UnitI Crystal Physics Introduction The matter is usually regarded to exist in solid state or fluid state. All the materials are composed of atoms and molecules. A solid is an essentially an ordered array of atoms, bound together by electric forces to form a very large molecule. There are three different types of solids. Crystalline, poly crystalline and amorphous. In a crystal, atoms are arranged into a regular periodically repeated structure that extends throughout the whole sample. The atoms are said to have long range order. Poly crystalline material is composed of many small crystals or grains of somewhat irregular size. In an amorphous solid a long range order is absent. (ie.,) they have short range order. There is no periodicity in which atoms are arranged in space. They are also regarded as super cooled liquids. Examples : metallic crystals : copper, silver, aluminum etc., Non metallic crystals: Germanium, silicon Amorphous or non crystalline materials: glass, rubber, plastic (a) Crystalline © Polycrystalline (Amorphous ifference between crystalline and amorphous material, S.No _| Crystalline ‘Amorphous 1 ‘Regular arrangement of atoms ‘Random arrangement of atoms does not gives definite and geometric shape. give definite and Geometrical shape. 2 They are anisotropic They are isotropic 3 They have sharp Melting Point ‘They do not have sharp Melting Point 4 They possess intemal symmetry They do not possess intemal symmetry“What is Crystal Physics? Crystal Physics’ ot ‘Crystallography’ is a branch of physics that deals with the study of all possible types of crystals and the physical properties of crystalline solids by the determination of their actual structure by using X-rays, neutron beams and electron beams, CLASSIFICATION OF SOLIDS. Solids can broadly be classified into two types based on the arrangement of units of matter. ‘The units of matter may be atoms, molecules or ions. They are, e bRERE + + Crystalline solids and + Non-erystalline (or) Amorphous solids CRYSTALLINE SOLIDS ‘A substance is said to be crystalline when the arrangement of units of matter is regular and periodic. A crystalline material has directional properties and therefore called as anisotropic substance. A crystal has a sharp melting point. It possesses a regular shape and if it is broken, all broken pieces have the same regular shape. A crystalline material can either be a single (mono) erystal or a polycrystal. A single crystal consists of only one crystal, whereas the polycrystalline material consists of many erystals separated by well-defined boundaries. Examples Metallic crystals — Cu, Ag, Al, Mg ete, Non-metallic crystals — Carbon, Silicon, Germanium, In amorphous solids, the constituent particles t arranged in an orderly manner. They are randomly distributed. They do not have directional properties and so they are called as ‘isotropic’ substances. They have wide range of melting point and do not possess a regular shape. Examples: Glass, Plastics, Rubber ete., SPACE LATTICE AA lattice is a regular and periodic arrangement of points in three dimensions. Itis defined as an infinite array of points in three dimensions in which every point has surroundings identical to that of every other point in the array. The Space lattice is otherwise called the Crystal latticeEE RRREE & Consider the points P, Q and R Let us join the points P and Q by a straight line, and the point P and R by another straight line. The line PQ is taken as X-axis and the line PR is taken as Y-axis. The distance between any two successive lattice points in the X-direction is taken as ‘a’ Similarly, the distance between any two successive lattice points along the Y-direction is taken as ‘b’ Here a and b are said to be lattice translational vectors. Consider a square lattice in which ab. Consider two sets of points A, B, C, D, E, F and A’, B’, C’, D’, E', F. In these two sets, the surrounding environment looks symmetrical; ie, the distances AB and AVB', AC and A’C’, AD and A'D’, AE and A’E! and AF and A'F’ are equal. Therefore, in the arrangement of points, if the surrounding environment looks the same when the arrangement is viewed from different lattice points, then that arrangement is said to be a space lattice, BASIS: A crystal structure is formed by associating every lattice