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FPEM1013 Chapter 1
FPEM1013 Chapter 1
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; these vary from relatively simple structures for metals to exceedingly
complex ones, as displayed by some of the ceramic and polymeric materials. The
present discussion deals with several common metallic crystal structures.
When describing crystalline structures, atoms (or ions) are thought of as being solid
spheres having well-defined diameters. This is termed the atomic hard sphere model
in which spheres representing
nearest-neighbor atoms touch one
another. An example of the hard
sphere model for the atomic
arrangement found in some of the
common elemental metals is
displayed in Figure 1-1c. In this
particular case all the atoms are
identical. Sometimes the term lattice
is used in the context of crystal
structures; in this sense “lattice”
means a three-dimensional array of
points coinciding with atom
positions (or sphere centers).
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1.2 Short-Range Order versus Long-Range Order
In different states of matter, we can find four types of atomic or ionic arrangements
(Figure 1-2).
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arrangements. Many polymers also display short-range atomic arrangements that
closely resemble the silicate glass structure. Polyethylene is composed of chains of
carbon atoms, with two hydrogen atoms attached to each carbon. Because carbon has
a valence of four and the carbon and hydrogen atoms are bonded covalently, a
tetrahedral structure is again produced [Figure 1-3(b)]. Tetrahedral units can be
joined in a random manner to produce polymer chains.
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Figure 1-5 shows a summary of classification of materials based on the type of atomic
order.
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1.3 Unit Cell
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. For
example, imagine the crystal as a three-dimensional puzzle for which each piece of
the puzzle is exactly the same. If we know what one puzzle piece looks like, we know
what the entire puzzle looks like, and we don’t have to put the entire puzzle together
to solve it. We just need one piece! To understand the unit cell concept, we start with
the crystal. Figure 1-6(a) depicts a hypothetical two-dimensional crystal that consists
of atoms all of the same type.
Next, we add a grid that mimics the symmetry of the arrangements of atoms. There is
an infinite number of possibilities for the grid, but by convention, we usually choose
the simplest. For the square array of atoms shown in Figure 1-6(a), we choose a
square grid as is shown in Figure 1-6(b). Next, we select the repeat unit of the grid,
which is also known as the unit cell. This is the unit that, when duplicated and
translated by integer multiples of the axial lengths of the unit cell, recreates the entire
crystal. The unit cell is shown in Figure 1-6(c); note that for each unit cell, there is
only one quarter of an atom at each corner in two dimensions. We will always draw
full circles to represent atoms, but it is understood that only the fraction of the atom
that is contained inside the unit cell contributes to the total number of atoms per unit
cell.
Thus, there is 1/4 atom / corner * 4 corners = 1 atom per unit cell, as shown in Figure
1-6(c). It is also important to note that, if there is an atom at one corner of a unit cell,
there must be an atom at every corner of the unit cell in order to maintain the
translational symmetry. Each unit cell has its own origin, as shown in Figure 1-6(c).
Figure 1-6 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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1.4 Metallic Crystal Structures
The atomic bonding in this group of materials is metallic and thus non-directional in
nature. Consequently, there are minimal restrictions as to the number and position of
nearest-neighbor atoms; this leads to relatively large numbers of nearest neighbors
and dense atomic packings for most metallic crystal structures. Also, for metals, using
the hard sphere model for the crystal structure, each sphere represents an ion core.
Table 1-1 presents the atomic radii for a number of metals. Three relatively simple
crystal structures are found for most of the common metals: face-centered cubic,
body-centered cubic, and hexagonal close-packed.
a = 2R√2
For the FCC crystal structure, each corner atom is shared among eight unit cells,
whereas a face-centered atom belongs to only two. Therefore, one-eighth of each of
the eight corner atoms and one-half of each of the six face atoms, or a total of four
whole atoms, may be assigned to a given unit cell. This is depicted in Figure 1-1a,
where only sphere portions are represented within the confines of the cube. The cell
comprises the volume of the cube, which is generated from the centers of the corner
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atoms as shown in the figure. Corner and face positions are really equivalent; that is,
translation of the cube corner from an original corner atom to the center of a face
atom will not alter the cell structure.
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—that is
For the FCC structure, the atomic packing factor is 0.74, which is the maximum
packing possible for spheres all having the same diameter. Metals typically have
relatively large atomic packing factors to maximize the shielding provided by the free
electron cloud.
