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Lecture 3

Quantum Mechanics and relationship to electron


motion in crystals
Reading:
Notes

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ECE 3080 - Dr. Alan Doolittle

Recall: Carrier Movement Within the Crystal


dv
dt
F force, v velocity, t time,

dv
F = qE = m
dt
F force, v velocity, t time,

F = qE = m*p

q electronic ch arg e,

q electronic ch arg e,

mn* electron effective mass

m*p hole effective mass

*
n

Ge and GaAs have lighter electrons than Si


which results in faster devices
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ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


People RARELY get quantum mechanics of their first exposure.
Many aspects of quantum mechanics are counter intuitive and thus,
visual learners will likely have more trouble than those that tend to
think in the abstract.
We will introduce it now in hopes it will be easier the more you are
exposed to it.

Parts of this discussion are taken from:


Solymar and Walsh Electrical Properties of Materials
Neudeck and Pierret Advanced Semiconductor Fundamentals
Dimitrijev Understanding Semiconductor Devices
Mayer and Lau Electronic Materials Science
Colclaser and Diehl-Nagle Materials and Devices for electrical engineers and physicists
Tipler Physics for scientists and engineers V4.

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ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


To fully understand the origin of the energy bandgap and effective mass concepts as
well as future topics of energy states in quantum wells and tunneling currents, one
must have at least a basic understanding of electron motion in free space and in the
presence of other sources of electrostatic potential (atomic cores for example).
This requires an understanding of the dual wave-particle nature of electrons and in
turn quantum mechanics.
Consider the electron microscope:
Electrons have a charge and thus can be focused...
...but also have a phase and thus can interfere with each other destructively or
h
constructively Electron Source
=
m
6.6 1034 Js
=
= 7.25 107 m / s
31
11
9.1 10 kg 10 meters
Deflection Plates

(voltage used to focus electrons)

Thin sample
(spatially varied charge creates multiple
phase delayed electron paths)

Phosphor Screen
(converts electron energy to visible light waves
constructively and destructively interfere to get light
and dark regions)
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KE =

1
m 2 = qV
2

9.1 1031 (7.25 107 m / s )


V=
= 15,000 V
2 1.6 1019 C
2

15KV gives sub atomic


resolution!
ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


What is the wavelength of macroscopic particles? Consider a bullet (1km/s 1 gram)?
6.6 1034 Js
1000m / s =
= 6.6 1034 m
3
1 10 kg

Though it acts as a wave, its wavelength is too small to ever measure/observe.


So an electron (or every particle) acts as a wave AND a particle simultaneously.
How can we describe this?

h
2
Other useful properties of energy-particle waves: E = hf =
(2f ) = h = mc
2
Or the momentum of the photon is...

p = mc =
p=

hf h
2
= = h
= hk
c

this is known as the de Broglie hypothesis

Where scalar, k, is known as the wave number. If momentum, p is expressed as a vector, k is


know as the wave vector.
Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


Why do we use k or k instead of p or p?

k=2/ is independent of mass. Classically, p=mv. However, we will show that the
mass* will change with crystalline direction allowing two parameters (m and v) to
change the momentum. Thus, k is simpler to consider.

*actually the effective mass is what changes with crystalline direction.


Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)

So how do we account for the wavelike nature of small particles like electrons?
Schrdenger Equation:
In Electrical Properties of Materials, Solymar and Walsh point out that there are NO
physical assumptions available to derive the Schrdenger Equation
Just like Newtons law of motion, F=ma, and Maxwells equations, the Schrdenger
Equation was proposed to explain several observations in physics that were previously
unexplained. These include the atomic spectrum of hydrogen, the energy levels of the
Planck oscillator, non-radiation of electronic currents in atoms, and the shift in energy levels
in a strong electric field.

