Chapter 2 Geometry of Crystals

2-2 Lattices
A crystal may be defined as a solid composed
of atoms, ions or molecules arranges in a pattern
periodic in three dimensions. There are certain
symmetry relationships in their arrangement.
To ignore the actual atoms, ions or moleculars
and to focus on the geometry of periodic arrays,
the crystal is represented as a lattice, that is, a
three-dimensional array of points (lattice points),
each of which has identical surroundings.
P = na + mb
假如n, m為整
數, 則P點必位
於晶格點上。
Basic symmetry elements:
1. Mirror plane
2. Rotation axis
3. Inversion center
Stacking the unit cells face-to-face is another way of
generating a lattice.

, a3

, a2
, a1
2.3 Designation of points, lines, and planes

A = ua + vb + wc
If u, v, w Z
The pont A must be
a lattice point and
its coodinates are
written simply as an
triple • u v w •.
 The direction of any line in a lattice may be described
by drawing a line through the origin. [uvw] are the indices
of the direction of the line. Whatever the values of u, v, w,
they are always converted to a set of smallest integers.
Thus [½ ½ 1], [112], and [224] all represent the same
direction, but [112] is the preferred form.
 Directions related by symmetry are called directions of a
form. For example, the four body diagonals of a cube,
[111], [111], [111], and [111], may all be represented by the
symbol <111>.
 To avoid the introduction of infinity into the description of plane
orientation, the reciprocal of the fractional intercept is used, this
reciprocal being zero when the plane and axis are parallel.
A workable symbolism results for the orientation of a plane in a
lattice, Miller indices, which are defined as the reciprocals of the
fractional intercepts which the plane makes with the
crystallographic axes.

Determining the Miller indices

of the plane as follows:

Axial lengths 4Å 8Å 3Å
Intercept lengths 1Å 4Å 3Å
Fractional intercepts ¼ ½ 1
Miller indices 4 2 1
Axial length a b c
Intercept length 12a 12b 6c
Fractional intercept 12 12 6
Reciprocal ratio 1/12 1/12 1/6
Miller index 1 1 2
** (112), (224), (336) are
identical planes here.
 There is a whole set of parallel equidistant (dhkl) planes, one of
which passed through the origin. In the atomic scale, the Miller
indices (hkl) usually refer that plane in the set which is nearest the
origin, although they may be taken as referring to any other plane
in the set or to the whole set taken together in crystal morphology.
The plane (nh nk nl) are parallel to the planes (hkl) and have
1/nth the spacing in atomic scale. The same planes may belong to
two different sets, the Miller indices of one set being multiples of
those of the other; thus the same plane (210) can belong to the (210)
set and the (420) set.
(120)

(240)
 The planes of larger spacing have low indices and pass
through a high density of lattice points, whereas the reverse is
true of planes of small spacing.
The interplanar spacing dhkl, measured at right angles to the
planes, is a function both of the plane indices (hkl) and the lattice
constants (a, b, c, , , ).
 The interplanar spacing dhkl, measured at right angles
to the planes, is a function both of the plane indices (hkl)
and the lattice constants (a, b, c, , , ).
2-4 Reciprocal lattice
The reciprocal space lattice is a set of imaginary points
constructed in such way that the direction of a vector from one
lattice point to another coincides with direction of a normal to the
real space planes and the separation (d-spacing ) of those points
(absolute value of the vector) is equal to the reciprocal of the real
interplanar distance.
The concept of the
reciprocal lattice was devised
to show two important
properties of crystal planes:
their slopes and their inter-
planar distances. (The slope
of a family of parallel planes
can be determined by just
one normal significantly
simplifies the description
of the orientation of the
crystal planes.)
 Vectors ai (i.e., a, b, and c) define the basis vectors of a 3-D
real lattice. This direct space lattice, however, is not the only way
that the periodicity and symmetry of a given arrangement of
lattice points can be represented.
As introduced by J. W. Gibbs, the physcal significance of the
reciprocal lattice in diffraction is due to Ewald. A reciprocal
lattice bi (i.e. unit vectors a*, b*, c* of a lattice in reciprocal space)
can be defined for every direct space lattice ai by
a2 x a3 a • b = abcos a x b = absin
b1 =
a1• a2 x a3
Unit of 3 axes: Å-1
a3 x a1
b2 = b1 ┴ a2 & a3; b1 ∞ 1/a1 ai • bj = 
a2• a3 x a1
b2 ┴ a1 & a3; b2 ∞ 1/a2 If i ≠ j,  = 0;
a1 x a2
b3 = b3 ┴ a1 & a2; b3 ∞ 1/a3 If i = j,  = 1
a3• a1 x a2
 c*
* = 180o - ; * = 180o - ; * = 180o - 
*
*
V* = a* • (b* x c*) = 1/ V (V: volume of unit cell) b*
*
a*

