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4 We will deal with crystalline solids, that is solids
with an atomic structure based on a regular
repeated pattern.

4 Many important solids are crystalline.

4 More progress has been made in understanding the

behaviour of crystalline solids than that of non-
crystalline materials since the calculation are easier
in crystalline materials.
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 G    


4 ˜olid state physics, also known as condensed matter

physics, is the study of the behaviour of atoms when
they are placed in close proximity to one another.

4 In fact, condensed matter physics is a much better

name, since many of the concepts relevant to solids
are also applied to liquids, for example.

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 G     

4 ·nderstanding the electrical properties of solids is

right at the heart of modern society and technology.

4 The entire computer and electronics industry relies

on tuning of a special class of material, the
semiconductor, which lies right at the metal-
insulator boundary. ˜olid state physics provide a
background to understand what goes on in
semiconductors.

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4 áew technology for the future will inevitably involve

developing and understanding new classes of
materials. By the end of this course we will see why
this is a non-trivial task.

4 ˜o, ˜˜ is the applied physics associated with

technology rather than interesting fundamentals.

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 E  
  
   
4 uow can this be? After all, they each contain a system of
atoms and especially electrons of similar density. And the
plot thickens: graphite is a metal, diamond is an insulator and
buckminster-fullerene is a superconductor.
They are all just carbon!

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4 Among our aims - understand ^
one is a metal and
one an insulator, and then the physical origin of the
marked features.
4 Also think about thermal properties etc. etc.

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ë

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4 lementary Crystallography
w ˜olid materials (crystalline, polycrystalline,
amorphous)
w Crystallography
w Crystal Lattice
w Crystal ˜tructure
w Types of Lattices
w ·nit Cell
w Directions- lanes-Miller Indices in Cubic ·nit Cell
4 Typical Crystal ˜tructures
(3D± 14 Bravais Lattices and the ˜even Crystal ˜ystem)
4 lements of ˜ymmetry
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 bj

By the end of this section you should:

4 be able to identify a unit cell in a symmetrical

pattern
4 know that there are 7 possible unit cell shapes
4 be able to define cubic, tetragonal,
orthorhombic and hexagonal unit cell shapes

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Ô

 
    


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 °
4 °ases have atoms or molecules that do not
bond to one another in a range of pressure,
temperature and volume.
4 These molecules haven¶t any particular order
and move freely within a container.

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    ë


4 ˜imilar to gases, liquids haven¶t any atomic/molecular

order and they assume the shape of the containers.
4 Applying low levels of thermal energy can easily
break the existing weak bonds.

Liquid crystals have mobile

molecules, but a type of long
range order can exist; the
molecules have a permanent
dipole. Applying an electric field
rotates the dipole and establishes
order within the collection of
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molecules.
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4 ˜olids consist of atoms or molecules
O O
 O
  about an
equilibrium position  O

 in space.
4 ˜olids can take the form of crystalline,
polycrstalline, or amorphous materials.
4 ˜olids (at a given temperature, pressure, and
volume) have stronger bonds between
molecules and atoms than liquids.
4 ˜olids require more energy to £O
 O
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Ô

Ô
 
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!


!
!

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4 ˜ingle crsytal, polycrystalline, and amorphous, are the
three general types of solids.

4 ach type is characterized by the size of ordered

region within the material.

4 An ordered region is a spatial volume in which atoms

or molecules have a regular geometric arrangement
or periodicity.

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 ë


4 Crystalline ˜olid is the solid form of a substance in
which the
   O
O are arranged in
a definite, repeating pattern in three dimension.
4 ˜ingle crystals, ideally have a high degree of order, or
regular geometric periodicity, throughout the OO
 O  O
O
.

