Unit 1

Crystallographic description of the crystalline materials

Structure of
Unit 1 (indexing of planes, Direction and Symmetry),
Material
Characterization of materials using XRD

In addition to slides, refer to class notes and textbooks.

Lecture 1
 Atomic structure
 Every atom consists of a small nucleus composed of
protons and neutrons, which is encircled by moving
electrons in their orbitals, specific energy levels.
 The top most ortibal electrons, valence electrons, affect
most material properties that are of interest to engineer.
E.g.: chemical properties, nature of bonding, size of atom,
optical/magnetic/electrical properties.
 Electrons and protons are negative and positive charges of
the same magnitude being 1.60x10-19 coulombs.
 Neutrons are electrically neutral.
 Protons and neutrons have approximately the mass,
1.67x10-27 kg, which is larger than that of an electron,
9.11x10-31 kg.
 Atomic structure (contd…)
 Atomic number (Z) - is the number of protons per
atoms.
 Atomic mass (A) - is the sum of the masses of protons
and
neutrons within the nucleus.
 Atomic mass is measured in atomic mass unit (amu) where
1amu=(1\12) the mass of most common isotope of carbon
atom, measured in grams.
 A  Z+N, where N is number of neutrons.
 Isotopes - atoms with same atomic number but different
atomic masses.
 A mole is the amount of matter that has a mass in grams
equal to the atomic mass in amu of the atoms. Thus a
mole of carbon has a mass of 12 grams.
 Atomic structure (contd…)
 The number of atoms or molecules in a mole of substance is
called the Avogadro’s number, Nay. Nay=1gram/1amu =
6.023x1023.
E.g.: Calculating the number of atoms per cm3, n, in a piece
of
material
n = Nav ofdensity
/ where
(g/cmM
3)
is the atomic mass in amu.
M,
Thus, for graphite (carbon) with a density  = 1.8 g/cm3 and M =12, n =
6.023 1023 atoms/mol 1.8 g/cm3 / 12 g/mol) = 9 1022
atoms/cm3.

 Most solid materials will have atomic density in the order of

6x1022, that’s about 39 million atoms per centimeter.
 Mean distance between atoms is in the range of 0.25 nm. It
gives an idea about scale of atomic structures in solids.
 Atomic Bonding in Solids
 Two questions need to be answered: why the atoms are
clustered together?, and how they are arranged?

 Bonds are two kinds – Primary, and Secondary

 Primary bonds – relatively stronger. Exists in almost

all solid
materials.
E.g.: Ionic, Covalent, and Metallic bonds.

 Secondary bonds – relatively weaker bonds. Exists in many

substances like water along with primary bonds.
E.g.: Hydrogen, and van der Waals forces.
 Atomic Bond in Solids

Atomic bonding

Primary bonding

Secondary bonding
ionic covalent metallic

Fluctuating Polar
permanent
induced induced
 Primary inter-atomic bonds

 These bonds invariably involves valence electrons.

 Nature of bond depends on electron arrangement in respective

atoms.

 Atoms tend to acquire stable electron arrangement in their

valence orbitals by transferring (ionic), sharing (covalent, and
metallic) valence electrons. This leads to formation of bonds.

 Bond energies are in order of 1000 kJ/mol.

 Ionic bond
 This primary bond exists between two atoms when transfer of
electron(s) results in one of the atoms to become negative (has
an extra electron) and another positive (has lost an electron).
 This bond is a direct consequence of strong Coulomb
attraction between charged atoms.
 Basically ionic bonds are non-directional in nature.
 In real solids, ionic bonding is usually exists along with
covalent bonding.

E.g.: NaCl. In the molecule, there are more electrons around

Cl, forming Cl- and fewer electrons around Na, forming Na+.
 Covalent bond
 This bond comes into existence if valence electrons are shared
between a pair of atoms, thus acquire stability by saturating
the valence configuration.
 Covalent bonds are stereospecific i.e. each bond is between a
specific pair of atoms, which share a pair of electrons (of
opposite magnetic spins).
 Typically, covalent bonds are very strong, and directional in
nature.

