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In crystalline solids, the atoms are arranged (stacked) in a regular manner, forming a three -

dimensional pattern. This pattern is obtained by a three dimensional repetition of a certain

pattern- unit. This repetition represents PERIODICITY. When this periodicity extends

throughout a certain piece of material, it is called a single crystal. In poly crystalline materials,

the periodicity is interrupted at the grain boundaries. Thus, it is made up of many grains, where

every grain is a single crystal. When the size of the grain becomes comparable to the pattern

unit, then one cannot talk of single crystal as the periodicity is completely lost. Such a solid is

called Amorphous.

For most solids, the Crystalline state is the natural one, since the energy of the ordered atomic

arrangement is lower than that of an irregular packing of atoms. If atoms are not allowed to

arrange themselves in order by hindering their mobility, they may not grow crystalline but

amorphous. Certain polymers are composed of very large and irregular molecules and in such

cases, crystalline packing is not easily obtained. In some cases, the molecular arrangement of

liquid state is fast frozen in and the molecules would not get time to arrange in order and glassy

substance may result; after annealing it may crystallize.

In another class of crystals, there is only two or one dimensional regularity, viz. the liquid

crystal. Such substances will actually flow and rise in a capillary tube.Normal crystals exhibit

flow under the action of external force. Though single ( perfect) crystal of a substance has

unique properties, a large number of properties of solids are determined by lattice imperfection

such as impurities, vacant lattice sites etc.

Lattice Points And Space Lattice : A space lattice is a three -dimensional array of points such

that the neighboring points of each one surround it in an identical way. Each point in the space

lattice is called lattice point. Every lattice point in a lattice is associated with one or more atoms

called the basis or the pattern. Thus lattice + basis = crystal structure.

b

a

Unit Cells and Bravais Lattice : Periodicity of structure is the fundamental feature of a crystal.

Since atoms in a crystal are arranged in a periodic array, it is possible to isolate a representative

unit cell in each variety of crystal - a group of ions atoms or molecules, as the case may be and

construct the entire crystal by repeatedly translating the unit cell in three dimensions. The choice

of unit cells is by no means unique. The unit cell in a 3 - dimensional lattice is characterised by

the lengths a, b & c and the angles , & . These are known as the unit cell parameter. From

these parameters, a total of seven crystal lattices can be constructed. In these crystal lattices

the unit cell has points only at the corners. This is known as the simple or primitive unit cell.

However, other arrangements of points are also possible which fulfill the requirements of a

space lattice i.e. each point in space has identical surroundings. If there are lattice points at the

corners and at the center of the unit cell then it is known as a body centered unit cell. If there

are lattice points at the corners and at the centers of some or all the faces then it is called

Face Centered Lattice. Thus for a cubic system there are three type of unit cells viz. Primitive ,

Body Centered & face centered.

Translation Vectors A lattice framework of geometrical points in three dimensional space is

described by the translation vector T = n 1 a + n2 b + n3 c , where a,b,c are three unit vectors

and n1 , n2 n3 take all possible integer values. Therefore parallellopiped formed by a,b & c as the

concurrent edges is called unit cell of the lattice. A unit cell repeated with translation vector T

fills all the space.

BRAVAIS LATTICE In order to describe the structure of crystals, Bravais in 1848 introduced

the concept of space lattice. A space lattice is a mathematical concept and is defined as an

infinite array of points in space, such that the arrangement of atoms about one point is same as

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 2

about any other point. The points of inter-section are called lattice points. Bravais showed that

there exists no more than fourteen (14) space lattice in three dimensions.

The Fourteen Bravais Lattices :

system lattice unit cell ( a,b & ( , & )

c)

Cubic 3 a=b=c = = = 90o

Tetragonal 2 a=bc = = = 90o SnO2 , NiSO4

Orthorhombic 4 abc = = =90o KNO3 , BaSO4

Monoclinic 2 abc = = 90o FeSO4, Na2SO4

Triclinic 1 abc 90o K2Cr2O7,CuSO4.5H2O

Trigonal 1 a=b=c = = 90o Sb, Bi, As

Hexagonal 1 a=bc = = 90o & =120o SiO2 , Zn , Mg

(1) Coordination Number (N) -- The coordination number is defined as the number of equidistant

nearest neighbours that an atom has in the given structure. Greater is coordination number, the

more closely packed up will be the structure.

