Electrical, Optical, Magnetic Properties of Materials-Didactic

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eafitz@mit.edu
Index of /323/
http://sauvignon.mit.edu/323/ [2002-05-11 22:21:15]
Edited by Foxit Reader
Copyright(C) by Foxit Software Company,2005-2007
For Evaluation Only.
323a1
1999 E.A. Fitzgerald 1999 E.A. Fitzgerald
3.23 Electrical, Optical, Magnetic Properties
of Materials (previously Physics and
Chemistry of Materials)
All EOM properties derived from electrons in materials
Electronic: response of free electrons in material
Optical: response of bound electrons and effect of electron
transitions in material
Magnetic: response of electron spin and electron motion in
material
Determining energy of electrons from electric and magnetic fields will
determine electron response and hence properties
Real materials: effect of imperfections on these materials
323a2
Origin of Conduction
Range of Resistivity
Why?
323a3
Response of material to applied potential
I
V R
e-
V
I
Linear,
Ohmic
Rectification,
Non-linear, Non-Ohmic
V=IR
V=f(I)
Metals show Ohmic behavior
Microscopic origin?
323a4
Remove geometry of material
V
L
W
I
V=IR=IR/L R=L/(A) J =E
In general,
! !
J E =
~
Isotropic material
Anisotropic material
E
J
E
J
J
J
J
E
E
E
x
y
z
xx xy xz
xy yy yz
xz yz zz
x
y
z

In cubic material,
All material info
323a5
Microscopic Origin: Can we predict Conductivity of Metals?
Drude model: Sea of electrons
all electrons are bound to ion atom cores except valence electrons
ignore cores
electron gas
J =E=-nev, by definition of flux through a cross-section
n=number of electrons per volume
v=velocity of the carriers due to electric field--> drift velocity
Therefore,
=-nev/E and we define v=-E
is mobility, since the electric field creates a force on the electron F=-eE
= ne
323a6
Current Density and Electron Density
A
J
J
n=#electrons/volume
dx
Volume=A*dx
Charge=dQ=-enAdx
dx=vdt
J =(1/A)(dQ/dt)=-nev
define : v=-E
therefore J =-nev=E
if =ne
323a7
Does this microscopic picture of metals give us Ohms Law?
F=-eE
E
F=ma
m(dv/dt)=-eE
v=-(eE/m)t
J =E=-nev=ne
2
Et/m
=ne
2
t/m
v,J ,,I
t
t
E
No, Ohms law can not be only from electric force on electron!
Constant E gives ever-increasing J
323a8
Hydrodynamic representation of e- motion
dp t
dt
p t
F t F t
( ) ( )
( ) ( ) ... = + + +
1 2
Response (ma)
p=momentum=mv
Drag Driving Force Restoring Force...
dp t
dt
p t
eE
( ) ( )

Add a drag term, i.e. the electrons have many collisions during drift
1/ represents a viscosity in mechanical terms
323a9
In steady state,
dp t
dt
( )
= 0
p t p e
t
( ) ( ) =
1

p eE
=
p
t
-eE
If the environment has a lot of collisions,

mv
avg
=-eE v
avg
=-eE/m
Now we have Ohms law

=
ne
m
2

=
e
m
323a10
Predicting conductivity using Drude
n
theory
from the periodic table (#valence e- and the crystal structure)
n
theory
=A
V
Z
m
/A,
where AV is 6.023x10
23
atoms/mole
m
is the density
Z is the number of electrons per atom
A is the atomic weight
For metals, n
theory
~10
22
cm
-3
If we assume that this is correct, we can extract
323a11
~10
-14
sec for metals in
Drude model
Extracting Typical for Metals
323a12
Thermal Velocity
So far we have discussed drift velocity v
D
and scattering time
related to the applied electric field
Thermal velocity v
th
is much greater than v
D
kT mv
th
2
3
2
1
2
=
m
kT
v
th
3
=
Thermal velocity is much greater than drift velocity
x
x
x
L=(v
D
+v
th
)t
323a13
Example: Conductivity Engineering
Objective: increase strength of Cu but keep conductivity high
v
m
e
m
ne
=
= =
"

2
Scattering length
connects scattering time
to microstructure
Dislocation
(edge)
l decreases, decreases, decreases
e-
323a14
Can increase strength with second phase particles
As long as distance between second phase<l, conductivity marginally
effected
L
S
L+S
Sn
Cu
L
X Cu

+L
+L
+
S
microstructure
Material not strengthened, conductivity decreases
dislocation
L
L>l
Dislocation motion inhibited by second
phase; material strengthened;
conductivity about the same
323a15
Scaling of Si CMOS includes conductivity engineering
One example: as devices shrink
vertical field increases
decreases due to increased scattering at SiO
2
/Si interface and
increased doping in channel need for electrostatic integrity (ionized
impurity scattering)
Scaling continues properly if device shrinks fast enough to
negate decrease in scattering time
E
vert
Ionized impurities
(dopants)
S
D
G
SiO
2
323a16
Determining n and : The Hall Effect
- - - - - - - - -
V
x
, E
x
I, J
x
B
z
+++++++++++
B v q E q F
!
!
! !
+ =
z D y
B ev F =
E
y
y y
eE F =
In steady state,
H Z D Y
E B v E = =
, the Hall Field
Since v
D
=-J
x
/en,
Z X H Z x H
B J R B J
ne
E = =
1
ne
R
H
1
=
ne =
323a17
A&M treatment using full equations of motion
units) (CGS
+ = + = B x
mc
p
E e
p
F
p
dt
p d
!
!
!
!
!
! !

Separate into x & y coupled equations:
k B B j p i p p
z y x
,

= + =
!
!
(p
x
xB is in +y direction, p
y
xB is in -x direction)
(CGS)
0
0
mc
eB
p eE
p
dt
dp
p eE
p
dt
dp
c
x c y
y y
y c x
x x
=
+ = =
= =
m
ne
e
p
e
p
E
e
p
e
p
E
o
y c y
y
y c
x
x
2
=
+ =
=
Since
y x c y o
x y c x o
J J E
J J E
+ =
+ =

In steady state,
0 =
=
y
x x o
J
J E
z x H z x x
o
c
y
B J R B J
nec
J E = = =
1

323a18
Experimental Hall Results on Metals
Valence=1 metals look like
free-electron Drude metals
Valence=2 and 3, magnitude
and sign suggest problems
323a19
Response of free e- to AC Electric Fields
Microscopic picture
e
-
t i
O Z
e E E

=
B=0 in conductor,
and
) ( ) ( B F E F
! ! ! !
>>
t i
e eE
t p
dt
t dp

=
0
) ( ) (
t i
e p t p

=
0
) (
0
0
0
eE
p
p i =
try
1
0
0
=
i
eE
p
>>1/, p out of phase with E
<<1/, p in phase with E
i
eE
p
0
0
= 0 , p
0 0
eE p =
323a20
Complex Representation of Waves
sin(kx-t), cos(kx-t), and e
-i(kx-t)
are all waves
e
-i(kx-t)
is the complex one and is the most general
real
imaginary
A
Acos
iAsin
e
i
=cos+isin
323a21
Momentum represented in the complex plane
Response of e- to AC Electric Fields
real
imaginary
p
p (<<1/)
p

(
>
>
1
/
)
Instead of a complex momentum, we can go back to macroscopic
and create a complex J and
i
e J t J

=
0
) (
0
2
0
0
)
1
(
E
i m
ne
m
nep
nqv J

= = =
m
ne
i
2
0
0
,
1
=
=
323a22
Low frequency (<<1/)
electron has many collisions before direction
change
Ohms Law: J follows E, real
High frequency (>>1/)
electron has few collisions when direction is
changed
J imaginary and 90 degrees out of phase with
E, is imaginary
Response of e- to AC Electric Fields
Qualitatively:
<<1, electrons in phase, re-irradiate, E
i
=E
r
+E
t
, reflection
>>1, electrons out of phase, electrons too slow, less interaction,transmission =
r
0

r
=1
Hz
cm x
cm x
c
14
8
10
14
10
10 5000
sec / 10 3
, sec, 10 = =

E-fields with frequencies greater than visible light frequency expected to be
beyond influence of free electrons
323a23
Need Maxwells equations
from experiments: Gauss, Faraday, Amperes laws
second term in Amperes is from the unification
electromagnetic waves!
Response of light to interaction with material
SI Units (MKS)
M H B
P E D
t
D
c
J
c
H x
t
B
c
E x
B
D
! ! !
! ! !
!
! !
!
!
!
!
4
4
1 4
1
0
4
+ =
+ =
+ =
=
=
=
0 0
0 0
0
;
0

r r
H M H B
E P E D
t
D
J H x
t
B
E x
B
D
= =
= + =
= + =
+ =
=
=
=
! ! ! !
! ! ! !
!
! !
!
!
!
!
Gaussian Units (CGS)
323a24
Waves in Materials
Non-magnetic material, =
0
Polarization non-existent or swamped by free electrons, P=0
t
E
J B x
t
B
E x
+ =
=
!
! !
!
!
0 0 0

t
B x
E x x
=
!
!
) (
2
2
0 0 0
2
0 0 0
2
] [
t
E
t
E
E
t
E
J
t
E
=

For a typical wave,
) ( ) ( ) (
) (
2
0 0 0
2
0
) (
0
r E r E i r E
e r E e e E e E E
t i t i r ik t r k i

=
= = =

Wave Equation

0
2
2
2
1 ) (
) ( ) ( ) (
i
r E
c
r E
+ =
=
) (
) (
) (
2
2
2
0

c
k
v
c
k
e E r E
r ik
= =
=
=

323a25
Waves slow down in materials (depends on ())
Wavelength decreases (depends on ())
Frequency dependence in ()
Waves in Materials
) 1 (
1 1 ) (
0
0
0

i
i i
+ = + =
m
ne
i
i
p
p
0
2
2
2
2
1 ) (
+ =
Plasma Frequency
For >>>1, () goes to 1
For an excellent conductor (
0
large), ignore 1, look at case for <<1

2
2
2
) (
p p
i
i
i
323a26
Waves in Materials
For a wave
Let k=k
real
+k
imaginary
=k
r
+ik
i
) (
0
t kz i
e E E

=
[ ]
z k
t z k i
i
r
e e E E

=

0
The skin depth can be defined by
+ =
+
=
= =
2
0
0
2
0
0
0
0
0
0
2 2
2
1
) (
c
i
c
i
c
k
i
c c
k
o o o
o
i
c
k
2 2 1
2
= = =
MKS CGS
323a27
For a material with any
0
, look at case for >>1
Waves in Materials
( )
2
2
1

p
=
<
p
, is negative, k=k
i
, wave reflected
>
p
, is positive, k=k
r
, wave propagates
R

p
323a28
Success and Failure of Free e- Picture
Success
Metal conductivity
Hall effect valence=1
Skin Depth
Wiedmann-Franz law
Examples of Failure
Insulators, Semiconductors
Hall effect valence>1
Thermoelectric effect
Colors of metals
K/=thermal conduct./electrical conduct.~CT
2
3
1
therm v
v c =
m
T k
v nk
T
E
c
b
therm b
v
v
3
;
2
3
2
= =
=
m
T nk
m
T k
nk
b b
b
2
2
3 3
2
3
3
1
=
=
m
ne
2
=
T
e
k
b
2
2
3
Therefore :
~C! Luck: c
vreal
=c
vclass
/100;
v
real
2
=v
class
2
*100
323a29
Wiedmann-Franz Success
Exposed Failure when
c
v
and v
2
are not both
in property
Thermoelectric Effect
T Q E =
e
nk
ne
nk
ne
c
Q
b
b
v
2 3
2
3
3
=
= =
Thermopower Q is
Thermopower is about 100 times too large!
323a30
Improvements? What are ion cores doing...
Scattering idea seems to work
any effect of crystal (periodic) lattice?
Diffraction
proves periodicity of lattice
proves electrons are waves
proves strong interaction between crystal and electrons (leads to
band structures=semiconductors and insulators)
useful characterization technique
Course: bias toward crystalline materials: many applications: materials
related to either end of spectrum (atomic/molecular or crystalline)
localized extended
Point defects,
atoms, molecules
Bands; properties of many
solids with or without extended defects
Polymers,
Si
Diffraction is a useful characterization in all these materials
323a31
Diffraction
Incoming must be on the order of the lattice constant a or so (<~
few tenths of a nanometers)
x-rays will work (later, show electrons are waves also and they can be
used for diffraction also)
x-rays generated by core e- transitions in atoms
distinct energies: E=hc/; E~10keV or so (core e- binding
energies)
Cu
single-crystal
diffraction
n=2dsin
Cooled Cu
target
e-
Thermionic
emission
sample
detector
Collimator crystal (decreases spread in and )
sample
detector
double crystal,
double axis diffraction
Add a channel crystal (also
called analyzer crystal) after the
sample and it is called triple axis
diffraction
323a32
Four Views of Diffraction
Bragg, Von Laue, Reciprocal lattice, Atomic origin
Start with review of Bragg diffraction
Constructive interference:
n=2dsin
In any system,
2 2 2
l k h
a
d
+ +
=
In cubic system,
g is a reciprocal lattice vector, and b
i
are the
primitive basis vectors describing the reciprocal
lattice
( )
2
3
2
2
2
2
2
1
2
2
2
2
2
b l b k b h g
d
hkl
! ! !
!
+ + = =
323a33
Example of Diffraction from Thin Film of
Different Lattice Constant
InGaAs on GaAs deposited by molecular beam epitaxy (MBE)
Can determine lattice constant (In concentration) and film thickness
from interference fringes
GaAs
In
x
Ga
1-x
As
In
0.05
Ga
0.95
As
GaAs
Interference fringes
from optical effect
X-ray
intensity
323a34
Example: Heavily B-diffused Si
B diffusion from borosilicate glass
creates p++Si used in micromachining
gradients created in B concentration and misfit dislocations
Si
Si:B
Graded
region
Si:B
Graded Si:B
Si
323a35
Double axis vs. Triple Axis
More common double axis: greater signal but lower resolution
Example: GaAsP Graded structure on GaAs substrate (for high-volume LEDs)
with rotational inhomogeneity in composition/thickness due to production
equipment
Double Axis Diffraction
Triple Axis Diffraction
323a36
Von Laue Representation
Equivalent to Bragg, more general
More convenient in picturing 3-D and often more convenient mathematically
leads to Ewalt sphere construction
R
!
' k
!
' k
!
k
!
k
!
n
'
n
n R
!
' n R
!
Red points are part of a periodic crystal lattice;
R represents a translation vector of the lattice
k
!
is the wave-vector vector of initial x-rays,
magnitude =2/
' k
!
is the wave-vector of the diffracted x-rays,
magnitude =2/
For constructive interference,
( ) ( )
( )
m k R
m k k R
m
n n
R
m n R n R
2
2 '
2
' 2 2
'
=
=
=

