The Structure of Crystalline

Solids
and Non-Crystaline Materials
Crystal Structures
are the way atoms, ions, or molecules are spatially arranged
Atomic or Ionic Arrangements
No Order
- Atoms or ions have no orderly arrangement.
Atomic or Ionic Arrangements
Short-Range Order
- If the special arrangement of the atoms extends only to the atoms
nearest neighbors.
- Examples are (b) water molecules in steam and (c) silicate glass.
Atomic or Ionic Arrangements
Long-Range Order
- The atoms or ions in these materials form a regular repetitive,
grid-like pattern, in three dimensions (crystal structure).
Unit Cells
- The unit cell is the basic structural unit or building block of the crystal
structure and defines the crystal structure by virtue of its geometry and the atom
positions within.
-More than a single unit cell may be chosen for a particular crystal structure, but our
goal in choosing a unit cell for a crystal structure is to find the single repeat
unit that, when duplicated and translated, reproduces the entire crystal structure.
Unit Cells
The atomic order in crystalline solids indicates that smallest
groups of atoms that form a repetitive pattern. Thus, in
describing crystal structures, it is often convenient to subdivide
the structure into small repetitive entities. The entire lattice is
generated by the repetition of the unit cell in different
directions.
Parameters of a Unit Cell
There are six parameters of a unit cell. These are the 3
edges which are a, b, c and the angles between the edges
which are α, β, γ. The edges of a unit cell may be or may not
be perpendicular to each other.
Characteristics of Unit Cell

The following characteristics define a unit cell:

 A unit cell has three edges a, b and c and three
angles α, β and γ between the respective edges
 The a, b and c may or may not be mutually
perpendicular
 The angle between edge b and c is α, a and c
is β and that of between a and b is γ
Types of Unit Cell
 Crystal Lattice
The crystal lattice is
the symmetrical three-dimensional
structural arrangements of atoms,
ions or molecules (constituent
particle) inside a crystalline solid as
points. It can be defined as the
geometrical arrangement of the
atoms, ions or molecules of the
crystalline solid as points in space.
Formation of Lattice
7 Basic Crystal
Lattice Systems
-Formation of unit cells
takes place in seven
forms, namely:

1. Cubic
2. Tetragonal
3. Orthorhombic
4. Rhombohedral
(Trigonal)
5. Monoclinic
6. Triclinic
7. Hexagonal
Formation of Lattice
Cubic Lattice: Cubic lattice is formed into three possible
geometries of unit cells: primitive, body-centred and face centred
unit cells. In a cubic lattice, all the edges are equal and the angle
between their faces is 90° that is, mutually perpendicular.

Tetragonal Lattice: The formation of tetragonal lattice takes

place in two geometries of unit cells: primitive and body centred
unit cells. In a tetragonal lattice, only one edge has different length
and angle between respective edges is 90° that is, mutually
perpendicular
Formation of Lattice
Orthorhombic Lattice: There are four types of orthorhombic lattice
mainly: primitive, end-centred, body-centred and face centred. In
orthorhombic lattice, the edge lengths are unequal in nature and the angle
between respective edges is 90° that is, mutually perpendicular

Monoclinic Lattice: Monoclinic lattice is formed from two types of unit cells
namely: primitive and end centred. Monoclinic lattice has unequal sides and
two angles between the faces of the lattice are 90°.

Hexagonal Lattice: Hexagonal lattice is formed from only one type of unit
cell that is, primitive. In hexagonal lattice, only one side and two angles are
90° and one angle is 120°.
Formation of Lattice
Rhombohedral Lattice: Rhombohedral Lattice is also formed
from one type of unit cell that is, primitive. In Rhombohedral
Lattice all the sides are equal and two angles between the faces
of the rhombohedral lattice are less than 90°.

Triclinic Lattice: The formation of triclinic lattice also takes place

from one type of unit cell that is, primitive. In triclinic lattice all the
sides are unequal and none of the angles between the faces of
the triclinic lattice are 90°.
Formation of Lattice
1. Cubic Lattice
a =b =c

𝛂 = 𝞫 = 𝝲 = 90o

3 Types of Cubic Systems

1. Simple
2. BCC
3. FCC
Polonium
Diamond

Copper
Garnet
2. Tetragonal Lattice
a =b ≠c

𝛂 = 𝞫 = 𝝲 = 90o

2 Types of Tetragonal Systems

1. Simple
2. BCC
Stannic oxide (SnO2) - abrasive, sometimes in
Titanium dioxide (TiO2) - paints, coatings,
mixtures with lead oxide, for polishing glass,
adhesives
marble, silver, and jewelry.