(2) Nearest NeighbourDistance (2r) --- The distance between the centres of two nearest

neighbouring atom is called nearest neighbour distance. It will be 2r if r is the radius of the atom.

(3) Atomic Radius (r) Atomic radius is defined as half the distance between nearest neighbours

in a crystal of pure element.

(4) Atomic Packing Factor -- The fraction of the space occupied by atoms in a unit cell is known

as atomic packing factor ( APF) or simply packing factor i.e. it is the ratio of the volume of the

atoms occupying the unit cell to the volume of the unit cell relating to that structure.

Simple Cubic StructureIn SCS, the unit cell contains lattice points (atoms)only at the eight

of atom per corner = 8 x 1/ 8 =1Therefore this cubic cell is also a primitive cell. Only polonium

exhibits this structure below 750 C .

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 3

Coordination number N = 6,

Nearest neighbour distance = 2 r,

Lattice distance a = 2 r

Hence the packing factor or density of packing is

SC structure is loosely packed structure.

Body Centered Cubic Structure Unit cell is as shown. It has in addition to the atoms at the

eight corners one atom at the centre. Thus there are 1/8 x 8 + 1 = 2 atoms per unit cell. The cell

is non-primitive. The primitive cell is 109 0 rhomohedron.

The corner atoms do not touch each other, but each corner atom touches the body centre atom

along the body diagonal. Coordination number is 8.

Nearest neighbour distance 2 r = a 3 / 2.

{(AC)2 = a2 + a2 = 2a2 , & (FC)2 = (AC)2 + (AF)2 = 3a2

4 r

Lattice constant a =

3

4 r 3

Volume of all the atoms in a unit cell = 2x

3

3

64 r

Volume of all the unit cell V = a3 =

3 3

3

v 8 r 3 3 3

Packing Fraction = x

3

068 or = 68%

V 3 64 r 8

B C C structure is a closely packed structure. Li, Na, K & Cr have this structure.

Face Centered Cubic Structure FFC unit cell has eight atoms at the corners of the unit cell

and six atoms at the center of the six faces. Atom at the center of the face is shared by two unit

cells. no. of atoms per unit cell is 1/8 x 8 + 1/2 x 6 = 4 . Considering the atom at the face

center as origin, it can be observed that there are twelve points surrounding it situated at a

distance equal to half the face diagonal of the unit cell. Thus the coordination number N = 12.

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 4

Lattice Constant a = 4 r / 2

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 5

a 2

Nearest neighbour distance, 2r =

2

4 r 3

Volume of all the atoms in a unit cell = 4x

3

64 r 3

Volume of all the unit cell V = a3 =

2 2

3

v 16 r 2 2 2

Packing Fraction = x

3

074 = 74%

V 3 64 r 6

Hexagonal Close Packed Structure The unit cell is as shown. It contains one atom at each

corner, one atom each at the centre of the hexagonal faces and three more atoms within the

body of the cell. Each atom touches three atoms in the layer below its plane, Six atoms in its

own plane and three atoms in the layer above. Hence coordination no. is 12. The atoms touch

each other along the edge of the hexagon

a = 2 r . The no. of atoms per unit cell = 1/2 x 2 + 12 x 1/6 = 1 + 2 + 3 = 6.

Let c be the height of the unit cell & a be the edge length.The three body atoms lie in a

horizontal plane at c / 2 from the orthocentres of the alternate equilateral triangles at the top or

base of the hexagonal cell. These three atoms just rest on the three atoms at the corner of the

triangles.