= +
! !
! ! !
!
! !
If the difference in k and k is a multiple of
a lattice spacing, then diffraction occurs
1 =
R k i
e
! !
or
323a37
Equivalence of Von Laue and Bragg
d
m
R
n
R
n
k
m k R

2
'
2
cos
2
2
= = =
=
! !
!
! !
Where R is defined as the translation
vector along k
k
!
' k
!
k
!
k
!
' k
!
k
!
If Von Laue condition holds, then reciprocal lattice

points exist at ends of k
k
!
' k
!
k
!
Bragg plane
B
d
m
d
m
k
k
B
2
2
2
2
1
2
1
sin

= =
= !
!
323a38
Reciprocal Lattice
Von Laue condition defines a set of diffraction points in 3-
D for 3-D crystal
m R G R k R k k 2 ) ' ( = = =
! ! ! ! ! ! !
Where G is termed a reciprocal lattice vector
A vector representation of this relation is:
( )
3 2 1
2 1
3
1 3
2
3 2
1
2
2
2
a a a V
V
a a
b
V
a a
b
V
a a
b
=
k
!
' k
!
G k
! !
=
B
Where a
i
are primitive vectors in
the real lattice, and the b
i
are the
corresponding primitive vectors
of the reciprocal lattice
or
j
j
a b
ij
ij
ij j i
= =
=
=
i when 1
i when 0
2
323a39
Ewalt Sphere Construction
A way to picture the generation of a diffraction image from the reciprocal
lattice
Draw reciprocal lattice
Draw incident k with vector head on
reciprocal point
All k are represented by a circle defined by
k as it is rotated about its tail (magnitude of
k and k are the same since they are defined
by )
All reciprocal lattice points that fall on the
circle or sphere (3-D) satisfy diffraction
condition
Diffraction pattern: reciprocal space
323b1
1999 E.A. Fitzgerald
Atomic Origin of Diffraction
Important for understanding structure factors, nanostructures
Why is reciprocal space the Fourier transform of the real lattice?
R
!
' k
!
k
!
incident wave, k, is a plane wave:
Reflected/scattered waves are spherical waves
D
1
2
Start off with two-beam analysis
r k i
o
e
!
!

ikD
o
e
D
f

1
) (
1
+

kD i
o
e
D
f
Recall =kR
Therefore, for D>>|R|,
TOT
[ ]
[ ]
R k i
TOT
R k i ikD
TOT
e f D
e e
D
f

+
+

1 ) (
1
0
From atom 1
From atom 2
f is the atomic scattering factor
323b2
Generalize for atoms
"

"
"
r k i
TOT
e f D) (
Where r
l
points to each atom from the reference atom
Thus,
TOT
is the Fourier Transform of (D) for small r
l
:

"
"
dr e D f
r k i
TOT
) (
r
l
r
g
r
g
d
i
Break r
l
into r
g
and d
i
, where units of r
g
point to the
unit cell (Bravais lattice), and d
i
point to the basis
Can generate all crystal structures this way
2
2
2

"
l
r k i
TOT
e f I
TOT
is the amplitude of the diffracted wave
I, the intensity, is proportional to the square of the amplitude
323b3
Origin of the lattice and structure factors
Summing over r
g
in three co-ordinate directions with crystal length in each direction being M
1
,M
2
,M
3
:
( ) ( )
S G e f
j g
d r k i
M
m
M
n
M
o
j TOT

+
1 2 3
M
1
M
2
M
3
1
1
1
1
]
1
,
_
,
_
1
1
1
1
]
1
,
_
,
_
1
1
1
1
]
1
,
_
,
_

g
g
g
g
g
g M
m
M
n
M
o
r ik
r k
r k M
r k
r k M
r k
r k M
e G
g
2
1
sin
2
1
sin
2
1
sin
2
1
sin
2
1
sin
2
1
sin
factor lattice
3 2 1
1 2 3
2 2
S G I
2/r
g
M very large
M small
Where k is written now as k for brevity and convention
323b4
The structure factor: connected to the crystal structure

atoms basis n
j
d ik
j
j
e f S
#
factor structure
Example: Body-centered cubic crystal structure
d
1
d
2
Basis:
( ) z y x
a
d
d

2
0
2
1
+ +
( )
( )
( )
( )
3 2 1
3 2 1
1 1 1

2
3 2 1

2
1
0
n n n
n n n i
k
z y x a ik
ik
k
e S
z n y n x n
a
k
e e S
+ +
+ +
+ +
+ +
+ +
+
Sk=2, if sum even

Sk=0 if sum odd (e.g. <111>disappear)
Extra scatterer in basis interferes with
simple cubic diffracted waves
Note: in structures with different atoms, e.g. GaAs,
j
d ik
j
j k
e f S

323b5
Compton, Planck, Einstein
light (xrays) can be particle-like
DeBroglie
matter can act like it has a wave-nature
Schrodinger, Born
Unification of wave-particle duality, Schrodinger
Equation
Wave-particle Duality: Electrons are not just particles
323b6
Light has momentum: Compton
No way for xray to change after interacting classically
Experimentally: Compton Shift in
Photons are particle-like: transfer momentum
e-
xray

graphite
I
d
e
t
e
c
t
o
r
( ) ( ) cos 1 cos 1
c
o
c m
h
323b7
Light is Quantized: Planck
Blackbody radiation: energy density at a given (or ) should be predictable
Missing higher frequencies! (ultra-violet catastrophe)
hollow cube,
metal walls
Heat to T
()d=energy per volume being emitted in +d
( )
( )
volume
E d N
d
wave

N() is the number density, i.e. number of waves in +d (#/frequency)
Finding N(): Inside box, metal walls are perfect reflectors for the E-M waves
L
L
) ( ) (
;
kz t i
or r
kz t i
oi i
e E E e E E
+

Perfect reflection, E
oi
=-E
or
[ ] kz e iE e e e E E
t i
oi
ikz ikz t i
oi tot
sin 2

323b8
{ } kz t E E
oi tot
sin sin 2 Real
Standing Waves
0 L
E-field inside metal wall
is zero (due to high
conductivity)
Therefore, sinkz must equal zero at z=0 and z=L
L
n
k n kL kL

2
; 2 ; 0 sin Also, since k=2/,
n
L L
n
2
or
2

In 3-D,
2 2 2
2
z y x
n n n
L
+ +

Note that the wavelength for E-M
waves is quantized classically just by
applying a confining boundary
condition
k n j n i n n
z y x

+ +
!
L
n c
L
n n n c
z y x
2 2
2 2 2
!
+ +

323b9
n
x
n
y
n
z
(n
x
,n
y
,n
z
)
c/2L
1 state (i.e. 1 wavelength or frequency) in
(c/2L)
3
volume in n-space
2 possible wave polarizations for each state
Using the assumption that >>c/2L,
(Note also that postive octant is only active one
since n is positive: shows as 1/8 factor below)
3
3 3
3
3
3
8
2 2
1
3
4
8
1
c
L
L
c
N

,
_
( )
3
2 3
8
c
L
d
dN
N

323b10
Now that N(), the number of E-M waves expected in +d, has been
determined simply by boundary conditions, the energy of a wave must be
determined for deriving ()
( )
( )
3
2
3
3
3 2
8
8
c
kT
L
kT
c
L
volume
E N
wave

The classical assumption was used, i.e. E
wave
=k
b
T
This results in a () that goes as
2
At higher frequencies, blackbody radiation deviates substantially from this dependence
323b11
Missing higher frequencies
~3m
~1m
~0.75m
Low OK: E=k
b
T
At high , E goes to zero
(i.e. no waves up there!)
2
323b12
Classical E=k
b
T comes from assumption that Boltzmann distribution determines
number of waves at a particular E for a given T
Since N() can not the problem with (), it must be E
E must be a function of in order to have the experimental data work out
Origin of E=k
b
T
Boltzmann distribution is ( )
T k
E
b
Ae E P
'
Normalized distribution is ( ) ( )
T k
A dE E P E P
b
1
; 1
0
'

Average energy of particles/waves with this distribution:

( )
( ) T k dE E EP
dE E P
dE E EP
E
b

0
0
0
normalized is P(E) if
) ( '
'
323b13
If P(E) were to decrease at higher E, than () would not have
2
dependence at higher
P(E) will decrease at higher E if E is a function of
Experimental fit to data suggests that E is a linear function in , therefore E=nh where h
is some constant
1
1
0
0

T k
h
T k
nh
b
T k
nh
b
b b
b
e
h
e
T k
e
T k
nh
E

Note: the integrals need to be

removed in the average and
replaced with sums since the
spacing of energies becomes
greater as E increases
( )
1
8
3
2
T k
h
b
e
h
c

h determined by an experimental fit and
equals
At small h/k
b
T, e
h/kT
~1+h/k
b
T and ()~k
b
T
At large h/k
b
T, ~he
-h/kT
which goes to 0 at high E
323b14
Lessons from Planck Blackbody
waves which are confined with boundary conditions
have only certain available: quantized
E=nh, and therefore E-M waves must come in chunks
of energy: photon E=h. Energy is therefore quantized
as well
Quantized energy can affect properties in non-classical
situations; classical effects still hold in other situations
323b15
Light is always quantized: Photoelectric
effect (Einstein)
Planck (and others) really doubted fit, and didnt initially believe h was
a universal constant
Photoelectric effect shows that E=h even outside the box
I,E,
e-
metal
block
Maximum
electron
energy,
E
max
c
E
max
=h(-
c
)
!
For light with <
c
, no matter what the intensity, no e-
323b16
Light is always quantized: Photoelectric
effect (Einstein)
E
E
F
vacuum
x
E
E
vac
=E
in
-E
E
in
=h
E
max
=E
in
-E=h-h
c

E
in
=h!
Strange consequence of Compton plus E=h: light has momentum but no mass
photon a for E since cp
p
h
E
hc

323b17
DeBroglie: Matter is Wave
His PhD thesis!
=h/p also for matter
To verify, need very light matter (p small) so is large enough
Need small periodic structure on scale of to see if wave is there (diffraction)
Solution:electron diffraction from a crystal
N=2dsin
For small , ~/d, so must be on order of
d in order to measure easily
323b18
Proof electron was wave by transmission and beackscattered experiments, almost simultaneously
Transmission
Backscattered
Diffraction
Spots
film
323b19
Modern TEM Modern SEM
323b20
Imaging Defects in TEM utilizing Diffraction
The change in of the planes around a defect changes the Bragg condition
Aperture after sample can be used to filter out beams deflected by defect
planes: defect contrast
39
323c1
Imaging Defects and Man-made Epitaxial Structures in
TEM utilizing Diffraction
Si
1-x
Ge
x
Layers
(each layer about 3000A)
Si
0.25
Ge
0.75
Si
0. 5
Ge
0. 5
/Ge superlattice
(each layer ~100A)
323d1
Unification: Wave-particle Duality
Need to reconcile old classical world with new results from duality
Introduce concept that classical results are averages over large
population of quanta
Automatically introduces the concept of uncertainty
E-M from Maxwell: I~|E|
2
~Nh
micro macro
I is an average over quantized behavior
Quantum
micro
Statistical Mechanics
averaging
Thermodynamics, Properties
macro
Schrodinger and Born introduce , the wave-function, to unify particles and waves
||
2
is the physical quantity: probability density
323d2
must be able to represent everything from a particle to a wave (the two
extremes)
Unification: Wave-particle Duality
wave
particle
( ) t kx i
Ae

=
k and p known exactly
( ) t x k i
n
n
n n
e a

=
= n to create a delta function in
2
generalized
( ) t x k i
n
n
n n
e a

=
323d3
Normalization of Wavefunctions
Probability of finding particle over a confining volume is 1
1
*
=
dr
V

