Crystal

Structure
MATECHE
3rd Term, AY 2018 - 2019
1
Classification of Solids by Order

 Solids may be classified according to the

regularity with which atoms or ions are
arranged with respect to one another.
 Crystalline
 Amorphous

2
Classification of Solids by Order

3
Classification of materials based
on the type of atomic order

4
Crystals

 Solids that exist in a regular array with basic

building blocks being repeated at regular
intervals are said to be crystalline.
 Crystals exhibit long-range order.

5
Order

 Materials that exhibit order over distances

greater than the bond length are said to have
long-range order (LRO).
 Meanwhile, the local arrangement of
nearest-neighbor atoms about a central atom
is known as short-range order (SRO).

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Order
(a) no order (e.g.,
Argon)
(b) short-range
order (e.g.,
water)
(c) short-range
order (e.g.,
silicate glass)
(d) long-range
order (e.g.,
metals)
7
Crystals

 When a crystalline material solidifies from

the liquid state, the atoms will position
themselves in a repetitive three-dimensional
pattern, in which each atom is bonded to its
nearest-neighbor atoms.

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Some Generalizations on Order

 All metals form crystalline structures under

normal solidification conditions.
 Ceramics and polymers may either be
crystalline, amorphous or a combination of
the two.

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Non-crystalline (Amorphous)

 Materials that do not crystalize lack long

range atomic order.
 These materials are said to be non-
crystalline or amorphous.

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Atomic Hard Sphere Model

 When describing crystalline structures,

atoms are thought of as being solid spheres
having well-defined diameters.
 Spheres represent nearest-neighbor atoms
that touch one another.

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Lattices and Unit Cells

 In crystals, atoms are arranged in a three-

dimensional array that repeats in space.
 This 3-D framework is known as a crystal
lattice.

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 Lattices and Unit Cells
 More formally, a lattice is an indefinitely
extended arrangement of points each of
which is surrounded by an identical
grouping of neighboring points.
 The smallest region in a lattice that
describes the pattern of the points is known
as the unit cell.

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Lattice and Lattice Points

14
Lattice and Lattice Points

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Lattice and Lattice Points

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 Lattices and Unit Cells
 The vertices of a unit cell are known as
lattice points.
 In crystals, the lattice points may either be
atoms or group of atoms.
 The lengths of the unit-cell edges are known
as the lattice parameters.

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Unit Cell
 A unit cell is chosen to represent the
symmetry of the crystal structure.
 All atom positions in the crystal may be
generated by translations of the unit cell
along each of its edges.

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Unit Cell
 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.

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 The Unit Cell
 The properties of a unit cell are the same as
those of the crystal.
 Hence, a unit cell is a convenient
representative structure that can be used to
calculate theoretical properties of a crystal,
such as density.

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Crystal Systems
 Crystals are grouped according to unit cell
configuration and/or atomic arrangements.
 One scheme is based on the unit cell
geometry.

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 The unit cell. (a) A two-dimensional crystal. (b) The crystal
with an overlay of a grid that reflects the symmetry of the
crystal. (c) The repeat unit of the grid known as the unit cell.
Each unit cell has its own origin.
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Crystal Systems
 An x, y, z coordinate system is established
with its origin at one of the unit cell corners.
 Each of the x, y, and z axes coincides with
one of the three parallelepiped edges that
extend from this corner.

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Crystal Systems
 The unit cell geometry is completely defined
in terms of six parameters:
 the three edge lengths a, b, and c
 the three inter-axial angles α, β, and 

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Definition of the lattice parameters and their use in cubic,
orthorhombic, and hexagonal crystal systems. 25
Seven Crystal Systems
 Cubic
 Tetragonal
 Hexagonal
 Orthorhombic
 Rhombohedral (a.k.a. trigonal)
 Monoclinic
 Triclinic

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Seven Crystal Systems

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Seven Crystal Systems

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Seven Crystal Systems

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 Seven
Crystal
Systems

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Seven Crystal Systems

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Seven Crystal Systems

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Seven Crystal Systems

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Seven Crystal Systems
 Cubic system
 has the greatest degree of symmetry
 a=b=c
 α=β=
 Triclinic system
 has the least symmetry
 a≠b≠c
 α≠β≠

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The Bravais Lattices
 The seven (7) crystal systems are actually
composed of fourteen (14) Bravais lattices.
 The unique three-dimensional arrangements
of lattice points are known as Bravais
lattices.