point with an unit assembly of atoms or molecules identical in composition, arrangement and orientation. This unit assembly is, called the ‘basis When the basis is repeated with correct periodicity in all directions, it gives the actual crystal structure. The crystal structure is real, while the lattice is imaginary. CRYSTAL STRUCTURE Crystal structure Latti + BasisUNIT CELL: + A unit cell is defined as a fundamental building block of a crystal structure, which can generate the complete erystal by repeating its own dimensions in various directions, CRYSTALLOGRAPHIC AXES: 4 Consider a unit cell consisting of three mutually perpendicular edges OA, OB and OC as shown in figure + Draw parallel lines along the three edges. 4 These lines are taken as crystallographic axes and they are denoted as X, Y and Z. axes. LATTICE PARAMETERS 4 Consider the unit cell as shown in figure. Let OA, OB and OC are the intercepts made by the unit cell along X, Y and Z axes respectively. +4 These intercepts are known as primitives. In crystallography the intercepts OA, OB and OC are represented as %, Band & 4 The angle between X and Y axes is represented asy. 4+ Similarly the angles between Y and Z and Z and X axes are denoted by ‘a and 'B' respectively as shown in the above figure. These anglesa, f} and 7 are called as interaxial angles or interfacial angles + Torepresent a lattice, the three interfacial angles and their corresponding intercepts are ‘essential. These six parameters are said to be lattice parameters. PRIMITIVE CE) 4 Itis the smallest unit cell in volume constructed by primitives. It consists of only one full atom A primitive cell is one, which has got the points or atoms only at the corners of the unit 's of more than one atom, then it is not a primitive cell. Example for primitive cell: Simple Cubic unit cell. Examples for non-primitive cell: BCC and FCC unit cell. CRYSTALS SYSTEMS: & A three dimensional space lattice is generated by repeated translation of three translational Ifa unit cell cons; vectors a, b and c. + Crystals are grouped under seven systems on the basis of the shape of the unit cell. + The seven crystal systems are distinguished from one another by their lattice parameters. The seven systems are, 1. Cubic 2. Tetragonal 3. Orthorhombic 4.Trigonal (rhombohedral) 5. Hexagonal 6. Monoclinic and 7. Triclinie The space lattices formed by unit cells ate marked by the following symbols.+ + + + Primitive lattice: P > having lattice points only at the corners of the unit cell. Body centred lattice: I -> having lattice points at the comers as well as at the body centre of the unit cell Face centred lattice: F > having lattice points at the comers as well as at the face centres of the unit cell Base centred lattice: C > having lattice points at the comers as well as at the top and bottom base centres of the unit cell, BRAVAIS LATTICES 4+. Bravais in 1948 showed that 14 types of unit cells under seven crystal systems are possible They are commonly called as “Bravais lattices’. SNo. Crystal system Axial length Interfacial angles. Example es Cubie abe ‘NaCl, CaF2, Au, Cu ‘Tetragonal whee Ordinary white, tin, Indium, Sn02 Orthorhombic abso a=B=y=90" Sulphur, Topaz, BaSO4, KNO3 Monoclinic abe 1=B=90"; 290° NaSog, FeSog, Gypsum Triclinic aebee oxen 90° CuSo4, K2Cr.07 Rhombohedral a=b =o a= P= ye 90° Calcite, Sb, Bi. Hexagonal abee =P=90"; Quartz, Zn, Mg. y= 120° MILLER INDICES: The crystal lattice may be regarded as made up ofan infinite set of parallel equidistant planes passing through the lattice points which are known as lattice planes. Miller indices are defined as the reciprocals ofthe intercepts made by the plane on the three crystallographic axes. In simple terms, the planes passing through lattice points are called ‘latice planes’ + Fora given latice, the latice planes can be chosen in a different number of ways. 4 The orientation of planes or faces in a crystal can be described in terms of their intercepts on the three axes, Miller introduced a system to designate a plane in a crystal | | | NX 4 He introduced a set of three numbers to specify a plane in a crystal +b This set of three numbers is known as ‘Miller Indices’ of the concerned plane.4 Miller indices are set of three possible integers represented as (h, k, 1) which is used to designate plane in the crystal, is the reciprocal of the intercept made by the planes on the crystallographic axes. Procedure for finding Miller Indices Step 1: Determine the intercepts of the plane along the axes X,Y and Z in terms of the lattice constants a,b and c. Step 2: Determine the reciprocals of these numbers. Step 3: Find the least common denominator (/ed) and multiply each by this led. Step 4: The result is written in paranthesis. This is called the "Miller Indices’ of the plane in the form (hk 1). This is called the "Miller Indices’ of the plane in the form (h k 1). 