CHAPTER 1 CRYSTAL STRUCTURE

1. CHAPTER 1CRYSTAL STRUCTURE Elementary Crystallography Typical Crystal Structures Elements Of Symmetry

2. By the end of this section you should: be able to identify a unit cell in a symmetrical pattern know that there are 7 possible unit cell shapes be able to define cubic, tetragonal, orthorhombic and hexagonal unit cell shapes Objectives Crystal Structure

3. matter Crystal Structure

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

5. Similar to gases, liquids haven’t any atomic/molecular order and they assume the shape of the containers. Applying low levels of thermal energy can easily break the existing weak bonds. Liquids and Liquid Crystals Liquidcrystalshave mobile molecules, but a type of longrangeorder can exist; themoleculeshave a permanentdipole. Applying an electricfieldrotatesthedipoleandestablishesorderwithinthecollection of molecules. + - + - + - + - + - + - + - Crystal Structure

6. Solids consist of atoms or molecules executing thermal motion about an equilibrium position fixed at a point in space. Solids can take the form of crystalline, polycrstalline, or amorphous materials. Solids (at a given temperature, pressure, and volume) have stronger bonds between molecules and atoms than liquids. Solids require more energy to break the bonds. Crytals Crystal Structure

7. ELEMENTARY CRYSTALLOGRAPHY Crystal Structure

8. Single crsytal, polycrystalline, and amorphous, are the three general types of solids. Each type is characterized by the size of ordered region within the material. An ordered region is a spatial volume in which atoms or molecules have a regular geometric arrangement or periodicity. Types of Solids Crystal Structure

9. Crystalline Solid • Crystalline Solid is the solid form of a substance in which the atoms or molecules are arranged in a definite, repeating pattern in three dimension. • Single crystals, ideally have a high degree of order, or regular geometric periodicity, throughout the entire volume of the material. Crystal Structure

10. Crystalline Solid • Single crystalhas an atomic structure that repeats periodically across its whole volume. Even at infinite length scales, each atom is related to every other equivalent atom in the structure by translational symmetry Single Pyrite Crystal Amorphous Solid Single Crystal Crystal Structure

11. Polycrystalline Solid • Polycrystalis a material made up of an aggregate of many small single crystals (also called crystallites or grains). • Polycrystalline material have a high degree of order over many atomic or molecular dimensions. • These ordered regions, or single crytal regions, vary in size and orientation wrt one another. • These regions are called as grains ( domain) and are separated from one another by grain boundaries. The atomic order can vary from one domain to the next. • The grains are usually 100 nm - 100 microns in diameter. Polycrystals with grains that are <10 nm in diameter are called nanocrystalline Polycrystalline Pyrite form (Grain) Crystal Structure

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

13. Departure From Perfect Crystal • Strictly 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. • Another example concerns the thermal vibrations of the atoms around their equilibrium positions for any temperature T>0°K. • As a third example, actual crystal always contains some foreign atoms, i.e., impurities. These impurities spoils the perfect crystal structure. Crystal Structure

14. CRYSTALLOGRAPHY What is crystallography? The branch of science that deals with the geometric description of crystals and their internal arrangement. Crystal Structure

15. Crystallography Crystallography is essential for solid state physics • Symmetry of a crystal can have a profound influence on its properties. • Any crystal structure should be specified completely, concisely and unambiguously. • Structures should be classified into different types according to the symmetries they possess. Crystal Structure

16. ELEMENTARY CRYSTALLOGRAPHY • A basic knowledge of crystallography is essential for solid state physicists; • to specify any crystal structure and • to classify the solids into different types accordingto the symmetries they possess. • Symmetry of a crystal can have a profound influence on its properties. • We will concern in this course with solids with simple structures. Crystal Structure

17. CRYSTAL LATTICE What is crystal (space) lattice? In crystallography, only the geometrical properties of the crystalare of interest, therefore one replaces each atom by a geometricalpoint located at the equilibrium position of that atom. Crystal lattice and structure of Platinum Platinum surface Platinum (scanning tunneling microscope) Crystal Structure

18. y B C D E α b O x a A Crystal Lattice • An infinite array of points in space, • Each point has identical surroundings to all others. • Arrays are arranged exactly in a periodic manner. Crystal Structure

19. Crystal Structure • 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. Crystal Structure = Crystal Lattice + Basis Crystal Structure

20. A two-dimensional Bravais lattice with different choices for the basis

21. y y B C D B C D E α b F G b x O x O a A a A Basis • A group of atoms which describe crystal structure E H a) Situation of atoms at the corners of regular hexagons b) Crystal lattice obtained by identifying all the atoms in (a) Crystal Structure