Formula: a x (b x c) = (a • c)b – (a • b)c

V* = a*• (b*x c*)
b* x c* = b* x ((a x b)/V) = (a/V)(b*• b) – (b/V)(b*• a)
. .
. b*• b = 1; b*• a = 0
.
. . b* x c* = a / V
V* = a* • (b* x c*) = a* • (a / V) = 1/ V
 a1 x a2
b3 = ( V = a1• a2 x a3 )
V
(area of parallelogram OACB)
=
(area of parallelogram OACB)(height of cell)
= 1 / OP = 1 / d001

It will tell us that the

magnitude of a vector in
reciprocal space is equal
to the reciprocal of the
interplanar distance
(d-spacing) in the real
space. Location of the reciprocal axis b3.
 If H is the reciprocal point of (hkl) plane, the definition
indicates that Hhkl is normal to (hkl) and then Hhkl is the
reciprocal of dhkl can be proved below. A vector Hhkl
drawn from the origin of reciprocal space to point H in
reciprocal space having coordinates h, k, l is perpendicular
to the plane in direct space whose Miller indices are hkl.
Here, it will show that the length Hhkl of the reciprocal lattice
vector Hhkl = h b1 + k b2 + l b3 equals the reciprocal of the
periodicity of (hkl), i.e., Hhkl =1 / dhkl.
a1/h + AB = a2/k AB = a2/k – a1/h
H•AB = (h b1 + k b2 + l b3)•(a2/k – a1/h)
= b2 • a2 – b1 • a1 = 1 – 1 = 0
Here, Hhkl is actually perpendicular
to the plane (hkl).
dhkl = ON = a1/h • n (n = H / H)
= a1/h • H /H
= a1/h • (h b1 + k b2 + l b3) /H
= 1/Hhkl
Cubic
crystal

Hexagonal
crystal
 In crystallography, all that is
needed to uniquely identify a set of
parallel lattice planes (hkl ) is their
orientation and their periodicity.
These are given in real space by
the normal to the planes (a single
direction) and the spacing between
the planes (dhkl). A single lattice
point in reciprocal space, defined
by vector Hhkl, is sufficient to
represent the infinite series of
physical direct space planes. In
other words, the transformation
from direct space to reciprocal
space maps all direct space planes
(hkl ) onto a single point (i.e., the
reciprocal lattice point with
coordinates h, k, l).
2-5 Symmetry
One type of repetition, lattice translation, underlies the
periodicity of one-, two-, three-dimentional nets, with each point
having identical surroundings.
Second symmetry are required to define the periodicity of
two-dimensional patterns or three-dimentional assemblies of
atoms, ions or molecules comprising crystals. The various
symmetry operators act to change the orientation of the repeated
features or motifs which populate a lattice.
There are in all four macroscopic symmetry operations:
reflection, rotation, inversion and rotoinversion.
The different symmetry operations (combination of symmetry)
acting through a point are termed point group. In 3-D, the
number of point groups is thirty-two.
 t1

t2
4
2-6 Crystal system
In defining a lattice with three non-coplanar lattice
vectors, unit cells of various shapes can result, depending
on the length and orientation of the vectors. It turns out
that only seven different kinds of cells are necessary to
include all the possible point lattices. These correspond
to the seven crystal systems into which all crystals can be
classified: cubic, tetragonal, orthorhombic, hexagonal,
rhombohedral, monoclinic and triclinic.
Some writers consider the rhombohedral system as a
subdivision of the hexagonal, thus reducing the number of
crystal system to six.
Hexagonal Rhombohedral
 Seven different point lattice can be obtained simply by
putting points at the corners of the unit cells of the seven
crystal systems (primitive).
However, there are other arrangements of points which
fulfill the requirements of a point lattice; namely, each
lattice point have identical surroundings.
The French crystallogrpher Bravais worked on this
problem and in 1848 demonstrated that there are fourteen
possible point lattices, Bravais lattices.
Fourteen Bravais lattices include primitive (simple) cells
(symblos P or R) and non-primitive cells (any other symbol):
primitive cells have only one lattice point per cell while
nonprimitive have more than one.
 The fourteen
Bravais lattices:
The number of lattice points per unit cell is given by
N = Ni + (Nf / 2) + (Nc /8)
Where Ni = number of interior points
Nf = number of points on faces
Nc = number of points on corners