Wulfenite – Molybdenum found on it can be

used to make connectors and wires in mobile
phones.
3. Orthorhombic Lattice
a≠ b≠c

𝛂 = 𝞫 = 𝝲 = 90o

4 Types of Orthorhombic
Systems

1. Simple
2. Base Centered
3. BCC
4. FCC
Magnesium sulfate (MgSO4) - short-term relief of
Potassium nitrate (KNO3) - preservatives,
constipation. It is also used as a soaking solution
fertilizers, tree stump removal, rocket
to relieve injuries.
propellants, and fireworks.

Tanzanite
4̀. Rhombohedral Lattice
The rhombohedral lattice is also known as trigonal,
a =b =c

𝛂 = 𝞫 = 𝝲 ≠ 90o
Quartz - used to make fiberglass, glass, bricks Sodium nitrate (NaNO3) - a common
and ceramics. preservative used in cured meat products
including bacon, deli meat, and jerky.

Agate and Tiger's Eyes

5. Monoclinic Lattice
a≠ b≠c

𝞫 = 𝝲 = 90o and 𝛂 ≠ 90o

2 Types of Monoclinic Systems

1. Simple
2. Base-Centered
Gypsum - used as a fertilizer and as the main Diopside - used in ceramics, glass-making,
constituent in many forms of plaster, blackboard biomaterials, nuclear waste immobilization, and
or sidewalk chalk, and drywall fuel cell technology
6. Triclinic Lattice
a≠ b≠c

𝛂 ≠ 𝞫 ≠ 𝝲 ≠ 90o
Turquoise Amazonite

Feldspar - glass for drinking, glass for

protection, fiberglass for insulation, the floor
tiles and shower basins, and the tablewares
7. Hexagonal Lattice
a =b ≠c

𝛂 = 𝞫 = 90o and 𝝲 = 120o

Aquamarine

Ice XI
Bravais Lattice
In 1850, Auguste Bravais showedthat crystals couldbe divided into14 distinctlattices.
Auguste Bravais - French Bravais Lattice - 14 different
physicist best remembered for 3-dimensional configurations
his work on the lattice theory into which atoms can be
of crystals; Bravais lattices are arranged in crystals.
named for him. Bravais was
responsible for the revival of
interest in the study of the
external forms of crystals and
their internal structures. After
intensive study of lattice
properties, he derived in 1848
the 14 possible arrangements
of points in space.
14 Bravais Lattices
1. Simple cubic
2. Face-centered cubic
3. Body/Volume-centered cubic
4. Hexagonal
5. Rhombohedral or Trigonal
6. Simple tetragonal
7. Body/Volume-centered
tetragonal
8. Simple orthorhombic
9. End/Base-centered
orthorhombic
10. Face-centered orthorhombic
11. Body/Volume-centered
orthorhombic
12. Simple monoclinic
13. Base-centered monoclinic
14. Triclinic
 4 Centering Operations

1. no centering (or “simple”)

2. face-centering
3. end or base-centering
4. body or volume-centering
MetallicCrystal Structures
Metallic Structures are
structures made entirely of
metal elements bonded
through metallic bonding.

Metallic Bonding - bonding

through an electrostatic
force between delocalised
electrons and positivvely-
charged metal atoms
Properties of Metallic Crystals

Very high melting and boiling point

good conductors of electricity and heat (thermal energy)

 ductile - capable of being stretched out to from thin wires

malleable - capable of being hammered out to thin sheets

 Body-centered
Cubic Structure

Another common metallic crystal

structure.
Atoms are located at all eight corners
and a single atom at the cube center.
Typically has less strength than metals
with FCC and HCP structure.
A total of 2 atoms may be assigned
to a given unit cell
The Three Main Crystalline Structure of Metals

Face-centered
Cubic Structure
one of the most common
crystalline structure
found among many metals
atoms located at each of the
corners and cennter of each
faces
 eight atoms distributed at the
eight corners, each of the eight
atoms are part of other adjacent
cubic structures as well.

 some of the familiar metals with

this crystal structure are copper,
aluminum, dilver, and gold.

 a total of 4 atoms may be

assigned to a given unit cell.
 Hexagonal Close-
Packed Crystal
Structure
More complex than FCC and BCC. Can
be found in several metals including
titanium, calcium, cobalt, zinc, and
zirconium.
HCP structure has a few ways where
slip ping can occur, giving the metal
high strength but a brittle failure
mode.
6 atoms are assigned to each unit cell.
Assigned Number of Atoms

Body-centered and Face-centered Cubic

Structure
Hexagonal Close-
Packed Crystal
Structure
Crystal Structures
Crystalline Materials - atoms are situated in repeating or periodic array over
large atomic distances.

