P461 - Solids 1

Solids - types
MOLECULAR. Set of single atoms or molecules
bound to adjacent due to weak electric force
between neutral objects (van der Waals). Strength
depends on electric dipole moment
No free electrons poor conductors
easily deformed, low freezing temperature

freezing boiling bonding energy
He 1 K 4 K
H 14 K 20 K
Ar 84 K 87 K .08 eV/molecule
H
2
O 273 K 373 K 0.5 eV/mol
CH
4
90 K 111 K 0.1 eV/mol

correlates with bonding energy


P461 - Solids 2
Ionic Solids
Positive and negative ions. Strong bond and high
melting point. no free electrons poor conductor





similar potential as molecule. ~5 eV molecules and
~6 eV solid (NaCl)
each Cl- has 6 adjacent Na+, 12 next Cl-, etc



energy levels similar to molecules except no
rotations.electronic in UV and vibrational in IR.
Often transparent in visible


R Potential vs sep
distance R

=
+ = =
+
R
e
all
R
e
Cl V
R
e
Na V
0
2
0
2
0
2
4
7 . 1
2 4
12
) 12 (
4
6
) 6 (
tc
tc
tc
P461 - Solids 3
COVALENT. Share valence electrons (C, H, etc)
strong bonds (5-10 eV), rigid solids, high melting
point
no free electrons insulators
usually absorb in both visible and UV
METALLIC. s-p shell covalent bonds. But d shell
electrons leftover (smaller value of n lower
energy but larger <r>)
can also be metallic even if no d shell if there is an
unfilled band
1-3 eV bonds, so weaker, more ductile, medium
melting temp
free electrons not associated with a specific
nuclei. Wavelength large enough so wavefunctions
overlap and obey Fermi-Dirac statistics
conductors
EM field of photon interacts with free electrons
and so absorb photons at all


P461 - Solids 4
Bands in Diatomic Molecules-Reminder
assume all valence electrons are shared
if both atoms are the same then |,
2
same if switch
atom(1) and atom(2) --- electron densities around
each atom are the same (even sort of holds if
different atoms like CO)
H(1s) <-- very far apart ---> H(1s)
close together H(1s)H(1s)
electron wavefunctions overlap -shared
two energy levels (S=0,1) (spatial
symmetric and antisymmetric)which have




2 2
| ) 1 , 2 ( | | ) 2 , 1 ( | =
E
R=infinity
(atoms)
1s*1s
Vib and rot
bands
P461 - Solids 5
Bands in Solids
lowest energy levels very similar to free atoms
large kinetic energy large p, small



little overlap with electrons in other atoms and so
narrow energy band
higher energy levels: larger wavefunctions of
electrons from different atoms overlap
need to use Fermi-Dirac statistics
many different closely spaced levels: Band



p
h
eV
n
Z
K = = 6 . 13
2
2
3s,3p
2s,2p
1s
4s,4p,3d
E
P461 - Solids 6
Multielectron energy levels


3/2 symmetric spin. Each 1/2 has different mixed
symmetry 3 different spacial wavefunctions and
(usually) 3 different energy levels
the need for totally antisymmetric wave functions
causes the energies to split when the separation
distance R < wavelength
if far apart N degenerate(equal) states
overlap still N states but different energy




2
1
2
1
2
3
2
1
2
1
2
1
: 3 = electrons
E
R
6 electrons
P461 - Solids 7


N different combinations of spatial wavefunctions
gives N energy levels
N based on how many electrons overlap large
for the outer shell
small AE between different levels an
almost continuous energy band
nature of the energy bands determines
properties of solid
-- filled bands
-- empty bands
-- partially filled bands
-- energy width of band
-- energy gaps between bands
-- density of states in bands



terms N N ! ) ... 4 , 3 , 2 , 1 (
P461 - Solids 8
Bands in Solids 2
as their atomic radii are larger (and wavelength
larger) there is more overlap for outer electrons
larger N (# shared) wider bands (well see later
when discuss Fermi gas)



valence electrons will also share though band width
is narrower
valence vs conduction depends on whether
band if filled or not



atoms
n Z
a n
r
eff
e
) (
0
2
~
valence
conduction
E
P461 - Solids 9
Conduction vs valence
energy levels in 4s/4p/3d bands overlap and will
have conduction as long as there isnt a large AE to
available energy states (and so can readily change
states)
00000000 x00000x0
xxxxxxxx T=0 xxx0xx0x T>0
xxxxxxxx xxxxxxxx
xxxxxxxx xxxxxxxx
x=electron 0=empty state (hole)
sometime current is due to holes and not electrons
good conductors have 1 or more conduction/free
electrons/holes per atom



valence
conduction
E
P461 - Solids 10
Li and Be Bands
Atoms: Li Z=3 1s
2
2s
1
unfilled conductor
Be Z=4 1s
2
2s
2
filled insulator
But solids have energy bands which can
overlap






there is then just a single 2p2s band
Be fills the band more than Li but the top (the
Fermi Energy) is still in the middle of the band. So
unfilled band and both are metals