KE + PE = ETotal
Kinetic energy
operator

h2 2

+ V = ih
2m
t

Potential electron
moves through
Energy
operator

Other operators exist:

Neudeck and Pierret Table 2.1

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ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


(x,y,z,t) is called the electron wave function
It is related to the probability of finding an electron at time t in a volume dxdydz.
Specifically, this probability is:

( x, y , z, t ) dxdydz or *dxdydz
2

But since is a probability,

or in 1D

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( x, y , z, t ) dxdydz = 1
2

[ dx ] = 1

Solymar and Walsh figure 3.1

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


To solve the Schrdinger equation one must make an assumption about the wave
function. Lets assume the wave function has separate spatial and temporal
components:
( x , y , z , t ) = ( x , y , z ) w( t )

Plugging this (*) into the Schrdinger equation and dividing both sides by (*) we arrive
at:

h 2 2

1 w

+ V = ih
w t
2m

Since the left hand side varies only with position, and the right hand side varies only with
time, the only way these two sides can equate is if they are equal to a constant ( we will
call this constant, total energy, E). Thus, we can break this equation into two equations:

1 w
E = ih
w t

h 2 2


+ V = E
2m

Consider first the time variable version (left side) then later we will examine the spatially
variable portion. This will give us time variable solutions and a separate spatially
variable solution.

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


Consider the time variable solution:

E = ih

1 w
w t

w
E
= i w
t
h

w( t ) = e

E
i t
h

or w(t ) = e (it )
where E = h

This equation expresses the periodic time nature of the wave equation.

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


Consider the space variable solution:

h 2 2


+ V = E
2m

The combined
operator is called
the Hamiltonian

momentum
operator

h2 2


+ V = E
2m

H = E

1
( jh )2 + V = E

2m

p 2

+ V = E
2m

Kinetic
Total
+ Potential =
Energy
Energy
Energy
Classically, momentum, p=mv and kinetic energy
is (mv2)/2 =(p2)/2m
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ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


Consider a specific solution for the free space (no electrostatic potential, V=0) wave
solution (electron traveling in the +x direction in 1D only):

h2 2


+ V = E
2m

h2 2
E = 0
2
2m x
( x ) = Aeikx + Be ikx
2

2mE
h 2k 2
=
where k =
or E =
2
h

2m
Since we have to add our time dependent portion (see (*) previous) our total solution is:

= ( x ) w(t ) = Ae i (t kx ) + Be i (t + kx )
This is a standard wave equation with one wave traveling in the +x direction and one wave
traveling in the x direction. Since our problem stated that the electron was only traveling in
the +x direction, B=0.
Classically, momentum, p=mv and kinetic energy
is (mv2)/2 =(p2)/2m
Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


An interesting aside: What is the value of A?
Since is a probability,

[ dx ] = 1

Aeikx Ae ikx dx = 1
A2eikx ikx dx = 1
A2dx = 1

This requires A to be vanishingly small (unless we restrict our universe to finite size) and is
the same probability for all x and t. More importantly it brings out a quantum phenomena: If
we know the electrons momentum, p or k, we can not know its position! This is a restatement
of the uncertainty principle:
p x
Where p is the uncertainty in momentum and x is the uncertainty in position

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


The solution to this free particle example brings out several important observations
about the dual wave-particle nature of our universe:
i (t kx )

= ( x ) w(t ) = Ae

While particles act as waves, their charge is carried as a particle. I.e. you can only say that
there is a probability of finding an electron in a particular region of space, but if you find it
there, it will have all of its charge there, not just a fraction.
Energy of moving particles follows a square law relationship:
Neudeck and Pierret Fig 2.3

Classically, momentum, p=mv and kinetic energy is (mv2)/2 =(p2)/2m


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p
h2k 2
E=
=
2m
2m

ECE 3080 - Dr. Alan Doolittle

Introduction to Quantum Mechanics (notes only)


What effect does this E-k square law relationship
have on electron velocity and mass?
The group velocity (rate of energy delivery) of a
wave is:

dE 1 dE
vg =
=
dp h dk

So the speed of an electron in


the direction defined by p is
found from the slope of the E-k
diagram.
2 2

hk
Similarly, since E =
2m

d E
m* = h 2 2
dk
2

So the effective mass of an


electron is related to the local
inverse curvature of the E-k
diagram
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After Mayer and Lau Fig 12.2

ECE 3080 - Dr. Alan Doolittle

What effect does an electrostatic potential have on an electron?