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The fourteen types of Bravais lattices grouped in seven crystal systems.
(First of Two Parts) 36
The fourteen types of Bravais lattices grouped in seven crystal systems.
(Second of Two Parts) 37
Crystal System

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39
 Crystal Systems
 Each unit cell repeats indefinitely in all
directions, up to the physical limits of the
crystal.

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The Crystal Structure in Solids

 Many metals have cubic structures and some

have hexagonal structures.
 Materials with ionic bonds (e.g., ceramics)
typically have larger, more complex crystal
structures than metals.
 Polymers also have complex bases and
crystal structures with large unit cells.

41
The Three Common Crystal Structures
 Body-Centered Cubic (BCC)
 Face-Centered Cubic (FCC)
 Hexagonal Close-Packed (HCP)

42
The models for simple cubic (SC), body-centered cubic (BCC), and face-
centered cubic (FCC) unit cells, assuming only one atom per lattice point.
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Illustration showing sharing of face and corner atoms.

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 Important characteristics of a crystal
structure
 Length of the lattice parameter (a0)
 The number of atoms in the unit cell
 The coordination number (# of nearest
neighbors) of each atom
 Atomic Packing Factor (APF)

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Body-Centered Cubic
 An atom lies at each corner of the cube and
one lies in the center.
 Each corner atom touches the central atom,
but the corner atoms do not touch each
other.
 Metals with BCC structure at room
temperature: tungsten, chromium, iron,
molybdenum, vanadium, etc.

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 Body Centered Cubic

For the body-centered cubic crystal structure,

(a) a hard-sphere unit cell representation, and
(b) a reduced sphere unit cell.
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Body Centered Cubic

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Body Centered Cubic

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Body-Centered Cubic
 Each corner atom is shared by eight unit
cells.
 Therefore, only 1/8 of any corner atom is
associated with each cell
 The center atom is totally contained within
the cell.

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Body-Centered Cubic
 The total number of atoms per unit cell is
 8 x 1/8 + 1 = 2
 In addition, each atom in the BCC structure
has eight nearest neighbors (coordination
number = 8).

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Atomic Packing Factor (APF)
It is the fraction of solid sphere volume in
a unit cell, assuming the atomic hard
sphere model

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Unit cell dimensions in a BCC

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BCC

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Face-Centered Cubic
 An atom is located at each corner of the
cube plus an additional atom at the center of
each face.
 Each corner atom touches the atoms in the
centers of the three adjacent faces, but
corner atoms do not touch other corner
atoms.

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Face-Centered Cubic

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Face-Centered Cubic

For the face-centered cubic crystal structure, (left graphic) a

hard-sphere unit cell representation, (right graphic) a reduced
sphere unit cell.
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Face-Centered Cubic

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Face-Centered Cubic
 Each corner atom is shared by eight unit
cells
 Each face atom is shared by two unit cell
 The total number of atoms per unit cell:
 6 x 1/2 + 8 x 1/8 = 4
 Also, each atom in the FCC has 12 nearest
neighbors.

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Face-Centered Cubic

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Face-Centered Cubic
 Examples of metals that are FCC at room
temperature are aluminum, calcium, copper,
gold, lead, nickel, platinum and silver

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Face-Centered Cubic

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The relationships between the atomic radius and
the lattice parameter in cubic systems.

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 Illustration of the coordination number in (a) SC and (b)
BCC unit cells. Six atoms touch each atom in SC, while eight
atoms touch each atom in the BCC unit cell.
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Hexagonal Close-Packed Structures
 The HCP structure is characteristic of many
metals, like cadmium, cobalt, magnesium,
titanium and zinc at room temperature.

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Hexagonal Close-Packed Structures
 The structure of a hexagonal system is most
easily visualized by considering three unit
cells arranged to form one larger cell.
 The upper and lower surfaces of the large
cell are hexagons.
 The six side faces are rectangles.

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HCP

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Hexagonal Close-Packed Structures
 There are six atoms at the corners of the top
and bottom planes, each shared by six unit
cells
 One atom is at the center of the upper and
lower basal planes, each shared by two cells.
 Three atoms are in the midplane.