2p
2s

1s
Atom solid
E
P461 - Solids 11
Magnesium Bands
Atoms: Z=12 1s
2
2s
2
2p
6
3s
2
filled insulator like
Be






the 3p level becomes a band with 6N energies. The
3s becomes a band with 2N energies
They overlap becoming 1 band with 8N energy
levels and no gaps
BUT, if R becomes smaller, the bands split (bonds)
giving an energy gap for C, Si, Ge

3p
3s

E
Atomic separation R
6N
2N
8N
P461 - Solids 12
C,Si,Ge Bands
similar valence C:2s
2
2p
2
Si:3s
2
3p
2
Ge:4s
2
4p
2









8N overlapping energy levels for larger R
R becomes smaller, the bands split into 4N bond
and 4N antibond. an energy gap for C (7eV) and
Si, Ge (~1 eV)

2p,3p,4p
2s,3s4s

E
Atomic separation R
6N
2N
4N
4N
empty
T=0
filled
T=0
E(gap)
P461 - Solids 13
Properties of Energy Bands
Band width, gaps, density of states depend on the
properties of the lattice (spacing, structure)
First approximation is Fermi Gas. But if
wavelength becomes too small, not overlapping
sets width of band
next approximation adds in periodic structure of
potential
can cause interference of traveling waves
(reflection/transmission). Essentially vibrational
modes of the solid
destructive interference causes energy gaps which
are related to dimensions of lattice
Note often the band energy is measured from the
bottom of the band (which is the electronic energy
level)
real calculation needs to use 3D structure of solid
complicated D(E), need measurements


P461 - Solids 14
Fermi Gas Model
Quantum Stats:





Ex 13-2. What are the number of conduction
electrons excited to E > E
F
for given T?(done
earlier)


3 / 2
2
2 / 1
3
2 / 1 3
/ ) (
3
8
) 0 (
) 2 ( 8
) (
1
1
) ( /
|
.
|

\
|
= =
= =
+
= =

t

t
m
h
T E
E
h
m V
E D states of density
e
E n energy probabilty
F
kT E E
F
eV
eV
E
kT
N
N
kT E D
E E D E n N
E
E
N
E D T at
E
h
m V
dE E D total N
F
F
F F
F
F
E
F
4
025 .
2
3
) 3 2 )( (
2
1
) ( ) (
2
3
) ( 0
)
8
(
3
) (
2 / 1
2 / 3
2 / 3 2 / 3
2
0
~ ~
A
=
A ~ A
= =
= = =
}
t
E
F

T=0
T>0
n*D
P461 - Solids 15
Fermi Gas Model II
Solids have energy bands and gaps






Can calculate density of states D(E) from lattice
using Fourier Transform like techniques (going
from position to wavelength space)
can change D(E) by changing lattice
- adding additional atoms during fabrication
- pressure/temperature changes
PHYS 566, 480, 690A techniques


E
ideal
real
D
bottom at E of ten
band in ies E D
gaps in E D
2 / 1
var ) (
0 ) (

=
P461 - Solids 16
Fermi Gas Model III
1D model. N levels and min/max energy






For 2D/3D look at density of states. Grows as E
.5

until circle in k-space fills up then density falls
(cant have wavelength ~ smaller than spacing)



E
D
) (
8
max
) ( 0 min 0
8 2 2
2
2
2
2 2
2
2 2
width band
ma
h
E N n
bottom band E n
mL
n h
m
h
m
p
E
= =
= =
= = =

2D/3D
Na=L
a
ky
kx
E
F

P461 - Solids 17
Interactions with Lattice
Study electron wavefunction interactions with the
lattice by assuming a model for the potential
Kronig-Penney has semi-square well and barrier
penetration
will sort of look at 1D really 3D and dependent
on type of crystal which gives inter-atom
separation which can vary in different directions
solve assuming periodic solutions
Bragg conditions give destructive interference but
different sine or cosine due to actual potential
variation. will have different points where
wavefunction=0


ref lected all a
wave traveling lef t e e
wave traveling right e e
i i
a x i ikx
a x i ikx

t
t

+ =
=
=

1
/
/
V
0

P461 - Solids 18
Interactions with Lattice
Get destructive interference at


leads to gaps near those wavenumbers
once have energy bands, can relate to conductivity
materials science often uses the concept of effective
mass. Electron mass not changing but inertia
(ability to be accelerated/move) is. So high m* like
being in viscous fluid larger m* means larger
interaction with lattice, poor conductor
m* ~ m in middle of unfilled band
m* > m near top of almost filled band
m* < m near bottom of unfilled band
always dealing with highest energy electron
(usually near Fermi energy)


a
k
t

t
= =
2
P461 - Solids 19
Semiconductors
Filled valence band but small gap (~1 eV) to an
empty (at T=0) conduction band
look at density of states D and distribution
function n