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1.4.2 The Body-Centered Cubic Crystal Structure
Another common metallic crystal structure also has a cubic unit cell with atoms
located at all eight corners and a single atom at the cube center. This is called a body-
centered cubic (BCC) crystal structure. A collection of spheres depicting this crystal
structure is shown in Figure 1-7c, whereas Figures 1-7a and 1-7b are diagrams of BCC
unit cells with the atoms represented by hard sphere and reduced-sphere models,
respectively. Center and corner atoms touch one another along cube diagonals, and
unit cell length a and atomic radius R are related through
4𝑅𝑅
𝑎𝑎 =
√3
Figure 1-7 For the body-centered cubic crystal structure, (a) a hard sphere unit
cell representation, (b) a reduced-sphere unit cell, and (c) an aggregate of many
atoms.
Chromium, iron, tungsten, as well as several other metals listed in Table 1-1 exhibit a
BCC structure. Two atoms are associated with each BCC unit cell: the equivalent of
one atom from the eight corners, each of which is shared among eight unit cells, and
the single center atom, which is wholly contained within its cell. In addition, corner
and center atom positions are equivalent. The coordination number for the BCC
crystal structure is 8; each center atom has as nearest neighbors its eight corner
atoms. Since the coordination number is less for BCC than FCC, so also is the atomic
packing factor for BCC lower—0.68 versus 0.74.
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1.4.3 The Hexagonal Close-Packed Crystal Structure
Not all metals have unit cells with cubic symmetry; the final common metallic crystal
structure to be discussed has a unit cell that is hexagonal. Figure 1-8a shows a
reduced-sphere unit cell for this structure, which is termed hexagonal closepacked
(HCP); an assemblage of several HCP unit cells is presented in Figure 1-8b. The top
and bottom faces of the unit cell consist of six atoms that form regular hexagons and
surround a single atom in the center. Another plane that provides three additional
atoms to the unit cell is situated between the top and bottom planes. The atoms in
this midplane have as nearest neighbors atoms in both of the adjacent two planes.
The equivalent of six atoms is contained in each unit cell; one-sixth of each of the 12
top and bottom face corner atoms, one-half of each of the 2 center face atoms, and all
3 midplane interior atoms. If a and c represent, respectively, the short and long unit
cell dimensions of Figure 1-8a, the c/a ratio should be 1.633; however, for some HCP
metals this ratio deviates from the ideal value. The coordination number and the
atomic packing factor for the HCP crystal structure are the same as for FCC: 12 and
0.74, respectively. The HCP metals include cadmium, magnesium, titanium, and zinc;
some of these are listed in Table 1-1.
Figure 1-8 For the hexagonal close-packed crystal structure, (a) a reduced-sphere
unit cell (a and c represent the short and long edge lengths, respectively), and (b) an
aggregate of many atoms.
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1.5 Lattice Parameters and Interaxial Angles
The lattice parameters are the axial lengths or dimensions of the unit cell and are
denoted by convention as a, b, and c. The angles between the axial lengths, known as
the interaxial angles, are denoted by the Greek letters α, β, and γ. By convention, α is
the angle between the lengths b and c, β is the angle between a and c, and γ is the
angle between a and b, as shown in Figure 1-9. (Notice that for each combination,
there is a letter a, b, and c whether it be written in Greek or Roman letters.)
Figure 1-9 Definition of the lattice parameters and their use in cubic,
orthorhombic, and hexagonal crystal systems.
In a cubic crystal system, only the length of one of the sides of the cube need be
specified (it is sometimes designated a0). The length is often given in nanometers (nm)
or angstrom (Å) units, where
The lattice parameters and interaxial angles for the unit cells of the seven crystal
systems are presented in Table 1-2.
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Table 1-2 Characteristics of the seven crystal systems
To fully define a unit cell, the lattice parameters or ratios between the axial lengths,
interaxial angles, and atomic coordinates must be specified. In specifying atomic
coordinates, whole atoms are placed in the unit cell. The coordinates are specified as
fractions of the axial lengths.
Number of Atoms per Unit Cell Each unit cell contains a specific
number of lattice points. When counting the number of lattice points belonging to
each unit cell, we must recognize that, like atoms, lattice points may be shared by
more than one unit cell. A lattice point at a corner of one unit cell is shared by seven
adjacent unit cells (thus a total of eight cells); only one-eighth of each corner belongs
to one particular cell. Thus, the number of lattice points from all corner positions in
one unit cell is
1
lattice point 8 corners 1 lattice point
�8 �� �=
corner cell unit cell
Corners contribute 1/8 of a point, faces contribute 1/2, and body-centered positions
contribute a whole point [Figure 1-10(a)].