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HCP

Hexagonal
Hexagonal Close Packed

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 For the hexagonal close-packed crystal structure, (left
picture) a reduced-sphere unit cell (a and c represent the
short and long edge lengths, respectively), and (right
picture) an aggregate of many atoms. 70
HCP

71
The hexagonal close-packed (HCP) structure (left) and its
unit cell. 72
Hexagonal Close-Packed Structures
 The total number of atoms in the large HCP
cell is six:
 12 x 1/6 + 2 x 1/2 + 3 x 1 = 6

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Hexagonal Close-Packed Structures

 The number of nearest neighbors in the HCP

system is 12.
 The central atom in the basal plane has six
nearest neighbors in its own plane and three
nearest neighbors in the parallel planes above
and below.

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 Comparison of BCC, FCC & HCP
BCC FCC HCP
a- R
relationship
Number of 2 4 6
atoms/cell
APF 0.68 0.74 0.74

Coordination 8 12 12
Number

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76
Theoretical Density

 A knowledge of the crystal structure of a

metallic solid permits computations of its
theoretical density .

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Theoretical Density

UNDERSTAND
THE FORMULA.
DO NOT
MEMORIZE IT!

 n = number of atoms per unit cell

 A = atomic weight
 Vc = volume of unit cell
 NA = Avogadro’s number

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Crystallographic
Directions and Planes

 When dealing with crystals, it is often

necessary to specify
 A point within a unit cell
 A crystallographic direction
 A crystallographic plane of atoms
 This is addressed by the use of three
numbers or indices.

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Crystallographic
Directions and Planes

 The basis for determining index values

(Miller Indices) is the unit cell
 A right-handed coordinate system consisting of
three axes (x, y, z) is situated at one of the
corners.
 The axes coincides with the unit cell edges.

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 Crystallographic
Directions and Planes
 The position of any point located within a
unit cell may be specified in terms of its
coordinates as fractional multiples of the
unit cell edge lengths (i.e., in terms of a, b,
and c).

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Point Coordinates

82
Point Coordinates

83
Point Coordinates

84
Point Coordinates

85
Crystallographic Directions
 A crystallographic direction is defined as a
line between two points.

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Crystallographic Directions

 Steps in determining crystallographic

direction:
1. Determine the coordinates of two points that
lie in the direction of interest.
2. Subtract the coordinates of the 2nd point from
those of the 1st point.
3. Clear fractions from the differences to give
indices in lowest integer values.

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Crystallographic Directions

 Steps in determining crystallographic

direction:
4. Write the indices in square brackets without
commas – [h k l].
5. Negative integer values are indicated by
placing a bar over the integer.

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Crystallographic Directions

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Crystallographic Directions

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Crystallographic Planes
1. Identify the x, y, and z- intercepts of the plane.
 If the plane is parallel to one of the axes, the intercept is taken as
infinity.
 If the plane passes through the origin, change the location of the
origin.

2. Take the reciprocal of the intercepts.

3. Cite planes in parenthesis, (h k l), placing bars
over negative indices.

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Crystallographic
Planes

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93
Crystallographic Planes

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Crystallographic Planes

95
Polymorphism and Allotropy

 Allotropy
 The possibility of the existence of two or more
different crystal structures for a substance
(generally an elemental solid).
 Polymorphism
 The ability of a solid material to exist in more
than one form of crystal structure.

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Polymorphism and Allotropy

 The prevailing crystal structure depends on

both the temperature and the external
pressure.
 Changes in density and other physical
properties often accompany a polymorphic
transformation.

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Polymorphism and Allotropy

 Example: Pure iron has a

BCC crystal structure at room
temperature, which changes to
FCC iron at 9120C.

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Carbon as diamond and graphite

Carbon as diamond Carbon as graphite

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Carbon as diamond

100
Carbon as diamond and graphite

Carbon as diamond Carbon as graphite

101
 Buckminsterfullerene (C60)

 A polymorphic form of carbon discovered in

1985.
 It exists in discrete molecular form and
consists of a hollow spherical cluster of
sixty carbon atoms.
 It is called Buckminsterfullerene (C60) or
“buckyball” for short.

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Buckminsterfullerene (C60)

 Each molecule is composed of groups of

carbon atoms that are bonded to one another
to form both hexagon and pentagon
geometrical configurations.
 The material composed of C60 molecules is
known as buckminsterfullerene in honor of
R. Buckminster Fuller, who invented the
geodesic dome.

