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3 States of Matter

Gas Liquid Solid fluid

Crystals

A crystal lattice is a periodic array of points in space

Crystal Lattice

(simple cubic)

Crystal Habits

(cubic)

From H. E. Hall

Atomic-scale terraces are visible Mounds appear as microscopic habits on an optically flat surface

100 nm

500 nm

High-Temperature Superconductor: YBa2Cu3O7 O Cu Building blocks of the crystal lattice can contain complex units Y

Ba

www.wfu.edu/~lawct/ybco.html

Crystals

A crystal lattice is a periodic array of points in space

Most simple chemical compounds in the solid state are crystalline There are many amorphous compounds: no long-range order (glass and vitreous are other terms also used for this)

Lattice: an infinite periodic array of points, each of which represents a quantity (basis) whose arrangement and orientation appear exactly the same at all points in the array.

Position vector:

r r r r R = n1a1 + n2 a2 + n3 a3

Primitive vectors: the set of the smallest translation vectors that make up the lattice

Any point on a lattice can be reached by an appropriate choice of n1, n2, n3 (integers)

Unit Cells

Primitive Unit Cell: Volume of space that can be translated through all primitive vectors of the lattice. It exactly fills space without overlapping or gaps. The definition is not unique.

r r r Vc = a3 (a2 a1 )

The Wigner-Seitz Primitive Cell a popular primitive cell construction Draw lines between neighboring atoms Draw lines perpendicular through the midpoint of these Wigner-Seitz cell is the smallest enclosed volume

Conventional Unit Cell (the Unit Cell): Can be primitive or nonprimitive cell (it can contain more than one lattice point/cell which would be included as a basis).

Primitive

Bravais Lattices

Symmetry group of a crystal contains both: Translational Symmetry Point Symmetry

2 Rotation n Cn

C1

C2

C3

C4

C5

C6

Reflection (mirror)

Inversion

r r r r

http://www.staff.ncl.ac.uk/j.p.goss/symmetry/Stereographs.html http://www.reciprocalnet.org/edumodules/symmetry/operations/index.html

http://www.staff.ncl.ac.uk/j.p.goss/symmetry/index.html

Bravais Lattices

Symmetry group of a crystal contains both: Translational Symmetry Point Symmetry

From Marder

3 Dimensions:

7 Crystal Systems 14 Bravais Lattices

http://frank.mtsu.edu/~njsmith/modernii/lec10I.html

Lowest symmetry

abc

a=b=c o = = = 90

2 Tetragonal Lattices

a=bc o = = = 90

4 Orthorhombic Lattices

abc o = = = 90

1 Hexagonal Lattice

c a a

a=bc o = = 90 o = 120

1 Trigonal Lattice

Rhombohedral or Trigonal

2 Monoclinic Lattices

abc o = = 90

From Kittel

From Kittel

Draw between neighboring atoms Draw lines perpendicular through midpoint of these Wigner-Seitz cell is the smallest enclosed volume

2D

BCC

From Kittel

From Kittel

Diamond Structure: Examples are group IV elements: C, Si, Ge, -Sn, but not Pb 2 Interpenetrating FCC based at: (0,0,0) & (a/4, a/4, a/4) Zinc-Blende Structure: Examples: ZnS, ZnSe, ZnTe, CdS, CdTe, CuF, CuCl, AgI III-V compounds: GaAs, AlAs, AlP, GaP, GaSb, InP 2 Interpenetrating FCC based at: Ga at (0,0,0) As at (a/4, a/4, a/4)

Rock Salt Structure: 2 Interpenetrating FCC based at: Na at (0,0,0) Cl at (a/2, a/2, a/2)

Examples are usually ionically-bonded salts such as: Alkali-Halides: NaCl, LiFetc Alkaline-Chalcoginides (II-VI): CaS, MgS, SrSe, BaO, etc AgF, AgCl (Ag is usually monovalent) Rare-Earth Arsenides such as ErAs (Er is trivalent)

BCC-like structure with: Cs at (0,0,0) Cl at (a/2, a/2, a/2)

CaF2 Structure

FCC Ca based at (0,0,0) SC F based at (a/4, a/4, a/4)

F Ca

Examples: Alkaline-Halides: CaF2 , BaF2 Alkali-Chalcoginides: Li2O, Na2S Others: HfO2, CeO2, Mg2Si

Perovskite Structure

Ba at (0,0,0) Ti at (a/2, a/2, a/2) O at Face-Centered sites

Ti Ba O

Examples: BaTiO3, LaAlO3, SrTiO3, KNiF3. High-Tc superconductors based on these structures.

Often exhibit structural transitions to lower symmetry from rotation or stretching of the oxygen octahedra which are often Ferroelectric.

Hexagonal Structures

X X

a2 a1 a2 120 a1

a1 = a2 = a

HCP FCC

ABABAB stacking sequence c=a(8/3)=1.633a (not true for Graphite)

From Kittel

(2,3,3) plane

1. 2. 3. Find intercept of plane on 3 axes Take reciprocals of these numbers Multiply to get smallest set of integers

(H,K,L) planes: {H,K,L} indicates all symmetry-related planes [H,K,L] indicates the direction in the crystal. For cubic crystals [H,K,L] is perpendicular to the (HKL) plane

From Kittel

14 Bravais Lattices in 3D

(Kittel)

http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/lecture1/lec1.html

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