only half belongs to the UC

Each of these atoms contributes ‘half-atom’ to the unit cell

Though this is the correct unit cell

Often unit cells will be drawn like this

 Unit cell in 1D is described by 1 (one) lattice parameter: a

 2D

 Unit cell in 2D is described by 3 lattice parameters: a, b,  b 

a

 Special cases include: a = b;  = 90 or 120

 Unit Cell shapes in 2D  Lattice parameters

 Square  (a = b,  = 90)
 Rectangle  (a, b,  = 90)
 120 Rhombus  (a = b,  = 120)
 Parallelogram (general)  (a, b, )
 2D

UC-1 Note: basis vectors

 (& included angle)

will change based on
b the ‘unit cell’ chosen
[which implies that
lattice parameters
90
 will change as well !]

Rectangular a
lattice

Note: these are the

basis vectors (and
included angle) for
UC-1 above

90

Note: Symmetry of the Lattice or the crystal is not altered by our choice of unit cell!!
 Different kinds of CELLS

Unit cell
A unit cell is a spatial arrangement of atoms which is tiled in three-dimensional
space to describe the crystal.
Primitive unit cell
For each crystal structure there is a conventional unit cell, usually chosen to make
the resulting lattice as symmetric as possible. However, the conventional unit cell is
not always the smallest possible choice. A primitive unit cell of a particular crystal
structure is the smallest possible unit cell one can construct such that, when tiled, it
completely fills space.
Wigner-Seitz cell
A Wigner-Seitz cell is a particular kind of primitive cell, which has the same
symmetry as the lattice.
 Q&A

How many ‘shapes’ of primitive unit cells are possible?

 1D → one.
 2D, 3D → Infinite (few examples in 2D given below).

1D

2D
 Wigner-Seitz Cell

 Is a primitive unit cell with the symmetry of the lattice

 Created by Voronoi tessellation of space
 The region enclosed by the Wigner-Seitz cell is closer to a
given lattice point than to any other lattice point

Square lattice
Centred Rectangular lattice

Wigner-Seitz
cells