PHY 527 Solid State Physics I

Introduction
Solids encompass tremendous variety of properties and
enormous number of elements and compounds.
Examples:
! Elec. conductivities from infinity (supercond.) to 10
-16
(!-cm)
-1
(insulators like
SiO
2
); piezoelectric, ferroelectric".
! Optical properties (visible)
" reflecting
" transparent (of a multitude of colors)
" Absorbing
! Non-magnetic, diamagnetic, paramagnetic, ferromagnetic, antiferromagnetic,
Ferrimagnetic (examples in metals, semiconductors and insulators).
! Can be prepared with remarkable purity (example is Ge; foreign atoms at a
level of 10
10
imp./cm
3
! mechanically very hard (diamond); mechanically very soft and malleable (Pb)
! Tremendous range of applications
What ties all these materials and properties together?
Crystal Structure
Answer: NOT MUCH!
1. AMOST ALL SOLIDS EXIST IN CRYSTALLINE FORM
2. FUNDAMENTAL PROPERTY THAT UNDERLIES MOST OF OUR
UNDERSTANDING OF PROPERTIES OF SOLIDS (AMORPHOUS
SOLIDS LIKE GLASSES ARE EXCEPTIONS)
CRYSTAL STRUCTURE
For this course well consider all solids to be crystals, i.e., there is an
underlying xtal lattice. This structure is periodic some fundamental unit is
repeated ad infinitum. Simple geometric regularities in macroscopic
structures are examples of this. e.g. facets on surfaces of large crystals.
Crystal structures are understood from purely geometric solid considerations
(symmetries).
Very important to understand.
Continually appears and reappears in SSP.
Crystal Structure
Bravais Lattice
Fundamental concept -- specifies periodic array
of points in 3D (or 2D or 1 D)
Definition:
Bravais lattice is an infinite array of points (doesnt specify whats on or
at the points, e.g., atoms, molecules) that appears the same from
whichever of the points the array is observed.
Operational or mathematical definition:
A 3D Bravais lattice consists of all points with position vectors of the
form
are any three
vectors not all in the same plane, and the are integers (pos., neg. and
0), Every point in the lattice must be able to be generated in this manner.
The are called primitive vectors and span the lattice.
See next slide for examples.

!
!
R

!
!
R = n
1
!
a
1
+ n
!
a
2
+ n
!
a
3
, where
!
a
1
,
!
a
2
, and
!
a
3
!
n
i
' s

!
!
a
i
2D examples (oblique net)
Crystal Structure
P
!
a
3
!
b
3
!
a
2
!
b
2
!
a
1
!
b
1
!
P
1
= 3
!
a
1
+
!
b
1
!
a
4
!
b
4
Not possible,
nor is P
P
!
P
2
= !
!
a
2
+2
!
b
2
!
P
3
= 6
!
a
3
+3
!
b
3
The a
i
and b
i
for 1 3 are primitive vectors; a
4
and b
4
are not
A Set of
primitive
vectors is not
unique
Bravais Lattices
2D honeycomb lattice
Crystal Structure
Important material
GRAPHENE (monolayer of
Graphite)
! Not a Bravais lattice
! Two sublattices (O, )
! Points P and Q are
inequivalent
(consider first definition
of a BL)
b
1

b
2
P
Q
!
2

R
Vector like R = n
1
!
1
+ n
2
!
2
generates points not on either sublattice; (!
1
+ !
2
)
is a vector R to the center of the hexagons. A Centered honeycomb
lattice IS a Bravais lattice.
3D Examples
Body centered cubic (bcc) two interpenetrating simple cubic
lattices (or simple cubic lattice with a two atom basis).
Primitive vectors:







These primitive vectors are not unique; could also pick centers of
three adjacent cubes as primitive vectors
y
x
z
3
a
!
Crystal Structure
a
a
a
1
a
!
2
a
!
!
a
1
= a

x
!
a
2
= a

y
!
a
3
=
a
2

x +

y +

z
( )
Crystal Structure
Face Centered Cubic: take simple cubic lattice and add point to
center of each face (6 faces). Closest pt. to any point lies in planes defined
by the cube faces at 45 degree angles to cube axes (four in
each plane). Each pt. has same surroundings # BL

Primitive vectors
x
y
z
!
a
1
=
a
2

x +

y
( )
;
!
a
2
=
a
2

y + z
( )
;
!
a
3
=
a
2

x + z
( )
a
a
a
1
a
!
2
a
!
3
a
!
What is another set of
primitive vectors?
Very important structure; enormous
variety of solids crystallize in fcc;
simple cubic is very rare ($phase
of Po)
Crystal Structure
Coordination Number:

Points in lattice closest to a given point are nearest neighbors (nn),
etc., nnn, nnnn. Every BL point has the same number of nns.
This is the coordination number.
Center point in top plane is
equidistant from corner points
and center points 12 nns