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4 ˜ingle crystal has an atomic structure that repeats
periodically across its whole volume. ven at infinite length
scales, each atom is related to every other equivalent
atom in the structure by translational symmetry


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4 olycrystal is a material made up of an aggregate of
 
 O


(also called crystallites or grains).
4 olycrystalline material have a high degree of order over many atomic or molecular
dimensions.
4 These OO O or single crytal regions, vary in size and orientation wrt
one another.
4 These regions are called as 
  
 and are separated from one another
by 
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4 The grains are usually Õ   Õ 
  
OO. olycrystals with grains
that are <10 nm in diameter are called nanocrystalline

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4 Amorphous (áon-crystalline) ˜olid is composed of randomly
orientated atoms , ions, or molecules that do not form defined
patterns or lattice structures
4 Amorphous materials have order only within a few atomic or
molecular dimensions.
4 Amorphous materials do not have any long-range order, but they
have varying degrees of short-range order.
4 xamples to amorphous materials include amorphous silicon,
plastics, and glasses.
4 Amorphous silicon can be used in solar cells and thin film transistors.

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 2        ë

4 ˜trictly speaking, one cannot prepare a perfect crystal. For
example, even the surface of a crystal is a kind of
imperfection because the periodicity is interrupted there.

4 Another example concerns the thermal vibrations of the atoms

around their equilibrium positions for any temperature T>0°K.

4 As a third example, actual

crystal always contains some
foreign atoms, i.e., impurities.
These impurities spoils the
perfect crystal structure.

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The branch of science that deals with the geometric

description of crystals and their internal arrangement.

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Crystallography is essential for solid state physics

4 ˜ymmetry of a crystal can have a profound influence

on its properties.
4 Any crystal structure should be specified completely,
concisely and unambiguously.
4 ˜tructures should be classified into different types
according to the symmetries they possess.

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 Ô
"

4 A basic knowledge of crystallography is essential

for solid state physicists;
w to specify any crystal structure and
w to classify the solids into different types according to
the symmetries they possess.

4 ˜ymmetry of a crystal can have a profound

influence on its properties.

4 We will concern in this course with solids with

simple structures.

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!  # !

In crystallography, only the geometrical properties of the
crystal are of interest, therefore one replaces each atom by
a geometrical point located at the equilibrium position of
that atom.

latinum latinum surface Crystal lattice and

 
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 # structure of latinum
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4 An infinite array of
points in space, B C D 
b A
4 ach point has O x
a A
identical surroundings
to all others.

4 Arrays are arranged

exactly in a periodic
manner.

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4 Crystal structure can be obtained by attaching atoms,

groups of atoms or molecules which are called basis
(motif) to the lattice sides of the lattice point.

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B C D 
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4 Don't mix up atoms with

lattice points
4 Lattice points are
infinitesimal points in
space
4 Lattice points do not
necessarily lie at the
centre of atoms


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 All atoms are of the same kind  Atoms can be of different kind
 All lattice points are equivalent  ˜ome lattice points are not
equivalent
A combination of two or more BL

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1) Bravais lattice is an infinite array of discrete points with

an arrangement and orientation that appears exactly the
same, from whichever of the points the array is viewed.
Lattice is invariant under a translation.

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2) áon
áon--Bravais Lattice
áot only the arrangement but also the orientation must
appear exactly the same from every point in a bravais lattice.

4 The red side has a neighbour to its

immediate left, the blue one instead
has a neighbour to its right.
4 Red (and blue) sides are equivalent
and have the same appearance
4 Red and blue sides are not
equivalent. ˜ame appearance can
be obtained rotating blue side 180º.

 
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A space lattice is a set of points such
that a translation from any point in the
lattice by a vector;


Rn = n1 a + n2 b

locates an exactly


 point,

 a point with the same environment
as  . This is translational symmetry.
The vectors ,  are known as lattice
vectors and (n1, n2) is a pair of
integers whose values depend on the

 * +%,+ lattice point.

- * +%,)*
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4 The two vectors a and b

form a set of lattice
vectors for the lattice.

4 rO

O  

O
O
   O.
Thus one could equally
well take the vectors a
and b¶ as a lattice vectors.

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An ideal three dimensional crystal is described by 3
fundamental translation vectors a, b and c. If there is a
lattice point represented by the position vector r, there is
then also a lattice point represented by the position vector
where ,  and  are arbitrary integers.