N=1 N=2 N=4 N=2

 The possession of a certain
minimum set of symmetry
elements is a basic property
of each crystal system, and
one system is distinguished
from another just as much by
its symmetry elements as by
the unit cell parameters. In
fact, these are interdepedent.
 Some crystals may possess more than the minimum
symmetry elements required by the system to which they
belong, but none may have less.
Symmetry operations apply not only to the unit cells
(geometric shape) but also to the point lattices associated
with them.
A lattice at right would be
classified in the tetragonal
system, which has no 3-fold axes
and in which accidental equality
of the a and c axes is allowed.
In addition, the cell can not
be replaced by a primitive
orthorhombic cell, which
symmetry is lower than that of
the tetragonal cell.
2-7 Primitive and nonprimitive cells
Any of the 14 Bravais lattices may
be referred to a primitive unit cell.
For example, the face-centered cubic
lattice shown in Fig. 2-13 may be
referred to the primitive cell,
rhombohedral cell, indicated by dashed
lines. However, it is usually more
convenient to use nonprimitive cells
than primitive ones because the former
suggests the cubic symmetry which
the lattice actually possesses.
In the general rhombohedral lattice, no restriction is placed
on the angle ; the result is a lattice of points with a single 3-fold
symmetry axis. When  becomes equal to 60o, the lattice has
four 3-fold axes, and this symmetry places it in the cubic system.
 The position of any lattice point in a cell may be given in
terms of its coordinates; if the vector from the origin of the
unit cell to the given point has components xa, yb, zc, where
x, y, and z are fractions (especially in a nonprimitive lattice
cell), then the coordinates of the point are x y z.
If one atom per unit lattice point:
Primitive cell: N=1
It has coordinates 000, if the atom is
located at the origin.
Face-centered cubic cell: N=4
They (A, B, C, D) have coordinates
000, 0½ ½, ½ 0½, ½ ½ 0, respectively.
Here, point E has coordinates
½ ½ 1 and is equivalent to point D,
being separated from it by the vector c.
The 4 point positions are related by the translation, <½ ½ 0>.
 The coordinates of a body-centered point are always
½ ½ ½, no matter whether the unit cell is cubic, tetragonal,
or orthorhombic, and whatever its size. The coordinates
of a point position, such as ½ ½ ½, may also be regarded
as an operator which will move or translate a point at the
origin to the position ½ ½ ½, the final position being
obtained by simple addition. <½ ½ ½> are called the
“body-centering translations,” since they will produce the
two point positions characteristic of a body-centered cell
when applied a point at the origin.
These centering translations,
summarized below, should be noted:
body-centering = <½ ½ ½> or [½ ½ ½]
face-centering = <½ ½ 0>
base-centering = [½ ½ 0] or [½ 0 ½]
or [0 ½ ½]
 Note that other unit cells always have more than one
atom per unit lattice point. Silicon, for example, has a face-
centered cubic Bravais lattice with atoms at 000 and ¼ ¼ ¼
plus face centering translations, for a total of four lattice
points but eight atoms per unit cell.
More complex molecular crystals have large numbers
of atoms of different types per lattice point.

Si

Si
 In any crystal system, there are sets Plane of a form &
of equivalent lattice planes related by plane of a zone
symmetry. These planes are called
planes of a form. And the indices of one
plane, enclosed in braces {hkl}, stand for
the whole set. In general, planes of a
form have the same spacing but
different Miller indices.
For example, the faces of a cube,
(100), (010), (100), (010), (001), and (001),
are planes of a form {100} since all of
them may be generated from any one by
operation of the 4-fold rotation axes
perpendicular to the cube faces. In the
tetragonal system, however, only the
planes (100), (010), (100), and (010)
belong to the form {100}; the other two
planes, (001) and (001), belong to the
different form {001}; the first four
planes mentioned are related by a 4-fold
axis and the last two by a two-fold axis.
 Planes of a zone are planes which are
[001]
all parallel to one line, called the zone zone
axis and the zone, i.e., the set of planes, axis
is specified by giving the indices of the
zone axis. Such planes may have quite
different indices and spacings, the only
requirement being that they are parallel
to a single line.
If the axis of a zone has indices [uvw],
then any plane belongs to that zone
whose indices (hkl) satisfy the relation:
hu + kv + lw = 0
Any two nonparallel planes are planes of a zone since they are
both parallel to their line of intersection. If their indices are (h1 k1 l1)
and (h2 k2 l2), then the indices of their zone axis [uvw] are given by
[h1 k1 l1] x [h2 k2 l2], that is, u = k1 l2 – k2 l1,
v = l1 h2 – l2 h1,
w = h1 k2 – h2 k1
2-8 Indexing in the hexagonal system
The indices of a plane in the hexagonal system, called Miller–
Bravais indices, refer to 4 axes and written (hkil). The index i is
the reciprocal of the fractional intercept on the a3 axis. Since the
intercept of a plane on a1 and a2 determine its intercept on a3, the
value of i depends on the value of h and k. The relation is h + k =
-i. Since i is determined by h and k, it is sometimes replaced by a
dot and the plane symbol written (hk . l). Sometimes even the dot
is omitted. (101) = (10 . 1)= (1011)
2-9 Crystal structure
The basic principle of crystal structure is that the atoms of
a crystal are set in space in some fixed relation to the points of a
Bravais lattice. It follows from this that this arrangement of
atoms will exhibit many of the properties of a Bravais lattice, in
particular many of its symmetry elements.