In the triangle ABY Cos 30o = AY/ AB

AY = AB 3 / 2 = a 3 / 2 A Y

2 2a 3 a

In triangle AXZ AX= AY

3 3x 2 3

2 2

a c a2 c2 c2 a2 2a 2

Substituting this in equ. (i) (AZ) 2 = a2 = a2

3 2 3 4 4 3 3

1 2

c 8

a 3

Volume of the unit cell Area of the base = 6 x area of the triangle AOB = 6x

1 a 3 3

ax 3 a 2

2 2 2

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 6

3

volume of the cell= area of the base x height = 3 a 2 . c

2

Lattice constant a=2r

nearest neighbour distance , 2r = a

3

4 r 3 24 a

Volume of all the atoms in a unit cell , v = 6x

a3

3 3 2

1 2

v a3 2 a 2 3 2

074

Packing Fraction = V 3 3 3 c 3 3 8 6 or 74 %

3 a 2c

2

Relation between lattice constant & density of the crystal material in a cubic lattice

Avogadro number of atoms will have volume = MA /

where MA is atomic weight of the material & is the density

MA 1

volume corresponding to each atom =

NA

MA 1

n atoms in the unit cell will occupy a volume = .n = a3

NA

1 3

M

a = A n

NA

Diamond Structure Diamond structure is a f.c.c. structure with basis of two atoms, one

located at (0,0,0) and another at (1/4, 1/4, 1/4 ) associated with each lattice point. A unit cell of

this structure is shown in fig.. The structure may be viewed as resulting from the interpenetration

of two face- centered cubic sub-lattices, one sublattice having its origin at (0 ,0 ,0 ) and the

other at (1/4, 1/4, 1/4)-- that is one quarter of the way along the body diagonal. Each atom in this

structure has four nearest neighbours (occupying the corner points of a regular tetrahedron) to

which it is bonded by strong covalent bonds. It clearly means that the structure is very loose, the

maximum proportion of the available volume i.e. the packing fraction which for diamond structure

is 3 16 = 0.34 which may be filled by atoms is only 34%. The importance of this structure

will become evident when we study semiconductors. Carbon (in diamond phase) silicon,

germanium and grey-tin all crystallize in diamond structure.

Zincblende (ZnS) Structure The zincblende structure is very closely related to the diamond

structure. In fact, it is identical to the diamond structure except that the two interpenetrating f.c.c.

sublattices are of different atoms: one composed entirely of Zn atoms, the other entirely of S

atoms. This is therefore also a true face-centered cubic structure with a basis of two different

atoms. There are four units of ZnS per unit cell. The four nearest neighbours to a particular atom

in this case are of opposite kind but disposed tetrahedrally as in diamond structure. This

structure is therefore as loosely packed as the diamond structure. It makes sense to note that

this structure does not posses a centre of inversion symmetry at the mid point of a line

connecting nearest neighbour atoms whereas a diamond structure does. The compounds InSb,

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 7

GaAs, GaSb, InP, Gap, CuF, CuCI, Agl, ZnSe, Znse, CdS, InAs, SiC, etc. crystallize with this

structure.

Sodium Chloride (NaCl) Structure --- The sodium chloride structure is shown in fig. This may

be viewed as consisting of two face-centered cubic sublattices, one of Na ions having its origin

at the point (0,0,0), and the other of CI ions, having its origin midway along a cube edge, say at

point (a/2, 0 , 0). The space lattice is therefore truly f.c.c. with a basis of one Na ion and one CI

ion separated by one-half the body diagonal of a unit cube. There are four molecules of NaCI--

Na : 0 0 0 ; 0 ; 0 ; 0

Cl : ; 0 0 ; 0 0 ; 0 0

This structure, thus, may also be considered as composed of two types of ions arranged

alternately at the lattice points of a simple cubic lattice. In crystal each ion is surrounded by six

nearest neighbours of the opposite kind (co-ordination number =6) and twelve next nearest

neighbours of the same kind as the reference ion. Representative crystals having the NaCl- type

arrangement are : LiH, NaCl, Kbr, KCI, Pbl, PbS, NH 4 I, AgBr, MgO, MnO, BaO, NiO, UO and all

alkali halides except CS CI , CS CI, CS Br, CS I at room temperature.