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4 The smallest component of the crystal (group of atoms,
ions or molecules), which when stacked together with
pure translational repetition reproduces the whole
crystal.

˜ ˜

˜ ˜ ˜
˜ ˜ ˜ ˜ ˜
m
˜ ˜ ˜ ˜ ˜

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4 The smallest component of the crystal (group of atoms,
ions or molecules), which when stacked together with
pure translational repetition reproduces the whole
crystal.

˜
  

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We define !
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 ; these are points with 








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Choice of origin is arbitrary - lattice points need not be
atoms - £$unit cell size should always be the same.

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This is also a unit cell -
it doesn¶t matter if you start from áa or Cl

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- or if you don¶t start from an atom

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This is áOT a unit cell even though they are all the
same - empty space is not allowed!

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In 2D, this I˜ a unit cell
In 3D, it is áOT

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*   b  !
b   

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·nit Cell in 3D

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·nit Cell in 3D

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Three common ·nit Cell in 3D

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 ˜ingle lattice point per cell

 ˜mallest area in 2D, or  More than one lattice point per cell
˜mallest volume in 3D  Integral multibles of the area of
primitive cell


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4 A unit cell just fills space when

translated through a subset of
Bravais lattice vectors.
4 The conventional unit cell is
chosen to be larger than the
primitive cell, but with the full
symmetry of the Bravais lattice.
4 The size of the conventional cell
is given by the lattice constant
a.

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—


 

  

Y Õ
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Y Õ
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rimitive and conventional cells
Body centered cubic (bcc):
conventional *primitive cell


Fractional coordinates of lattice points in
m conventional cell:
000,100, 010, 001, 110,101, 011, 111, ½ ½ ½

˜imple cubic (sc):

primitive cell=conventional cell

Fractional coordinates of lattice points:
000, 100, 010, 001, 110,101, 011, 111
m
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rimitive and conventional cells

Body centered cubic (bcc):

primitive (rombohedron) *conventional cell

m Fractional coordinates:
000, 100, 101, 110, 110,101, 011, 211, 200

Face centered cubic (fcc):

conventional * primitive cell
Fractional coordinates:

000,100, 010, 001, 110,101, 011,111, ½ ½ 0, ½
0 ½, 0 ½ ½ ,½1 ½ , 1 ½ ½ , ½ ½ 1
m
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rimitive and conventional cells-hcp
points of primitive cell

uexagonal close packed cell (hcp):

conventional primitive cell


Fractional coordinates:
100, 010, 110, 101,011, 111,000, 001

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 ë

4 The unit cell and, consequently,

the entire lattice, is 


determined by the six lattice
constants: a, b, c, A, ȕ and ö.
4 Only 1/8 of each lattice point in a
unit cell can actually be assigned
to that cell.
4 ach unit cell in the figure can be
associated with 8 x 1/8 = 1 lattice
point.

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4 A primitive unit cell is made of primitive
translation vectors a1 ,a2, and a3 such
that there is no cell of smaller volume
that can be used as a building block for
crystal structures.

4 A primitive unit cell will fill space by

repetition of suitable crystal translation
vectors. This defined by the parallelpiped
a1, a2 and a3. The volume of a primitive
unit cell can be found by

4 V = a1.(a2 x a3) (vector products) $£

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 rimitive ·nit Cell
4 The primitive unit cell must have only one lattice point.
4 There can be different choices for lattice vectors , but the
volumes of these primitive cells are all the same.
mÕ

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A simply way to find the primitive
cell which is called Wigner-˜eitz
cell can be done as follows;

1. Choose a lattice point.

2. Draw lines to connect these
lattice point to its neighbours.
3. At the mid-point and normal
to these lines draw new
lines.

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4 Within a crystal lattice it is possible to identify sets of equally
spaced parallel planes. These are called lattice planes.
4 In the figure density of lattice points on each plane of a set is
the same and all lattice points are contained on each set of
planes

  
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a a

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Miller Indices are a symbolic vector representation for the orientation of
an atomic plane in a crystal lattice and are defined as the reciprocals of
the fractional intercepts which the plane makes with the crystallographic
axes.