Fermi energy on center of gap for undoped. Always
where n(E)=0.5 (problem 13-26)
D(E) typically goes as sqrt(E) at top of valence
band and at bottom of conduction band
E
F

D
valence
conduction
n
D*n
If T>0
P461 - Solids 20
Semiconductors II
Distribution function is






so probability factor depends on gap energy




estimate #electrons in conduction band of
semiconductor. Integrate over n*D factors at
bottom of conduction band


kT E
g
gap F
kT E E kT E E
g
F F
e E n
T eV kT E E E if
e e
E n
2 /
/ ) ( / ) (
) (
300 @ 025 . 2 /
1
1
1
) (

~
= = >> =
~
+
=
C n eV E
Si n eV E
g
g
65
11
10 6
10 1

= =
= =
P461 - Solids 21
Number in conduction band using Fermi Gas
model =






integrate over the bottom of the conduction band
the number in the valence band is about


the fraction in the conduction band is then


kT kT A e E E E A e N
valence as same AE E E D
conduction bottom E E E
dE E E D E n N
kT E
bot
kT E
bot
gap F bot
E
bot
g g
bot
2 ) ( ) (
) (
2 /
) ( ) (
5 . 0
2 /
5 . 0
2 /
5 . 0

= A ~ A
=
+ =
= A
}
2 / 3
2 /
0
5 . 0
3
2
F
E E
AE dE AE N
gap F
}

~ =
005 . 0
10 1 ,
4
025 .
) ( 3
14
2 /
2 / 3
= ~
A

~
A
= =
~
A

F
g
F
kT E
F
E
kT
N
N
metal
N
N
eV E
E
kT
f or
e
E
kT
N
N
g
P461 - Solids 22
Conduction in
semiconductors
INTRINSIC. Thermally excited electrons move
from valence band to conduction band. Grows with
T.
PHOTOELECTRIC. If photon or charged
particle interacts with electrons in valence band.
Causes them to acquire energy and move to
conduction band. Current proportional to number
of interactions (solar cells, digital cameras, particle
detection.)
EXTRINSIC. Dope the material replacing some of
the basic atoms (Si, Ge) in the lattice with ones of
similar size but a different number (+- 1) of valence
electrons



P461 - Solids 23
Doped semiconductors
Si(14) 3s
2
3p
2
P(15) 3s
2
3p
3
Al(13) 3s
2
3p
1
Si
|| 4 covalent bonds. Fill all valence
Si= Si =Si energy levels (use all electrons)
|| 1 eV gap
Si
Si
|| single electron loosely bound to P
Si= P =Si (~looks like Na)
|| 0.05 eV conduction band
Si
Si =Si
|| || 0.06 eV can break one of the Si=Si
Si= Al -Si bonds. That electron Al. The hole
|| || || moves to the Si atom
Si=Si



e
hole
P461 - Solids 24
Doped semiconductors II

The Fermi Energy is still where n(E
F
) = .
doping moves E
F

Complex compounds shift Fermi Energy and D(E)
(Al
x
O
y
Y
z
...)



conduction band
valence band
.05 eV
.06 eV
donor electrons
acceptor holes
P-doped n-type
extra e
.05 eV to move from
donor to conduction band
Al-doped p-type
missin e= (hole)
.06 eV to move from
valence to conduction band
E
P461 - Solids 25
Doped Semiconductors III
Adding P (n-type). Since only .05 eV gap some
electrons will be raised to conduction band
where n(E)= is in donor band










adding Al (p-type). some electrons move from
valence to acceptor band. n(E)= now in that
band
E
F

D
valence
conduction
D(E)
E
F

n-type
p-type
P461 - Solids 26
Doped Semiconductors IV
undoped semicon. have N
cond
~ 10
-11
N
valence

doping typically 10
-7
increases conductivity
but if raise T then the probability to move from
valence band to conduction band increases e
-E/kT
.
Can see this as a change in Fermi Energy with
temperature at some point all the donor
electrons are in the conduction band and many
valence move to conduction E
F
back in middle
of gap
E
T
donor
E
F