= =
=
=

V V
r k i
r k i
dr
V
dr
e
V
e
V
1
1
1
1
*
*
!
!
!
!
Example:
real
i
||
2
323d4
Consequence of Wave-Particle Duality and
Quantization
323d5
Consequence of Wave-Particle Duality and
Quantization
323d6
Consequence of Electrons as Waves on
Free Electron Model
Boundary conditions will produce quantized energies for
all free electrons in the material
Two electrons with same spin can not occupy same
electron energy (Pauli exclusion principle)
Imagine 1-D crystal for now
Traveling wave picture
Standing wave picture
e
i(kx-t)
e
-i(kx+t)
e
i(kx-t)
+e
-i(kx+t)
=e
-it
(e
ikx
+e
-ikx
)
=e
-it
(2coskx)
Since material is usually big and electron small, traveling wave picture used
323d7
Consequence of Electrons as Waves on
Free Electron Model
Standing wave picture
Traveling wave picture
0 L
0
L
L
n
k
e
e e
L x x
ikx
L x ik ikx
2
1
) ( ) (
) (
=
=
=
+ =
+
J ust having a boundary condition means that k and E are quasi-continuous,
i.e. for large L, they appear continuous but are discrete
323d8
Representation of E,k for 1-D Material
m
p
m
k
E
2 2
2 2 2
= =
"
E
k
k=2/L
Quasi-continuous
k
m
k
E
m
k
dk
dE
=
=
2
2
"
"
states
electrons
E
n
E
n-1
E
n+1
m=+1/2,-1/2
All e- in box accounted for
E
F
k
F
k
F
Total number of electrons=N=2*2k
F
*L/2
323d9
2
1
2
2 2 1
) (
2
= = =
=
E
m
k
m
L dE
dk
dk
dN
E g
L k
N
F
" "
g(E)=density of states=number of electrons per energy per length

n=is the number of electrons per unit length, and is
determined by the crystal structure and valence
The electron density, n, determines the energy and velocity of
the highest occupied electron state at T=0
2
or
2 2
2

n
k
mE
k
L
N
n
F
F
F
= = = =
"
m
k
dk
dE
mE
k
m
k
E
2
2 2
2
;
2
"
"
"
=
= =
323d10
E(k
x
,k
y
)
k
x
k
y
m
k k
E
y x
2
) (
2 2 2
+
=
"
323d11
k
x
k
y
k
z
(k
x
,k
y
,k
z
)
2/L
m
k k k
E
z y x
2
) (
2 2 2 2
+ +
=
"
Fermi Surface or Fermi Sphere
k
F
m
k
v
F
F
"
=
m
k
E
F
F
2
2 2
"
=
B
F
F
k
E
T =
3 2
2
) (
"
mE m
E g
=
( )
3
1
2
3 n k
F
=
323d12
So how have material properties changed?
The Fermi velocity is much higher than
kT even at T=0! Pauli Exclusion raises
the energy of the electrons since only 2
e- allowed in each level
Only electrons near Fermi surface can
interact, i.e. absorb energy and
contribute to properties
T
F
~10
4
K (T
room
~10
2
K),
E
F
~100E
class
, v
F
2
~100v
class
2
323d13
Effect of Temperature (T>0): Coupled electronic-thermal
properties in conductors (i.e. c
v
)
Electrons at the Fermi surface are able to increase energy: responsible for
properties
Fermi-Dirac distribution
NOT Bolltzmann distribution, in which any number of particles can occupy
each energy state/level
Originates from:
...N possible configurations
T=0 T>0
E
F
1
1
) (
+
=

T k
E E
b
F
e
f
If E-E
F
/k
b
T is
large (i.e. far from
E
F
) than
T k
E E
b
F
e f
) (
=
323d14
Fermi-Dirac Distribution: the Fermi Surface
when T>0
~E
F
f(E)
1
T=0
T>0
0.5
k
b
T
k
b
T
E
All these e- not
perturbed by T
f
Boltz
Boltzmann-like tail, for
the larger E-E
F
values
v
v
T
U
c

=
Heat capacity of metal (which is ~heat capacity of free e- in a metal):
( ) [ ] ( ) ( )
2
~ ~ ~ T k E g T k E g T k N E U
b F b F b

U=total energy of
electrons in system
T k E g
T
U
c
b F
v
v
2
) ( 2 =
=
Right dependence, very close to exact derivation
323d15
Heat Capacity (c
v
) of electrons in Metal
Rough derivation shows c
v
~const. x T , thereby giving correct
dependence
New heat capacity is about 100 times less than the classical
expectation
RT
T k
E
nk
E
T k
nk
c
c
b
F
b
F
b
b
vquant
vclass
@ 100 ~
3
2
2
3
2
2
=
( )
F b v
E g T k c =
2
2
3
Exact derivation:
323d16
Remaining Issues
Electron wave picture has fixed some thermal/electrical properties and
electron velocity issues
Still can not explain:
Hall coefficients
Colors of metals
Insulators, Semiconductors
Can not ignore the ions (i.e. everything else but the valence electrons
that we have been dealing with so far) any longer!
Whatever we modify, can not change the electron wave picture that is
now working well for many materials properties
HOW DO THE VALENCE ELECTRON WAVES INTERACT
WITH THE IONS AND THEIR POTENTIALS?
323d17
Electrons in a Periodic Potential
Rigorous path: H=E
We already know effect: DeBroglie and electron
diffraction
Unit cells in crystal lattice are 10
-8
cm in size
Electron waves in solid are =h/p~10
-8
cm in size
Certain wavelengths of valence electrons will diffract!
323d18
Diffraction Picture of the Origin of Band Gaps
Start with 1-D crystal again
~a
a
1-D
sin 2d n =
d=a,
sin=1
a
n
k
k
a n
=
=
=
2
2
Take lowest order, n=1, and
consider an incident valence
electron moving to the right
x
a
i
o o
x
a
i
i i
e
a
k
e
a
k
= =
= =
;
;
Reflected wave to left:
Total wave for electrons with diffracted wavelengths:
x
a
i
x
a
o i a
o i s
o i

sin 2
cos 2
= =
= + =
=
a
k k k
o i
2
= =
323d19
Diffraction Picture of the Origin of Band Gaps
Probability Density=probability/volume of finding electron=||
2
x
a
x
a
s
a
2
2
2
2
cos 4
sin 4
=
=
a
a
Only two solutions for a diffracted wave
Electron density on atoms
Electron density off atoms
No other solutions possible at this wavelength: no free traveling wave
323d20
Assume electrons with wave vectors (ks) far from diffraction
condition are still free and look like traveling waves and see ion
potential, U, as a weak background potential
Electrons near diffraction condition have only two possible solutions
electron densities between ions, E=E
free
-U
electron densities on ions, E=E
free
+U
Exact solution using H=E shows that E near diffraction conditions
is also parabolic in k, E~k
2
Nearly-Free Electron Model
323d21
Nearly-Free Electron Model (still 1-D crystal)
m
p
m
k
E
2 2
2 2 2
= =
"
E
k
k=2/L
Quasi-continuous
k
m
k
E
m
k
dk
dE
=
=
2
2
"
"
states
/a -/a
0
E
g
=2U
Diffraction,
k=n/a
Away from k=n/a,
free electron curve
k=2/a=G=reciprocal lattice vector
Near k=n/a,
band gaps form, strong
interaction of e- with
U on ions
323d22
At k=/a, there must be also a k=-/a wave, since there is absolute
diffraction at this k
True for every k=n/a
Creates a parabola at every nG
Consequences of Diffraction on E vs. k curves
E
k
/a -/a
0
G
2/a 2/a
k=-/a in
reference
parabola
k=/a in
reference
parabola
0
-/a
2/a
Standing wave at
diffraction
condition
323d23
Extended-Zone Scheme
Bands form, separated by band gaps
Note redundancy: no need for defining k outside +-/a region
E
k
/a -/a
0
2/a
2/a
Band 2
Band 1
Band gap E
g
323d24
Reduced-Zone Scheme
Only show k=+-/a since all solutions represented there
/a
/a
323d25
Real Band Structures
GaAs: Very close to what we have derived in the nearly free electron model
Conduction band minimum at k=0: Direct Band Gap
323d26
Real Band
Structures
Ge: Very close to GaAs,
except conduction band
minimum is in <111>
direction, not at k=0
Indirect Band Gap
323d27
Trends in III-V and II-VI Compounds
Band
Band
Gap
Gap
(
(
eV
eV
)
)
Lattice Constant (A)
Lattice Constant (A)
SiGe
SiGe
Alloys
Alloys
Larger atoms, weaker bonds, smaller U, smaller E
g
, higher , more costly!
323e1
Schrodinger Equation
For quantitative understanding, need to develop equation
to calculate energy of wavefunctions (electrons) in
different environments
Newtons Laws for wave-particles
Equation was postulated
New equation needs:
Duality
Energy conservation
Analogous to operations with E-M waves
(superposition)
Solutions must be waves
h E
p
h
;
U
m
p
E +
2
2

i
i i
c
( ) t kx i
Ae

323e2
Schrodinger Equation
h E
p
h
;
U
m
p
E +
2
2

i
i i
c
( ) t kx i
Ae

( )
( )

!
!
+

+
t x U
m
k
k
h t x U
m
h
,
2
2 ;
2
,
2
2 2
2
2
Equation must be linear in
: no powers of , in
every term
2
2
2
k
x
t

( )
t
t x U
x

+
,
2
2
( ) t kx i
Ae

try
!
!
i
m

;
2
2
( )
( ) ( )
( )
t
t x
i t x t x U
x
t x
m

+
,
, ,
,
2
2
2 2
!
!
( ) ( ) ( )
( )
t
t r
i t r t r U t r
m

+
,
, , ,
2
2
2
!
!
kinetic potential total
323e3
Time-Independent S.E.
( )
( ) ( )
( ) ( ) ( ) ( )
U
m
H
operator
x E x x U x
t x e Ae Ae
t i ikx t kx i
+
+

2
2
2
2
2
implied an is H where
E H
abreviated be can T.I.S.E. or S.E. general
2m
-
S.E. into insert
!
!

H is the Hamiltonian, the energy operator
323e4
General Representation of Electron Wave
Functions in Periodic Lattice
Often called Bloch Electrons or Bloch Wavefunctions
E
k
/a
0
Away from Bragg condition, ~free electron
m
k
E e
m
U
m
H
ikx
o
2
; ;
2 2
2 2
2
2
2
2
! ! !

Near Bragg condition, ~standing wave electron
( ) ( ) ( ) x U E x u Gx Gx x U U
m
H
o o o
+
; sin or cos ;
2
2
2
!
Since both are solutions to the S.E., general wave is
( ) x u e
ikx
lattice free

termed Bloch functions
323e5
Block Theorem
If the potential on the lattice is U(r) (and therefore
U(r+R)=U(r)), then the wave solutions to the S.E. are a
plane wave with a periodic part u(r) that has the periodicity
of the lattice
( ) ( )
( ) ( ) R r u r u
r u e r
r ik
+

Note the probability density spatial info is in u(r):
( ) ) (
*
2
*
r u r u
o

An equivalent way of writing the Bloch theorem in terms of :
( )
( )
( )
( )
( )
( ) ( ) r e R r
e
r
e R r u e R r
R ik
r ik
R r ik R r ik
+
+ +
+ +
323e6
Implications of Bloch Electron Waves
Bloch electrons are not free electrons
( ) ( ) ( ) [ ]
r ik r ik
e r u i k r u e i i p
p
k

! ! ! !
!
general in
generally not zero
Velocity: no degradation, no time dependence, =group velocity of
wave packet
k ! =crystal momentum
( ) ( ) ( ))
1
(
1
k E
dk
d
v k E k v
k k k

! !
323e7
Energy Bands!, and E invariant to shifts in k by G
( )
( )
( ) ( ) r e r e R r
G k k
R ik R G k i
+
+
+ ' '
'
invariant to shift in G
( ) ( ) ( )
( ) ( ) ( )
( ) ( )
( ) ( ) ( ) ( ) ( ) ( ) ( ) R r r E r e r E r e H R r H
r e R r
R r R r E R r H
r r E r H
ikr ikr
ikr
+ +
+
+ + +

(r) can have E(r), E(r+R),-->Energy Bands
k
k k+G
E
Implies a maximum in E even
though k continues to increase
323e8
Since E is invariant to k shifted by G (same as diffraction argument):
E
k
x
/a -/a 0 2/a 2/a
G
E(k)
E(k+G) E(k-G)
E(k)+E(G
y
and/or G
z
)
1-D
( )
m
G m k
E
x x x
2
2
2
t
!
3-D
( ) ( ) ( ) [ ]
m
G m k G m k G m k
E
z z z y y y x x x
2
2 2 2
2
+ + + + +
!
Note: key difference in 1-D to 3-D in
graph on left is that we are looking
along k
x
, but in 3-D the value can
change due to G
y
and/or G
z
323e9
General Derivation of NFE
We know that the wavefunctions will look like plane waves
We know that lattice potential from the lattice ions have the periodicity
of real space and G in k-space
( )
iqr
q
q
e c r