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Figure 1-10 (a) Illustration showing sharing of face and corner atoms. (b) The
models for simple cubic (SC), body-centered cubic (BCC), and face-centered cubic
(FCC) unit cells, assuming only one atom per lattice point.
The number of atoms per unit cell is the product of the number of atoms per lattice
point and the number of lattice points per unit cell. The structures of simple cubic
(SC), body-centered cubic (BCC), and face-centered cubic (FCC) unit cells (with one
atom located at each lattice point) are shown in Figure 1-10(b).
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Atomic Radius versus Lattice Parameter Directions in the unit cell
along which atoms are in continuous contact are close-packed directions. In simple
structures, particularly those with only one atom per lattice point, we use these
directions to calculate the relationship between the apparent size of the atom and the
size of the unit cell. By geometrically determining the length of the direction relative
to the lattice parameters, and then adding the number of atomic radii along this
direction, we can determine the desired relationship.
If we refer to Figure 1-11, we find that atoms touch along the edge of the cube in SC
structures. The corner atoms are centered on the corners of the cube, so
a0 = 2r
In BCC structures, atoms touch along the body diagonal, which is in length. There are
two atomic radii from the center atom and one atomic radius from each of the corner
atoms on the body diagonal, so
4r
a0 =
√3
In FCC structures, atoms touch along the face diagonal of the cube, which is in length.
There are four atomic radii along this length—two radii from the face centered atom
and one radius from each corner, so
4r
a0 =
√2
Figure 1-11 The relationships between the atomic radius and the lattice parameter
in cubic systems.
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In cubic structures containing only one atom per lattice point, atoms have a
coordination number related to the lattice structure. By inspecting the unit cells in
Figure 1-12, we see that each atom in the SC structure has a coordination number of
six, while each atom in the BCC structure has eight nearest neighbors. Each atom in
the FCC structure has a coordination number of twelve, which is the maximum.
Figure 1-12 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.
The FCC arrangement represents a close-packed structure (CP) (i.e., the packing
fraction is the highest possible with atoms of one size). The SC and BCC structures are
relatively open. Metals with only metallic bonding are packed as efficiently as possible.
Metals with mixed bonding, such as iron, may have unit cells with less than the
maximum packing factor. No commonly encountered engineering metals or alloys
have the SC structure, although this structure is found in ceramic materials.
If a material is ionic and consists of different types of atoms or ions, this formula will
have to be modified to reflect these differences.
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1.5.1 Points, Directions, and Planes in the Unit Cell
Coordinates of PointsWe can locate certain points, such as atom positions, in the
lattice or unit cell by constructing the right-handed coordinate system in Figure 1-13.
Distance is measured in terms of the number of lattice parameters we must move in
each of the x, y, and z coordinates to get from the origin to the point in question. The
coordinates are written as the three distances, with commas separating the numbers.
Figure 1-13 Coordinates of selected points in the unit cell. The number refers to the
distance from the origin in terms of lattice parameters.
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Example below illustrates a way of determining the Miller indices of directions.
Determine the Miller indices of directions A, B, and C in Figure 1-14.
SOLUTION
Direction A
• Two points are 1, 0, 0, and 0, 0, 0
• 1, 0, 0 - 0, 0, 0 = 1, 0, 0
• No fractions to clear or integers to reduce
• [100]
Direction B
• Two points are 1, 1, 1 and 0, 0, 0
• 1, 1, 1 - 0, 0, 0 = 1, 1, 1
• No fractions to clear or integers to reduce
• [111]
Direction C
• Two points are 0, 0, 1 and 1/2, 1, 0
• 0, 0, 1-1/2, 1,0 = -1/2, -1, 1
• 2 (-1/2 , -1, 1) = -1, -2, 2
• [1� 2� 2]
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1.5.3 Planes in the Unit Cell
Certain planes of atoms in a crystal also carry particular significance. For example,
metals deform along planes of atoms that are most tightly packed together. The
surface energy of different faces of a crystal depends upon the particular
crystallographic planes. This becomes important in crystal growth. In thin film
growth of certain electronic materials (e.g., Si or GaAs), we need to be sure the
substrate is oriented in such a way that the thin film can grow on a particular
crystallographic plane.
Miller indices are used as a shorthand notation to identify these important planes, as
described in the following procedure.
• Identify the points at which the plane intercepts the x, y, and z coordinates in
terms of the number of lattice parameters. If the plane passes through the
origin, the origin of the coordinate system must be moved to that of an
adjacent unit cell.
• Take reciprocals of these intercepts.