Consider the electron moving in an electrostatic potential, Vo. The wave solution
(electron traveling in the +x direction in 1D only):

h2 2


+ V = E
2m

h2 2
(E Vo ) = 0
2
2m x
( x ) = Aeikx + Be ikx
2

h 2k 2
2mE Vo
=
Vo
where k =
or E =
2
h

2m
Since we have to add our time dependent portion (see (*) previous) our total solution is:

= ( x ) w(t ) = Ae i (t kx ) + Be i (t + kx )
This is, again, a standard wave equation with one wave traveling in the +x direction and one
wave traveling in the x direction. Since our problem stated that the electron was only
traveling in the +x direction, B=0.
When the electron moves through an electrostatic potential, for the same energy as in
free space, the only thing that changes is the wavelength of the electron.
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ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


Consider the electron moving incident on an electrostatic potential, Vo. The wave
solution (1D only):
V(x<0)=0
V(x>0)=Vo
Vo

Region I

x=0

Region II

We have already solved these in regions I and II. The total solution is:

I = I ( x ) wI (t ) = AI e i (t k I x ) + BI e i (t + k I x )
II = II ( x ) wII (t ) = AII e i (t k II x ) + BII e i (t + k II x )
where k I =

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2mE
2
2mE Vo
and
k
=
=
II
h2
h2
II

ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


Vo
contd...
Region I

x=0

Region II

I = I ( x ) wI (t ) = AI e i (t k I x ) + BI e i (t + k I x )

II = II ( x ) wII (t ) = AII e i (t k II x ) + BII e i (t + k II x )


where k I =

2mE
2
2mE Vo
and
k
=
=
II
II
h2
h2

When the wave is incident on the barrier, some of it is reflected, some of it is


transmitted. However, since there is nothing at x=+ to reflect the wave back, BII=0.
Since is a wave, both and its first derivative must be continuous across the
boundary at x=0 for all time, t. Thus,

I ( x = 0) = II ( x = 0)

AI + BI = AII

and

and
ik I ( AI BI ) = ik II AII

I ( x = 0) II ( x = 0)
=
x
x

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


Vo

contd...
Region I

x=0

Region II

We can define a reflection coefficient as the amplitude of the reflected wave relative
to the incident wave,

BI k I k II
R
=
AI k I + k II

And likewise, we can define a transmission coefficient as the amplitude of the


transmitted wave relative to the incident wave,

AII
2k I
=
AI k I + k II

The probability of a reflection is R*R while the probability of transmission is T*T


kI =

2mE
2
2mE V
and k II =
=
2
h
h2
II

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


contd...
Consider 2 cases: Case 1: E>V
Both kI and kII are real and thus, the particle moves with a wave of different wavelength in the
two regions.
However, R*R is finite. Thus, even thought the electron has an energy, E, greater than V it will
have a finite probability of being reflected by the potential barrier.
If E>>V, this probability of reflection reduces to ~0 (kI kII)

I
R
T
kI =

II

BI k I k II
=
AI k I + k II
AII
2k I
=
AI k I + k II
=

2mE
2
2mE V
and k II =
=
2
h
h2
II

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Region I

x=0

Region II

ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


contd...
Case 2: E<V
kI is real but kII is imaginary. When an imaginary kII is placed inside our exponential, exp(ikIIx),
a decaying function of the form, exp(-ax) results in region II.
However, T*T is now finite, so even thought the electron has an energy, E, less than V it will
have a finite probability of being found within the potential barrier. The probability of finding the
electron deep inside the potential barrier is ~0 due to the rapid decay of .

R
T
kI =

BI k I k II
=
AI k I + k II
AII
2k I
=
AI k I + k II
=

2mE
2
2mE V
and k II =
=
2
h
h2
II

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Region I

x=0

Region II

ECE 3080 - Dr. Alan Doolittle

What about an electrostatic potential step?


Without proof (see homework), consider the following potential profile with an electron of
energy E<Vo.