( )
iGr
G
G
e U r U

E H
iqr
q
q
e c q
m m
2
2
2
2
2 2

! !
,
_
,
_

q
iqr
q
G
iGr
G
e c e U U
turn the crank!
0
2
'
'
'
2 2
+
,
_
G q
G
G q
c U c E
m
q !
323e10
Proof of Bloch Theorem from General
Derivation
For a given k, central equation shows that the coefficients c
q
that
matter are those that are a multiple of G from k
( )

G
r G k i
G k
iqr
q
q k
e c e c
In our diffraction example, k=/a, and c
q
and c
q-G
were 1 at the diffraction condition,
r
a
i r
a
i
a
k
e e

+
Continuing,
( )
( )
iGr
G
G k
ikr
G
iGr
G k
ikr
k
e c r u
r u e e c e

,
_

Bloch waves are indeed the general solution
323e11
Central Equation near the Bragg Plane
E
k
x
/a 0
2/a
G
1/2 G
E(q)
E(q-G)
Evaluate at q=+or -1/2 G
Assume since U(r) goes as 1/r,
that only nearest two potentials are
relevant
For q=1/2 G, For q=-1/2 G,
0
2
1
2
2
1
2
1
2
2
+
,
_
,
_
G
G
G
c U c E G
m
!
reciprocal lattice points
0
2
1
2
2
1
2
1
2
2
+
,
_
,
_

G
G
G
c U c E G
m
!
G=G G=-G
E
G/2
E
-G/2
( )
( )
G G
G G G
G G G G
U U
E E c U
c U c E E
+
+
Also,
0
0
2 / 2 / 1
2 / 1 2 / 1 2 /
323e12
Central Equation near the Bragg Plane
( )
( )
0
2 /
2 /
E E U
U E E
G G
G G
( )( ) 0
2
2 / 2 /

G G G
U E E E E
( )
2
2
2 / 2 / 2 / 2 /
2 2
G
G G G G
U
E E E E
E +
1
]
1

t
+

At the Bragg plane, E
G/2
=E
-G/2
G G G G
U E U E E t t
2 /
2
2 /
E
/a 0
U
G
U
G
E
G/2
Plugging back into one of the equations,
2 / 2 / G G
c c

t
( )
2 / 2 /
) 2 / (
2 / 2 /
) 2 / (
2 / 2 /
;
;
G G
r G i
G G
r G q i
q G q
r G i
G G
iqr
q q
e c e c
e c e c
t
t

a
&
b
323e13
Central Equation just off the Bragg Plane
E
/a 0
2/a
1/2 G
E(q)
E(q-G)
q
E
( )
( )
U
E
U
E E
E
U
E
E E
E
U
E E E E
E
G q q
G q q
G q q G q q
2
2
2
2
8
1
2
4
1
1
2
4 2
t t
+
,
_
+ t
+
t
+

1 <<
U
E
( ) ( ) ( )
( )
( ) ( )
( )

,
_
+
+
,
_
,
_
8 2 2
2
2
2
2
2
2
2
2
2
2
2
2
2
G
q
m
q E q E
q
m
G
q E
m
G
q
m
G
q
q E q E q E
G q q
G q q
!
!
! !
( )
( )
( )
( )
o
U q
m
E
U
q
m
G
U
m
G
q
m
E
+
+
,
_
t t +
2
2
2
2
2
2 2
2
2
2
1
2
8
1
16 2
!
!
! !
m
G
U U
mU
G
o
16
;
16
2 2 2 2
! !
+ t
Let m*=m/(1+)
( )
* 2
2
2
m
q
U E
o
t
!
Can make band edges near band
gaps free-electron-like
323e14
Far from the Bragg condition, there is little effect of the periodic ion potential
In the language of the central equation, all the c
q-G
are small except for one of
them
Central Equation Far from Bragg Condition
2
2
2
2
2
2
2
2
0
2
q
m
E
q
m
E c U E c c q
m
eff o q q
!
! !

+
The electrons are free electrons if the wavevector is far from a
wavevector value that diffracts strongly
323e15
Chemistry Approach
Lets build the solid atom by atom!
For many atoms, arrive at same band picture that we have achieved
Important since systems with small numbers of atoms need to be treated
differently
understand matter from a few atoms to the infinite solid
Recall that we have always been dealing with 1 e- in a periodic potential
-->easier problem for S.E.
We will eventually run into the many-bodied problem
-->many electrons, many atoms
We will make approximations to continue, and arrive at similar results to the NFE
chain chain chain
molecule molecule molecule
atomic atomic atomic
E H
E H
E H

( )
solid ions s e valence solid
E E H +
'
323e16
Review of H atom
S.E. in spherical co-ordinates
Separation of variables; separation constants are basically quantum numbers; 3
for 3 dimensions
Creates atom structure for periodic table
+
z
y
x
Atomic number
(atomic charge)=Z
e-
r
M m
r
Ze
z y x
Ze
U
1 1
1
2
2 2 2
2
+
+ +
Problem easier if we choose U(r)

Reduced mass keeps problem a single body problem
E r U
m
+
) (
2
2
!
Where the del is in spherical co-ordinates:
,
_
,
_

sin
sin
1
sin
1 1
2 2
2
2 2
2
2
2
r r r
r
r r
323e17
Review of H atom
( ) ( ) ( )

E H
r R

Do separation of variables; each variable gives a separation constant
separation yields m
l
gives
r gives n
"
After solving, the energy E is a function of n
( )
2
2 2
2
4 2
6 . 13
2 4
n
eV
n
e Z
E
o
m
l
and in and give the shape
(i.e. orbital shape)
"
The relationship between the separation constants (and therefore the quantum numbers are:)
n=1,2,3,
=0,1,2,,n-1
m
l
=- , - +1,,0,, -1,
(m
s
=+or - 1/2)
"
"
"
"
0
-13.6eV
U(r)
323e18
Relationship between Quantum Numbers
s
p
d
Origin of the periodic table
s
s
p
323e19
Hydrogen Wavefunctions
323e20
Physical Nature of Orbitals (
2
)
( )
l
m l r P , ,
* 2

Probability density
Radial Probability Density =R*R4r
2
dr
Look at only probability of finding electron in
a shell of thickness dr at r from the nucleus
can be negative; cross over is 0 in
2
Compare to Bohr
( )
( )
1
]
1
1
]
1
+
+

2
2
0
2
0
1
1
2
1
1
4 * , ,
n
l l
Z
a n
r
dr r R rR dr m l r rP r
o
l

A
e
a
Z
a n
r
o
o
Bohr
52 . 0 ;
2
2 2

!
Bohr radius
r
1s
2s
2p
3s
3p
3d
323e21
and functions give shape
Physical Nature of Orbitals (
2
)
l=3 (f shell)
323e22
Multielectron Atoms
Recall previous wavefunctions were for single electron in different
possible orbits
What about a real atom with mulitple electrons?
Screening, so E=-13.6Z
2
/n
2
doesnt work well always
empirically: Z=Z
eff
Can solve exactly by putting other electrons in U through an electron
density,
Pick a starting and
H
Determine c
q
, E
New c
q
, define
new , :
check for
minimum E
323e23
What about building up our solid:
multiatoms?
Simplest case: H
2
+, hydrogen molecular ion (1e-, 2 protons)
+
+
R
r
1
r
2
e-
ions repel
electrons attract ions together
when in between ions (bond)
1
]
1
+
R r r
e U
molecule
1 1 1
2 1
2
Born-Oppenheimer Approximation
!protons fixed (R const.): get energy of electron
!determine proton-proton energy separately and superimpose
,
_

2 1
2
1 1
r r
e U
el
Solve H
mol
=E
mol
( )
R
e
R E E
el mol
2
+
323e24
Multiatoms:H
2
+
Assume that the molecular wavefunction for the electron is a linear
combination of the atomic wavefunctions (LCAO)
o o
a
r
o
a
r
o
e
a
e
a
s
c c
2 1
3
2
3
1
2 2 1 1
1
;
1
: 1

+

( ) ( )
( )( )
+ +
+ +

dV c c c c
dV c c H c c H
dV
dV H
E
E H
E H
2 2 1 1
*
2 2
*
1 1
2 2 1 1
*
2 2
*
1 1
*
*
*
*
* *

323e25
Multiatoms:H
2
+
We will get three kinds of integrals that we will abbreviate:
Coulomb Integrals
Bond Integrals
Overlap Integrals
dV H dV H H
2 2 22 1 1 11
H ;

dV H H
2 1 12
dV S
2 1 12

Assume
functions) real (i.e. ;
2
*
2 1
*
1

and ) normalized are (they 1
*
dV
i i

12 2 1
2
2
2
1
12 2 1 22
2
2 11
2
1
2
2
S c c c c
H c c H c H c
E
+ +
+ +
Apply variational method: pick s to get

the lowest E; minimize E with respect to
c
1
and c
2
323e26
Multiatoms:H
2
+
( ) ( )
( ) ( )
( ) ( ) 0
integrals atomic atoms, identical For
0
0
2
12 12 2 1
2
2 1
22 11
22 2 12 12 1
2
12 12 2 11 1
1

+
ES H c c E H c c
H H H
E H c ES H c
c
E
ES H c E H c
c
E
12
12 12
12
12 12
1
1
S
HS H
H E
S
HS H
H E
B
A
+
E
A
E
B
H H
anitbonding
bonding
323e27
Multiatoms:H
2
+
Use Es in original equations:
( )
( )
2 1 1
2 1 1
2 1

+
t
c
c
c c
A
B
Note: 2 atoms, 2 levels
Bonding
Anti-Bonding
2
323e28
Multiatoms:H
2
+
R
E
Nuclear repulsion
Electron energy
R
e
2
R
o
( )
( )
o
o
R R K F
R R
K
E

2
2
Atoms connected by springs
R
E
Nuclear repulsion
R
e
2
Electron energy
Bonding
Anti-Bonding
323f1
LCAO: Adding more atoms
Assume H
2
solution similar to H
2
+
Lets use Li as the atom to build our solid
Molecular orbital notation
( )
( )
2 1 1
2 1
1
*

+ =
=
c
c
1*
1
1s 1s
anitbonding
bonding
+ -
+
Representation of
2
Sign of wavefunction
323f2
Li: 1s
2
2s
1
Look at Li
2
Li
2
2*
2
2s 2s
1*
1
1s 1s
E
+ -
+
1s are buried inside above pictures and more
atomic-like (experience less delocalization
since they are not valence electrons)
323f3
Conservation of states
more nodes for higher energy molecular wavefunctions
4 14 3 13 2 12 1 11 1
4 24 3 23 2 22 1 21 2
4 34 3 33 2 32 1 31 3
4 44 3 43 2 42 1 41 4

c c c c
c c c c
c c c c
c c c c
+ + + =
+ =
+ =
+ =
Li
4
nodes
0
1
2
3 + - + -
+ + -
-
+
+
2s 2s
j=1
j=2
j=3
j=4
4 states, 4 valence e- in extended orbital
323f4
Generalize to N Li atoms
+
+ =
+ +
= =

=
1
cos 2 ;
1
sin
1
2
;
1
N
j
E
N
ji
N
c c
j ji i
N
i
ji j
orbital index
atom index
bond integral
known as the Debye-Huckel model
examples:
N=2
N=4
N=large
-
+
-0.6
+0.6
-1.6
+1.6
j=1
j=4
E
F
-2
+2
323f5
Generaliztion of Debye-Huckel for large N
Same as tight-binding model
a
N
L=Na
Index i=Z/a
Z
N+1~N=L/a
L
jz
N
c
j
sin
2
L
k N j

,
( )
( ) ka E
kz
N
c
L
j
k
cos 2
sin
2
~

+ =
=
E
k
2
2
/a
-/a
ka
a
k
E
v
g
sin
2 1
! !
=
323f6
Bonding of other elements across periodic table
Li
N
: all spherical shells
across periodic table (1s
2
2s
2
2p
x
), encounter p-orbitals
leads to -bonds as well as -bonds
+ -
+ -
+ =
-
+
+
2p
z
2p
z
3
+ - + - +
=
+- +-
3*
+
-
+
+
-
=
-
+
2p
y
2p
y

y
+
-
+
+
-
=
+- + -
y
*
More wiggles,
higher energy
323f7
Example: Oxygen (O
2
)
Bonding of other elements across periodic table
1*
1
1s 1s
2*
2
2s 2s
3
2p 2p
3
x
,
y
x
,
y
From Hunds rules:
put 1e- in each orbital
first (maximize spin)
O
2
is paramagnetic
O has eight electrons,
thus O
2
distributes 16
electrons over 10
molecular levels
For O
2
and F
2
, the
3 is lower than the
-orbitals
For Li
2
to N
2
, the -
orbitals are actually
lower than the 3
323f8
Visualization of orbitals
Example: 4 Carbon chain, unsaturated (C
4
H
6
)
C
C
C
C
H
H
H
H
H
H
bonds
bonds
bonds extend over entire chain
E
Nodes
+- +-
+ - + -
+
-
+
-
-
+
+ -
- +
+
-
3
2
1
0
4
=c
1
1
-c
2
2
+c
3
3
-c
4
3
=c
1
1
-c
2
2
-c
3
3
+c
4
2
=c
1
1
+c
2
2
-c
3
3
-c
4
1
=c
1
1
+c
2
2
+c
3
3
+c
4
4
-1.6
-0.6
+0.6
+1.6
electrons: each carbon
contributes 1 e- to the extended
E=+2coska
may change from
to , but principle the
same
323f9
Bonding of atoms with different levels/orbitals
Example: LiF
*
F 2p
18.6 eV
5.4 eV
0
Li 2s
1 2
2 1 *
2 1
c c
c c
c c
F Li
>>
>>
+ =

