Introduction to Solid State Physics y

Goan, Hsi-Sheng Hsi Sheng

Department of Physics National Taiwan University

Why study Solid State Physics?

Condensed matter physics, the largest branch of modern physics, mostly concerns the study of solids, solids but has been extended to amorphous substances, glasses, and liquids. Almost all compounds are solids under suitable conditions of temperature and pressure. Most of the research is done on solids:
What makes a material be a metal, insulator, or semiconductor? New physics?

Solids are of immense technological importance importance.

1
1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr

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11

12

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14

15

16

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(periodic table) ( i di t bl )
4 Be B 12 Mg g 20 Ca 38 Sr 56 Ba 88 Ra --21 Sc 39 Y 57 La 89 Ac --22 Ti 40 Zr 72 Hf 104 Rf --23 V 41 Nb 73 Ta 105 Db --24 Cr 42 Mo 74 W 106 Sg 25 Mn 43 Tc 75 Re 107 Bh 26 Fe 44 Ru 76 Os 108 Hs --27 Co 45 Rh 77 Ir 109 Mt --28 Ni 46 Pd 78 Pt 110 Uu n --29 Cu 47 Ag 79 Au 111 Uu u --30 Zn 48 Cd 80 Hg 112 Uu b 5 B 13 Al 31 Ga 49 In 81 Tl 6 C 14 Si 32 Ge 50 Sn 82 Pb 7 N 15 P 33 As 51 Sb 83 Bi 8 O 16 S 34 Se 52 Te 84 Po 9 F 17 Cl 35 Br 53 I 85 At

2 He 10 Ne N 18 Ar 36 Kr 54 Xe 86 Rn

Basic definitions
Crystal: constructed by the infinite p groups repetition of identical g p of atoms. Basis: a group of atoms. L tti Lattice: th set of mathematical points t the t f th ti l i t to which the basis is attached. An infinite array of points in space, in which each point has identical surroundings to all others.

Translational Sy a s at o a Symmetry et y

T Translationally symmetric or periodic: b i i a point l ti ll ti i di bringing i t back to an equivalent point in the crystal. yp p y g g One can reach any point in space by adding an integer number of translation vectors. If the lattice was infinite, you could not tell if you moved or not not.

Lattice and basis

Don't mix up atoms with lattice points Lattice points are infinitesimal points in space Atoms are physical objects Lattice points do not necessarily lie at the centre of atoms

Crystal structure
Lattice

+
Basis

Crystal structure

Crystal structure

Even if there is only one type of atoms in the crystal, we y yp y , have to use a basis made up with two atoms.

Lattice vectors
We need to identify the symmetry (lattice t (l tti vectors) and lattice contents (basis) to fully describe a crystal structure. How do we choose lattice vectors? (this will lead us to thinking about unit cell or primitive cell.

Unit cell
Unit cell is the basic building block of the crystal structure (it fills space). The choice of unit cell is arbitrary arbitrary. The choice of the origin for unit cells is arbitrary as well. bi ll The only requirement is that the lattice must look the same when translated by a crystal translational vector:

T = u1a1 + u1a2 + u3 a3
where u1 , u2 and u3 are integers.

Building Blocks
Different crystal faces are developed even with identical building g blocks.

Rock salt

Primitive cell
A primitive cell is a type of unit cell. A primitive cell is the parallelepiped defined by the primitive translation vectors (axes) a1 , a2 and a3 such that there is no cell of smaller volume that can be used as a building block for crystal structure. A primitive cell is a minimum-volume cell. The volume of a primitive cell is

Vc = a1 (a2 a3 )
A primitive cell will fill space by the repetition of suitable crystal translation vectors vectors.

Choice of primitive cells

A, B and C are primitive cells. cells Why? D, E and F are not. Why? The volume of A B and A, C are the same and the choice of the origin is different. But this does not matter. There is only one lattice p point p p per primitive cell.

