# Solid State Theory Physics 545

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1 Solid State Theory Physics 545

2 CRYSTAL STRUCTURES Describing periodic structures Terminology Basic Structures Symmetry Operations

3 Ionic crystals often have a definite habit which gives rise to particular crystal shapes with particular crystallographic faces dominating and easy cleavage planes present. Single crystal of NaCl being cleaved with a razor blade

4 Early observations of the regular shapes of crystals and their preferred cleavage plans lead to the suggestion that they are built up from simple units. This suggestion was made long before the atomic theory of matter was developed. For example the pictures below are from a work on the form of crystals from R.J.Hauy in 1801.

5 The unit cell shape must fill space and so there are restrictions on the cell shapes that can be used. For example in 2-Dimensions it is not possible to have a pentagonal unit cell.

6 The repeating pattern of atoms in a crystal can be used to define a unit cell. This is a small volume of the material that can be translated through space to reproduce the entire crystal. The translation of the unit cell follows the vectors given by its sides, these are the cell vectors (2D a & b, in 3D a,b & c). If the unit cell contains only one formula unit it is a primitive cell. b a

7 Space transformations. Translation symmetry. Crystallography is largely based Group Theory (symmetry). Symmetry operations transform space into itself. Simplest symmetry operator is unity operator(=does nothing). (=Lattice is invariant with respect to symmetry operations) Translation operator, T R, replaces radius vector of every point, r, by r =r+r.

8 The unit cell is the basic repeat unit for the crystal. If each unit cell is thought of as a single point the crystal can be simplified to a lattice. We can always move to an equivalent point in a lattice by taking an integer combination of the lattice vectors: T = ua + vb + wc (u,v,w) being integers. b T (3,1) a

9 TERMINOLOGY Lattice Point- Point that contains an atom or molecule Unit itcell- Region defined dby a,b,c which hihwhen translated ltdby integral it multiple of these vectors reproduces a similar region of the crystal Basis Vector-A set of linearly independent vectors (a,b,c),, ) which can be used to define a unit cell

10 Unit Cells E F Atwo two-dimensional lattice showing translation of a unit cell by r = 3a + 2b.

11 Unit Cells Basis Vectors = 2a,2b2b Unit Cell = ODE F Primitive Unit Cell = ODEF Primitive Basis Vectors = a,b

12 Lattice Vector R=ha+kb+lc h,k,l are integers Miller Indices A displacement of any lattice point by R will give a new position in the lattice that has the same positional appearance as the original position

13 Unit cell vs. primitive cell. A primitive cell (PC) is the smallest unit which,when repeated indefinitely in three dimensions, will generate the lattice. A unit cell (UC) is the smallest unit that has all the symmetry elements of the lattice. C 4 C 3 C 2 Example: BCC Primitive cell 1 atom. Unit cell 2 atoms=1+8/8. Symmetry: 3C 4,4C 3, 12C 2, 6m m C n is n-fold symmetry axis. m is mirror plane i=c 2 m inversion (center of symmetry).

14 TERMINOLOGY Primitive Unit Cell- The smallest unit cell, in volume, that can be defined dfor a given lattice Primitive Basis Vectors- A set of linearly independently vectors in that can be used to define a primitive unit cell

15 Single species A B C F D a G b A - G : Primitive unit cells All have same area All smallest unit cell All have 1 atom/cell a : Not a unit cell b :Unit cell not tprimitive iti

16 Multi Species Non Primitive Primitive 2 Red, 2green 1 Red, 1 Green

17 The positions of the atoms within one unit cell are referred to as the basis of the crystal structure. To describe the whole crystal we require a lattice and a basis. Within the unit cell the separation of two atoms will be given by: r r r 12 = 2 1 The crystal lattice tells us that for every pair of atoms in the atomic basis with this separation there will be an identical pair at a separation of: r r r + ' 12 = 2 1 Where T is any b r 2 lattice vector: T r 1 a T = ua + vb + wc

18 Definition of lattice A spatial arrangement of atoms (S) represents a periodic lattice if this arrangement is invariant with respect to T R, where R is an integer linear combination of one, two or three basic (=fundamental, primitive) vectors. R = n au T ( S) = S R + n bu + n cu n 123 1,2,3 are any integer numbers; a, b and c are the lattice constants; au 1, bu 2, cu 3 are the translation ti vectors. In general u 1, u 2 and u are not 3 orthogonal. α = u1u 2 β = u2u3 γ = u1u 3 There are 6 parameters that There are 6 parameters that define a lattice a, b, c, α, β and γ.

19 3 D, Bravis Lattices Each unit cell is such that the entire lattice can be formed by displacing i the unit cell llby R with no gaps in the structure (close packed) ie sctructures with 3, 4 and 6 fold symmetry can be close packed. 5-fold (ie pentangles) cannot In 3 dimensions there are only 14 ways of arranging gpoints symmetrically in space that can give no gaps These arrangements are the BRAVIS LATTICES These can be further subdivided into 7 crystal structures

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21 14 Bravais Lattices

22 Bravais lattices : In three dimensions there are only 14 space filling lattices, the Bravais lattices. These are classified by 7 crystal systems (shapes): triclinic : a b c α β γ monoclinic : a b c α = γ = 90, β orthorhombic : a b c α = β = γ = 90 tetragonal : a = b c α = β = γ = 90 hexagonal : a = b c α = β = 90, γ = 120 rhombohedral : a = b = c α = β = γ cubic : a = b = c α = β = γ = 90