+
-
+
Li 2s
F p
x
+
Zero overlap
+ - + +
=
+
-
bond
ionic
Li
F
323f10
Hybridization
Two ways to look at it
solutions to S.E. that minimize E are s that look like
combinations of s and p orbitals
orbital distorts to reach out and bond
Examples Hybrid
H H Be Linear, sp
H B
H
H
Planar, sp
2
H C
H
H
H
Tetrahedral, sp
3
+
+
2s
1s
+
H
H
Be
+
H
+
H
+ +
- -
sp hybridization
+
-
+
-
+
-
B
323f11
Bonding and Hybridization
Energy level spacing decreases as atoms are added
Energy is lowered as bonding distance decreases
All levels have E vs. R curves: as bonding distance decreases, ion core
repulsion eventually increases E
E
R
s
p
Debye-Huckel
hybridization
NFE picture,
semiconductors
323f12
Properties of non-free e-
Electrons near the diffraction condition are not
approximated as free
Their properties can still be viewed as free e- if an
effective mass m* is used
/a
/a
2
2
2
*
*
2 2
2
k
E
m
m
k
E
ec
ec
=
=
!
!
2
2
2
*
*
2 2
2
k
E
m
m
k
E
ev
ev
=
=
!
!
Note: These
electrons have
negative mass!
m
k
E
2
2 2
!
=
323f13
1-D Crystal Metals and Insulators
How do band gaps affect properties of materials?
Only electrons near E
F
participate in properties
If E
F
is in the middle of the band, free e- and metallic behavior
If E
F
is near the band gap, changes in materials properties may occur
Need to find out where E
F
is!
/a
/a
a
L L k
N
F
2 2
= =
Where k
F
=/a if we
want to see how many
electrons are in first
band
Note: L/a is the number of unit
cells in the 1-D crystal; therefore,
the number of electrons per unit
cell, which depends on valence
and the crystal structure,
determine where E
F
is with
respect to the band gap
E
F
with 2e- per unit cell
E
F
with 1e- per unit cell
323f14
2e- per unit cell: E
F
at band edge: 2 possibilities
Band gap >> kT: electrons at band max can not accept
energy from electric fields; no conduction, insulating
behavior
Band gap near kT: some thermal fluctuations large
enough to allow population of second band; carriers are
there, but less than for free e-, semimetal
1e- per unit cell: E
F
in middle of band: free e-, metallic
1-D Crystal Metals and Insulators
Note: crystal structure (number of atoms per primitive cell) and
valence (number of conduction electrons per atom), combined
with band gap size, determine the electronic properties
323f15
Higher Dimensions (2 and 3-D)
1-D: E(k
x
); 2-D: E(k
x
,k
y
); 3-D: E(k
x
,k
y
,k
z
)
/a
/a
1-D
First zone
0
Zone center
/a
/a
/a
/a
k
x
k
y
0
E
2-D
0 /a
/a
3-D
First zone
Zone center
Fermi Surface
323f16
Higher Dimensions: Visualizing the Fermi
Sphere and Bragg Plane Intersections
Use Ge band diagram to
demonstrate how to show
E
F
intersecting two
important directions
E
F
323f17
Bands and Zones
Examine 2-D simple cubic crystal, or a slice through a 3-D cubic
crystal
Bragg planes exist at bisection of every pair of reciprocal lattice points
As k
f
increases, E
f
increases and crosses Bragg planes; when crossing,
going to next band
323f18
Bands and Zones
1st band
Electron surface Hole surface
G
2nd band
Reduced zone Extended zone
323f19
Carrier Dynamics at Fermi Surfaces
Recall velocity is proportional to
Carriers have mass inversely proportional to curvature
Bulk electronic properties average over all surfaces
Example: Si
[100]
[010]
v
g
k
E
v
g
2
2
*
k
E
m
m
l
* m
t
*
In magnetic field, carriers move along the Fermi Surface
Can measure the Fermi Surface this way
v
g
from E-field
v total since F~vxB
323f20
Metals and Insulators
Covalent bonds, weak U seen by e-, with E
F
being in mid-band area: free e-, metallic
Covalent or slightly ionic bonds, weak U to
medium U, with E
F
near band edge
E
F
in or near kT of band edge: semimetal
E
F
in gap: semiconductor
More ionic bonds, large U, E
F
in very large
gap, insulator
323f21
Insulators
Very large band gaps=no conduction electrons at
reasonable temperatures
All electrons are bound
Optical properties of insulators are derived from
the electric field being able to temporarily move
electrons: polarization
We will return to the interaction of E-field with
bound electrons in Dielectrics Section
323f22
Semiconductors
Band gaps not large enough to prevent all
carriers from getting into next band: three
mechanisms
photon absorption
thermal
impurity (i.e. doping)
Carriers that make it to the next band are
like free carriers with new mass, m*
323f23
Semiconductors: Photon Absorption
When E
light
=h>E
g
, an electron can be promoted
from the valence band to the conduction band
E
c
near band gap
E
v
near band gap
E
k
E=h
Note: Most absorption near the band gap since the density of states is highest there
Creates a hole in the valence band
323f24
Holes and Electrons
Instead of tracking electrons in valence band, more convenient to track vacancies of
electrons, or holes
Also removes problem with negative electron mass: since hole energy increases as holes
sink, the mass of the hole is positive as long as it has a positive charge
Both carriers at the band edge can be thought of as classical free carriers like the Drude
model had, as we shall see
Decreasing electron energy
Decreasing electron energy
Decreasing hole energy
323f25
Conductivity of Semiconductors
Need to include both electrons and holes in the conductivity expression
*
2
*
2
h
h
e
e
h e
m
pe
m
ne
pe ne

+ = + =
p is analogous to n for holes, and so are and m*
Note that in both photon stimulated promotion as well as thermal
promotion, an equal number of holes and electrons are produced, i.e. n=p
323f26
Thermal Promotion of Carriers
We have already developed how electrons are promoted in energy with T:
Fermi-Dirac distribution
J ust need to fold this into picture with a band-gap
E
F
f
(
E
)
1
E
g(E)
g
c
(E)~E
1/2
in 3-D
g
v
(E)
Despite gap, at non-zero
temperatures, there is some
possibility of carriers getting
into the conduction band (and
creating holes in the valence
band)
E
g
323f27
Density of Thermally Promoted of Carriers
=
c
E
dE E g E f n ) ( ) (
Density of electron states per volume per dE
Fraction of states occupied at a particular temperature
Number of electrons per
volume in conduction
band
( ) dE e E E e
m
n
T k
E
E
g
T k
E
e b
g
b
F

=
2
1
2
3
2
*
2
2
2
1
!
Since
2
0
2
1
dx e x
x
, then
T k
E
T k
E
b e
b
g
b
F
e e
T k m
n
=
2
3
2
*
2
2
!
N
C
( )
( )
T k E E e
e
E f
b F
T k
E E
T k
E E
b
F
b
F
>>
+
=
) ( when
1
1
) (
T k
E E
C
b
g F
e N n
=
( )2
1 2
3
2
*
2
2
2
1
) (
g
e
c
E E
m
E g
=
!
323f28
A similar derivation can be done for holes, except the density of states
for holes is used
Even though we know that n=p, we will derive a separate expression
anyway since it will be useful in deriving other expressions
Density of Thermally Promoted of Carriers
( )2
1 2
3
2
*
2
2
2
1
) ( E
m
E g
h
v

=
!
) ( 1 where , ) ( ) (
0
E f f dE E g E f p
h v h
= =

T k
E
b h
b
F
e
T k m
p
=
2
3
2
*
2
2
!
T k
E
v
b
F
e N p
=
323f29
Thermal Promotion
Because electron-hole pairs are generated, the Fermi level is
approximately in the middle of the band gap
The law of mass action describes the electron and hole populations,
since the total number of electron states is fixed in the system
+ = =
*
*
ln
4
3
2
gives
e
h
b
g
F
m
m
T k
E
E p n
Since m
e
* and m
h
* are close and in the ln term, the
Fermi level sits about in the center of the band gap
( )
T k
E
v e
b
i
b
g
e m m
T k
n n p
2
4
3
* *
2
3
2
2
2 or
= =
!
323f30
Law of Mass Action for Carrier Promotion
( )
T k
E
h e
b
i
b
g
e m m
T k
np n
= =
2
3
* *
3
2
2
2
4
!
T k
E
V C i
b
g
e N N n
=
2
;
Note that re-arranging the right equation leads to an expression similar to a
chemical reaction, where E
g
is the barrier
N
C
N
V
is the density of the reactants, and n and p are the products
[ ] [ ] [ ] p n N N
g
E
V C
+
[ ][ ]
[ ]
[ ]
[ ]
V C
i
T k
E
V C
N N
n
e
N N
p n
b
g
2
= =
Thus, a method of changing the electron or hole population without increasing the population of the
other carrier will lead to a dominant carrier type in the material
Photon absorption and thermal excitation produce only pairs of carriers: intrinsic semiconductor
Increasing one carrier concentration without the other can only be achieved with impurities, also called
doping: extrinsic semiconductors
323f31
Intrinsic Semiconductors
Conductivity at any temperature is determined mostly by the size of the band gap
All intrinsic semiconductors are insulating at very low temperatures
*
2
*
2
h
h
e
e
h e
m
pe
m
ne
pe ne

+ = + =
Recall:
( )
T k
E
h e i
b
g
e e n
2
int
+ =
For Si, Eg=1.1eV, and let
e
and
h
be approximately equal at 1000cm
2
/V-sec (very good Si!)
~10
10
cm
-3
*1.602x10
-19
*1000cm
2
/V-sec=1.6x10
-6
S/m, or a resistivity of about 10
6
ohm-m max
One important note: No matter how pure Si is, the material will always be a poor
insulator at room T
As more analog wireless applications are brought on Si, this is a major issue for
system-on-chip applications
E-M waves lose strength since e- are responding to wave: loss and low Q
resonant circuits
This can be a
measurement
for E
g
323f32
Extrinsic Semiconductors
Adding correct impurities can lead to controlled domination of one carrier type
n-type is dominated by electrons
p-type if dominated by holes
Adding other impurities can degrade electrical properties
Impurities with close electronic
structure to host
Impurities with very different
electronic structure to host
isoelectronic
hydrogenic
x
x
x
x
Ge
Si
P
x
x
x
x
x
x
x
x
Au
Si
deep level
E
c
E
v
E
c
E
v
E
c
E
v
E
D
E
DEEP
-
+
323f33
Hydrogenic Model
For hydrogenic donors or acceptors, we can think of the electron or hole,
respectively, as an orbiting electron around a net fixed charge
We can estimate the energy to free the carrier into the conduction band or
valence band by using a modified expression for the energy of an electron in
the H atom
2 2 2 2
4
6 . 13
8 n n h
me
E
o
n
= =
2
*
2 2 2 2 2
4 *
2 2 2
4
1 6 . 13 1
8 8
2
2

m
m
n n h
e m
n h
me
E
r o
e
e
o
n
r
= =
=
(in eV)
Thus, for the ground state n=1, we can see already that since is on the order
of 10, the binding energy of the carrier to the center is <0.1eV
Expect that many carriers are then thermalize at room T
Experiment:
B acceptor in Si: .046 eV
P donor in Si: 0.044 eV
As donor in Si: 0.049
323f34
The Power of Doping
Can make the material n-type or p-type: Hydrogenic impurities are nearly fully
ionized at room temperature
n
i
2
for Si: ~10
20
cm
-3
Add 10
18
cm
-3
donors to Si: n~N
d
n~10
18
cm
-3
, p~10
2
(n
i
2
/N
d
)
Can change conductivity drastically
1 part in 10
7
impurity in a crystal (~10
22
cm
-3
atom density)
10
22
*1/10
7
=10
15
dopant atoms per cm
-3
n~10
15
, p~10
20
/10
15
~10
5
/
i
~(p+n)/2n
i
~n/2n
i
~10
5
!
Impurities at the ppm level drastically change the conductivity
(5-6 orders of magnitude)
323f35
Expected Temperature Behavior of Doped
Material (Example:n-type)
3 regimes
ln(n)
1/T
Intrinsic
Extrinsic
Freeze-out
E
g
/2k
b
E
b
/k
b
323g1
Doping Statistics and Law of Mass Action
If electron population rises, hole concentration decreases (and reverse)
Dopant dominates conductivity, assuming dopant concentration much greater
than intrinsic
( )
= <<
=
=
=
=
=
=
=
n
n
n
n
n n n
n n n
n p
n np
p n
p n
i
i
i
i
i
, 1
4 1
2 2
0
extrinsic for 0
intrinsic for 0
2
2 2
2
2
323g2
Contrasting Semiconductor and Metal
Conductivity
Semiconductors
changes in n(T) can dominate over
as T increases, conductivity increases
Metals
n fixed
as T increases, decreases, and conductivity decreases

=
ne
m
2
323g3
General Interpretation of
Metals and majority carriers in semiconductors
is the scattering length
Phonons (lattice vibrations), impurities, dislocations,
and grain boundaries can decrease
...
1 1 1 1 1
+ + + + =
gb disl impur phonon