Wigner-Seitz Wigner Seitz cell

Another way of choosing a primitive cell. Procedure: 1. Draw lines to connect a g e att ce point all given lattice po t to a nearby lattice points 2. At the midpoint and normal to these lines lines, draw new lines (or planes in 3D) 3. 3 The smallest volume enclosed in this way is the Wigner-Seitz primitive cell. i iti ll

Counting Lattice Points/Atoms

Unit cell is primitive (1 lattice point) but contains two atoms in the basis. Atoms at the corner of the 2D unit cell contribute only 1/4 to unit cell count Atoms at the edge of the 2D unit cell contribute only 1/2 to unit cell count . Atoms within the 2D unit cell contribute 1 ( (i.e. uniquely) to that q y) unit cell A single layer of graphite

Symmetry operations
Crystal lattice can be carried or mapped into themselves by the lattice translations T and by various other symmetry operations. Physicists use the symmetry of the unit cells to classify crystal y p structures and how they fill space. This involves the use of point group operations and translation operations. By lattice point group we mean the collection of symmetry operations which, applied about a lattice point, carry the lattice into itself. Examples: mirror reflection, inversion, n-fold rotational axis symmetry t

The symmetry planes and axes of a cube

Two-dimensional Two dimensional lattice types

There are only five distinct lattices in 2D. These are defined by how you can y y rotate the cell contents ( and get the same cell back). Bravais lattice: common phrase for a distinct lattice type. type Unit cells made of these 5 Bravais lattices in 2D can fill space All other ones space. cannot.
oblique lattice

Fivefold rotations and quasicrystals

Pentagons do not fit together to fill all space p

Penrose tiling in 2D

It turns out that one can fill space by using rotation of unit cells by 2, 2/2, 2/3, 2/4, and 2/6 radians. But rotation of 2/5, and 2/7 do not fill space. A quasicrystal is a quasi-periodic nonrandom assemble of two types of distinct designs of tiles.

The 14 Bravais lattices in 3D

P=primitive (1 lattice point) I=Body-centered (2 lattice pts) F F F=Face-centered t d (4 lattice pts) C=Side-centerd (2 lattice pts) In this course, we will concentrate upon only a few of these types.

Cubic space lattices p

For cubic systems, we have three Bravais lattice: the simple cubic (SC), body-centered cubic (BCC) b d t d bi (BCC), and face-centered cubic (FCC).

Packing fraction g

atomic volume cell volume

Simple cubic lattice

Counting atoms (lattice points) in 3D cells Atoms in different positions in a cell are shared by y differing numbers of unit cells V t atom shared b 8 Vertex t h d by cells 1/8 atom per cell Edge atom shared by 4 cells 1/4 atom per cell Face atom shared by 2 y cells 1/2 atom per cell Body unique to 1 cell 1 atom per cell. cell
a1 = x; a2 = y;

a3 = z.
e.g., Po (Polonium)

One lattice point per unit cell, with a total volume of a3 Number of nearest neighbors: 6 Nearest neighbor distance: a Number of next-nearest neighbors: 12 Next-nearest neighbor distance: Packing fraction: / 6

2a a

Body-Center cubic lattice

1 a ( x + y z); 2 1 a2 = a ( x + y + z ) ; 2 1 a3 = a ( x y + z ) . 2 a1 =
e.g., Li, Na, K, Rb, Cs, V, Cr, Fe, e g Li Na K Rb Cs V Cr Fe

Primitive cell: rhombohedron

2 lattice points per cell, with a primitive cell volume of a3/2 i iti ll l f Number of nearest neighbors: 8 Nearest neighbor distance: 3a / 2 Number of next-nearest neighbors: 6 g Next-nearest neighbor distance: a Packing fraction: 3 / 8

Wigner-Seitz cells in 3D g
http://www.chembio.uoguelph.ca/educmat/chm729/wscells/construction.htm

BCC lattice

SC lattice

Procedure: Choose any lattice site as the origin. Starting at the origin draw vectors to all neighbouring lattice points. Construct a plane p p p perpendicular to and p passing through the midpoint g g p of each vector. The area enclosed by these planes is the Wigner-Seitz cell.

Unit cells of BCC lattice

Primitive cell of a rhombohedron defined by translation vectors.

Primitive cell of a truncated octahedron constructed by the Wigner-Seitz cell.

The Wigner-Seitz cell may look a bit strange, but it h th f ll point t b t has the full i t symmetry of its lattice point and will be useful when we look at the reciprocal space space. movie

Face-centered cubic (FCC) lattice

4 lattice points per cell, with a primitive cell volume of a3/4 Number of nearest neighbors: 12 g Nearest neighbor distance: a / 2 Number of next-nearest neighbors: 6 Next-nearest neighbor distance: a Packing fraction: 2 / 6

Primitive cells of FCC latice

1 a ( x + y); 2 1 a2 = a ( y + z ) ; 2 1 a3 = a ( x + z ) . 2 a1 =

Movies

Hexagonal unit cell

Primitive cell is a right p prism based on rhombus with an included angle of 120o. Later we will look at the hexagonal closepacked (hcp) structure structure, which is this structure with a basis.

a1 = a2 a3

Indexing system for crystal p g y y planes

Since crystal structures are obtained from diffraction experiments (in which particles diffract from planes of atoms), it is useful to ) develop a system for indexing lattice planes. We can use the lattice constants a1, a2, a3, but it turns out to be more useful to use what are called Miller Indices.