Cesium Chloride (CSCI) Structure The cesium chloride structure is shown in fig. This

structure may be considered as resulting from the combination of two simple cubic sublattices,

one of Cs ions and the other of Cl ions, disposed such that a corner of one sublattice is the body

center of the other. The space lattice is therefore actually simple cubic with a basis of one Cs ion

at (0 0 0) and one Cl ion at ( ) i.e. separated by one-half of the body diagonal of the

unit cube. There is only one molecule per unit cell. Each ion at the centre of a cube of ions of the

opposite kind and so the coordination number of this structure = 8. Representative crystals

having the CsCl-type structure are : TIBr, TII, NH4 Cl, RbCl (1900 ), CuZn, AgMg, LiHg, AINi,

BeCu and some other ionic crystals.

LATTICE PLANES & MILLER INDICES Lattice Planes :--- A crystal lattice may be

considered as an aggregate of a set of parallel equidistant planes, passing through the lattice

points. These are called lattice planes. For a given lattice these sets of planes can be chosen in

number of different ways the spacing between the successive planes accordingly varies, as also

the density of lattice points per unit area in each plane. The method of specifying planes is as

follows -- (1) Let the intercepts by the given plane on the three crystal axis be in the ratio pa : qb

: rc where a,b,c are the corresponding unit vectors lengths and p.q.r are integers. (2) Take the

reciprocal of p,q,r. (3) Get the smallest possible integers h,k,l such that h,k,l = p -1 : q-1 : r-1 .

These numbers h,k,l are known as Miller indices of the given set of planes and the plane is

specified as (h,k,l).Thus Miller indices may be defined as the reciprocals of the intercepts made

by the plane on the crystallographic axes when reduced to smallest numbers.

Thus all the parallel equidistant planes have the same Miller indices. Thus the miller indices

define a set of parallel planes. A plane parallel to one of the coordinate axis has an intercept of

infinity. If an intercept is negative the corresponding Miller index is written with a bar at the top

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 8

e.g. 2 For planes parallel to the xz plane we have p = r = and r finite, therefore the Miller

indices are (010)

Separation Between Lattice Planes In a Cubic Crystal Consider the planes ( h,k,l). Let the

reference plane passes through the origin. The next plane (hkl) will have intersects 1/h, 1/k, 1/l

of the respective unit lengths i.e. intercepts are pa, qb, rc = ( a/h, b/k, c/l )

If Cos , Cos & Cos are the direction cosines of the normal ON then Cos 2 + Cos2 + Cos2

d d d

=1 where Cos = a h

Cos = b k

Cos = c l

2 2 2

hd kd ld

Therefore 1

a b c

d 2 d 2 d 2

d 2 1

a b c

1

d 1/ 2

d d 2 d 2

2

a b c

1 a

For cubic crystal a=b=c d= h 2 k 2 l 2 a h 2 k 2 l 2

(I) ( 0 1 0 ) Plane

In this plane a= 2 r

Since a2 area contains 1 atom Unit area will contain 1/ a2 = 1 / 4r2 atoms

(ii) ( 1 1 0 ) Plane

Area of the plane is 2 a2

1 1

Atoms per unit area = 2

2 a 2 4 r 2

(iii) (1 1 1 ) Plane

3

Area of the plane is a2

2

Number of atoms = 3x 1/ 6 = 1 / 2

1

2 1 1 1

Atoms per unit area = 3

3 a 2 3 4r 2

a2

2

Reciprocal space: Reciprocal space is also called Fourier space, k- space, or momentum space

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 9

The concept of the reciprocal lattice was devised to tabulate two important properties of crystal

planes: their slopes and their interplanar distances.

Definition: The reciprocal space lattice is a set of imaginary points constructed in such a way

that the direction of a vector from one point to another coincides with the direction of a normal

to the real space planes and the separation of those points (absolute value of the vector) is equal

to the reciprocal of the real interplanar distance.

It is convenient to let the reciprocal lattice vector be 2 times the reciprocal of the

interplanar distance. This convention converts the units from periods per unit length to radians

per unit length. Radians per centimeter (cm-1) are widely used units. It simplifies comparison of

different periodic phenomena. For instance k , the wavevector, has an absolute value of 2/. If

we choose the above convention, we are able to compare the two values directly. Henceforth

this convention will be used. All it does is expand the size of the reciprocal lattice.