To determine Miller indices of a plane, take the following steps;

1) Determine the intercepts of the plane along each of the three

crystallographic directions

2) Take the reciprocals of the intercepts

3) If fractions result, multiply each by the denominator of the smallest

fraction

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Axis ;  
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Miller İndices (100)

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[2,3,3š lane intercepts axes at


â
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2 Õ Õ Õ
Reciprocal numbers are:  




Indices of the plane (Miller): (2,3,3)
2
m Indices of the direction: [2,3,3š
3

(200)
(111)
(110) (100)

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4 ˜ometimes when the unit cell has rotational symmetry,

several nonparallel planes may be equivalent by virtue of this
symmetry, in which case it is convenient to lump all these
planes in the same Miller Indices, but with curly brackets.

Õ  — Õ   Õ   Õ  Õ   Õ   Õ 
ÕÕÕ — ÕÕÕ ÕÕ Õ  Õ Õ Õ  Õ ÕÕ  Õ Õ Õ   Õ Õ Õ  Õ Õ Õ  Õ Õ Õ 

Thus indices {h,k,l} represent all the planes equivalent to the

plane (hkl) through rotational symmetry.
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4 There are only seven different shapes of unit cell which

can be stacked together to completely fill all space (in 3
dimensions) without overlapping. This gives the seven
crystal systems, in which all crystal structures can be
classified.

4 Cubic Crystal ˜ystem (˜C, BCC,FCC)

4 uexagonal Crystal ˜ystem (˜)
4 Triclinic Crystal ˜ystem (˜)
4 Monoclinic Crystal ˜ystem (˜, Base-C)
4 Orthorhombic Crystal ˜ystem (˜, Base-C, BC, FC)
4 Tetragonal Crystal ˜ystem (˜, BC)
4 Trigonal (Rhombohedral) Crystal ˜ystem (˜)
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4 Coordinatıon áumber (Cá) : The Bravais lattice points

closest to a given point are the nearest neighbours.

4 Because the Bravais lattice is periodic, all points have

the same number of nearest neighbours or coordination
number. It is a property of the lattice.

4 A simple cubic has coordination number 6; a body-

centered cubic lattice, 8; and a face-centered cubic
lattice,12.
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 3! 

4 Atomic acking Factor (A F) is defined as

the volume of atoms within the unit cell
divided by the volume of the unit cell.

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4 ˜imple Cubic has one lattice point so its primitive cell.
4 In the unit cell on the left, the atoms at the corners are cut
because only a portion (in this case 1/8) belongs to that cell.
The rest of the atom belongs to neighboring cells.
4 Coordinatination number of simple cubic is 6.

b
c

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4 BCC has two lattice points so BCC

is a non-primitive cell.
4 BCC has eight nearest neighbors.
ach atom is in contact with its
neighbors only along the body-
diagonal directions.
4 Many metals (Fe,Li,áa..etc),
including the alkalis and several
b c
transition elements choose the
BCC structure.
a
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4 There are atoms at the corners of the unit cell and at the
center of each face.
4 Face centered cubic has 4 atoms so its non primitive cell.
4 Many of common metals (Cu,ái, b..etc) crystallize in FCC
structure.

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FCC Î,=;


  

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Counting the number of atoms within the unit cell

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corner 8 cells 1/8
face centre 2 cells 1/2
body centre 1 cell 1
edge centre 2 cells 1/2

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1 [=8 x 1/8š
I 2 [=(8 x 1/8) + (1 x 1)š
F 4 [=(8 x 1/8) + (6 x 1/2)š
C 2 [=(8 x 1/8) + (2 x 1/2)š
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4 A crystal system in which three equal coplanar axes

intersect at an angle of 60 , and a perpendicular to the
others, is of a different length.

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E,

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4 Triclinic minerals are the least symmetrical. Their three axes
are all different lengths and none of them are perpendicular
to each other. These minerals are the most difficult to
recognize.

