5.16 Engineering Physics infrared optics (lithium fluoride), transistors (Ge,Si), Lasers (Ruby, Gallium Ar. senide) and tunnel diodes (Gallium Arsenide). Hence the method of preparing sin. gle crystals, of various substances itself becomes a separate field requiring much attention. 5.4 Crystallography Many of the properties of solid materials depend mainly on their structures, These solids can be broadly classified as either crystalline or nonerystalline. In a crystal the atoms are arranged in a periodic manner in all three directions whereas in a noncrystalline solid the arrangement is random. A crystalline solid can either be a single crystal, or an aggregate of many crystals called polycrystalline. Noncrystalline substances are called amorphous and they have no directional properties and therefore they are called isotropic substances. They do not pos- sess any regular shape and they have a wide range of melting points. A crystal has regular shape and when it is broken, all broken pieces have the same regular shape. A crystal has sharp melting point. Since the crystals may have different periodic arrangements’ in all three directions, the physical properties vary with direction and therefore they are called anisotropic substances. Crystalline solids may be made up of metallic crystals or non metallic crystals. Copper, silver, aluminium,tungsten and magnesium are the examples of metallic crystals while carbon, crystallized polymers and plastics are examples of nonmetallic crystals. The thermal, electrical, mechanical and optical properties of crystals depend mainly on their structural properties. X-ray diffraction methods and neutron diffrac- tion methods are mainly used for the study of crystal structure of solids, First let us introduce the concepts of elementary crystallography namely crys- tal geometry, conventions associated with representing directions and planes in crystals. 5.5 Space Lattice ‘The arrangement of atoms in a crystal is called crystal structure. It is very conve- nient to imagine periodic arrangement of points in space about which these atoms are located. This leads to the concept of space lattice. A space lattice is defined as an infinite array of points in three dimensions in which every point has sur- roundings identical to that of every other ‘point in the array. Let us now consider the case of a two dimensional square array of points as shown in Fig. 13. By repeated translation of the two vectors a and b on the plane of the paper, we can generate the square array.Solid State Physics 5.17 & « : : 3 . 4 2 PTT pee . . | . a z id . . . Fig. 13 A two-dimensional square array of points ‘The magnitudes of a and b are equal and can be taken to be uni t . The I | between them is 90°. a and b are c: aletional ters alled the fundamental translational vectors | that generate the square array. Let us choose any arbitrary point 0 as origin. If we choose a lattice point P at position r it can be represented by translational vectors as FP =la+mb where l and m are integers. In Fig. 3.1,1 = 2andm =1 For three dimensional lattice F=la+mb+ne |__ Thusa three dimensional space lattice is generated by repeated translation of three | foncoplanar vectors a, b and c. 5.5.1 Unit cell A space lattice can be defined by referring to a unit cell. The unit cell is the Smallest unit which, when repeated in space indefinitely, generates the space lattice. In Fig. 13, the square obtained by joining four neighbouring lattice points Tepresents a unit cell. Since each lattice point is common to four unit sore meeting / at that corner, the effective number of lattice points in the unit cell is (Gx4 rae One only. Instead, the unit cell can be visualized by taking one lattice Poin is centre of the square. These two possible ways of choosing unit cell are sho\ the Fig. 13. Eo ald5.18 Engineering Physics ciate with each lattice point, a group of atoms or molecules identical ee alled the basis or the pattern, crystal structure is generated. The 1 of atoms per lattice point, their types, mutual orienta- tion. in compos : is provides the numbel nd distances of se} lattice + basis — crystal structure 5.5.2 Bravais space lattices * Fig. 14 Lattice parameters of an unit cell The lines drawn parallel to the lines of intersection of any three faces