22. Crystal structure • Don't mix up atoms with lattice points • Lattice points are infinitesimal points in space • Lattice points do not necessarily lie at the centre of atoms Crystal Structure = Crystal Lattice + Basis Crystal Structure

23. Crystal Structure

24. Nb film Types Of Crystal Lattices 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. Crystal Structure

25. Honeycomb Types Of Crystal Lattices 2) Non-Bravais Lattice Not only the arrangement but also the orientation must appearexactly the same from every point in a bravais lattice. • The red side has a neighbour to its immediate left, the blue one instead has a neighbour to its right. • Red (and blue) sides are equivalent and have the same appearance • Red and blue sides are not equivalent. Same appearance can be obtained rotating blue side 180º. Crystal Structure

26. Translational Lattice Vectors – 2D 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 equivalent point, i.e. a point with the same environment as P . This is translational symmetry. The vectors a, bare known as lattice vectors and (n1, n2) is a pair of integers whose values depend on the lattice point. P Point D(n1, n2) = (0,2) Point F (n1, n2) = (0,-1) Crystal Structure

27. Lattice Vectors – 2D • The two vectors a and b form a set of lattice vectors for the lattice. • The choice of lattice vectors is not unique. Thus one could equally well take the vectors a and b’ as a lattice vectors. Crystal Structure

28. Lattice Vectors – 3D 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 u, v and ware arbitrary integers. r’ = r + ua + vb + wc      (1) Crystal Structure

29. Five Bravais Lattices in 2D Crystal Structure

30. S S S S S S S S S S S S S b a Unit Cell in 2D • The smallest component of the crystal (group of atoms, ions or molecules), which when stacked together with pure translational repetition reproduces the whole crystal. 2D-Crystal S S Unit Cell Crystal Structure

31. S S S S Unit Cell in 2D • The smallest component of the crystal (group of atoms, ions or molecules), which when stacked together with pure translational repetition reproduces the whole crystal. 2D-Crystal The choice of unit cell is not unique. b a Crystal Structure

32. 2D Unit Cell example -(NaCl) We define lattice points ; these are points with identical environments Crystal Structure

33. Choice of origin is arbitrary - lattice points need not be atoms - but unit cell size should always be the same. Crystal Structure

34. This is also a unit cell - it doesn’t matter if you start from Na or Cl Crystal Structure

35. - or if you don’t start from an atom Crystal Structure

36. This is NOT a unit cell even though they are all the same - empty space is not allowed! Crystal Structure

37. In 2D, this IS a unit cellIn 3D, it is NOT Crystal Structure

38. Why can't the blue triangle be a unit cell? Crystal Structure

39. Unit Cell in 3D Crystal Structure

40. Unit Cell in 3D Crystal Structure

41. Three common Unit Cell in 3D Crystal Structure

42. Body centered cubic(bcc) Conventional ≠ Primitive cell Simple cubic(sc) Conventional= Primitive cell Crystal Structure

43. The Conventional Unit Cell • A unit cell just fills space when translated through a subset of Bravais lattice vectors. • The conventional unit cell is chosen to be larger than the primitive cell, but with the full symmetry of the Bravais lattice. • The size of the conventional cell is given by the lattice constant a. Crystal Structure

44. Primitive and conventional cells of FCC Crystal Structure

45. Primitive and conventional cells of BCC Primitive Translation Vectors:

46. Primitive and conventional cells Body centered cubic (bcc): conventional ¹primitive cell Fractional coordinates of lattice points in conventional cell: 000,100, 010, 001, 110,101, 011, 111, ½ ½ ½ Simple cubic (sc): primitive cell=conventional cell Fractional coordinates of latticepoints: 000, 100, 010, 001, 110,101, 011, 111 Crystal Structure

47. Primitive and conventional cells Fractional coordinates: 000, 100, 101, 110, 110,101, 011, 211, 200 Body centered cubic (bcc): primitive (rombohedron) ¹conventional cell Face centered cubic (fcc): conventional¹ 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 Crystal Structure

48. Primitive and conventional cells-hcp points of primitive cell 120o Hexagonal close packed cell (hcp): conventional=primitive cell Fractional coordinates: 100, 010, 110, 101,011, 111,000, 001 Crystal Structure

49. The unit cell and, consequently, the entire lattice, is uniquely determined by the six lattice constants: a, b, c, α, β and γ. Only 1/8 of each lattice point in a unit cell can actually be assigned to that cell. Each unit cell in the figure can be associated with 8 x 1/8 = 1 lattice point. Unit Cell Crystal Structure

50. Primitive Unit Cell and vectors • A primitive unit cell is made of primitive translation vectors a1 ,a2, and a3 such that there is no cell ofsmaller volume that can be used as a building block for crystal structures. • 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 • V = a1.(a2 x a3) (vector products) Cubic cell volume = a3 Crystal Structure