Crystal Structures
Crystal Structures
Crystal Structures
A crystalline material is one in which the atoms are situated in a repeating or periodic
array over large atomic distances; that is, long-range order exists, such that upon
solidification.
Crystals are highly symmetrical arrays of atoms which substantially simplifies their
analysis
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.
Crystal Lattice
Crystal lattice is the periodic and systematic arrangement of atoms that are found in
crystals with the exception of amorphous solids and gases.
In the simplest of terms, the crystal lattice can be considered as the points of intersection
between straight lines in a three-dimensional network.
The physical properties of crystals like cleavage, electronic band structure and optical
transparency are predominantly governed by the crystal lattice.
Motif/Basis A group of one /more atoms located in a particular way with respect to each
other and associated with lattice point
Crystal Lattices
The concept of a lattice is directly related to the idea of translational symmetry. A lattice
is a network or array composed of single motif which has been translated and
repeated at fixed intervals throughout space. For example, a square which is
translated and repeated many times across the plane will produce a planar square lattice.
The unit cell of a lattice is the smallest unit which can be repeated in three dimensions in
order to construct the lattice. In a crystal, the unit cell consists of a specific group of atoms
which are bonded to one another in a set geometrical arrangement. This unit and its
constituent atoms are then repeated over and over in order to construct the crystal lattice.
The surroundings in any given direction of one corner of a unit cell must be identical to the
surroundings in the same direction of all the other corners.
The corners of the unit cell therefore serve as points which are repeated to form a lattice
array; these points are termed lattice points.
The vectors which connect a straight line of equivalent lattice points and delineate the
edges of the unit cell are known as the crystallographic axes.
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Unit Cell
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.
Non-Primitive
Primitive
Symmetry restricts the unit cells to certain shapes so that the entire space is covered without gaps and overlaps
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Crystal Symmetries
The concept of symmetry describes the repetition of structural features. Crystals therefore
possess symmetry, and much of the discipline of crystallography is concerned with
describing and cataloging different types of symmetry.
Symmetries are most frequently used to classify the different crystal structures.
In general one can generate 14 basic crystal structures through symmetries. These are
called Bravais lattices. Any crystal structures can be reduced to one of these 14 Bravias
lattices.
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Lattice Parameters
The physical properties of solids depend entirely upon the arrangement of the atoms that
make up the solid and the distances between them.
The arrangement of the atoms in a crystal structure is a combination of the size and shape of
the unit-cell and the arrangement of atoms inside the unit-cell.
The shape of the unit cells is described by the lattice symmetry. Unit cell = 3-dimensional unit
that repeats in space
The size of the unit-cell is described in terms of its unit-cell parameters. These are the
edge lengths and the angles of the unit-cell.
The unit cell geometry is defined in terms of six parameters: the three
edge lengths a, b, and c, and the three inter-axial angles , , and
indicated in Figure 3.4, and are termed the lattice parameters or
lattice constants of a crystal structure
Bravais Lattice
By assigning specific values for axial lengths and inter-axial angles, unit cells of different
types can be constructed
Crystallographers have shown that only 7 different types of crystal systems are necessary
to create and construct all the lattices
Bravais showed that there are 14 possible ways of constructing the crystal lattice from
seven crystal systems.
7
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Notations
Atomic radius It is defined as half the distance between the centres of the neighboring
atoms
Coordination Number The no. of atoms which are directly surrounding the particular atom;
it is also defined as the no. of nearest neighbors for that particular atom
Atomic Packing fraction Close packing of atoms in a unit cell of the crystal structure is
known as APF
The APF is the sum of the sphere volumes of all atoms within a
unit cell (assuming the atomic hard-sphere model) divided by
the unit cell volume
Both the total atom and unit cell volumes may be calculated in
terms of the atomic radius R
atoms per
unit cell
Volume = a3
Crystal structure
0.52
cube edges
0.68
body diagonal
12
0.74
face diagonal
12
0.74
hexagonal side
Crystal Structures
The Body-Centered Cubic Crystal Structure
APF = 0.68
Some
of
the
materials
that
sodium,
potassium,
barium,
vanadium,
alpha-iron
and tungsten
Metals dont crystallize into simple hexagonal structure since the APF is too low
The atoms in the hcp structure are also packed along close-packed planes.
It should also be noted that both the FCC and HCP structures are known as close-packed
structures with crystallographic planes having the same arrangement of atoms;
However, the order of stacking the planes is different. Atoms in the hexagonal closepacked planes (called the basal planes) have the same arrangement as those in the FCC
close-packed planes
top/bottom
plane
center
atoms
Allotropy
Polymorphism in elemental solids (e.g., carbon)
When dealing with crystalline materials, it often becomes necessary to specify a particular
point within a unit cell, a crystallographic direction, or some crystallographic plane of
atoms.
The basis for determining index values is the unit cell, with a
right-handed coordinate system consisting of three (x, y, and z)
axes situated at one of the corners and coinciding with the unit
cell edges, as shown in Figure.
Point Coordinates
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
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).
Thus, the position of P is designated using coordinates q r s with values that are less than
or equal to unity. Furthermore, we have chosen not to separate these coordinates by
commas or any other punctuation marks (which is the normal convention).