4 Plane ABC has intercepts of 2 units along X-axis, 3 units along Y-axis and 2 units along Z-axis. DETERMINATION OF ‘MILLER INDICES’ Step 1: The intercepts are 2, 3 and 2 on the three axes. Step 2: The reciprocals are 1/2, 1/3 and 1/2. Step 3: The least common denominator is ‘6°. Multiplying each reciprocal by LCD, we get 3, 2 and 3. Step 4: Hence Miller indices for the plane ABC is (3 23) IMPORTANT FEATURES OF MILLER INDICES For the cubic crystal especially, the important features of Miller indices are, 4+ A plane which is parallel to any one of the co-ordinate axes has an intercept of infinity (co). Therefore the Miller index for that axis is zero; i.e. for an intercept at infinity, the corresponding, index is zero. EXAMPLE (100) plane ( Plane parallel to Y and Z axes) In the above plane, the intercept along X axis is 1 unit, + The plane is parallel to Y and Z axes. So, the intercepts along Y and Z axes are ‘o” + Now the intercepts are 1, o0 and. 4 The reciprocals of the intercepts are = 1/1, L/s0 and 1/=, i Therefore the Miller indices for the above plane is (1 0 0). vMILLER INDICES OF SOME IMPORTANT PLANES. z z z ($00)Phane (110 Plane (149) Pune a + mn Direction x7 1100, Dimeton SEPARATION BETWEEN LATTICE PLANES. 4 Consider a cubic crystal of side ‘a’, and a plane ABC. 4 This plane belongs to a family of planes whose Miller indices are (hk 1) because Miller indices represent a set of planes. 4 Let ON =d, be the perpendicular distance of the plane A B C from the origin. 4 Let a1, Br and y: (different from the interfacial angleso,, f andy) be the angles between co ordinate axes X, Y, Z and ON respectively. sb The intercepts of the plane on the three axes are, OA =", op = * and oc = * —_. gy k 1From the figure, we have, d d d cos a’ =— ,cosf' = — and cosy! =—L OA Ol Cc From the property of direction of cosines, 201 2p1 21) cosa! + cos’B' +cos*y' =1 ¢ Using equation 1 in 2, we get, dh cosa! = ——, cos! a ak and cosy! dig a ‘Substituting equation (4) in (3), we get, 2 2 2 any (se) (Af 1 ale aie a a a a a de yep a ay? 4k? 4) = SW +k? +P) =1 ma y= a ae a’ 2 = 6) (+k? +P) i.e. the perpendicular distance between the origin and the Ist plane ABC is, Wier? 4 Now, let us consider the next parallel plane. 4 Let OM=d» be the perpendicular distance of this plane from the origin. 4 The intercepts of this plane along the three axes are OM=d = 2 VirTherefore, the interplanar spacing between two adjacent parallel planes of Miller indices (h k 1) is, given by, NM = OM - ON i.e.interplanar spacing Vi? +k Characteristics of unit cell: + Number of atoms per unit cell + Coordination number + Atomic radius + Atomic Packing factor or Packing Density + Number of atoms per unit cell: The number of atoms present in the unit cell. + Coordination number: The number of equidistant nearest neighbouring atoms surrounding the particular atom considered + Atomic Radius (1): It is defined as half the distance between the nearest neighbouring atoms in a crystal. Atomic Packing factor or Packing Density: It is the ratio of the volume occupied by the atoms in a unit cell (v) to the volume of the unit cell (V). It is also called packing fraction or packing density. Simple cubie structure Body centred cubic structure ee Face centered cubic structure + Hexagonal closed packed structure Simple Cubic Structure: The simple cubic system consists of one lattice point on each comer of the cube. Each atom at the lattice points is then shared equally between eight adjacent cubes, and the unit cell therefore contains in total one atom (“ * 8). :, The number of atoms per unit cell is nCo-ordination Numb: In this case, there are 8 comer atoms one at each comer of the unit cell. Around