Vo

Region I

x=0

x=a

Region II

The electron has a finite probability to tunnel through the barrier and will do so if the barrier is
thin enough. Once through, it will continue traveling on its way.

Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Now consider an periodic potential in 1D


Kronig-Penney Model
Consider what potentials an electron would see as it moves
through the lattice (limited to 1D for now). The electrostatic
potential, V(x) is periodic such that V(x+L)=V(x).
The Bloch theorem states that since the potential repeats
every L lengths, the magnitude of the wavefunction (but not
necessarily the phase) must also repeat every L lengths.
This is true because the probability of finding an electron at a
given point in the crystal must be the same as found in the
same location in any other unit cell.

Since V(x + L) = V(x)


(x + L) = eikL (x)

The wavefunction in one unit cell is


merely a phase shifted version of
the wavefunction in an adjacent
unit cell.

* (x + L) (x + L) = e-ikL * (x)e ikL (x) = * (x) (x)


We MUST have standing waves in the crystal that have a
period equal to a multiple of the period of the crystals
electrostatic potential. (Similar to a multilayer antireflection
coating in optics)
It is important to note that since, the wavefunction repeats
each unit cell, we only have to consider what happens in one
unit cell to describe the entire crystal. Thus, we can restrict
ourselves to values of k such that /a to +/a (implying ka
1 or (2/)a1)
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After Neudeck and Peirret Fig 3.1

ECE 3080 - Dr. Alan Doolittle

Now consider an periodic potential in 1D


Kronig-Penney Model
Assumptions of Kronig-Penney Model:
Simplifying the potential to that shown
here:
1D only
Assume electron is a simple plane
wave of the form,
ikx

...modulated by the periodic


crystalline potential, U(x)
The crystalline potential is periodic,
U(x)=U(x+L)
Thus the wave function is a simple
plain wave modulated by the periodic
crystalline potential:

(x) = U(x)e ikx


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Neudeck and Peirret Fig 3.2

ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model

Resonant reflectance/transmission creates standing waves in the crystal. Only


certain wavelengths (energies) can pass through the 1D crystal.
By analogy, a multiple layer optical coating has similar reflection/transmission
characteristics. The result is the same, only certain wavelengths (energies) are
transmitted through the optical stack. In a since, we have an optical bandgap.

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ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
For 0<x<a:

For -b<x<0:
0


2 + V = E
2m

2
2
+
=0

2
x
2mE
where =
h2
2

h2 2

+ V = E

2m
2
2
+

=0
2
x
2m (E U o )
=
for E > U o
h2

a ( x ) = A sin(x ) + B cos(x )

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2m(U o E )
for 0 < E < U o
2
h

b ( x ) = C sin( x ) + D cos( x )

ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
For 0<x<a:

For -b<x<0:

a ( x ) = A sin(x ) + B cos(x )

b ( x ) = C sin( x ) + D cos( x )

Applying the following boundary conditions:

a ( x ) = b ( x )
da ( x )
db ( x )
=
dx x =0
dx x =0
a ( x = a ) = eik ( a +b ) b ( x = b)
da ( x )
db ( x )
= eik ( a +b )
dx x =a
dx x = b

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BC for continuous
wave function at the
boundary

BC for periodic wave


function at the
boundary

ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
Applying the boundary conditions, we get:

B=D

A = C
A sin(a ) + B cos(a ) = eik ( a +b ) [ C sin( b) + D cos( b)]

A cos(a ) + B sin(a ) = eik ( a +b ) [C cos( b) + D sin( b)]


Eliminating the variables C and D using the above equations, we get:

ik ( a +b )
Asin(a ) + e
sin( b) + B cos(a ) eik ( a +b ) cos( b) = 0

] [

A cos(a ) eik ( a +b ) cos( b) + B sin(a ) eik ( a +b ) sin( b) = 0


This equation set forms a matrix of the form:

w x A 0
y z B = 0


A and B are only non-zero (non-trivial solution) when the determinate of the above
set is equal to zero.
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ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
Taking the determinate and simplifying we get:

