麻省理工大学固体物理课件

１分子－简单固体（ＰＤＦ）
Ｌｅｃｔｕｒｅ　１：　Ｍｏｌｅｃｕｌｅｓ–ｔｈｅ　Ｓｉｍｐｌｅ　Ｓｏｌｉｄ　（ＰＤＦ）
２氢分子中的振动和旋转态（ＰＤＦ）
Ｌｅｃｔｕｒｅ　２：　Ｖｉｂｒａｔｉｏｎａｌ　ａｎｄ　Ｒｏｔａｔｉｏｎａｌ　Ｓｔａｔｅｓ　ｉｎ　Ｈｙｄｒｏｇｅｎ　（ＰＤＦ）
３金属中的自由电子气（ＰＤＦ）
Ｌｅｃｔｕｒｅ　３：　Ｍｅｔａｌ　ａｓ　ａ　Ｆｒｅｅ　Ｅｌｅｃｔｒｏｎ　Ｇａｓ　（ＰＤＦ）
４固体中的振动（ＰＤＦ）
Ｌｅｃｔｕｒｅ　４：　Ｖｉｂｒａｔｉｏｎｓ　ｉｎ　Ｓｏｌｉｄｓ　（ＰＤＦ）
５格波的比热（ＰＤＦ　－　１．４　ＭＢ）
Ｌｅｃｔｕｒｅ　５：　Ｓｐｅｃｉｆｉｃ　Ｈｅａｔ　ｏｆ　Ｌａｔｔｉｃｅ　Ｗａｖｅｓ　（ＰＤＦ　－　１．４　ＭＢ）
８一维单原子晶体中的格波（ＰＤＦ）
Ｌｅｃｔｕｒｅ　８：　Ｌａｔｔｉｃｅ　Ｗａｖｅｓ　ｉｎ　１Ｄ　Ｍｏｎａｔｏｍｉｃ　Ｃｒｙｓｔａｌｓ　（ＰＤＦ）
９一维双原子链中的格波（ＰＤＦ）
Ｌｅｃｔｕｒｅ　９：　Ｌａｔｔｉｃｅ　Ｗａｖｅｓ　ｉｎ　１Ｄ　ｗｉｔｈ　Ｄｉａｔｍｏｍｉｃ　Ｂａｓｉｓ　（ＰＤＦ）
１０　＆１１离散晶格的比热（ＰＤＦ　－　１．１　ＭＢ）
Ｌｅｃｔｕｒｅ　１０　＆　１１：　Ｓｐｅｃｉｆｉｃ　Ｈｅａｔ　ｏｆ　Ｄｉｓｃｒｅｔｅ　Ｌａｔｔｉｃｅ　（ＰＤＦ　－　１．１　ＭＢ）
１２周期结构的固体中的电子（ＰＤＦ）
Ｌｅｃｔｕｒｅ　１２：　Ｅｌｅｃｔｒｏｎｓ　ｉｎ　ａ　Ｐｅｒｉｏｄｉｃ　Ｓｏｌｉｄ　（ＰＤＦ）
１３周期结构的固体中的电子（ＰＤＦ）
Ｌｅｃｔｕｒｅ　１３：　Ｅｌｅｃｔｒｏｎｓ　ｉｎ　ａ　Ｐｅｒｉｏｄｉｃ　Ｓｏｌｉｄ　（ＰＤＦ）
１４周期结构的固体中的电子（ＰＤＦ　－　３．２　ＭＢ）
Ｌｅｃｔｕｒｅ　１４：　Ｅｌｅｃｔｒｏｎｓ　ｉｎ　ａ　Ｐｅｒｉｏｄｉｃ　Ｓｏｌｉｄ　（ＰＤＦ　－　３．２　ＭＢ）
１５周期结构的固体中的电子（ＰＤＦ　－　３．１　ＭＢ）
Ｌｅｃｔｕｒｅ　１５：　Ｅｌｅｃｔｒｏｎｓ　ｉｎ　ａ　Ｐｅｒｉｏｄｉｃ　Ｓｏｌｉｄ　（ＰＤＦ　－　３．１　ＭＢ）
１６近自由电子能带（ＰＤＦ　－　１．２　ＭＢ）
6.730 Physics for Solid State Applications
Lecture 1: Molecules – the Simple Solid
Rajeev J. Ram
6.730
PSSA
• Molecules
Syllabus • Approximate models for molecular bonding
• Vibrational and rotational modes
• Continuum Models of Solids