E.g.: H2 molecule, where an electron from each of the atom

shared by the other atom, thus producing the covalent bond.
 Metallic bond

 This bond comes into existence if valence electrons are shared

between number of atoms, i.e. arranged positive nucleuses
are surrounded by electron pool.
 Shared electrons are not specific to a pair of atoms, in contrast
to Covalent bond, i.e. electrons are delocalized.
 As shared electrons are delocalized, metallic bonds are non-
directional.
 Very characteristic properties of metals like high thermal and
electrical conductivities are result of presence of delocalized
electron pool.
 Secondary inter-atomic bonds

 These bonds involves atomic or molecular dipoles.

 Bonds can exist between induced and permanent dipoles

(polar molecules).

 Bond comes into existence because of Columbic attraction

between positive end of one dipole and negative end of
another dipole.

 Bond energies are in order of 10 kJ/mol

 Secondary inter-atomic bonds (contd...)
 Existence of these depends on three kinds of dipoles –
fluctuating dipoles, Polar-molecule dipoles and Permanent
dipoles.

 Permanent dipole bonds are also called Hydrogen bonds as

covalently bonded hydrogen atoms – for example C-H, O-H,
F-H – share single electron becomes positively charged
proton that is capable of strong attractive force with the
negative end of an adjacent molecule.

 Hydrogen bonds is responsible for water to exist in liquid

state at room temperature.
 Crystal Structures
 All solid materials are made of atoms/molecules, which are
arranged in specific order in some materials, called crystalline
solids. Otherwise non-crystalline or amorphous solids.

 Groups of atoms/molecules specifically arranged – crystal.

 Lattice is used to represent a three-dimensional periodic array

of points coinciding with atom positions.

 Unit cell is smallest repeatable entity that can be used to

completely represent a crystal structure. It is the building
block of crystal structure.
 Unit cell

It is characterized by:
 Type of atom and their radii, R
 Cell dimensions, a and c (for hexagonal structures)
 Number of atoms per unit cell, n
 Coordination number (CN)– closest neighbors to an atom
 Atomic packing factor, APF

Most common unit cells – Face-centered cubic, Body-

centered cubic and Hexagonal.
Schematic Unit Cells
 Common Crystal Structures

Unit Cell n CN a/R APF

Simple Cubic 1 6 4/ 4 0.52

Body-Centered Cubic 2 8 4/ 3 0.68

Face-Centered Cubic 4 12 4/ 2 0.74

Hexagonal Close Packed 6 12 0.74

Lecture 2
 Ideal Crystal

• An ideal crystal is a periodic array of structural units, such

as atoms or molecules.
• It can be constructed by the infinite repetition of these
identical structural units in space.
• Structure can be described in terms of a lattice, with a group
of atoms attached to each lattice point. The group of atoms
is the motif.
 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.
Motif
 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 2π about any lattice point.
 Lattices and Crystal Systems

There are 5 possible planar (2-d) lattices in

different coordinate systems:

Translating these lattices into the 3 rd dimension

generates the 14 unique Bravais Lattices
Two Dimensional Lattices
Honeycomb net: Bravais lattice with two point basis

Pairs of points joined be heavy solid lines are

identically placed in the primitive cells
(parallelograms) of the underlying Bravais
lattice
Honeycomb: NOT Bravais; the array of points
has the same appearance when viewed from P
or Q; the view from R is rotated through 180˚
Three Dimensional Lattice Types

Cubic
The Bravais Lattices

Cubic
The Bravais Lattices
 System Type Edge - Angle Relations Symmetry

Triclinic P abc Ī

The Six Crystal Systems



Monoclinic P (b = twofold abc

axis)  =  = 90   2/m
C
P (c = twofold abc
axis)    = 90  
C
Orthorhombic P
C (or A, B) abc mmm
I  =  =  = 90
F

Tetragonal P a1 = a2  c 4/mmm
I  =  =  = 90
Hexagonal R a1 = a2  c m
P  =  = 90,  = 120 6/mmm

Cubic P a1 = a2 = a3
I  =  =  = 90 m3m
F

P=Primitive F=Face Centered I=Body Centered C=Centered on opposing faces

Fourteen Bravais Lattices in Three Dimensions
Fourteen Bravais Lattices …
Lecture 3
 Symmetry

Two types of repetitions underlie the periodicity

of 1-D, 2-D and 3-D lattices:

• Lattice translation

• Symmetry – various symmetry operators act

to change the orientation of the motif of the
lattice
Symmetry
 Symmetry Operations