Crystal structures are made up of:

Crystal Lattice - symmetrical three- dimensional structural arrangements

of constituent particles.

Crystal Basis - repeating units of atoms that can form the overall
crystal structure.
 Crystal Structures
Crystalline Materials
- One in which the atoms are situated in a repeating or periodic array over large
atomic distances (long-range order), and are bonded to its nearest neighbor atoms.
- Examples includes metals (e.g., Cu, Al, Fe, W, Mg), semiconductors (e.g., Si, Ge,
GaAs),
advance ceramics (e.g., ZrO2, Al2O3, BaTiO3), diamond, and other materials.
Crystal Structures
Single Crystal
- Crystalline material consist of one large
crystal.
Crystal Structures
Polycrystalline
- Composed of many small crystals with varying
orientations in space.
Crystal Structures
Polycrystalline Material
- Grain and Grain Boundaries
Polycrystalline
Polycrystalline materials are solids that consist of many small crystals (the “grains”). The
grains are separated by grain boundaries and normally have random crystallographic
orientations. The size of the grains may vary from nanometers to millimeters.

Polycrystalline solids are composed of many numbers of crystalline solids. Crystalline solids
or crystals have ordered structures and symmetry, but in a polycrystalline structure, the long-
range order has been disrupted.
Polycrystalline
One of the common use of polycrystalline is on making of Solar Panels.

Compared to their efficiency, polycrystalline solar panels have less cost per watt making them cheaper
than the monocrystalline type. The reason for this is that the manufacturing process creates less waste and
uses less energy resulting in less production costs.
Crystal Structures
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.
- There is an extremely large number of different crystal structures all having long-
range atomic order.
Determination of Crystal Structures
X-Ray Diffraction and Bragg’s Law
relationship among x-ray wavelength, interplanar spacing, and angle of diffraction
for constructive interference.

The structure of the crystal

causes the X-rays to diffract in
specific directions. Through
analysis of the intensities and
angles of these beams, the
position and arrangement of
electrons within the crystalline
structure can be determined.
Isotropy and Anisotropy : Materials
Isotropy and Anisotropy : Crystals

Anisotropy in crystals is due to the different Disordered entities is observed in

arrangement of entities along different different directions, this same
directions. disorder causes isotropy.
Polymorphism and Allotropy
What is Polymorphism?

Polymorphism is the ability of a solid material to exist in more than one form
or crystal structure. We can find this characteristic in any crystalline material
such as polymers, mineral, metal, etc.

Polymorphism describes molecules, while Allotropy is used to describe

atoms. Polymorphism has many uses whether it was in pharmaceutical,
explosives or even food.

Polymorphism is the presence of several different forms of the same solid

material. It means that the compounds of this type may have more than one
crystal structure. Polymorphism occurs in chemical compounds whereas
Allotropy occurs in chemical elements.
Reasons Why Polymorphism Occurs in
Crystalline Materials:
• Polarity of solvent

• Presence of impurities

• The level of supersaturation at which the material

starts to crystalize

• Temperature

• Changes in stirring conditions

Polymorphism and Allotropy
What is Allotropy?

Allotropy is the existence of two or more different physical forms of a

chemical element. These forms exist in the same physical state, mostly in
the solid state. Allotropes contain atoms of the same chemical element that
binds with each other in different ways.

Moreover, these different forms may have different physical properties

because they have different structures and their chemical behaviors may
vary as well. One allotrope may convert into another when we change
some factors such as pressure, light, temperature, etc. Therefore these
physical factors affect the stability of these compounds.
Common Examples of Allotropes
• Carbon - diamond, graphite, graphene,
fullerenes, etc.

• Phosphorous - white phosphorous, red phosphorous,

diphosphorous, etc.

• Oxygen - dioxygen, ozone, tetraoxygen, etc.

• Boron - amorphous boron, alpha rhombohedral boron, etc.

• Arsenic - yellow arsenic, grey arsenic, etc.