an atom ina SC cell, there would be six equally spaced nearest neighboring atoms each at a distance ‘a’ from that atom. Four atoms lie in the plane of the atom while one is vertically above it and one vertically below. Therefore the coordination number is 6. Atomic radius: In simple cubic structure, the comer atoms touch each other along the edges. Let us consider one face of the SC structure. Here. the nearest neighboring distance is the lattice constant a=2r. Therefore atomic radius r= a/2. Volume of one atom = 4/3(nr)? Packing factor = av/V = 4/3 (ary a= 4/3(mr 80 = 1/6 Packing factor f = 0.52 This stmucture is thus a loosely packed one. Polonium is the only element which exhibits this structure.Body Centered Cubic Structure (BCC): Number of atoms per unit cell: In this structure, the atoms are arranged in such a way that there is an atom occupying the centre position of the body in addition to the eight atoms existing at the comers of the cubic structure, Hence, there are 8 atoms at the 8 comers and another atom at the body centre. The atom at the centre of the unit cell entirely belongs to the structure in addition to the contribution fiom 8 comer atoms. Each comer atom is shared by 8 surrounding unit cells = 1/3" of each comer atom. Hence the share of each unit cell 1/8x8+ 1= 1 ~*. total number of atoms in one cell 2 atoms. .. Number of atoms per unit cell = 2. Co-ordination Number: In this case, there are 8 corner atoms one at each corner of the unit cell and one atom at the body centre, For any comer atom of the unit cell, the nearest atoms are the body centred atoms. As such, each comer atom is surrounded by 8 unit cells having 8 body centred atoms. Hence co-ordination number is 8. The corner atoms do not touch each other. but each comer atom touches the body centre atom along the diagonal. Hence the co-ordination number is 8. Atomic Radius: In this type of crystal, in an unit cell there are eight atoms at the comers and one atom at the centre. Each comer atom touches the centre atom. The side of the unit cell is ‘a’ Consider the atoms at F, C and at the centre of the cell. These atoms lie in one straight line along the diagonal FC of the cube.From the figure, it is obvious that, (acy=a ta Also, (AD)= (AC)? +(CD)? a. = 2a?ta?= 30? From the fig it is also clear that, AD = 41. Hence, (ry = 3a? 2 _16r? 4r =>a=—= 3 a And therefore, 3 4 Packing Factor: Number of atoms per unit cell = 2. Volume of two atoms (v) =2 x 4/3m° Side of the Unit Cell ‘a° = a v3 Volume of the Unit Cell (V) =a? ., Atomic Packing Factor APF = v/V _ 2«(4/3)ar? _ 2x (4/3)? _ 30 Packing Factor f = 0.68 or 68% Hence we can say that 68% volume of the unit cell of BCC is occupied by atoms and remaining 32% volmne is vacant. As the packing density is 68% which is higher than that of simple cubic, it has tightly packed structure when compared to simple cubicFace Centered Cubic Structure (FCC): In this structure, we have two types of atoms, viz, (i) corner atoms and (ii) face centred atoms. There are eight corner atoms, one at each comer of the unit cell and six atoms at the centres of the six faces of the unit cell as shown in the figure. @ Number of cor Each and every atom is shared by eight adjacent unit cells. Hence the share of each toms per unit cell: comer atom to the unit cell = 1/8" ofan atom. -. the total number of corner atoms per unit cell = (1/8) * 8= 1. (ii) Number of face centred atoms per unit cell: Each face centred atom is shared by only two unit cells, which lie on either side of the atom. Similarly. we have six face centred atoms in an unit cell Hence the share of each face centered atom to the unit cell is unit cell = % of an atom. Hence, the total number of face centred atoms per unit cell = (1/2)x6= 3 ‘Therefore, the total number of atoms per unit cell in fee = 143 = Co-ordination Number: Ina FCC cell, each comer atom is in contact with the face centered atom. It would therefore be in contact with 4 atoms in the xy plane, 4 atoms in the yz plane and 4 atoms in the zx plane. Therefore, the total number of nearest atoms to any corner atom is 4444 = 12. Hence, the co-ordination number is 12.Atomic Radius: In fee structure, the corner atoms do not touch each other. But each comer atom touches the face centred atoms along the diagonal of the