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Point Coordinates
Point Coordinates
Specification of Point Coordinates
Specify point coordinates for all atom positions for a BCC unit cell
Crystallographic Directions
Crystallographic Directions
Crystallographic Directions
For some crystal structures, several nonparallel directions with different indices are
crystallographically equivalent; this means that the spacing of atoms along each direction
is the same.
The directions in a crystal are given by specifying the coordinates (u, v, w) of a point on a
vector passing through the origin. It is indicated as [uvw]. For example, the direction [110]
lies on a vector whose projection lengths on x and y axes are one unit.
Directions of a form or family like [110], [101], [011] are written as <110>
<111> family
Hexagonal Crystals
The three a1, a2, and a3 axes are all contained within a single
plane (called the basal plane) and are at 120 angles to one
another.
Hexagonal Crystals
Conversion from the three-index system to the four-index system,
[uvw] [uvtw]
is accomplished by the following formulas:
1
u = (2u v)
3
1
v = (2v u )
3
t = (u + v )
w = w
_ _
u = 1; v = 1; w = 1
Multiplication of the preceding indices by 3 reduces them to the lowest set, which yields
values for u, v, t, and w of 1, 1, 2 and 3,_respectively.
Hence, the [111] direction becomes [1123].
Crystallographic Planes
Crystallographic Planes
The procedure used to determine the h, k, and l index numbers is as follows:
1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.
2. At this point the crystallographic plane either intersects or parallels each of the three axes;
the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
3. The reciprocals of these numbers are taken. A plane that parallels an axis may be
considered to have an infinite intercept, and, therefore, a zero index.
4. If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.3
5. Finally, the integer indices, not separated by commas, are enclosed within parentheses,
thus: (hkl).
Crystallographic Planes
Crystallographic Planes
Crystallographic Planes
Crystallographic Planes
Linear Densities
Linear density (LD) is defined as the number of atoms per unit length whose centers lie on
the direction vector for a specific crystallographic direction;
LD =
Determine the linear density of the [110] direction for the FCC crystal structure
<110> directions in the FCC lattice have 2 atoms (1/2 x 2 corner atoms + 1 center atom) and
the length is 4R
LD110
2
2atoms
1
=
=
=
4R
2R
a
Planar Densities
Planar density (PD) is taken as the number of atoms per unit area that are centered on a
particular crystallographic plane
PD =
PD110
2atoms
1
2
=
=
= 2
2
2
8R 2 4 R 2 a
For a crystalline solid, when the periodic and repeated arrangement of atoms is perfect or
extends throughout the entirety of the specimen without interruption, the result is a single
crystal.
All unit cells interlock in the same way and have the same orientation.
single crystals have become extremely important in many of our modern technologies, in
particular electronic microcircuits, which employ single crystals of silicon and other
semiconductors
Most crystalline solids are composed of a collection of many small crystals or grains; such
materials are termed polycrystalline.
Small crystallite
nuclei.
Upon completion of
solidification,
grains
having irregular shapes
have formed.
more
disordered
and
Noncrystalline
Summary
Fundamental Concepts: Atoms in crystalline solids are positioned in orderly and repeated
patterns that are in contrast to the random and disordered atomic distribution found in
noncrystalline or amorphous materials.
Unit Cells: Crystal structures are specified in terms of parallelepiped unit cells, which are
characterized by geometry and atom positions within.
Metallic Crystal Structures: Most common metals exist in at least one of three relatively
simple crystal structures:
Unit cell edge length (a) and atomic radius (R) are related (See Equations for facecentered cubic, and body-centered cubic.
Atomic packing factorthe fraction of solid sphere volume in the unit cell.
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Summary
Density Computations: The theoretical density of a metal () is a function of the number of
equivalent atoms per unit cell, the atomic weight, unit cell volume, and Avogadros
number.
Polymorphism and Allotropy
Polymorphism is when a specific material can have more than one crystal structure.
Allotropy is polymorphism for elemental solids.
Crystal Systems
The concept of crystal system is used to classify crystal structures on the basis of unit cell
geometrythat is, unit cell edge lengths and interaxial angles. There are seven crystal
systems: cubic, tetragonal, hexagonal, orthorhombic, rhombohedral, (trigonal),
monoclinic, and triclinic.
Summary
Point Coordinates, Crystallographic Directions, Crystallographic Planes
Crystallographic points, directions, and planes are specified in terms of indexing
schemes. The basis for the determination of each index is a coordinate axis system
defined by the unit cell for the particular crystal structure.
The location of a point within a unit cell is specified using coordinates that are fractional multiples of the cell
edge lengths.
Directional indices are computed in terms of the vector projection on each of the coordinate axes.
Planar (or Miller) indices are determined from the reciprocals of axial intercepts.
For hexagonal unit cells, a four-index scheme for both directions and planes is found to
be more convenient.
Summary
Single Crystals, Polycrystalline Materials
Single crystals are materials in which the atomic order extends uninterrupted over the
entirety of the specimen; under some circumstances, single crystals may have flat faces
and regular geometric shapes.
The vast majority of crystalline solids, however, are polycrystalline, being composed of
many small crystals or grains having different crystallographic orientations.
A grain boundary is the boundary region separating two grains, wherein there is some
atomic mismatch.
Anisotropy
Anisotropy is the directionality dependence of properties. For isotropic materials,
properties are independent of the direction of measurement.