• Elasticity Phonons
• Free electron gas Electron
• Lattice (‘Atomic’) Models of Solids

• Crystal structure
• Phonons (lattice waves) on discrete lattice
• Bloch electrons
• Single Electron Transport

• ‘Electrons’ and ‘holes’
• Chemical potential and band bending
• Electron Scattering
• Electron-phonon scattering; mobility
• Electron-photon scattering; absorption and gain
• Statistical Theory of Electron Transport

• Boltzmann transport
6.730 • Drift-diffusion; hot electron effects
PSSA
General Course Information
Required Text :
Fundamentals of Carrier Transport, Second Edition, by Mark Lundstrom, Cambridge University
Press, 2000
Notes will be handed out to cover the first two-thirds of the class. This required text be used for the
last third of the class.
Suggested Text :
Solid State Physics , N.W. Aschroft and M.D. Mermin, Saunders College Publishing, 1976.
This text is not required, but if you wish to purchase a textbook that covers some of the material in
the first two-thirds of the class I would suggest this text because it is the one used in 6.732.
Problem Sets :
All homework sets are due at the beginining of class on the assigned due date. You may work
together on the problem sets but you are required to write up your own solution and code.
Students will make oral presentations on the homework.
FINAL : GRADES:
There will be a final examination for 40% Group Project (30% written report and 10%
the class.
presentation)
40% Problem Sets (25% written and 15% presentation)
6.730 20% Final Examination
PSSA
Band Formation in 1-D Solid
Simple model for a solid: the one-dimensional solid, which consists of a single, infinitely long
line of atoms, each one having one s orbital available for forming molecular orbitals (MOs).
When the chain is extended:

Î The range of energies covered by the MOs
is spread
Î This range of energies is filled in with more
and more orbitals
Î The width of the range of energies of the
MOs is finite, while the number of molecular
orbitals is infinite: This is called a band .
6.730
PSSA
Band Formation in 1-D Solid with s & p orbitals
Before we can build models for the solid, we need to

understand a simple diatomic molecule.
6.730
PSSA
The Simplest Molecule: H2
, the wavefunction for the entire system of nuclei and electrons
me
M1
r M2
R1
R2
6.730
PSSA
Approximate Models: Simplifying H2
Born-Oppenheimer Approximation
The electrons are much lighter than the nuclei (me/mH≅1/1836), their
motion is much faster than the vibrational and rotational motions of the
nuclei within the molecule.
Î A good approximation is to neglect the coupling terms between the
motion of the electrons and the nuclei: this is the Born-Oppenheimer
approximation. The Schrödinger equation can then be divided into two
equations:
Linear Combination of Atomic Orbitals (LCAO)

Even the electron part of the problem is too hard to solve exactly
6.730
PSSA
me
M1 r M2
R1
R2
Electronic Part:
Nuclear Part:
6.730 where E is the energy of the entire molecule

PSSA
Electronic Part: LCAO
For example, if we consider 1s orbitals only…
6.730
PSSA
Normalization of Electronic Part: LCAO cont.
Normalize to guarantee the probability of finding an

electron anywhere is still 1
where
6.730
PSSA
Approximate Electronic Energy
6.730
PSSA
6.730
PSSA
Nuclear and Electronic Energy Together
(Energy - IH) / IH
6.730
PSSA
First Excited State Energy: Antibonding
6.730
PSSA
First Excited State Energy: LCAO
(Energy - IH) / IH
6.730
PSSA
Lecture 2: Vibrational and Rotational States in Hydrogen
Rajeev J. Ram
Review Lecture 1: H2
, the wavefunction for the entire system of nuclei and electrons
me
M1
r M2
R1
R2
Approximate Models: Simplifying H2
The electrons are much lighter than the nuclei (me/mH≅1/1836), their
motion is much faster than the vibrational and rotational motions of the
nuclei within the molecule.
Î Works since vibrational and rotational energy of molecule is typically
much less than the binding energy
Linear Combination of Atomic Orbitals (LCAO)