2 + 2
sin(a ) sin( b) + cos(a ) cos( b) = cos(k ( a + b) )

2
Plugging in the definitions for and we get:

1
2

2mU
Uo
E 2mU o
o
sin b

sin a
2

U
h
h2


o
E E

2 U U 1
o
o

2mU o E 2mU o
E

cos b

1 + cos a
2

U
U
h
h2
o
o

1 = cos(k ( a + b) ) for E > U o


Uo

1 2
2mU
2mU

Uo
E
o
o
b

sinh
sin a

2
2

h
h
U

o
E
E

2 U 1 U
o
o

2mU
2mU o E

E
o
b

1
+ cos a
cosh
2
2

h
h
U
U
o
o

E
1
= cos(k ( a + b) ) for 0 < E < U o
U o

The right hand side is constrained to a range of +/- 1 and is a function of k only. The limits of
the right hand side (+/- 1) occurs at k=0 and +/- /(a+b) where a+b is the period of the crystal
potential.
The left hand side is NOT constrained to +/- 1 and is a function of energy only.
Georgia Tech

ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
The right hand side is constrained to a range of +/- 1 and is a function of k only. The limits of
the right hand side (+/- 1) occurs at k=0 to +/- /(a+b).

Left or Right hand side of Kronig-Penney Solution

The left hand side is NOT constrained to +/- 1 and is a function of energy only.
Within these forbidden energy
ranges, no solution can exist (i.e.
electrons can not propagate.

E/Uo

Various Bands or allowed energy exist


where the energy E is a function of the
choice of k (see solution equation)

for the specific case where,


a
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2mU o
2mU o
=b
=
2
h
h2

ECE 3080 - Dr. Alan Doolittle

Kronig-Penney Model
Replotting the previous result in another form recognizing the lower k limit is shared by +
and /(a+b) while the upper limit is for k=0.
There are at most 2 k-values for each allowed energy, E
The slope, dE/dK is zero at the k-zone boundaries at k=0, k= /(a+b) and k= + /(a+b)
Thus we see that the velocity of the electrons approaches zero at the zone boundaries.
This means that the electron trajectory/momentum are confined to stay within the allowable
k-zones.

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After Neudeck and Peirret Fig 3.5

ECE 3080 - Dr. Alan Doolittle

Now consider an periodic potential in 1D


Kronig-Penney Model

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After Neudeck and Peirret Fig 4.1

ECE 3080 - Dr. Alan Doolittle

Now consider the 3D periodic potential in a cubic crystal


Different potentials exist in
different directions
Electron wavelength and crystal
momentum, k=2/, differs with
direction
Many different parabolic E-k
relationships exist depending on
our crystalline momentum

Cubic GaN

kz

ky
kx
Crystal Momentum Space
http://britneyspears.ac/physics/dos/dos.htm

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Real Space
ECE 3080 - Dr. Alan Doolittle

Now consider the 3D periodic potential in a cubic crystal

Cubic GaN

All equivalent directions give redundant information and


thus are not repeated
Most important k-space points
-point is the center of crystal momentum space (kspace) at k=0
X-point is the edge of the first Brillouin zone (/L
edge) of crystal momentum space (k-space) in the
<100> direction
L-point is the edge of the first Brillouin zone (/L
edge) of crystal momentum space (k-space) in the
<111> direction
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Neudeck and Peirret Fig 3.13

ECE 3080 - Dr. Alan Doolittle

Now consider the 3D periodic potential in a hexagonal crystal

Full Band Diagram

k
z

k
k

Crystal Momentum Space

Real Space

Suzuki, M, T. Uenoyama, A. Yanase, First-principles calculations of effective-mass parameters of AlN and GaN, Phys. Rev. B 52, 11 (1995), 8132-8139.

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ECE 3080 - Dr. Alan Doolittle

Where are the electron trajectories/momentum vectors in the crystal?

Neudeck and Peirret Fig 3.13

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Neudeck and Peirret Fig 3.14

ECE 3080 - Dr. Alan Doolittle

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