The features
associated with
each lattice point
are termed the
basis of the lattice,
and this applies to
1-, 2-, 3-D lattices.
Crystal structure
= Bravais lattice
+ Basis (基底)
 The simplest crystals imaginable are those formed by placing
atoms of the same kind on the points of a Bravais lattice. Many
metals crystallize in this simple fashion.

(N=2) (N=4)

However, when two or more atoms of the same kind are

associated with each point of a Bravais lattice, the number
of total atoms in a Bravais cell will be different from that of
the lattice point.
 When two or more atoms of the same kind are
associated with each point of a Bravais lattice:

A Bravais lattice of base- (Base-centered orthorhombic cell)

centered orthorhombic, centered
on the C face is shown at left.
Atoms occur in pairs through the
structure, each pair associated
with a lattice point. Consequently,
there are 4 identical atoms per
unit cell, located at 0 y ¼, 0 y ¾,
½ (½ + y) ¼, and ½ (½ - y) ¾.
Here y is a variable
parameter in the
atomic coordinates.
 For some unlike atoms in a Bravais lattice:

Turning to the crystal structure of compound

(AxBy) of unlike atoms, structures are built on the
skeleton of a Bravais lattice. Then the arrangement of
atoms in AxBy must satisfy the following conditions:
1. Body-, face-, or base-centering translations, if present,
must begin and end on atoms of the same kind.
2. The set of A atoms in the crystal and the set of B atoms
must separately possess the same symmetry elements.
In particular, the operation of any symmetry element
present must bring a given atom into coincidence with
another atom of the same kind.
 For example: the lattice of CsCl is simple cubic, not
body-centered, because Cs and Cl are unlike atoms.
The cerium is situated at 000 and the chlorine at ½ ½ ½.
The term “molecule” therefore has no real physical
significance in such a crystal in most inorganic
compounds and alloys.
Unit cell of NaCl contains 8 ions, located as follows:

Na+ at 0 0 0 + face-
centering translations:
0 0 0, ½ ½ 0, ½ 0 ½, 0 ½ ½

Cl- at ½½½ + face-

centering translations:
½ ½ ½, 0 0 ½, 0 ½ 0, ½ 0 0
 Diamond has 8 atoms per unit cell (diamond cubic),
located at
C(1): 0 0 0 + face-centering translations
C(2): ¼ ¼ ¼ + face-centering translations
ZnS (zinc blend) is of face-centered cubic cell, Zn and
S atoms are located at
Zn: 0 0 0 + face-centering translations
S: ¼ ¼ ¼ + face centering translations
 Ferrite has the formula MO‧Fe2O3, where M is a divalent
metal ion like Mn, Ni, Fe, Co, etc. Their structure is related to
that of the mineral spinel. The Bravais lattice of the ferrites is
face-centered cubic, and the unit cell contains 8 molecules or a
total of 8 x 7 = 56 ions. There are therefore 56/4 or 14 ions
associated with each lattice point. Thus, the number of atoms
per unit cell in any crystal is partially dependent on its Bravais
lattice type. However, the reverse of these proportions is not true.
For example: the unit cell of the
intermediate phase AuBe contains
8 atoms and yet it is based on a
simple cubic Bravais lattice. The
atoms are located as follows:
4 Au at u u u, (½+u) (½ - u) u,
u (½+u) (½-u), (½-u) u (½+u)

4 Be at w w w, (½-w) w (½+w),
w (½+w)(½-w), (½+w)(½-w) w
 There is another way of
arranging unlike atoms
on a point lattice:

1.Disordered solid solution:

BCC on the average

2.Ordered solid solutions:

The solute atoms take
up an ordered, periodic
arrangement. The solid
solution is then said to be
ordered and to possess a
superlattice.