Even the electron part of the problem is too hard to solve exactly
me
M1 r M2
R1
R2
Electronic Part:
Nuclear Part:
where E is the energy of the entire molecule

Nuclear and Electronic Energy Together
(Energy - IH) / IH
First Excited State Energy: Antibonding
First Excited State Energy: LCAO
(Energy - IH) / IH
Decrease of electron density
Increase of electron density

A Closer Look at Nuclear Motion
Molecular Vibration and Rotation
me
M1
r M2
R1
R2
LCAO for electron

in Veff
Divide and Conquer
me
M1 r M2
R1 Born-Oppenheimer
R2
Center-of-mass and LCAO for electron

Relative nuclear
in Veff
motion
Vibrational and
rotational motion
Center-of-Mass and Relative Nuclear Motion
Center-of-mass Relative
Note that R is the C-of-M coordinate now

Center-of-Mass and Relative Nuclear Motion
Total energy is the sum of CM motion and relative:
If this is the total energy, where is the electron energy ?

Center-of-Mass Nuclear Motion
Schrodinger equation for center-of-mass

is same as free particle:
Eigenstate: Eigenenergy:
me me
M1 M1
M2 M2
center-of-mass
Relative Nuclear Motion
Schrodinger equation for relative motion

is a central potential problem just like the hydrogen atom:
Radial kinetic energy Angular kinetic energy
is the angular momentum operator

Relative Nuclear Motion
Separation of Radial and Angular Components
is the spherical Bessel function

Vibrational Motion of Nuclei
Harmonic Oscillator
For no rotation, this simplifies to…

(Energy - IH) / IH
Harmonic Oscillator
Approximation: Born-Oppenheimer, parabolic effective potential

Rigid Rotor
Assuming that the vibrational motion

produces only small displacements…
Divide and Conquer
me
M1 r M2
R1
R2
Approximations
• Born-Oppenheimer
Nuclei inside electron cloud act as if they
are embedded in an elastic medium (Veff)
• Effective potential (Veff) is parabolic
Vibrations of simple harmonic oscillator
• Rigid rotor
Vibrations only displace nuclei slightly from
equilibrium bond length
Total Energy of the H2 Molecule
Binding Vibrational Rotational Translational
H2 1.4 eV 0.5 (n + ½) eV 7.5 l (l+1) meV
O2 1.0 eV 0.1 (n + ½) eV 30 l (l +1) meV
30 THz 3-30 THz 0.3-3 THz

Generalizations from Molecules to Solids
• The source of the binding energy is primarily the electrostatic potential

between the nuclei and the electrons. The localization energy can also
play a role (metal).
• Nuclear motions of the ions contribute a very small part to the binding
energy.
• Sharing electrons between nuclei lowers the energy of the solid.
• The potential between the nuclei is of the same form as the molecule.
• Exicted states exists.

Assumptions for Electronic States
• One electron energy levels
• No spin or exchange energies
• LCAO a good approximation
• Ignore motion of the nuclei

to first order
Lecture 3: Metal as a Free Electron Gas
Rajeev J. Ram
Generalizations from Molecules to Solids
• The source of the binding energy is primarily the electrostatic potential

between the nuclei and the electrons. The localization energy can also
play a role (metal).
• Nuclear motions of the ions contribute a very small part to the binding
energy.
• Sharing electrons between nuclei lowers the energy of the solid.
• The potential between the nuclei is of the same form as the molecule.
• Exicted states exists.