Simple cubic = 6
Body centered cubic = 8
Crystal Structure
Primitive Unit Cell:
Definition:
Volume of space that, when translated through ALL vectors of the BL,
just fills all space without overlapping or leaving voids (like stacking building
blocks of odd shapes. There is NO UNIQUE CHOICE!
Example (2D oblique lattice)
B
A
C
D
IV
III
II
Primitive cell contains ONE lattice point;
n = density of points in lattice (#/vol. or area)
v = vol. of unit cell; then nv = 1 (useful later)
I
Obvious prim. cell is the oblique one
shown in red. (each corner point is shared
Among 4 identical cells so each cell has
one atom (4 x # ).
The hexagonal cells are also primitive cells:
one atom in each and exactly the same area.
Show by translating I through CD, III through
AD, and II through BD --- generates the
hexagonal cell
Crystal Structure
x
z
y
!
a
1
3
a
!
2
a
!
( ) ( ) ( )
( ) ( )
( ) ( )
4
1 0 0 0 1 0
8
0 ) (
8
) (
8
is cell primitive of vol.

2
;
2
;
2
3
3 3
3
3 2 1
3 2 1
a
a
y x z y x
a
z x z y y x
a
a a a v
z x
a
a z y
a
a y x
a
a
=
+ + + + + = + + + ! + =
+ " + + = " =
+ = + = + =
! ! !
! ! !
1/4 vol. of
cubic cell
Primitive Unit cell (3D example):
Face Centered Cubic (fcc)
Primitive Vectors
2D example
Draw lines connecting center
point to all nearby lattice points
Draw perpendicular bisectors
(lines or planes)
Smallest volume enclosed is
W-S unit cell
3D examples
bcc truncated octahedron
Wigner-Seitz unit cell
fcc rhombic
dodecahedron
Lattice with a basis
Real crystal described by an underlying BL together with a
particular arrangement of atoms, molecules, etc. !within an
individual Primitive Cell
Identical copies of the same physical unit (the Basis) translated
through all vectors of the BL reproduce the crystal
With a single atom or ion as basis the lattice is called a monatomic
BL
Simple 2D example
x
y
Basis
Lattice + Basis = crystal
Lattice Points
Non-primitive Unit Cell
Can also describe monatomic BL as a lattice with a basis by
choosing non-primitive Unit cell
Example: Conventional (cubic) unit cell for fcc or bcc
( ) z y x r r
z a a y a a x a a
a
, 0 basis
, ,
2 2 1
3 2 1
+ + = =
= = =
! !
! ! !
y
x
z
bcc is simple cubic cell with two-point basis
fcc is simple cubic cell with four-point basis
(same cubic primitive cell as above) y
x
z
!
r
3
( ) ( ) ( ) x z
a
r z y
a
r y x
a
r r
2
,
2
,
2
, 0
4 3 2 1
+ = + = + = =
! ! ! !
!
r
1
!
r
2
!
r
4
!
r
1
!
r
2
Described as fcc BL with a two-point basis:
( ) z y x
a
r r
4
, 0
2 1
+ + = =
! !
2
r
!
W
Two interpenetrating fcc lattices
Displaced along the body diagonal by
" the length of the diagonal
Important Examples
Diamond (and Zinc-blende) structure
Diamond: (carbon, Silicon, Germanium, grey-tin)

Zinc- blende:
Two interpenetrating fcc lattices
that make up the diamond structure
are occupied by different atoms ( and )
Most III-V compound semiconductors
(GaAs,GaP, GaSb, InP, InSb, InAs,!)
and many II-VIs.
ZnSe, CdTe, HgTe, !.)
y
x
z
!
r
1
Hexagonal Close-Packed Structure
!
a
3
!
a
1
!
a
2
Top View
HCP structure not BL, but very important.
(30 elements). Underlying structure is simple
centered hexagonal (BL); stack 2D triangular
nets directly above one another three prim.
vectors
z c a y
a
x
a
a x a a ,
2
3

2
,
3 2 1
= + = =
! ! !
a
b
a
Stacking sequence:
ababab
x
y
x a a
1
=
!
y
a
x
a
a
2
3

2
2
+ =
!
60
Every other triangle in a hexagon in an
a- layer has a b-layer atom underneath it
Displaced along z-direction by c/2.
The ideal hexagonal
Close-packed
structure has a
c/a ratio = ! !#"
To get hcp: take two interpenetrating
simple hexagonal BLs and displace one
from the other by

!
a
1
3
+
!
a
2
3
+
!
a
3
2
=
a
2
x +
a
3
3
2
y +
c
2
z
NaCl Structure
y
x
z
Again, two interpenetrating fcc lattices
- displaced along body diagonal by half the
diagonal length
fcc BL with two atom basis
( ) z y x
a
r r
2
, 0
2 1
+ + = =
! !
2
r
!
CsCl Structure
Each atom has 6 nn of the other kind (along cube edges)
Two interpenetrating simple cubic lattices
- displaced along body diagonal by half the
diagonal length

Simple cubic BL with two atom basis
( ) z y x
a
r r
2
, 0
2 1
+ + = =
! !
Each atom has 8 nn of the other kind (along body diagonals)