of the unit cell which do not lie in the same plane are called crystallographic axes. Naturally the three translational vectors a, b and ¢ lie along the crystallographic axes. In Fig. 14 a unit cell is shown with three crystallographic axes x,y and z. The intercepts a,b and c define the dimensions of an unit cell and are known as its ~ primitives, The angles between the three crystallographic axes are known as interfacial angles. The angle between b and c is a, the angle between c and a is (3, and that between a and b is y. The primitives a, b and c and the interfacial angles a, and ¥ are the basic lattice parameters because they determine the form and actual size of the unit cell. The unit cell formed by the primitives a, b and c is called primitive cell. A primitive cell will have only one lattice point. If there are two or more lattice points, then it is not a primitive cell, Most of the unit cells of various crystal lattice contain two or more lattice points and hence it is not necessary that the unit cell should be a primitive cell. But all the primitive cells are unit cells.Solid State Physics 5.19 je have seen that @ three dimensional space lattice is generated by repeated trans- n of three noncoplanar vectors a, b and c. There are nly fourteen distin- able ways of arranging points in three dimensional spuce. ‘These 14 space ces are known as Bravais space lattices. ‘They belong to seven crystal sys- tems. Table 3 lists the seven crystal systems and the relationship between the jattice parameters. ation Table 3 Crystal systems Crystal system | Unit vector | Angles Cubic a=b=c ‘Tetragonal a=b¥e Orthorhombic | a#b#e Monoclinic [af#b¢#e [a=B=90 47 Triclinic atb#e |atBF1F90" Trigonal a=b=c |a=p=7F90 - Hexagonal a=b4e |a=p=9%7= 120 ‘The different Bravais lattices and their names are listed in Table 4. There are fourteen Bravais lattices within the seven crystal systems and they are sketched in Fig. 15. ‘Table 4 Bravais lattices and crystal types Crystal type | Bravais lattices | Symbols Cubic Simple Body centred Face centred Tetragonal _| Simple P 1 F P Body centred 1 Orthorhombic | Simple P Base-centred Cc Body centred 1 Face centred F Monoclinic | Simple P Cc P P P Base-centred Triclinic Simple Trigonal Simple Hexagonal Simple MoS) mii5.20 Engineering Ph ysics Cubic P ‘Triclinic P ‘Trigonal P Fig. 15 The 14 Bravais or space lattices | 5.6 Crystal Directions ) = directions in a crystal (b) Some important directions Fig. 16 (a) Notation for inacubic crystali Solid s s ' =a Es Simple Crystal Structures Mae Physics 5.39 we have already seen the fo, es Bravais lati py an atom. For the sake of simplicity, it ig ices. Each lattice point i Pun 2 spheres. To study how these atoms oc assumed that 'Soccupied 1 ay! - e the ato pa of the important fundamentaj ae the unit celis, first we flint all soliq = Rua () Nearest neighbour distance (2r) a nearest neighbour distance. If distance is 2r. (ii) Atomic radius (r) Atomic radius is defined as half the di 7 lista . atoms in a crystal. nce between the nearest neighbouring (ili) Coordination number (N) Coordination number is defined as the number of equidistant nearest neighbours that an atom has in a given structure. More closely packed structure has greater coordination number. (iv) Atomic Packing Factor or Packing density Atomic packing factor is the ratio of the volume occupied by the atoms in an unit cell (v) to the total volume of the unit cell (V). It is also called packing fraction or packing density. ih ie., Packing Factor = Vv 5.8.1 Simple cubic (SC) structure ii i i tal structure. The simplest and easiest structure to describe is the simple cubic crys jmple cubic lattice, ; : é je structure. In a simp Fig. 20 shows the unit cell of a simple ee of the unit cell. The atoms touch there is oné atom at each of the eight co along cube edges. : & Hence nearest neighbour distance, 2r sce constant a = 25,28 Engineering Physics Fig.20 Simple cubic structure Hence atomic radius r = a/2 Each corner atom touches four atoms in its horizontal plane. It is also in touch with two more atoms, one above it and another below it i.e., each-atom is sur- rounded by six equidistant nearest neighbours. Hence the coordination number is 6. Each corner atom contributes }th to the unit cell and since there are eight corner atoms the effective number of atoms per unit cell is ( 3 x8 =) 1. Hence in this case, the unit cell is a primitive cell. Volume of all atoms in the unit cell Volume of the unit cell Packing factor 43 1x 37" Anr3 =—~e)s_ = 3ar8 F = 0.52 i.e.,52% " This structure is thus a loosely packed one. Polonium is the only element which exhibits this structure. 