Assumptions for Electronic States
• One electron energy levels
• No spin or exchange energies
• LCAO a good approximation
• Ignore motion of the nuclei

to first order
Overview of Electron Transport
Goal: Calculate electrical properties (eg. resistance) for solids

Approach:
• Macroscopic theory: V, I, R
• Microscopic theory: J, E, σ
• Phenomenological model of transport: n, τ, m
• Relate parameters in phenomenological theory to electronic energy

levels and wavefunction
Overview of Electron Transport
Approach:
In the end calculating resistance boils down to calculating the
electronic energy levels and wavefunctions; to knowing the
bandstructure
You will be able to relate a bandstructure to macroscopic

parameters for the solid
Why this approach ?:

This first principles approach will make assumptions and
approximations explicit. The phenomenological theory fails for
modern devices – the channel in the MOSFET on the Pentium chip.
Microscopic Variables for Electrical Transport
Drude Theory
Balance equation for forces on electrons:
In steady-state when B=0:

Recovering macroscopic variables:

Balance equation for energy of electrons:
In steady-state:
In the continuum models, we assume that electron scattering is

sufficiently fast that all the energy pumped into the electrons is
randomized; all additional energy heats the electrons
How do we relate ∆E and T ?

Equipartition Theorem
The theorem of equipartition of energy states that molecules

in thermal equilibrium have the same average energy
associated with each independent degree of freedom of their
motion
So in this simple theory, ∆E and T are proportional to each other…

Specific Heat and Heat Capacity
Again assume that the heat and change in internal energy are the same:
(heat capacity)
Take constant volume since this ensures

none of the extra energy is going into work
(think ideal gas)
(specific heat)
Specific heat is independent of temperature…Law of Dulong and Petit

Specific Heat Measurements
(hyperphysics.phy-astr.gsu.edu)
Specific heat is independent of temperature…NOT TRUE !
To get this correct we will need to (a) quantize electron energy
levels, (b) introduce discreteness of lattice and (c) the heat
capacity of lattice
Quantum Free Electron Gas
Crystal as Infinite Well Potential
Electron confined in crystal of size L on a side

no interaction with nuclei
not for periodic b.c.
single particle approximation
periodic boundary conditions
Quantum Free Electron Gas
Periodic Boundary Conditions
Estimating Electron Number
Probability of a particular energy level being occupied by an electron:
Total number of electrons:
spin
Limit for Large Crystals
Zero-Temperature Limit
Fermi Energy and Temperature
Electronic Energy
Average energy per electron:

Finite Temperatures
Ensemble Averages at Finite Temperatures
Where Fk is any property of the electron
where g(E) is number of states at E per unit volume
By comparing the above two expressions…

Density of States in Large 3D Solid
Density of States in Different Solids
Low Temperature Specific Heat of the Free Electron Gas
Sommerfeld Approximation

capacity of lattice
Conductivity of the Free Electron Gas
Only electrons near EF contribute to current !

Sommerfeld recovers the phenomenological results !

Sommerfeld Expansion
Sommerfeld Expansion for Electron Density
Sommerfeld Expansion for Electron Energy
Density of States is the Central Character in this Story
Approach:
bandstructure

Lecture 4: Vibrations in Solids
Outline
• Review Lecture 3
• Sommerfeld Theory of Metals
• 1-D Elastic Continuum
• 1-D Lattice Waves
Drude Theory
Balance equation for forces on electrons:
In steady-state when B=0:

Density of States
In steady-state:
In the continuum models, we assume that electron scattering is

sufficiently fast that all the energy pumped into the electrons is
randomized; all additional energy heats the electrons
How do we relate ∆E and T ?

Specific Heat and Heat Capacity
Again assume that the heat and change in internal energy are the same:
(heat capacity)
Take constant volume since this ensures

none of the extra energy is going into work
(think ideal gas)
(specific heat)
Specific heat is independent of temperature…Law of Dulong and Petit

Specific heat is independent of temperature…NOT TRUE !
capacity of lattice
Outline
Low Temperature Specific Heat of the Free Electron Gas
Only electrons near EF contribute to current !

Sommerfeld recovers the phenomenological results !