Crystalline and Non-Crystalline Materials
CRYSTALLINE VS. AMORPHOUS

Crystalline material is one in which the atoms Amorphous material contains atoms and ions
are situated in a repeating or periodic array over that are not arranged in a long-range, periodic,
large atomic distances that is, long-range order and repeatable manner and possess only short-
(LRO) exists, such that upon solidification, the range order (SRO). This means that order
atoms will position themselves in a repetitive exists only in the immediate neighborhood of
three-dimensional pattern, in which each atom is an atom or a molecule.
bonded to its nearest neighbor atoms.
Examples: glasses, polymers
Examples: metals, alloys,
Crystalline and Non-Crystalline Materials
CRYSTALLINE VS. AMORPHOUS
Types of Solids
Crystalline Solids Amorphous Solids
1. Regular Arrangement of Particles 1. Irregular Arrangement of Particles
Crystalline and Non-Crystalline Materials
CRYSTALLINE VS. AMORPHOUS
Types of Solids
Crystalline Solids Amorphous Solids
2. Long order in arrangement of particles. 2. Short order in arrangement of particles.
3. They are called “True Solids” 3. They are called “Pseudo Solids”
 True Properties of Solids  Fake Properties of Solids
- Regular Arrangement - Irregular Arrangement
- Long Order - Short Order
Crystalline and Non-Crystalline Materials
CRYSTALLINE VS. AMORPHOUS
Types of Solids
Crystalline Solids Amorphous Solids
4. Sharp Melting Point. <5°Centigrade 4. Ranged Melting Point. >5°Centigrade
Example: NaCl Example: Glass
Melting Point = 801°Centigrade Melting Point = 1400-1600°Centigrade

5. More Examples: 5. More Examples:

Salt, Iron, Gold, Sugar, etc. Glass, Rubber, Wax, etc.
Crystalline and Non-Crystalline Materials
CLASSIFICATION OF CRYSTALLINE SOLIDS
1. Ionic Solids
Made up of positive and negative ions and held together by electrostatic attractions. They're characterized
by very high melting points and brittleness and are poor conductors in the solid state.

Properties:
• Ionic Bonds
• Cations and Anions
• High Melting Point
• Brittle
• Insulators in Solid State
• Conductors in Molten State

Examples:
• NaCl, CaCO3, MgO
2. Molecular Solids
Molecular solids are composed of discrete molecules held together by intermolecular forces. Because
these interactions are relatively weak, molecular solids tend to be soft and have low to moderate melting
points

Properties:
• Covalent Bonds
• Molecules and/or Atoms
• Low Melting Point
• Soft
• Insulator

Examples:
• Ice, Sugar, CO2
3. Covalent Network Solids
Composed of atoms covalently bonded together into a three-dimensional network or layers of two-
dimensional networks.

Properties:
• Covalent Bonds
• Non-Metal Atoms
• High Melting Point
• Hard
• Poor Conductor
• Semi-Conductor

Examples:
• Diamond, Graphite, Silicon Dioxide
4. Metallic Solids
Solids composed of metal atoms that are held together by metallic bonds. These bonds are like huge
molecular orbitals that span across the whole solid. This means the electrons in metallic solids are
delocalized. They are not just held between a couple of atoms in a sigma bond.

Properties:
• Metallic Bonds
• Metal Atoms
• High Melting Point
• Malleable and Ductile
• Good Conductor

Examples:
• Iron, Gold, Silver
Crystalline and Non-Crystalline Materials
Doping
is a technique used to vary the number of electrons and holes in semiconductors. Doping is the process of
adding impurities to intrinsic semiconductors to alter their properties.

Advantage of Doping
- Because the band gap is so small for semiconductors, doping with small amounts of
impurities can dramatically increase the conductivity of the material.
Video Presentations
Crystal Lattice and Unit Cell
https://www.youtube.com/watch?v=JmmOlTeckqI&t=2s

The Structure of Crystalline Solids

https://www.youtube.com/watch?v=GSw2Cq_Afew

The 7 Crystal Systems

https://www.youtube.com/watch?v=ZJXe6QENzSg

Simple Cubic Crystal Structure

https://www.youtube.com/watch?v=Pthx506At88

Body-centered Cubic Crystal Structure BCC

https://www.youtube.com/watch?v=_9RnbGqtkd4

Face-centered Cubic Crystal Structure FCC

https://www.youtube.com/watch?v=GSPVC34ijIA

Hexagonal Close Packed Crystal Structure HCP

https://www.youtube.com/watch?v=_OhQv5gsoSQ

Allotropy and Polymorphism

https://www.youtube.com/watch?v=Oj8ar0vanEk
Thank you!