Index

Rules for determining Miller indices g

(1) Fi d th i t Find the intercepts on t the axes in terms of the lattice constants a1, a2, a3. (2) Take the reciprocals of these numbers and then reduce to three integers having the same ratio, usually the smallest of the three integers. The result, result listed as (hkl) is (hkl), called the index of the p plane.
An example:

Intercepts: a, , Reciprocals: a/a, a/, a/ = 1, 0, 0 Miller index for this plane : (1 0 0) (note: this is the normal vector for this l thi plane) )

Examples of Miller indices

Intercepts: a, a, Reciprocals: a/a, a/a, a/ = 1, 1, 0 Miller index for this plane : (1 1 0)

Intercepts: a,a,a Reciprocals: a/a, a/a, a/a = 1, 1, 1 Miller index for this l Mill i d f thi plane : (1 1 1)

Examples of Miller indices

Intercepts: 1/2a, a, Reciprocals: 2a/a, a/a, a/ , , = 2, 1, 0 Miller index for this plane : (2 1 0)

Intercepts: 3a1, 2a2, 2a3 Reciprocals: a1/3a1, a2/2a2, a3/2a3 = 1/3, 1/2, 1/2 The smallest three integers having the same ratio: 2 3 3 h i 2, 3, Miller index for this plane : (2 3 3)

Plane and direction indices

(hkl) might mean a single plane, or a i ht i l l set of planes If a plane cuts a negative axis, we p_ place a minus signs above the index: g (hkl) Planes equivalent by symmetry are denoted with curly brackets {hkl} The t f b f Th set of cube faces are denoted d t d {100} which include (100), (010), _ _ _ (001), (100), (010), and (001) faces. The direction of a crystal is denoted with [uvw] (for example, The [100] direction for a cubic crystal is along x axis ) In bi I cubic crystals, th di ti [hkl] is t l the direction i perpendicular to the plane (hkl) having the same indices, but this isnt necessarily true for other crystal systems t (001) face

[100] direction

[001] di ti direction

Important planes in a cubic crystal p p y

The l Th plane (200) means a plane parallel t (100) b t cutting the a1 axis at a/2. l ll l to but tti th i t /2

Examples of common structures: Sodium Chloride (NaCl) structure S di Chl id (N Cl) t t

Th space lattice of NaCl The l tti f N Cl structure is FCC. The basis consists of one Na+ ion and one Cl- ion, separated by one-half of the body diagonal of a unit cube. There are four units of NaCl in each unit cube. At Atom positions: iti Cl: 000 ; 0; 0; 0 Na: ; 00; 00; 00 Each atom has 6 nearest neighbors of the opposite kind. kind

Often described as 2 interpenetrating FCC lattices

NaCl structure
Crystal LiH MgO MnO NaCl AgBr PbS KCl KBr a () 4.08 4.20 4.43 4 43 5.63 5.77 5.92 6.29 6.59 6 59
ClNa+

movie

Cesium Chloride (CsCl) structure

The space lattice of CsCl structure is SC. The basis consists of one Cs atom and one Cl atom, with each atom at the center of a cube of atoms of the opposite kind. There is on unit of CsCl in each unit cube Atom positions: Cs : 000 Cl : (or vice-versa) Each atom has 8 nearest neighbours of the opposite kind.

Often described as 2 p g interpenetrating SC lattices

CsCl structure
Crystal C t l BeCu AlNi CuZn CuPd AgMg LiHg NH4Cl TlBr CsCl TlI a () 2.70 2.88 2 88 2.94 2.99 2 99 3.28 3.29 3 29 3.87 3.97 3 97 4.11 4.20 4 20
a

Why are the a values smaller for the CsCl structures than for the NaCl (in general)?

Closed packed Closed-packed structures

What does stacking fruit have to do with solid state physics?

Closed-packed structures
There are an infinite number of ways to arrange identical spheres in a regular array that maximize the packing fraction.
The centers of spheres at A, B, and C positions iti

There are different ways you can pack spheres together. This y y p p g shows two ways, one by putting the spheres in an ABAB arrangement, and the other with ABCABC.