Sommerfeld Expansion
Sommerfeld Expansion for Electron Density
Sommerfeld Expansion for Electron Energy

capacity of lattice
Density of States is the Central Character in this Story
Approach:
bandstructure

Outline
1-D Elastic Continuum
Stress and Strain
uniaxial loading
Lo
L
Stress:
Strain: Normal strain:
If ux is uniform there is no strain, just rigid body motion.

METALS :
Young’s Modulus
Tungsten (W) 406
Chromium (Cr) 289
Berylium (Be) 200 - 289
Nickel (Ni) 214
Iron (Fe) 196
Low Alloy Steels 200 - 207
Stainless Steels 190 - 200
Young’s Modulus For Various Materials (GPa)
Cast Irons 170 - 190
from Christina Ortiz Copper (Cu) 124
CERAMICS GLASSES AND SEMICONDUCTORS Titanium (Ti) 116
Diamond (C) 1000 Brasses and Bronzes 103 - 124
Tungsten Carbide (WC) 450 -650 Aluminum (Al) 69
Silicon Carbide (SiC) 450
Aluminum Oxide (Al2O3) 390 PINE WOOD (along grain): 10
Berylium Oxide (BeO) 380
Magnesium Oxide (MgO) 250 POLYMERS :
Zirconium Oxide (ZrO) 160 - 241 Polyimides 3-5
Mullite (Al6Si2O13) 145 Polyesters 1-5
Silicon (Si) 107 Nylon 2-4
Silica glass (SiO2) 94 Polystryene 3 - 3.4
Soda-lime glass (Na2O - SiO2) 69 Polyethylene 0.2 -0.7
Rubbers / Biological
Tissues 0.01-0.1
Dynamics of 1-D Continuum
1-D Wave Equation
Net force on incremental volume element:

1-D Wave Equation
Velocity of sound, c, is proportional to stiffness and inverse prop. to inertia

1-D Wave Equation Solutions
Clamped Bar: Standing Waves

1-D Wave Equation Solutions
Periodic Boundary Conditions: Traveling Waves

Volume Dilatation
Lo apply load L
Volume change is sum of all three normal strains

Poisson’s Ratio
ν is Poisson’s Ratio – ratio of lateral strain to axial strain
Poisson’s ratio can not exceed 0.5, typically 0.3

Poisson’s Ratio Example
Aluminum: EY=68.9 GPa, ν = 0.35
5kN
5kN 75mm
20mm
5kN
5kN 75mm
20mm
5kN
5kN 75mm
20mm
Shear Strain
Shear loading Shear plus rotation Pure shear

φ
2φ
Pure shear strain
Shear stress
G is shear modulus
Stress and Strain Tensors
For most general isotropic medium,
Initially we had three elastic constants: EY, G, e
Now reduced to only two: λ, µ

If we look at just the diagonal elements
Inversion of stress/strain relation:

Example of Uniaxial Stress
Lo
L
3-D Wave Equation
Total force is the sum of the forces on all the surfaces

3-D Wave Equation
Net force in the x-direction:

3-D Wave Equation
Finally, 3-D wave equation….

Fourier Transform of 3-D Wave Equation
Anticipating plane wave solutions, we Fourier Transform the equation….
Three coupled equations for Ux, Uy, and Uz….

Dynamical Matrix
Express the system of equations as a matrix….
Turns the problem into an eigenvalue problem for

the polarizations of the modes (eigenvectors) and
wavevectors q (eigenvalues)….
Solutions to 3-D Wave Equation
Transverse polarization waves:
Longitudinal polarization waves:

Summary
1. Dynamical Equation can be solved by inspection
2. There are 2 transverse and 1 longitudinal polarizations for each q
3. The dispersion relations are linear
4. The longitudinal sound velocity is always greater than

the transverse sound velocity
Lecture 5: Specific Heat of Lattice Waves
Outline
• Lattice Density of Modes
• Specific Heat of Lattice
A prismatic bar with length L = 200 mm and a circular cross

section with a diameter D = 10 mm is subjected to a tensile
load P = 16 kN. The length and diameter of the deformed
bar are measured and determined to be L’ = 200.60 mm
and D’ = 9.99 mm. What are the modulus of elasticity and
the Poisson’s ratio for the bar?
Shear Strain
Shear loading Shear plus rotation Pure shear