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4 ˜odium Chloride ˜tructure áa+Cl-

4 Cesium Chloride ˜tructure Cs+Cl-
4 uexagonal Closed- acked ˜tructure
4 Diamond ˜tructure
4 Zinc Blende

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4 This structure can be
considered as a face-
centered-cubic Bravais lattice
with a basis consisting of a
sodium ion at 0 and a chlorine
ion at the center of the
conventional cell,
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m  


4 LiF,áaBr,KCl,LiI,etc
4 The lattice constants are in
the order of 4-7 angstroms.
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4 The translational symmetry of this
structure is that of the simple cubic
Bravais lattice, and is described as a
simple cubic lattice with a basis
consisting of a cesium ion at the origin ,
and a chlorine ion at the cube center
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m 


4 CsBr,CsI crystallize in this structure.The

lattice constants are in the order of 4
angstroms.
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8 cell

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4 

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Bravais Lattice : uexagonal Lattice a=b a=120, c=1.633a,
ue, Be, Mg, uf, Re (°roup II elements) basis : (0,0,0) (2/3a ,1/3a,1/2c)
ABABAB Type of ˜tacking

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3!
Close pack

A A A A A A A A
B B
A A A  A
   A A A
B B
A A A  A A
    A A A
A A  A  A
  
˜equence AAAA«
˜equence ABABAB..
- simple cubic
-hexagonal close pack
˜equence ABAB«
˜equence ABCABCAB..
- body centered cubic
-face centered cubic close pack
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4 The coordination number of diamond

structure is 4.
4 The diamond lattice is not a Bravais
lattice.
4 ˜i, °e and C crystallizes in diamond
structure.

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4 Zincblende has equal numbers of zinc and

sulfur ions distributed on a diamond lattice
so that each has four of the opposite kind as
nearest neighbors. This structure is an
example of a lattice with a basis, which must
so described both because of the
geometrical position of the ions and
because two types of ions occur.
4 AgI,°aAs,°a˜b,InAs,
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Zinc Blende is the name given to the mineral Zn˜. It has a cubic
close packed (face centred) array of ˜ and the Zn(II) sit in
tetrahedral (1/2 occupied) sites in the lattice.

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4 ach of the unit cells of the 14 Bravais lattices has one

or more types of symmetry properties, such as
inversion, reflection or rotation,etc.

˜
MMTR

IáVR˜IOá RFLCTIOá ROTATIOá

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Lattice goes into itself through
˜ymmetry without translation

Operation lement

Inversion oint

Reflection lane

Rotation Axis

Rotoinversion Axes
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4 A center of symmetry: A point at the center of the molecule.
(x,y,z) --> (-x,-y,-z)
4 Center of inversion can only be in a molecule. It is not
necessary to have an atom in the center (benzene, ethane).
Tetrahedral, triangles, pentagons don't have a center of
inversion symmetry. All Bravais lattices are inversion
symmetric.
Ô :

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4 A plane in a cell such that, when a mirror reflection

in this plane is performed, the cell remains invariant.

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4 Triclinic has no reflection plane.

4 Monoclinic has one plane midway between and
parallel to the bases, and so forth.

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We can not find a lattice that goes

into itself under other rotations

‡ A single molecule can have any degree

of rotational symmetry, but an infinite
periodic lattice ± can not.

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,
?

*+,? *@,?

4 This is an axis such that, if the cell is rotated around it

through some angles, the cell remains invariant.

4 The axis is called n-fold if the angle of rotation is 2ʌ/n.

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Axis of Rotation

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5-fold symmetry

Can not be combined with translational periodicity!

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°roup discussion
4 Kepler wondered why snowflakes have 6 corners,
never 5 or 7.By considering the packing of polygons
in 2 dimensions, demonstrate why pentagons and
heptagons shouldn¶t occur.

E


 

 

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,?
4 Triclinic has no axis of rotation.
4 Monoclinic has 2-fold axis (ș= 2ʌ/2 =ʌ) normal to the
base.

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