5.8.2 Body centred cubic (BCC) structure See has one atom at the centre of the cube and one atom at each corner. oe, eae at he eenite touches all the eight corner atoms, the coordination enter 8} a a ee the unit cell of a body centred cubic structure. Ina unit pea © centre atom, each corner atom contributes }th to the unit ae er of atoms per unit cell is (1 + (4) x8= i s ‘ouch along the body diagonal, di i 5 no aaa V3a. }, diagonal length = 47. Also the body diagonal isFig.21 Body centred cubic structure ie. » VBa = 4r Atomic radius + = Y3, 4 Lattice constant a= 4. v v3 Packing factor = 7 vi 77 = 0.68 = 68% Tungsten, sodium, iron, barium and chromium have this type of structure. 5.8.3 Face centred cubic (FCC) structure The unit cell of this structure is shown in Fig. 22. It has one atom at each corner and one atom at the centre of each face. The centre atom touches four corner atoms in its plane, four body centred atoms in each of two Planes on either side of its plane. Thus its coordination number is 12. Fig.22 Face centred cubic structure530 Engineering Physics ell = contribution due to 8 corner atoms + contribution Number of atoms per unit c due to 6 face centred atoms iL iL te, = (tx) + (4x6) =1+3=4. Its face diagonal is 4r. From Fig. 22 Face diagonal AC = Via = 4r v2 a ic radius tT = 7" = 5.75 4 Hence atomic radius r = “7° ~ 9,/9 4 Lattice constant a = 2Vvar R Packing factor = z 4 3 a a q 16,, ars 160 = 3 e a) 3x 16V2 « =, =0.74 3v2 = 74% C and BCC, this has the highest packing factor Most of | When compared with St the metals like copper, aluminium, lead, gold and silver have this structure. ate A 1B BT 5.8.4 Hexagonal close packed (HCP) structure Fig. 23(a) shows the unit cell of a simple hexagonal crystal. The number of atoms in an unit cell is only 3. Its packing fraction is low and hence metals do not crystallize in this simple hexagonal structure. Fig. 23(b) shows the unit cell of the close packed hexagonal structure and (c) shows arrangement of atoms in such @ structure. ‘ Simple hexagonal structure has two layers of atom in it. At the top as well as bottom layers, the central atom has 6 nearest neighbouring atoms in the same plane. In close packed hexagonal structure, in addition to these two layers the central layer has 3 atoms as shown in Figs. 23(b) and (c). If we consider the central atom at the top layers of HCP structure, it touches 6 atoms in its plane, 3 atoms in the plane just below st and 3 atoms in the plane Jost above it. Hence the coordination number is 12. | |i? Solid State Physics 531 ® Fig. 23 a) Unit cell of Hexagonal structure b) Unit cell of hexagonal close packed structure and c) hexagonal close packed structure ‘The top layer has 7 atoms; of the seven the central one contributes } to the unit cell; 3 unit cells share the lower half of the corner atom and 3 unit cells share | the upper half of the corner atom. Thus one corner atom is being shared by 6 unit cells. Hence each corner atom contributes % th to each unit cell. Hence the top layer contributes (6 x 4) + (1 x 3) = 3 atoms. Similarly the bottom layer’ contributes 3 atoms. In addition, the 3 atoms in the middle layer belong to the unit cell. Hence number of atoms per unit cell is (3 + 3 +3 =) 6. Calculation of c/a ratio Fig.24 (a) Bottom layer of HCP structure (b) Triangle ABO a ‘ Let ‘c’ be the height of the unit cell and a be its edge. Also a = 2r, Hence | atomic radius _ r = a/2. The three body atoms lie in a horizontal plane at height c/2 from the bottom layer. From the Fig; 24(b) in the triangle ABA’ ZA'AB = 30° AA 30° = SS cos asas ey ae “\ietune of Ona Cell LO jneering Physics ) ne! i wend wy “ut Therefore A'A = AB cos 30° ee =a gnale ANC. AC? = AX? 4.¢x2 ‘lculation of packing factor Area of the base = 6 x area of the triangle A BO. =6x 4x ABx00' 3 =3xax 4, 7 Be Volume of unit cell V = area of the base x height 0 Gulp OW : i yee Vit Packing factor = 75 i 6 x 4x78