1
1
=
= =
i i i
i i th th
i
i
N l
N v v
l
where is the cross-section of the scatterer, N is the

number of scatterers per volume, and l is the average
distance before collisions
The mechanism that will tend to dominate the scattering will be the mechanism with the
shortest l (most numerous), unless there is a large difference in the cross-sections
Example: Si transistor,
phonon
dominates even though
impur
gets worse with scaling
323g4
Limiting Scattering Mechanism
As temperature is decreased, phonon scattering ceases to be main scattering
mechanism
Low T can be used to determine ultimate material quality
Expected dependence in metals: ~T
T
Phonon-limited
defect-limited
T
intrinsic
extrinsic
323g5
Estimate of T dependence of conductivity
~l for metals
~l/v
th
for semiconductors
First need to estimate l=1/N
2
1
x
N
l
ion
ion ion
ph

=
x=0
+

+

=
dx
dx x
x
*
2 *
2
Use for harmonic oscillator, get:
1
2
= =
kT
e
E x k
!
!
Average energy of harmonic oscillator
323g6
Estimate of T dependence of conductivity
1
1
2
=
=
= =
T
kT
e
k
E
k
e
E x k
!
!
!
Therefore, <x
2
>is proportional to T if T
large compared to :
T N v
x N v
v
l
T
x
l
T x
T
e
ion F
ion F
F
cond
T
1 1
1 1 1
1
2
2
2
= =

+
For a metal:
For a semiconductor, remember that the carriers at the band edges are classical-like:
2
3
2
1
*
1
3

= = T
T
T
m
kT
l
v
l
th
2
3
*
= T
m
e
323g7
Example: Electron Mobility in Ge
~T
-3/2
if phonon dominated
(T
-1/2
from v
th
, T
-1
from x-section )
At higher doping, the
ionized donors are the
dominate scattering
mechanism
323g8
Other Interpretation of
Minority carriers in semiconductors
can think of as the time to recombination: recombination time
does not affect Drude model in any way
E
c
E
v
, l
Imagine p-type material, so there are many more holes than electrons
holes=majority carrier
electrons=minority carrier
Recombination event: electron disappears
x
E
is referred to in this context as the minority carrier lifetime
323g9
Recombination and Generation (E
c
to E
v
)
Generation
intrinsic: photon-induced or thermally induced, G=#carriers/vol.-sec
extrinsic:deep levels due to traps
G
o
is the equilibrium generation rate
Recombination
intrinsic: across band gap, R=#carriers/vol.-sec
extrinsic: deep levels due to traps
R
o
is the equilibrium recombination rate, which is balanced by G
o
Non-equilibrium intrinsic recombination
n-type material
p-type material
o
o
h
R
p p
R =
=
h
;
Non-equilibrium extrinsic recombination

Where p
o
is the equilibrium minority carrier concentration
Where n
o
is the equilibrium minority carrier concentration
o
o
e
R
n n
R =
=
h
;
t th h
h
N v
1
=
h
p
R
=
e
n
R
=
t th e
e
N v
1
=
Where
h
is the capture cross section for
holes and N
t
is the concentration of
recombination centers
Equilibrium:
R=G
therm
323g10
Proof that Minority Carrier Dominates
Recombination (non-equilibrium)
Equilibrium recombination:
o o
o
o o o
p n
R
B
p Bn R
=
= = sec - g/vol recombinin carriers number
Non-Equilibrium recombination:
( )

+ = + + + = =
+ =
+ =
o o
o o o o o
o o
o
o
o
p
p
n
n
R p n p n n p p n
p n
R
Bnp R
p p p
n n n
1
Assume low-level injection, n, p <<n
o
,p
o
n-type, n/n
o
<<1, R=p/
h
,
h
=p
o
/R
o
p-type, p/p
o
<<1, R=n/
e
,
e
=n
o
/R
o
323g11
Other Recombination Pathways
Deep levels in semiconductors act as carrier traps and/or enhanced
recombination sites
E
c
E
v
Recombination through deep level
E
x
E
deep
Barrier to capture carrier is E
g
/2
Since the probability of the carrier transition is ~e
-E/kT
, trapping a carrier with a deep state is
very probable
A trapped carrier can then help attract another carrier, increasing recombination through the
deep state
deep rinsic

1 1 1
int
+ =
323g12
Trap-dominated Recombination
e.g. n-type material
t th h
h
N v
1
=
p N v
p
R
t th h
h
=
323g13
Effect of Traps (Defects) on Bands
Trapping (Fermi level in defect) creates depleted regions around defect
+ =
C
d
b g F
N
N
T k E E ln
E
F
position in semiconductor away from
traps in n-type material
E
F
pulled to mid-gap in defect/trap area
E
c
E
F
E
v
E
F
pulled to trap level in defect
E
trap
Depleted regions; internal electric field
E
donor
323h1
Response of Semiconductors to Stimulus
Can apply E-field, light
light in, G increase
T increase, G increase
Defects increase, R increase and G increase in E-field
Stimulus removed: return to equilibrium
Example: GaAs surface states
E
c
E
F
E
v
Surface: Fermi level
pinned to defect
level
Without applied voltage or
concentration gradient, E
F
is
flat
x
V
x
n
and
determine properties
323h2
Key Processes: Drift and Diffusion
Electric Field: Drift
Concentration Gradient: Diffusion
E en J A env I
E ep J A epv I
e e d e
h h d h
= =
= =
;
;
n eD J
p eD J
e e
h h
=
=
n eD E en J
p eD E ep J
e e eTOT
h h hTOT
+ =
=
323h3
Continuity Equations
For a given volume, change in carrier concentration in time is related to J
G R
TOT
G R
TOT
G R diff drift
t
p
t
p
J
e t
p
t
n
t
n
J
e t
n
t
n
t
n
t
n
t
n
t
n
1
1
1-D,
G Bnp
x
p
D
x
E
p
t
p
G Bnp
x
n
D
x
E
n
t
n
h h
e e
+
2
2
2
2
323h4
Minority Carrier Diffusion Equations
In many devices, carrier action outside E-field controls properties-->minority
carrier devices
Only diffusion in these regions
e
h
h
e
n
Bnp
p
Bnp
G Bnp
x
p
D
t
p
G Bnp
x
n
D
t
n
=
+
type, - p in
type, - n in
2
2
2
2
Assuming low-level injection,
t
n
t
n
t
n
t
n
o
therefore
material type - n in
material type - p in
2
2
2
2
G
p
x
p
D
t
p
G
n
x
n
D
t
n
h
h
e
e
+
323h5
Use of Minority Carrier Diffusion Equations
Example: Light shining on a surface of a semiconductor
h
G at x=0 (assume infinite
absorption coefficient to simplify
example)
G
p
x
p
D
t
p
h
h
+
2
2
n-type
p(x)?
0
Steady state solution
=0 in bulk
x
h h
h h
ax ax
ax ax
ax ax
h h
D
a
D
Be Ae
Be a Ae a
Be Ae p
D
p
x
p
1
2 2
2
2
=
+
= +
+ =
try
Now use boundary conditions of the problem:
h h
D
x
Be p
A
p x
=
=
= =
0
0 , @
Units of length:
minority carrier
diffusion length, L
h
h
L
x
h
h
h
e G p
G B
G p x
=
=
= =
, 0 @
p
x
G
h
x
p
eD J
h h

=
323h6
The p-n J unction (The Diode)
Derivation of ideal diode equation covered in the SMA Device Course
Development here introduces the fundamental materials concepts
p-type material in equilibrium n-type material in equilibrium
p~N
a
n~N
d
n~n
i
2
/N
a
p~n
i
2
/N
d
+ =
C
d
b g F
N
N
T k E E ln
=
V
a
b F
N
N
T k E ln
E
c
E
c
E
F
E
v
E
F
E
v
What happens when you join these together?
323h7
J oining p and n
E
c
E
F
E
v
p
n
Carriers flow under driving force of diffusion until E
F
is flat
-
- -
-
+
+
+
+
Holes diffuse
Electrons diffuse
323h8
-
- -
-
+
+
+
+
Holes diffuse
Electrons diffuse
+
+
+
+
-
- -
-
-
- -
-
+
+
+
+
-
- -
-
+
+
+
+
An electric field forms due to the fixed nuclei in the lattice from the dopants
Therefore, a steady-state balance is achieved where diffusive
flux of the carriers is balanced by the drift flux
E
323h9
-
- -
-
+
+
+
+
-
- -
-
+
+
+
+
W: depletion or space charge width
Metallurgical junction
E
V
V
bi
dx
x
E
) (
dx x E V
= ) (
p a n d
x N x N =
x
p
x
n
) (
2
a d a
d bi o r
p
N N N
N
e
V
x
+
=

) (
2
a d d
a bi o r
n
N N N
N
e
V
x
+
=

a d
d a bi o r
N N
N N
e
V
W
+
=
2
323h10
What is the built-in voltage V
bi
?
E
c
E
F
E
v
p
n
eV
bi
=E
Fn
-E
Fp
=
d V
i
b
V
n
b Fn
N N
n
T k
N
p
T k E
2
ln ln
=
V
a
b
V
b Fp
N
N
T k
N
p
T k E ln ln
=
2
ln
i
d a b
bi
n
N N
e
T k
V
We can also re-write these to show that eV
bi
is the barrier to minority carrier injection:
T k
eV
n p
b
bi
e n n
=
T k
eV
p n
b
bi
e p p
=
n
n
n
p
p
n
p
p
eV
bi
eV
bi
323h11
Qualitative Effect of Bias
Applying a potential to the ends of a diode does NOT increase current through
drift
The applied voltage upsets the steady-state balance between drift and
diffusion, which can unleash the flow of diffusion current
Minority carrier device
E
c
E
F
E
v
n
n
n
p
p
n
p
p
eV
bi
eV
bi
T k
V V e
n p
b
a bi
e n n
) (
=
T k
V V e
p n
b
a bi
e p p
) (
=
+eV
a
-eV
a
323h12
Forward bias (+to p, - to n) decreases depletion region, increases diffusion
current exponentially
Reverse bias (- to p, +to n) increases depletion region, and no current flows
ideally
E
c
E
F
E
v
n
n
n
p
p
n
p
p
eV
bi
-e|V
a
|
Qualitative Effect of Bias
E
c
E
F
E
v
n
n
n
p
p
n
p
p
eV
bi
+e|V
a
|
eV
bi
-e|V
a
|
eV
bi
+e|V
a
|
Forward Bias Reverse Bias
+
-
V
a
+ = 1 1
2 2
T k
qV
o
T k
qV
d
i
h
h
a
i
e
e
b
a
b
a
e J e
N
n
L
D
N
n
L
D
q J
q
T k D
b
i
i
=
i i i
D L =
V
I
Linear,
Ohmic
Rectification,
Non-linear, Non-Ohmic
V=IR
V=f(I)
Solve minority
carrier diffusion
equations on each
side and determine
J at depletion edge
323h13
Devices
Solar Cell/Detector
LED/Laser
E
c
E
F
E
v
Reverse Bias/Zero Bias
J
edrift
J
hdrift
E
c
E
F
E
v
J
ediff
J
hdiff
Laser
population inversion
reflectors for cavity
323h14
Transistors
Bipolar (npn)
E
c
E
F
E
v
emitter
base
collector
J
diff
J
drift
Barrier, controlled by V
EB
V
EB
V
BC
base
emitter
collector
323h15
Transistors
FET
n n p
x
gate
drain source
x=metal is a MESFET
x=metal/poly Si/oxide is a MOSFET
CMOS
323h16
Other means to create internal potentials:
Heterojunctions
Different semiconductor materials have different band gaps and electron
affinity/work functions
Internal fields from doping p-n must be superimposed on these effects:
Poisson Solver (dE/dx=V=/)
E
F
Vacuum level
1
2
E
g1
E
g2
Thin films
S
u
b
s
t
r
a
t
e
Potential barriers for holes
and electrons can be created
inside the material
323h17
Quantum Wells
E
C
E
V
L
n=1
n=2
n=3
h
If we approximate well as having infinite potential boundaries:
L
n
k