We can describe the reciprocal lattice in the same way we describe the real ones, but we

should keep in mind the difference: one indicates the location of real objects (atoms) and has

dimensions of m, the other indicates the positions of abstract points (magnitude and direction

of momentum ) and has dimensions of m-1.

If the unit cell axes and angles of the direct cell are known by the letters a, b, c, , , , the

corresponding parameters for the reciprocal cell are written with the same symbols, adding an

asterisk: a*, b*, c*, *, *, *. It should also be clear that these reciprocal axes (a*, b*, c*) will

correspond to the vectors G100 , G010 and G001 , respectively, so that any reciprocal vector can be

expressed as a linear combination of these three reciprocal vectors:For hkl planes:

Ghkl = ha* + kb* + lc*

The geometric relationships between the direct (= real) and reciprocal cells imply the following

well-defined metric relations between them:

Pick some point as an origin, then:

a) from this origin, lay out the normal to every family of parallel planes in the direct lattice;

b) set the length of each normal equal to 2 times the reciprocal of the interplanar spacing for

its particular set of planes;

c) place a point at the end of each normal.

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 10

reciprocal

direct

Two lattices (direct with blue points, reciprocal in green) showing their geometrical relations. For clarity it

is assumed that the third direct axis (c), not shown, is perpendicular to the screen

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 11

Thus:

The reciprocal lattice simplifies the interpretation of x-ray diffraction from crystals

The reciprocal lattice facilitates the calculation of wave propagation in crystals (lattice

vibrations, electron waves, etc.)

Animation: http://www.xtal.iqfr.csic.es/Cristalografia/parte_04-en.html

Summarizing:

Direct lattice is a lattice in ordinary space whereas the reciprocal lattice is a lattice in the

Fourier space.

The primitive vectors in reciprocal lattice has the dimensions of (length) -1 whereas the

primitive vectors of the direct lattice have the dimensions of length

A diffraction pattern of a crystal is a map of the reciprocal lattice of the crystal whereas a

microscopic image is a map of direct lattice

When we rotate a crystal, both direct and reciprocal lattice rotates

Each point in the reciprocal lattice represents a set of parallel planes of the crystal lattice

If the coordinates of reciprocal vector G have no common factor, then G is inversely

proportional to the spacing of the lattice planes normal to G

The volume of unit cell of the reciprocal lattice is inversely proportional to the volume of

unit cell of the direct lattice

The direct lattice is the reciprocal of its own reciprocal lattice

The unit cell of the reciprocal lattice need not be parallelepiped

Father Sir William Henry Bragg and Son Sir William Lawrence Bragg proposed that Bragg's diffraction

occurs when electromagnetic radiation or subatomic particle wave with a wavelength comparable to atomic

spacing is incident upon a crystalline sample and scattered in a specular fashion by the atoms in the system

and undergoes a constructive interference.

For a crystalline solid, the waves are scattered from lattice planes separated by the inter-planar distance d.

When the scattered waves interfere constructively, they remain in phase (demonstrated later) since the path

length of each wave is equal to an integer multiple of the wavelength. Constructive interference only occurs

for certain ' s correlating to a (hkl ) plane, specifically when the path difference is equal to n wavelengths.

The path difference between the two waves undergoing constructive interference is given by 2d sin, where

is the scattering angle. This leads to Bragg's law, which describes the condition for constructive

interference from successive crystallographic planes (hkl ) of the crystalline lattice. Wavelength of X-rays

used in crystallography: 1 - 3 ( = 10-10m) most commonly 1.54 (Cu )

Frequency = c/l =(3x108m/s) /(1.54x10-10m) 2x1018 s-1

X Ray diffraction Analysis : Braggs law

of X-ray diffracto-

meter geometry and its components are shown in Figure.