Hexagonal closed-packed (HCP) structure

The HCP structure is made up of stacking spheres in a ABABAB configuration. The HCP structure has the primitive cell of the hexagonal lattice, with a basis of two identical atoms Atom positions: 000, 2/3 1/3 1/2 (remember, the unit axes are not all perpendicular) The number of nearest-neighbors is 12.

e.g., Be, Sc, Te, Co, Zn, Y, Zr, Tc, Ru, Gd, Tb, Py, Ho, Er, Tm, Lu, Hf, Re, Os, Tl

Rotate three times To get the full structure Primitive cell has a1= a2 Conventional HCP unit cell

FCC (also called the cubic closed-packed structure, or CCP) l d k d t t

FCC (CCP) structure has the stacking arrangement of t t h th t ki t f ABCABCABC sequence along the [111] direction.

HCP and FCC stacking arrangement

HCP lattice

ABABAB

y x
FCC lattice ABCABCABC

HCP and CCP (FCC) stacking arrangement t

[0 0 1] HCP FCC (CCP) (looking along [111] direction di ti [1 1 1]

ABAB sequence

ABCABC sequence

movies

HCP and FCC structures

The hexagonal-closed packed (HCP) and FCC structures both have the ideal id l packing f ti of ki fraction f 0.74. The ideal ratio of c/a for this packing is (8/3)1/2 = 1.633 (see Problem 3 in Kittel) Why arent these values perfect for real materials? Why would real materials pick HCP or FCC (what does it matter if they pack yp the same?)?
Crystal C t l He(hcp) Be Mg Ti Zn Cd Co Y Zr Gd Lu c/a ratio / ti 1.633 1.581 1 581 1.623 1.586 1.861 1.886 1.622 1.570 1.594 1.592 1.586

Diamond structure

2 interpenetrating FCC lattices

The space lattice is FCC. The primitive basis has two identical atoms at the 000 and positions. There are 8 atoms in each conventional unit cube Number of the nearest neighbors: 4 Number of the next nearest neighbors: 12 Packing fraction: 0.34 (show this!) Crystal a () 3.567 5.430 5.658 5 658 6.49

C Si Ge G Sn

Diamond structure
FCC lattice + basis of 2 atoms at (0,0,0) and (1/4,1/4,1/4)
0 3/4 1/2 1/4 0 1/2 0 3/4 0 Tetrahedral bonding : 4 nearest neighbors 12 next nearest neighbors 1/2 1/4 1/2 0

two FCC displaced from each other by of a body diagonal

Maximum packing fraction = 0.34

Cubic Zinc Sulfide (ZnS) structure

The space lattice is FCC. The primitive basis has two different atoms at the 000 and positions (i.e., Zn and S) There are 4 units of ZnS in each conventional unit cube. About each atom, there are 4 nearest neighbors atoms of the opposite kind arranged at the corners of a t t h d f tetrahedron. Crystal y SiC ZnS AlP GaP GaAs
movie

a () ( ) 4.35 5.41 5.45 5.45 5.65 5.66

AlAs

Periodic table of the elements

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1 H 3 Li 11 Na 19 K 37 Rb 55 Cs 87 Fr

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(periodic table) ( i di t bl )
4 Be B 12 Mg g 20 Ca 38 Sr 56 Ba 88 Ra --21 Sc 39 Y 57 La 89 Ac --22 Ti 40 Zr 72 Hf 104 Rf --23 V 41 Nb 73 Ta 105 Db --24 Cr 42 Mo 74 W 106 Sg 25 Mn 43 Tc 75 Re 107 Bh 26 Fe 44 Ru 76 Os 108 Hs --27 Co 45 Rh 77 Ir 109 Mt --28 Ni 46 Pd 78 Pt 110 Uu n --29 Cu 47 Ag 79 Au 111 Uu u --30 Zn 48 Cd 80 Hg 112 Uu b 5 B 13 Al 31 Ga 49 In 81 Tl 6 C 14 Si 32 Ge 50 Sn 82 Pb 7 N 15 P 33 As 51 Sb 83 Bi 8 O 16 S 34 Se 52 Te 84 Po 9 F 17 Cl 35 Br 53 I 85 At

2 He 10 Ne N 18 Ar 36 Kr 54 Xe 86 Rn

Crystal structure of the elements

Structure Change
Many crystals undergo structural changes with T, P: For example:
-ferrite
BCC FCC

-ferrite
BCC Liquid Temperature T t 1400oC 2100oC

Fe F

910oC

BCC

FCC 371K

Liquid Temperature

Na

36K

Density and atomic concentration