• Translational
• Reflection at a plane
• Rotation about an axis
– Inversion through a point
• Glide (=reflection + translation)
• Screw (=rotation + translation)
 Translations
There is a new 2-D symmetry operation when we
consider translations
The Glide Plane:
A combined reflection repeat
and translation

Step 2: translate

Step 1: reflect
(a temporary position)
 Reflection
Rotation
Symmetry Elements
Center of
Symmetry

Note: front back inverted front

Notice notation 2 bar
Rotation with _
define: Motif Inversion note 2 = m
Symmetry operators: (a) 1-fold, (b) 2-fold (c) 3 fold, (d)
4-fold, (e) 6-fold axes, (f) mirror plane,m (g) mirror
plane + 2-fold axis 2m (h) mirror plane + 4-fold axis
 Home Assignments

Find out Symmetry Elements in

Tetrahedron
Octahedron & Cube
3-D Symmetry
Symmetry Elements in Tetrahedron
Symmetry elements characterizing the tetrahedron are:

1. four 3-fold rotation axes, each one perpendicular to a

face and passing through the opposite vertex

2. three 4-fold rotoinversion axes, each one passing

through the middle points of a pair of opposite edges

3. six mirror planes, each one passing through both the

edge shared by two faces and the middle point of the
opposite edge shared by the other two faces split into
2 equal parts by the plane itself.

4. From a crystallographic point of view it belongs to

the 43m point group (in the symbol of the point
group, 4 indicates a 4-fold rotoinversion axis, 3 a 3-
fold rotation axis and m a mirror plane).
Symmetry Elements in Cube and Octahedron
The two polyhedra share the same symmetry elements,
characteristic of m3m crystallographic point group:

1. three 4-fold rotation axes, each one perpendicular

to a pair of parallel faces of the cube and passing
through two opposite vertices of the octahedron

2. three mirror planes perpendicular to these 4-

fold rotation axes, named principal planes

3. four 3-fold rotation axes each one perpendicular to

a pair of parallel faces of the octahedron and
passing through two opposite vertices of the cube
4. six 2-fold axes passing through the
middle points of opposite edges in both
polyhedra

5. three mirror planes perpendicular to

these 2-fold rotation axes,
named secondary planes

6. an inversion centre, as a consequence of

the association of even rotation axes
(both 2-fold and 4-fold) with planes
placed orthogonally to them
There are 32 point group symmetry and 230 space group symmetry
 Hermann-Mauguin Symbols
• To begin, write a number representing each of the unique
rotation axes present. A unique rotation axis is one that
exists by itself and is not produced by another symmetry
operation.
• In this case, all three 2-fold axes are unique, because
each is perpendicular to a different shaped face, so we
write a 2 (for 2-fold) for each axis, A:

2 2 2
 Hermann-Mauguin Symbols
• Next we write an "m" for each unique mirror
plane. Again, a unique mirror plane is one that is
not produced by any other symmetry operation.

• In this example, we can tell that each mirror is

unique because each one cuts a different looking
face. So, we write:

2m2m2m
 Hermann-Mauguin Symbols

• If any of the axes are perpendicular to a mirror

plane we put a slash (/) between the symbol for
the axis and the symbol for the mirror plane.
• In this case, each of the 2-fold axes are
perpendicular to mirror planes, so our symbol
becomes:

2/m2/m2/m
Concept Check (Revision)
Symmetry
 Symmetry
Translations (Lattices)
2-D translations = a net

b
Unit cell

Unit Cell: the basic repeat unit that, by translation only, generates
the entire pattern
 Symmetry
Translations (Lattices)
2-D translations = a net
b

Pick any point

Every point that is exactly n repeats from that point is an equipoint to the
original
 Translations
The lattice and point group symmetry interrelate, because
both are properties of the overall symmetry pattern

6 6 6 6 6 6 6 6
9 9 9 9 9 9 9 9

6 6 6 6 6 6 6 6
9 9 9 9 9 9 9 9

6 6 6 6 6 6 6 6
9 9 9 9 9 9 9 9

6 6 6 6 6 6 6 6
9 9 9 9 9 9 9 9

Good unit cell choice. Why? Are there other symmetry elements ?
 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.

Primitive and Non Primitive Cells
Choice of Primitive Cells
 Wigner-Seitz Cells
[How to Choose Primitive Unit Cell]
Primitive cell of a three dimensional
space lattice
Unit and Primitive Cells – FCC and BCC