103
Buckminsterfullerene (C60)

The molecular
structure of C60

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Buckminsterfullerene (C60)

Liquid Form
Solid Form

105
 Geodesic Dome

Spaceship Earth at Epcot, Walt Disney World

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 Geodesic Dome

The Montréal Biosphère, formerly the American Pavilion of Expo 67,

by R. Buckminster Fuller, on Île Sainte-Hélène, Montréal, Québec
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 Geodesic Dome

The Climatron Greenhouse at

Missouri Botanical Gardens 108
Close-Packed Crystal Structures

 Both FCC and HCP crystal structures may

be generated by the stacking of close-packed
planes of atoms on top of one another.
 For HCP: ABABAB….
 For FCC: ABCABCABC…

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Close-Packed Crystal Structures

The AB stacking sequence

Packing in an HCP crystal

110
Close-Packed Crystal Structures

A portion of a close-packed plane of atoms, with

A, B, and C positions indicated.
111
The ABC stacking
sequence for an
FCC crystal

112
Single Crystals

 For a crystalline solid, when the periodic

and repeated arrangement of atoms is
perfect or extends throughout the entirety of
a specimen without interruption, the result is
a single crystal.

113
Single Crystals

Photograph of a garnet single crystal that was

found in Tongbei, Fujian Province, China.
114
Polycrystalline Materials

 Crystalline solids composed

of a collection of many small
crystals (or grains).
 The regions where the grains
meet form the grain
boundaries.

115
Stages in the solidification of a polycrystalline specimen.
Square grids depict unit cells. 116
(Left picture) Photograph of a silicon single crystal.
(Right graphic) Micrograph of a polycrystalline stainless steel
showing grains and grain boundaries

117
Grain Boundaries

 When two adjacent grains grow together during

freezing, the atoms of the last liquid to solidify are
mutually attracted to both grains.
 Since the orientations of the two grains differ, the
atoms cannot form on either lattice, but must
occupy the region between the grains (grain
boundary).

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Grain Boundaries

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Grain Boundaries
 Grain boundaries interrupt the continuity of
the lattice planes and greatly increases the
resistance of the metals to cold deformation.
 A small grain size is desirable in a metal
because it tends to make a metal ductile.

120
Anisotropy

 It is the directional dependence of

properties.
 For example, the elastic modulus, the
electrical conductivity, and the index of
refraction may have different values in the
[100] and [111] directions.

121
Anisotropy

 Substances in which measured properties are

independent of the direction of measurement
are called isotropic.
 If the properties depend on the
crystallographic direction, then the
substance is described as anisotropic.

122
 Anisotropy
 Note that a material such as aluminum, which is
crystallographically anisotropic, may behave as
an isotropic material if it is in a polycrystalline
form.
 This is because the random orientation of different
crystals in a polycrystalline material will mostly
cancel out any effect of the anisotropy as a result of
crystal structure.
 In general, most polycrystalline materials exhibit
isotropic properties.
123
Non-crystalline Solids
• It has been mentioned that non-crystalline solids
lack a systematic and regular arrangement of atoms
over relatively large atomic distances.
• Sometimes such materials are also called
amorphous (meaning literally “without form”), or
supercooled liquids, inasmuch as their atomic
structure resembles that of a liquid.

124
 Two-dimensional schemes of the
structure of (a) crystalline silicon dioxide
and (b) noncrystalline silicon dioxide.
125
Imperfections in Solids
 Point defects
 Vacancies – there is a lattice site without a
component
 Interstitial atoms – A component which is
not common (solute) lies at a point that is not
a lattice site
 Self-interstitial atoms – Interstitial atoms of
the most common component
 Substitutional atoms – there is a component
in the lattice site different from what it is
supposed to be
126
Point Defects
Shottky defects increase
conductivity

127
Imperfections in Solids
 Dislocations and Disclinations
 Effect becomes evident in the force needed to
deform the crystalline solid
 Edge dislocations
 Screw dislocations

128
Imperfections in Solids
 Planar Defects and Grain Size
 Plane defects separate regions of different
crystalline structures
 Grain size is the crystal volume confined by
grain boundaries
 Grain size can influence material properties
(e.g. malleability and ductility)

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Defect Detection
 Scanning electron microscopy (SEM) –
studies inclinations in boundaries
 Electron microscopy techniques – help
observe point defects
 Transmission techniques (TEM) –
determines dislocations

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Defect Detection

TEM with Lamellar twin dislocations (Kattan et al., 2015)

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Defect Detection

Scanning Tunneling Microscopy (STM) to analyze point defects

of TiO2 rutile (110)
132