= for standing waves in the potential well
2 *
2 2
*
2 2
8 2 L m
n h
m
k
E = =
!
We can modify electronic
transitions through quantum wells
323h18
Strain and the Band Alignment in
GeSi/Si
GeSi strained to Si substrates
GeSi strained to Si substrates
Si strained to Relaxed GeSi/Si
Si strained to Relaxed GeSi/Si
Advantages of Relaxed Structure Advantages of Relaxed Structure: :
both electron and hole confinement for n & p channels both electron and hole confinement for n & p channels
no alloy scattering for electrons no alloy scattering for electrons
transverse electron mass (lighter in-plane) transverse electron mass (lighter in-plane)
modulation doping: no direct ionized impurity scattering modulation doping: no direct ionized impurity scattering
Si Si
Si
GeSi
GeSi GeSi
323h19
Graded, Relaxed SiGe
_______1 m
_____17 m
XTEM of graded structure Plan-view EBIC of graded structure
t
=7x10
5
cm
-2
Si
0.70
Ge
0.30
Si
323h20
Impact of Relaxed SiGe on Future
Systems
-Si
Relaxed
SiGe
-enhanced
CMOS
Heterostructure
CMOS (HCMOS)
(buried channel)
SiGe
MODFETs
GaAs-based
HEMTs,
detectors, light
emitters
on Si
All-FET Wireless or High Performance
System on a Chip
end-of-roadmap, largest volume wireless to the masses
Wireless Circuit Boards,
Optical Interconnects
323h21
NMOS Results
Strained Si greatly enhances mobility in real SiO
2
/Si surface channels
Effective Electron Mobility vs. Effective Vertical Field
no well implant
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
0E+0 1E+5 2E+5 3E+5 4E+5 5E+5 6E+5 7E+5 8E+5 9E+5 1E+6
Effective verti cal field (V/cm)
E
f
f
e
c
t
i
v
e

e
l
e
c
t
r
o
n

m
o
b
i
l
i
t
y

(
c
m
2
/
V
s
)
Bulk Si
10%SiGe
15%SiGe
20%SiGe
25%SiGe
30%SiGe
Universal
323h22
Dielectric and Optical Properties
As with conductivity, we will start with macroscopic property and
connect to the microscopic
All aspects of free electrons have been covered: only bound electrons left
Capacitance, Optical properties -->,n -->molecules and atoms
Review of capacitance and connection to dielectric constant
First, no material in capacitor
t
o
V
o
C
dt
dV
C i
dt
dq
CV Q
= =
=
i
V
t
V
V
o
323h23
The Capacitor
+V
+
+
+
+
+
+
-
-
-
-
-
-
I=0 always
in capacitor
E
V
t
d
A
C
A
Qd
V
C
Q
A
Qd
Edx V
A
Q t
dx E
E
o
o
o
d
d
o o
d
t
d o
o
=
= =
= =
= = =
=
2
2
2
2
d/2 d/2
323h24
The Capacitor
The air-gap can store energy!
If we can move charge temporarily without current flow, can store even more
Bound charge around ion cores in a material can lead to dielectric properties
Two kinds of charge can create plate
charge:
surface charge
dipole polarization in the volume
Gauss law can not tell the difference
(only depends on charge per unit area)
323h25
Material Polarization
+
+
+
+
+
+
+
-
-
-
-
-
-
+
+
+
+
+
-
-
-
-
-
-
-
-
E
E

+ = + =
=
= + =
=
1 1
'
E
P
E P E D
P E
o
r
o r
o
P is the Polarization
D is the Electric flux density or the Dielectric
displacement
is the dielectric or electric susceptibility
d
A
C
o r

=
All detail of material response is in
r
and therefore P
323h26
Origin of Polarization
We are interested in the true dipoles creating polarization in materials (not
surface effect)
As with the free electrons, what is the response of these various dipole
mechanisms to various E-field frequencies?
When do we have to worry about controlling
molecular polarization (molecule may have non-uniform electron density)
ionic polarization (E-field may distort ion positions and temporarily create dipoles)
electronic polarization (bound electrons around ion cores could distort and lead to
polarization)
Except for the electronic polarization, we might expect the other mechanisms
to operate at lower frequencies, since the units are much more massive
What are the applications that use waves in materials for frequencies below the
visible?
323h27
Application for different E-M Frequencies
Methods of detecting
these frequencies
Cell phones
=14-33cm
DBS (TV)
=2.5cm
Other satellite, 10-50GHz
=3cm-6mm (mm wave)
Fiber optics
=1.3-1.55m
MMIC, pronounced mimic
mm wave ICs
In communications, many E-M waves travel in insulating materials:
What is the response of the material (
r
) to these waves?
323h28
Wave Eqn. With Insulating Material and
Polarization
( )
) (
0
E P E D
t
E
B x
t
P E
J B x
t
D
J H x
t
B
E x
insulating
o
nonmag
" " " "
"
"
" "
" "
"
" "
"
"

= + =
+
+ =
+ =
=
2
2
2 2
2
0 0
2
t
E
c t
E
E
r
r
=

k
n
c
k
c
k
c
c
r E
r E
e r E e e E e E E
optical
r
r
r
t i t i r ik t r k i
=
=
=
= = =

2
2
2
2
2
2
0
) (
0
) (
) (
) (
So polarization slows down the
velocity of the wave in the
material
323h29
Compare Optical (index of refraction)
and Electrical Measurements of
Material Optical, n
2
Electrical,
diamond 5.66 5.68
NaCl 2.25 5.9
H
2
O 1.77 80.4
Only electrical polariztion
Electrical and ionic polariztion
Electrical, ionic, and
molecular polariztion
Polarization that is active depends on material and frequency
323i1
Microscopic Frequency Response of
Materials
Bound charge can create dipole through charge displacement
Hydrodynamic equation (Newtonian representation) will now have a
restoring force
Review of dipole physics:
- +
d
!
d q p
!
!
Dipole moment:
+q
-q
p
!
Applied E-field rotates dipole to align with field:
E x p
!
! !

Torque
cos E p E p U
!
!
!
!

Potential Energy
323i2
For a material with many dipoles:
Materials
) ( E p E N p N P
!
!
!
!
!

(polarization=(#/vol)*dipole polarization)
=polarizability

N
E
P
o
so , !
!
E p
!
!

Actually works well only for low density of dipoles, i.e. gases: little screening
For solids where there can be a high density: local field
E
ext
E
loc
For a spherical volume inside (theory of local field),
o
ext loc
P
E E
3
!
! !
+
323i3
We now need to derive a new relationship between the dielectric constant and
the polarizability
Materials
,
_

+
3
2
r
ext loc
ext o ext o r
ext o ext o r
E E
E E P
P E E D

Plugging into P=NE
loc
:
( )
( ) ( ) 2
3
1
3
2
+
+

r o r
ext
r
ext o ext o r
N
E N E E

Clausius-Mosotti Relation:
o o r
r
N
3 3 2
1

+
Where v is the volume per dipole (1/N)

Macro Micro
323i4
Different Types of Polarizability
Atomic or electronic,
e
Displacement or ionic,
i
Orientational or dipolar,
o
Highest natural frequency
Lowest natural frequency
Lightest mass
Heaviest mass
o i e
+ +
t i
o
e E E

As with free e-, we want to look at the time dependence of the E-field:
Kx eE
t
x m
t
x
m
2
2
Response Drag
Driving
Force
Restoring Force
( )
m
K
m
eE
m
K
m
eE
x
Kx eE x m
e x x
Kx eE x m
o
o
o o
o
o o o
t i
o
,
_
2 2
2
2
) (
" "
So lighter mass will have a
higher critical frequency
323i5
Classical Model for Electronic Polarizability
Electron shell around atom is attached to nucleus via springs
+
E
!
+
E
!
p
! K
K
r
t i
o loc i i
e r r eE Z Kr r m Z

assume ,
" "
Z
i
electrons,
mass Z
i
m
323i6
Electronic Polarizability
,
_
i
o
o
mZ
K
m
eE
r
2
( )
( )
( )
2
2
2 2
2
2 2
2
2 2
,
0 ,
;
;
oe
i
e oe
e oe
oe
i
e
o e o
o
i
o
t i
o i
i
oe
oe
o
o
m
e Z
m
e Z
E E
m
e Z
p
e p p er Z qd p
mZ
K
m
eE
r
<<
>>
If no Clausius-Mosotti,
( )
2
2 2
2
1 1 n
m
e NZ N
oe o
i
o
e
r

+ +

oe
1
( )
2
2
1
oe o
i
m
e NZ

+
323i7
QM Electronic Polarizability
At the atomic electron level, QM expected: electron waves
QM gives same answer qualitatively
QM exact answer very difficult: many-bodied problem
( )
#
0 1
10
2 2
10
10
2
;
E E f
m
e
e

E
1
E
0
f
10
is the oscillator strength of the transition (
1
couples to
o
by E-field)
For an atom with multiple electrons in multiple levels:
( )
#
0
0
0
2 2
10
0
2
;
E E
j
f
m
e
j
j
j
j
e

323i8
Ionic Polarizability
Problem reduces to one similar to the electronic polarizability
Critical frequency will be less than electronic since ions are more massive
The restoring force between ion positions is the interatomic potential
E(R)
R
Nucleii repulsion
Electron bonding in between ions
Parabolic at bottom near R
o
) (
2
) (
2
o
o
R R k
R
E
F
R R k
E

R
o
- +
kl ijkl ij
C kx F
323i9
- +
E
loc
+
-
p
u+
u-
2 coupled differential eqns
1 for +ions
1 for - ions
( )
( )
2 2
2
2 2
2
,
,
2
1 1
1
,

+
+

+
+ +
oi
i
o i o o
oi
oi
o
o
t i
o
t i
o loc
loc
M
e
E ew p
M
K
M
eE
w
e w w e E E
eE Kw w M
M M
M
u u w u u w
" "
" " " " " "
Ionic materials always have ionic and
electronic polarization, so:
( )
2 2
2

+ + +
+
oi
e i tot
M
e
323i10
Usually Clausius-Mosotti necessary due to high density of dipoles
( )
1
]
1
+ +
+
+
2 2
2
3
1
3 2
1

oi o o
tot
r
r
M
e
v
N
By convention, things are abbreviated by using
s
and
:
( )
1
]
1
+ +
+
<<
+
2
2
3
1
2
1
,
oi o s
s
oi
M
e
v

[ ]
+
+
+
>>

v n
n
o
oi
3
1
2
1
2
1
,
2
2
,
_
+
+
2
2
,
1

2 2
2
2
s
oi T
T
s
r
T
n
2
=
s
323i11
Orientational Polarizability
No restoring force: analogous to conductivity
H
H
O
p
+ -
C
O
O
p=0
+q
-q
For a group of many molecules at some temperature:

T k
pE
T k
U
b b
e e f
cos

After averaging over the polarization of the

ensemble molecules (valid for low E-fields):
T k
p
b
DC
3
~
2
Analogous to conductivity, the

molecules collide after a certain
time t, giving:
i
DC
o
1
323i12
Dielectric Loss
For convenience, imagine a low density of molecules in the gas phase
C-M can be ignored for simplicity
There will be only electronic and orientational polarizability

i
n
n
N
n
i
N
n
so
r
o
DC
so r
o
DC
o e r
+
+ <<
+ + +
1

3
, , 1
) 1 ( 3
1
2
2
2
2
We can write this in terms of a real
and imaginary dielectric constant if
we choose:

2 2
2
so
2 2
2
2
1
' ' ;
1
'
' ' '
+
+
+
n n
n
i
so
r
log
-2
0
+2
,
n
2
so

e
+
i
e
Water molecule: =9.5x10
-11
sec, ~10
10
microwave oven, transmission of E-M waves
323i13
Dielectric Constant vs. Frequency
Completely general due to the localized charge in materials
1/

T

oe
1
n
2
e
molecules
ions
electrons
Dispersion-free regions, v
g
=v
p
323i14
Dispersion
Dispersion can be defined a couple of ways (same, just different way)
when the group velocity ceases to be equal to the phase velocity
when the dielectric constant has a frequency dependence (i.e. when d/d not 0)
k
Dispersion-free
Dispersion
k
c
r

g
r
p
v
k
c
k
v
g
r
p
v
k
c
k
v
) (
323i15
Characteristics of Optical Fiber
Snells Law
n
1
n
2
2
Refraction
Boundary conditions for E-M wave gives
Snells Law:
2 2 1 1
sin sin n n
n
2
n
1

1

2
Internal Reflection:
1
=90
2
1
1
2
sin
n
n
c

Glass/air,
c
=42
323i16
Attenuation
Absorption
OH- dominant, SiO
2
tetrahedral mode
Scattering
Raleigh scattering (density fluctuations)
R
~const./
4
(<0.8 m
not very useful!)
Dispersion
material dispersion (see slide i13)
modal dispersion
x
Light source always has
parts of pulse with different l propagate at
different speeds
Black wave arrives later than red wave
Solution: grade index
y
n
n
2
n
1
323i17
323i18
323i19
LED =30nm
Laser =3nm
Laser =0.1nm
323i20
Ferroelectrics
Confused atom structure creates metastable relative positions of
positive and negative ions
323i21
Each unit cell a dipole!
Very large Ps (saturated polarization, P(E=0)
No iron involved; Ferro since hysterisis loop analogous to magnetic
materials
Ferroelectrics
E
R
R
o
E
Two equal-energy atom positions
Can flip cell polarization by applying
large enough reverse E-field to get over
barrier
E
P
normal dielectric
P
s
E
c
323j1
Magnetic Materials
The inductor
( )
Law) s Faraday' (explicit
1
Theorem) s (Green'
density flux magnetic
1 1
(CGS)
1
t c
d E V
d E EdS
t c
BdS
t c
EdS
t
B
c
E
B
B
B

!
!
,
_

2
2
2
1

2
1
2
1
Energy
Power
capacitor) for the (recall
CV) (Q
CV capacitor
I N LI LIdI dt Power
t
I
LI VI
t
V
C I
t
I
L V
t
I
L
t
N
V
t
I
L
t
LI
B
B
EMF
B
B
323j2
The Inductor
lA n
c I
BA N
I
N
L
nl length n N
In
c
B
I
c
dS J
c
d B BdS
t
E
c
J
c
B
B
2
4 ) (
4
4 4
1 4