φ
2φ
Pure shear strain
Shear stress
G is shear modulus
For most general isotropic medium,
Initially we had three elastic constants: EY, G, e
Now reduced to only two: λ, µ

If we look at just the diagonal elements
Inversion of stress/strain relation:

Example of Uniaxial Stress
Lo
L
3-D Wave Equation
Total force is the sum of the forces on all the surfaces

3-D Wave Equation
Net force in the x-direction:

3-D Wave Equation
Finally, 3-D wave equation….

Fourier Transform of 3-D Wave Equation
Anticipating plane wave solutions, we Fourier Transform the equation….
Three coupled equations for Ux, Uy, and Uz….

Dynamical Matrix
Express the system of equations as a matrix….
Turns the problem into an eigenvalue problem for

the polarizations of the modes (eigenvectors) and
wavevectors q (eigenvalues)….
Solutions to 3-D Wave Equation
Transverse polarization waves:
Longitudinal polarization waves:

Direct Measurements of Sound Velocity
Ge at 1.9 K
Bolometer signal
Time (microseconds)
LA phonons are faster,

since real solids are not isotropic the TA phonons travel at different velocity
Summary
1. Dynamical Equation can be solved by inspection
2. There are 2 transverse and 1 longitudinal polarizations for each q
3. The dispersion relations are linear
4. The longitudinal sound velocity is always greater than

the transverse sound velocity
Counting Vibrational Modes
Solid as an Acoustic Cavity
For each of three polarizations:
If the plane waves are constrained to the solid with dimension L

and we use periodic boundary conditions:
number of states in dω :
Specific Heat of Solid
How much energy is in each mode ?
Need to approximate the amount of energy in each mode

at a given temperature…
If we assume equipartition, we will again

Dulong-Petit which is not consistent with experiment for solids…
Approach:
• Quantize the amplitude of vibration for each mode
• Treat each quanta of vibrational excitation as a bosonic particle, the phonon
• Use Bose-Einstein statistics to determine the number of phonons

in each mode
Lattice Waves as Harmonic Oscillator
Treat each mode and each polarization as an

independent harmonic oscillator:
is the quantum number associated with harmonic
Now, we think of each quantum of excitation as a particle…
lattice waves electromagnetic waves

acoustic cavity (solid) optical cavity (metal box)
quanta observed quanta observed
by light scattering by photoelectric effect
bosons ? bosons (eg. laser)
Lattice Waves in Thermal Equilibrium
Lattice waves in thermal equilibrium don’t have a single well

define amplitude of vibration…
For each mode, there is a distribution of amplitudes…
Bose-Einstein distribution
Total Energy of a Lattice in Thermal Equilibrium
number of states in dω :
Specific Heat of a Crystal Lattice
Aside: Thermal Energy of Photons
Energy density of blackbody:
Specific heat :
Lecture 8: Lattice Waves in 1D Monatomic Crystals
Outline
• Overview of Lattice Vibrations so far
• Models for Vibrations in Discrete 1-D Lattice
• Example of Nearest Neighbor Coupling Only
• Relating Microscopic and Macroscopic Quantities
Continuum Models
1-D Wave Equation
Velocity of sound, c, is proportional to stiffness and inverse prop. to inertia
Periodic Boundary Conditions: Traveling Waves

Continuum Models
T3 Specific Heat
The Atomistic Perspective
Arrangement of Atoms and Bond Orientations
Arrangement of Atoms and Bond Orientations
Diamond Crystal Structure:

Silicon
Bond angle = 109.5º
• Add 4 atoms to a FCC

• Tetrahedral bond arrangement
• Each atom has 4 nearest neighbors and
12 next nearest neighbors
(Energy - IH) / IH
Strain in a Discrete Lattice
Example of Nearest Neighbor Interactions
equilibrium
n-3 n-2 n-1 n n+1 n+2 n+3
un-3 un-2 un-1 un un+1 un+2 un+3
strained
is the discrete displacement of an atom from its equilibrium position