face of the cube as shown in fig (1.36). ‘Therefore, the two comer atoms (A and C) situated at the opposite ends of the same face can be joined by drawing a diagonal as shown in the figure. From the geometry of the figure, we can write, (Ac) = (ABY + BO? But from the same fig, the diagonal of the cube AC = 4r. Therefore 4r= av2 Or, Atomic Radius r is, Packing Factor: In fee structure. the number of atoms per unit cell = 4. Therefore volume of four atoms = 4 (4/3) mr? Where (4/3) mr’ is the volume of one atom. Radius of the atom in fec (r) = © 2 4 a2 4 5 “Volume occupied by the atoms per unit cett (v) = 122 ef 3 Volume of the unit cell V=a* <. Atomic Packing Factor APF = , a2 Packing Factor f= = =0.74 or 74%Therefore, we can say that 74% volume of the unit cell of fec is occupied by atoms and remaining 26% volume is vacant. Thus packing density is 74%. Since the packing density is very high, the fec structure has a tightly packed structure. Hexagonally Closely Packed Structure (ACP): In the HCP structure. an unit cell contains three types of atoms viz. (a) 12 corner atoms, one at each and every comer of the hexagon, (b) 2 base centred atoms. one at the top face of the hexagon and another at the bottom face of the hexagon and (c) 3 atoms im between the top and bottom face of hexagon. Co-ordination Number: The hep structure is considered to have 3 layers viz, (i) Bottom layer (i) Top layer and (iii) Middle layer. Tn the top and bottom layers, the base centred atom is surrounded by 6 comer atoms, Ta the middle layer. we have 3 atoms sacked inside the unit cell. For every atom taken in the bottom layer or top layer, there are 6 neighbouring atom in its own plane. Further. at a distance of c/2 it has 3 atoms in the middle layer and 3 more atoms in the middle layer. Therefore, the total number of neighboring atoms is, 6-3+3 = 12. Number of atoms per unit cell: ‘As in the hep structure. there are 3 types of atoms namely corner atoms. base atoms and middle layer atoms. we can calculate each one individually and then combine them together.comer atom to the unit cell is (1/6)" of an atom. We have 12 comer atoms in an unit cell. Therefore, the number of comer atoms per unit cell = (1/6) « 12 =2. Number of base centred atoms per unit cell:- There is an atom at the centre of each hexagonal face, which is shared by two adjacent unit L cells. Therefore, the number of base centred atoms per unit cell = (*4) ‘Number of middle layer atoms per unit cell:~ Three atoms forming a triangle in the middle layer are within the body of the unit cell and can not be shared by any adjacent cells.. -.the total number of middle layer atoms per unit cell = 3. ., The total number of atoms per unit cell in hep structure N is N= {Number of comer atoms per unit cell} + (Number of base atoms per unit cell} + {Number of middle layer atoms per unit cell} “ N=24143=6. Atomic Radius: ‘The atoms are in contact along the edges of the hexagon as seen in the figure. Therefore Qr=a or r=a/2 that is, the atomic radius [r= a/2| c/a ratic In the hep structure, let the height of the unit cell be ‘c’ and the distance between two neighbouring atoms is ‘a’, Now consider the A ABO in the bottom layer of the hep structure. Here A, B and O are the lattice points and exactly above these at a perpendicular distance c/2, the next layer of atoms lie at C AY In the triangle ABY, Cos30° AY = ABCos 30°= a3/2But AX =2/3. And AY = 334 } = In the triangle AXC, (AC)? = (AX)? + (CXY. Substituting the values for AC*, AX”, CX’. We have, Packing factor: PE=nv/V = 6x(4/3)ar’/ 3N2(21)* w/3N2 f=0.74. Therefore, we can say that 74% volume of the unit cell of hep is occupied by atoms and remaining 26% volume is vacant. Thus packing density is 74%. Since the packing density is very high, the hep structure has a tightly packed strncture as is the case with fee structure,DIAMOND CUBIC STRUCTURE From A! XAZ XZ? = XA2+AZ? = (a2/16) +( a2/16) = (a?/8) From A! XYZ XY? = XZ?4¥Z? = (a?/8) +( a?/16) = (3a?/16) XY = V3a /4 Atomic Radius 2r=XY=V3a /4 r= Ba /8 No. of atoms/unit cell 8 ‘Atomic Radius vaa/8 Coordination No. 4 APE fiv3/16 or 0.34POLYMORPHISM -Ability of material having more than one structure ALLOTROPHY - If the change in structure is reversible Example: Cobalt at ordinary temp. -HCP and at 477°C -FCC