• Clear fractions but do not reduce to lowest integers.
• Enclose the resulting numbers in parentheses (). Again, negative numbers
should be written with a bar over the number.
The following example shows how Miller indices of planes can be obtained.
Determine the Miller indices of planes A, B, and C in Figure 1-15.
SOLUTION
Plane A
• x = 1, y = 1, z = 1
1 1 1
• x = 1, y = 1, z = 1
• No fractions to clear
• (111)
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Plane B
• The plane never intercepts the z axis, so x = 1, y = 2, and z = ∞
1 1 1 1
• x = 1, y = 2, z = 0
1 1 1
• Clear fractions: x = 2, y = 1, z = 0
• (210)
Plane C
• We must move the origin, since the plane passes through 0, 0, 0. Let’s move
the origin one lattice parameter in the y-direction. Then, x = ∞, y = -1, and z
= ∞.
1 1 1
• x = 0, x = -1, z = 0
• No fractions to clear.
• (01� 0)
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Close-Packed Planes and Directions In examining the relationship
between atomic radius and lattice parameter, we looked for close-packed directions,
where atoms are in continuous contact. We can now assign Miller indices to these
close-packed directions, as shown in Table 1-3.
You may remember from the discussion on metallic crystal structures that both face-
centered cubic and hexagonal close-packed crystal structures have atomic packing
factors of 0.74, which is the most efficient packing of equal-sized spheres or atoms. In
addition to unit cell representations, these two crystal structures may be described
in terms of close-packed planes of atoms (i.e., planes having a maximum atom or
sphere-packing density); a portion of one such plane is illustrated in Figure 1-16a.
Both crystal structures may be generated by the stacking of these close-packed planes
on top of one another; the difference between the two structures lies in the stacking
sequence. Let the centers of all the atoms in one close-packed plane be labeled A.
Associated with this plane are two sets of equivalent triangular depressions formed
by three adjacent atoms, into which the next close-packed plane of atoms may rest.
Those having the triangle vertex pointing up are arbitrarily designated as B positions,
while the remaining depressions are those with the down vertices, which are marked
C in Figure 1-16a.
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Figure 1-16 (a) A portion of a close-packed plane of atoms; A, B, and C positions are
indicated. (b) The AB stacking sequence for close packed atomic planes.
A second close-packed plane may be positioned with the centers of its atoms over
either B or C sites; at this point both are equivalent. Suppose that the B positions are
arbitrarily chosen; the stacking sequence is termed AB, which is illustrated in Figure
1-16b. The real distinction between FCC and HCP lies in where the third close-packed
layer is positioned. For HCP, the centers of this layer are aligned directly above the
original A positions. This stacking sequence, ABABAB . . . , is repeated over and over.
These close-packed planes for HCP are (0001)-type planes, and the correspondence
between this and the unit cell representation is shown in Figure 1-17.
For the face-centered crystal structure, the centers of the third plane are situated over
the C sites of the first plane (Figure 1-18a). This yields an ABCABCABC . . . stacking
sequence; that is, the atomic alignment repeats every third plane. It is more difficult
to correlate the stacking of close-packed planes to the FCC unit cell. However, this
relationship is demonstrated in Figure 1-18b. These planes are of the (111) type; an
FCC unit cell is outlined on the upper left-hand front face of Figure 1-18b, in order to
provide a perspective.
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Figure 1-18 (a) Close-packed stacking sequence for face-centered cubic. (b) A
corner has been removed to show the relation between the stacking of close-packed
planes of atoms and the FCC crystal structure; the heavy triangle outlines a (111)
plane.
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1.6 Single Crystals
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 exist in nature, but they may also be produced artificially.
They are ordinarily difficult to grow, because the environment must be carefully
controlled. If the extremities of a single crystal are permitted to grow without any
external constraint, the crystal will assume a regular geometric shape having flat
faces, as with some of the gem stones; the shape is indicative of the crystal structure.
A photograph of a garnet single crystal is shown in Figure 1-19. Within the past few
years, 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.
Figure 1-19 Photograph of a garnet single crystal that was found in Tongbei, Fujian
Province, China.
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characterized by atomic or molecular structures that are relatively complex and
become ordered only with some difficulty. Furthermore, rapidly cooling through the
freezing temperature favors the formation of a non-crystalline solid, since little time
is allowed for the ordering process. Metals normally form crystalline solids, but some
ceramic materials are crystalline, whereas others, the inorganic glasses, are
amorphous. Polymers may be completely non-crystalline and semi-crystalline
consisting of varying degrees of crystallinity.
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