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 12

Consider a plane lattice crystal with inter planar distance d . Suppose a beam of X-rays of wavelength is

incident on the crystal at an angle , the beam will be reflected in all possible atomic planes. The path

difference between any two reflected waves is equal to the integral multiple of wavelength. The ray P gets

reflected from the surface while the ray Q has to

undergo some path difference. The extra distance

traveled by the ray Q from the figure is (BC +CD).

From the diagram either BC or CD is equal to d

sin .

So the path difference is

d sin + d sin = n

2 d sin = n

Here n is the order = 1,2, 3 .This is Braggs law

X-ray diffraction pattern

A diffraction pattern is obtained by measuring the intensity of scattered waves as a function of scattering

angle. Very strong intensities known as Bragg peaks are obtained in the diffraction pattern when scattered

waves satisfy the Bragg's Law.

Following Bragg's law, each dot (or reflection) in the diffraction pattern above forms from the constructive

interference of X-rays passing through a crystal. The data can be used to determine the crystal's atomic

structure.

The figures above show experimental x-ray diffraction patterns of cubic SiC using synchrotron radiation. We

can see Bragg peaks clearly from the figures.

Shape and dimension of the unit cell can be deduced from Bragg peaks

Content of the unit cell (basis) determined from intensities of reflections

Thus An X-Ray diffraction pattern of the lattice Can be interpreted as a map of the reciprocal

lattice of the crystal.

T.Y. P.I I/ I / I CRYSTAL PHYSICS NKapoor 13

Extra

What is the need of using reciprocal lattice? Why should we not use direct lattice?

Here were my answers:

To describe crystal structures once it is known we need only direct lattice. But how to get the information

about the crystal structure , i.e. the details of atomic arrangement? The ready answer is of course X-ray

diffraction. Now X-ray diffraction is not a direct microscopic technique. We do not see the atoms directly by

this technique. We only see Bragg peaks in different positions and directions after the X-ray is scattered

from a single crystal (Debye rings for powder samples) and detected on a film or by single or multidetectors.

So we can determine the angular positions and of course their intensities. We can collect these information

and plot them somehow. What is the relationship between these information and the actual crystal structure?

We do not see directly the atoms by X-ray diffraction. We have to live with the information we have

obtained from X-ray diffraction experiments. Now it turns out that we can relate the Bragg spots (or Debye

rings) with the atomic planes of the direct lattice that you obviously like very much. The atomic planes can

be defined with the help of miller indices (hkl). So each Bragg peak we have detected and measured in the

diffraction experiment has a particular set values (hkl). But we still do not know the relationship between

the direct crystal and the Bragg position and intensity. The relationship is not obvious because the diffracted

spots are arranged in lattice, albeit on a distorted one. It is not easy to look at and understand their

arrangement. Now physicists (and crystallographers) being intelligent guys, thought of some tricks to

transform the angular information of the Bragg spots (arranged on a distorted lattice) in terms of a regular

arrangement of a lattice. This transformed arrangements bears a simple reciprocal relationship to the direct

lattice. This is called the reciprocal lattice. We can arrange the Bragg spots on this lattice and even can

ascribe intensity values to all of these spots. Now surprise surprise! Each set of direct atomic planes has

become now a point in the reciprocal lattice and carry the same miller indices (hkl) as the corresponding

atomic planes and we now even know the intensity. This reciprocal lattice has lot of symmetry that are

related to the symmetry of the direct lattice. As long as we do not know the unknown crystal structure and

analyze the diffraction data for solving the crystal structure it is convenient to stay in the space for which we

have direct experimental information. Once we analyze the data and determine the crystal structure we can

then transform the information to the direct space. You must know that these two spaces are related by

Fourier transforms. The information of the reciprocal lattice gives only the symmetry and translational

properties but not the actual atomic positions. For that we must use the intensity values corresponding to

the each reciprocal lattice point (hkl). Here I have illustrated how the reciprocal space is used to analyze the

crystal structure only. Now if you real the text book of Kittel then you will see that the same reciprocal

space is the most convenient space for the calculation of solid state properties and electronic structure. You

can do these calculations in the direct space as well but the calculations would be more difficult.

I hope that I have convinced you about the usefulness of the reciprocal space. If not then come back again

to me and ask questions.

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