23 In addition to the shape of the unit cell a label is added to indicate the degree of centring of lattice points: P,R : the cell is not centred, Primitive, only 1 lattice point. C : side centred cells. F : face centred cells. I : body centred cells. Bravais lattices

24 Cubic Lattices BCC and FCC are not primitive. bcc has 4 atoms/cell, fcc has 8 atoms/cell fcc has closest packing, then bcc then sc (for cubic) (fcc and bcc more common than sc) Primitive iti have 1 atom/cell, Both are Rhombohedral h (Trigonal) (McKelvey p10)

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26 Rhombohedral or Trigonal Rhombohedral (R) Or Trigonal a = b = c, α = ß = γ 90 o

27 Triclinic Monoclinic Triclinic (Primitive) a b c, α ß γ 90 o Monoclinic (P) a b c, α = γ = 90 o, ß 90 o Monoclinic (BaseC) a b c, α = γ = 90 o, ß 90 o

28 Orthorhombic Orthorhombic (BaseC) Orthorhombic (P) a b c, α = ß = γ = 90 o a b c, α = ß = γ = 90 o

29 Orthorhombic Orthorhombic (BC) a b c, α = ß = γ = 90 o Orthorhombic (FC) a b c, α = ß = γ = 90 o

30 Hexagonal Hexagonal (P) a = b c, α = ß = 90 o, γ = 120 o

31 Tetragonal Tetragonal (P) Tetragonal (BC) a = b c, α = ß = γ = 90 o a = b c, α = ß = γ = 90 o

32 Diamond Structure (C, Si Ge) A B Tetrahedral bonding of carbon, Si and Ge each atom bonds covalently to 4 others equally spread about atom in 3d. Unit cell of resulting lattice is a double fcc A is corner of on fcc, B is corner of second

33 Sdi Sodium chloride, NCl NaCl A face centered cubic arrangement of anions with the cations in all of the octahedral holes 8 unit cells Space group Fm3m (225)

34 Fluorite, CaF 2 The cations lie in a face centered cubic arrangement and the anions occupy all of the tetrahedral holes 8 unit cells Space group Fm3m (225)

35 Rutile, TiO 2 Each titanium atom is surrounded by an approximate octahedron of oxygen atoms, and each oxygen atom is surrounded by an approximate equilateral triangle of titanium atoms. 8 unit cells Space group P4 2 /mnm (136)

36 Quartz, SiO 2 Each silicon atom is surrounded by a tetrahedron of oxygen atoms 4 unit cells Space group P (152)

37 Planes In all the structures, there are planes of atoms extended surfaces on which lie regularly spaced atoms These planes have many other planes parallel to them These sets of planes occur in many orientations A B C D

38 Planes (continued) Orientation of Planes are identified by Miller Indices (hkl) Method for defining (hkl) 1) Take the origin at any lattice point in the crystal, and coordinate axes in the direction of the basis vectors of the unit cell 2) Locate the intercepts of a plane belonging to the desired system along each of the coordinate axes, and express them as integral multiples of a,b,c along each axis 3) take the reciprocals of these numbers and multiply through by the smallest factor that will convert them to a triad of (h,k,l) having the same ratios.

39 Intercepts (A,B,C) are at 2a, 4b and 3c reciprocal values are 1/2, 1/4 and 1/3 Smallest common factor is 12 (hkl) = 12 (1/2,1/4,1/3) = (6,3,4) The inter-plane separation (d hkl ) is calculated from = d hkl 2 2 h k a 1 b l c 2 2

40 Miller Planes To identify a crystal plane a set of 3 indices are used. c The Miller indicies are defined by taking the 2 intercepts of the plane with the cell vectors: 2 3 a b Here the intercepts are (2,3,2). We take the inverse of the intercepts : 1 1 1,, The Miller indices are the lowest set integers which have the same ratio as these inverses: (323).

41 2 a c b In cases where the plane is parallel to one or more axis the plane is taken to intercept at infinity. Here, intercepts are (2,, ). Inverses are 1,0,0 2 Lowest integers (100) This shows that the plane intercepting a at 2 vector lengths and parallel to b & c is equivalent to the plane intercepting at a.

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43 Miller lattices and directions. Equivalent faces are designated by curly brackets (braces). Thus the set of cube faces can be represented as {100} in which h {100}=(100)+(010)+(001)+(100)+(010)+(001) Directions: A line is constructed through the origin of the crystal axis in the direction [001] under consideration and the coordinates of a point on the line are determined in multiples of lattice parameters of the unit cell.the indices of the direction are taken as the smallest integers proportional to these coordinates and are closed in square brackets. For example, suppose the coordinates are x =3a,y =b and z =c/2,then the smallest integers proportional to these three numbers are 6,2 and 1 and the line has a [621]direction.

44 Axis system for a hexagonal unit cell (Miller Bravais scheme).

45 Figure 1 4 Packing of hard spheres in an fcc lattice.

46 Packing density. Simple cube vs. closed packed. the atomic packing factor (APF). The APF is defined as the fraction of solid sphere volume in a unit cell. APF = volume of atoms in a unit cell ttl total unit cell volume APF BCC =0.68 BCC APF FCC =0.74 APF HCP =0.74

47 Packing and interstitial sites. Unoccupied interstitial site in the FCC structure: tetragonal and octahedral. FCC Unoccupied interstitial site in the BCC structure: interstitial with distorted octahedral and octahedral symmetry. BCC Interstitials are very important in formation of solid solutions. Example: C:Fe steel.

48 Packing density and stability of the lattice. Instability of Ti is related to a series of successful phase transitions in BaTiO 3 BaTiO 3 TiO 2 -anatase TiO 2 -rutile

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