+

!
Insert magnetic material
Magnetic dipoles in material can line-up in magnetic field
M H H H B 4 4 + +
B magnetic induction
magnetic susceptibility
H magnetic field strength (applied field)
M magnetization
H B M B
H
M
H M

+
+
1 4
4 1
323j3
H and B
H has the possibility of switching directions when leaving the material;
B is always continuous
p
q
H
B
At p:
At q:
B H
M=0
M
M
M
H
B
323j4
Maxwell and Magnetic Materials
Amperes law
For a permanent magnet, there is no real current
flow; if we use B, there is a need for a fictitious
current (magnetization current)
Magnetic material inserted inside inductor
increases inductance
0
I d H !
( )

lA n
c I
N
L
A In
c
HA MA BA
B
B
2
2
4
4
4 4 4 ~
,
_

L increased by ~ due to
magnetic material
Material Type

Paramagnetic +10
-5
-10
-4
Diamagnetic -10
-8
-10
-5
Ferromagnetic +10
5
323j5
Microscopic Source of Magnetization
No monopoles
magnetic dipole comes from moving or spinning electrons
L
A
e-
I
is the magnetic dipole moment
cos H H E Energy
"
"
What is ? For =0,
2
2
2
2

2
and
~
L loop 1 for and ~ energy since
r
c
e
r A
c
e
I
IA HAI I H
HA dS H
I
LI I H E
B
B
B
B

Orbital Angular Momentum
323j6
Classical mechanics gives orbital angular momentum as:
Microscopic Source of Magnetization
! !
#
#
" "
"
!
,... 0 ,...,
2
2 2
2

,
_

m L
mc
e
L L
mc
e
L
mc
e
mr p r L
Z
B
Z B Z QM L
E(H=0)
+
B
H
-
B
H
0
Example for l=1:
Spin Moment

s
spin electron for 2
2
1
2
0
0 0
. .
t

g m S
S g S
mc
e
g S
mc
e
S Z
Z B z
M Q
s

#
E(H=0)
-(1/2)
B
g
0
H
+(1/2)
B
g
0
H
323j7
Total Energy Change for Bound Electron in
Magnetic Field
Simple addition of energies if spin-orbital coupling did not exist
( ) H H S g L H E
T Z Z B
+
0
"
"
But spin-orbit coupling changes things such that:
( )
Z B Z Z B T
J S g L +
0
( ) ( )
( )
H J g H J g H E
J J
L L S S
g
J g
Z B B T
Z B T

1
]
1
+
+ +
+
" " "

"
1
1 1
2
1
2
3
QM definitions:
Z
s Z
Z
J J
S L J
m S S
m L L
#
# #
# #
!
+

323j8
Kinetic energy from Lorentz force has not been included
Total Energy Change for Bound Electron in
Magnetic Field
( ) ( ) H r H r
mc
e
m
p
H r
c
e
p
H
"
"
"
"
"
"

2
2 2
8 2
change Energy
2
Lorentz for circular orbit
For the plane perpendicular to H and assuming circular orbit:
( )
( )
2 2 2
2
2
2 2 2
2
2
2 2
2
2
8
8 8
change Energy
y x H
mc
e
HJ g E
H y x
mc
e
H r
mc
e
Z B TOT
+ +
+
Numbers:
B
H for
H=10
-4
Gauss
=10
-4
eV
for
H=10
-4
Gauss
=10
-9
eV
The Lorentz effect is minimal with respect to magnetic moment interaction, if it exists
323j9
Atoms with Filled Shells
J =0 (L=0, S=0)
Only Lorentz contribution
Leads to diamagnetism
( )
2 2 2
2
2
8
y x H
mc
e
E +
Need to sum over all e- in atom:
i
i
i
i
i
i atom
Z r
V
N
mc
e
Z r
V
N
mc
e
r
V
N
mc
e
H
M
H
E
V
M
H
E
r H
mc
e
E
2
2
2
2
2
2
2
2
2
2
2
2 2
2
2
6
6 6

1
V
N
-
shells) spherical a (for
3
2
12

,
_
~-10
-5
323j10
J not zero
Need Hunds rules from QM
Fill levels with same ms to maximize spin
maximize L (first e- goes in largest l)
J =|L-S| for n<=(2l+1), J =|L+S| for n>(2l+1)
Conventional notation:
J =0 when L and S are not zero is a special case
2nd order effect--> perturbation theory
Partially filled shells give atoms paramagnetic behavior
Atoms with Partially Filled Shells
( )
J
S
X
1 2 +
L 0 1 2 3 4 5 6
X S P D F G H I
Z B
HJ g E
(+10
-2
-10
-3
>10
-9
eV for diamagnetic component)
323j11
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Zn
Ce
Pr
Nd
Pm
Sm
Eu
Gd
Tb
Dy
Ho
Er
Tm
Yb
323j12
Temperature Dependence of Paramagnetism
Temperature dependence determined by thermal energy vs. magnetic
alignment energy (same derivation as for molecular polarizability in the case
of electric dipoles)
T k
pE
T k
U
b b
e e f
cos

for electric dipoles;

T k
H
T k
U
b b
e e f
cos

for magnetic dipoles;
fd
fd
Z
Z
For low H fields and/or low T,

T T k
J J g
V
N
T k
J
V
N
T k
H J
V
N
M
T k
H J
T k
H
b
B
QM
b
B
b
B
b
B
b
Z
1

) 1 (
3
1
3
3
3 3
2 2
2 2
2 2
2 2 2
Curies Law
323j13
Effect of De-localized electrons on Magnetic
Properties
Pauli Paramagnetism
dues to the reaction of free e- to magnetic field
E(H=0)
H g E
B
0
S g
B

0

( )
+
n n M
B
(n
+
is the density of free electrons parallel to the H field)
E(H=0)
H g E
B
0

( ) ( )
( ) ( ) E g E g
E g E g
2
1
2
1
+
( ) ( )
( ) ( ) H E g E g
H E g E g
B
B
+
2
1
2
1
For exact solution, need
to expand about E
f
for n+
and n-
Only e- near Fermi surface matter:
( ) ( )
( )
( ) ( )
F B F B
B F
F
B
E g E Hg M
H E g n
E
E g n n n
H g E
2 2
0
,
2

+
Note: Pauli paramagnetism has no T
dependence, whereas Curie paramagnetism has
1/T dependence
323j14
Landau paramagnetism
Effect of bands/Fermi surface on Pauli paramagnetism
F=qvxB for orbits
orbit not completed under normal circumstances
however, average effect is not zero
Effect of De-localized electrons on Magnetic
Properties
Pauli Land

3
1

323j15
Ferromagnetism
Most important but not common among elements
Net magnetization exists without an applied magnetic field
To get ~10
4
-10
5
as we see in ferromagnetism, most moments in
material must be aligned!
There must be a missing driving force
NOT dipole-dipole interaction: too small
( )( ) [ ] eV r r
r
E
dipole
4
2 1 2 1
3
10 ~ 3
1

" " " "
Spin Hamiltonian and Exchange
constant exchange
ij j i ij
spin
J S S J H
Assuming spin is dominating magnetization,
( ) ( ) ( ) ( )

R
B
R R
R S H g R R J R S R S H
" " "
" " " " " " "
' '
2
1
' ,
323j16
Exchange
E~-J S
1
S
2
J negative, E~+S
1
S
2
--> Energy if
J positive, E~-S
1
S
2
--> Energy if
Fe, Ni, Co ---> J positive!
Other elements J is negative
Rule of Thumb:
5 . 1
radius) 2(atomic
distance c interatomi
2
>
a
r
r
J is a function of distance!
323j17
Ferromagnetism
M
T
T
C
( ) ( )
( ) ( ) 1.4 - 1.3
0.37 - 0.33

T T T
T T T M
C
C
H
B=H+4M
normal paramagnet
B
r
, M
s
H
c
Irreversible boundary displacement
Domain rotation
reversible boundary displacement
Easy induction, softer
Magentic anisotropy
hardness of loop dependent on crystal direction
comes from spin interacting with bonding
323j18
Domains in Ferromagnetic Materials
B
M
N
S
Magnetic energy
dV B
2
8
1
Magnetic domain
Domain wall or boundary
N N
N
N
S S
S S
Flux closure
No external field
3.23 Electrical, Optical, Magnetic Properties of Materials

Prof. Eugene A. Fitzgerald
Rm 13-4053, x8-7461, eafitz@mit.edu
Prof. Yoel Fink, x3-4407, yoel@mit.edu

Grader: ?

Class: Tuesday/Thursday 8:30-10, 4-237
Recitation: to be announced (3 recitations)

Problem Sets: one a week, 1-3 problems, Due outside Prof. Finks office

Exams: 3 exams, NO final

Grading: problem sets 10%, each exam 30%

Outline {first numbers refer to chapters to be read in A&M, second reference after comma
refers to text and chapters for background reading in the topic area}
Dates are approximate

Conductivity and Bands
Sept. 7
Origin of Ohms Law {1, O 4}
Hydrodynamic representation of electrons in solids {1, O 4}
Sept. 12
Hall effect {1, O 4}
Sept. 14
AC response of electron particles;
The plasma frequency; E-M waves in materials {1 O 4}
Sept. 19,21
Electron waves and diffraction {4 5 6 , C 2 3 4}
Origin of structure factor, Diffraction {4 5 6, C 2 3 4}
Sept. 26
Wave-particle duality: DeBroglie, Compton, Planck, Einstein {-, E&R 1 2 3}
Sept. 28, Oct. 3
Electron waves in solids {2, O 5}
Quantized electron energy {2, O 5}
Density of electron states {2, O 5}
Boltzmann and Fermi-Dirac distributions {2, O 5}
Heat capacity of electron waves {2, O 5}
Oct. 5
Nearly free electrons in solids
Origin of band gaps and band structure {9, O 5}
Schroedinger equation and application to electron waves in solids {8, E&R 5 O 5}
Oct. 12
Bloch waves and general solution from S.E.
Oct. 17 First Exam
Oct. 19
H atom {-, E&R 7}
Chemistry approach: H
2
+
, tight-binding model {-, O 5}
Bonding: connection to mechanical properties
Oct. 24,26,31
Buliding materials atom by atom: Debye-Huckel model
Electronic structure of polymer chains
Hybridization
Metals and insulators
Bands and zones
Carriers in bands
Effective mass {-,K 8}
Nov. 2
Intrinsic/Extrinsic Semiconductors {28, P&N vol. 1}
Electrical activity of defects
Hydrogenic model of extrinsic semiconductors {28, P&N vol. 1}
Nov. 7
Carrier Scattering, Recombination, and Generation in semiconductors
Defects: Traps/R-G centers
Nov. 9,14
Drift, diffusion, and the continuity equations {-, P&N vol. 1}
The ideal diode: depletion region, built-in voltage, and operation {-, P&N vol. 2}
Band offsets
Electrons in V(x): step, well, infinite well {-, S&W 3}
Quantum wells
Resonant tunnel diode operation
2DEG in Si/SiGe and transistor applications
Nov. 16 Second Exam

Dielectric and Optical Properties of Materials: The Capacitor {27, O 8}
Nov. 21
Application of Maxwells equations to capacitance
Dielectric constant and polarizability
Dielectric response at optical frequencies
Nov. 28,30
Hydrodynamic representation of polarizability
Local field and Clausius-Mossetti
Orientational, electronic, and ionic polarizability
Pyroelectrics and ferroelectrics
Defects and dielectric loss
Dispersion, attenuation in optical fibers
Dec. 5
Photonic Band Gaps

Magnetic Properties of Materials: The Inductor {31 32 33, O 9}
Dec. 7
Application of Maxwells equations to inductance
Magnetization: paramagnetism, diamagnetism, ferromagnetism {31}
Microscopic origin of magnetization {31}
Central QM equation for magnetization and Hunds rules {31}
Pauli paramagnetism {31}
Exchange and ferromagnetism {32 33}
Mean-field theory {32 33}
Applications: bubbles, magneto-optic storage
Defects and domain pinning
Dec. 12 Third Exam

Texts
Main text: Ashcroft and Mermin, Solid State Physics {A&M}
Highly recommended: Omar, Elementary Solid State Physics {O}
Cullity, Elements of X-ray Diffraction {C}
Eisberg and Resnick, Quantum Physics {E&R}
Kittel, Introduction to Solid State Physics {K}
Pierret and Neudeck, Modular Series on Solid State Devices {P&N}
Solymar and Walsh, Lectures on the Electrical Properties of Materials {S&W}
Pankove, Optical Processes in Semiconductors {P}
Livingston, Electronic Properties of Engineering Materials

Electrical, Optical, Magnetic Properties of Materials-Didactic

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Index of /323/

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If the environment has a lot of collisions,

If Von Laue condition holds, then reciprocal lattice

Sk=2, if sum even

Average energy of particles/waves with this distribution:

Note: the integrals need to be

g(E)=density of states=number of electrons per energy per length

Problem easier if we choose U(r)

Apply variational method: pick s to get

where is the cross-section of the scatterer, N is the

Non-equilibrium extrinsic recombination

no alloy scattering for electrons no alloy scattering for electrons

Where v is the volume per dipole (1/N)

For a group of many molecules at some temperature:

After averaging over the polarization of the

Analogous to conductivity, the

" " "

for electric dipoles;

for magnetic dipoles;

For low H fields and/or low T,

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