General Expansion
The potential energy associated with the strain is a complex function of

the displacements.
where
and the force on each lattice atom

Harmonic Matrix
Spring Constants Between Lattice Atoms
Harmonic Matrix:
Dynamics of Lattice Atoms
Force on the jth atom (away from equilibrium)…

Solutions of Equations of Motion
Convert to Difference Equation
Time harmonic solutions…
Plugging in, converts equation of motion into coupled difference equations:

We can guess solution of the form:
This is equivalent to taking the z-transform…

Consider Undamped Lattice Vibrations
We are going to consider the undamped vibrations of the lattice:

Dynamical Matrix
Dynamical Matrix
equilibrium
n-3 n-2 n-1 n n+1 n+2 n+3
strained
Harmonic matrix:
Dynamical matrix:
k= - π/a k=π/a k
2nd Brillouin zone 1st Brillouin zone 2nd Brillouin zone

ω
k=-2π/a k=-π/a A k=π/a B k=2π/a k
From what we know about Brillouin zones the points A and B

(related by a reciprocal lattice vector) must be identical
This implies that the wave form of the vibrating atoms must also be identical.
ω
A: k=-0.7π/a
κ=-2π/a κ=-π/a A κ=π/a B κ=2π/a κ B: k=1.3π/a
n-5 n-4 n-3 n-2 n-1 n n+1 n+2 n+3 n+4 n+5
But: note that point B represents a wave travelling right, and point A one travelling left
ω
c Consider point C at the zone boundary
When k=π/a, λ=2a, and motion becomes

that of a standing wave (the atoms are
bouncing backward and forward against
κ=-2π/a κ=-π/a κ=π/a κ=2π/a κ each other
λ=2a
n-5 n-4 n-3 n-2 n-1 n n+1 n+2 n+3 n+4 n+5
In the limit of long-wavelength, we should recover the continuum model…
Linear dispersion, just like the sound waves for the continuum solid
Lecture 9: Lattice Waves in 1D with Diatmomic Basis
Outline
• 1-D Lattice with Basis
• Example of Nearest Neighbor Coupling
• Optical and Acoustic Phonon Branches
Strain in a Discrete 1-D Monatomic Lattice
General Expansion
equilibrium
n-3 n-2 n-1 n n+1 n+2 n+3

strained
Equations of Motion for Lattice Atoms
Harmonic Matrix:
Force on the jth atom (away from equilibrium)…

Assuming time-harmonic solutions, converts into coupled difference equations:

equilibrium
n-3 n-2 n-1 n n+1 n+2 n+3
strained

ω

Summary of Phonon Dispersion Calculation
• Taylor series expansion for total potential stored in all bonds

• Neglect first order since in equilibrium F=0
• Truncate expansion at second order, assume small amplitudes
• Determine harmonic matrix from potential energy
• Represents bond stiffness
• Assume time harmonic and discrete ‘plane wave’ solutions

• Determine dynamical matrix from harmonic matrix plus phase progression
• Determine dispersion relation

Strain in a Discrete Lattice with Basis
equilibrium
n-1 α1 α2 n n+1
uj[n-2] ui[n-1] uj[n-1] ui[n] uj[n] ui[n+1] uj[n+1]

strained
Harmonic Matrix for 1-D Lattice with Basis
Equations of Motion
The force on the l th basis atom in the nth unit cell…

Matrix Representation of Equations of Motion
Can collect system of equations for each atom in the basis as a matrix…
Plane Wave Solutions & the Dynamical Matrix
equilibrium
n-1 α1 α2 n n+1
u2[n-2] u1[n-1] u2[n-1] u1[n] u2[n] u1[n+1] u2[n+1]

strained
Dynamical Matrix for 1-D Lattice with Basis
Example of Nearest Neighbor Coupling
Dispersion Relation for 1-D Lattice with Basis
Dispersion Relation for 1-D Lattice with Basis
optical branch
acoustic branch
k
Lattice Waves at k=0
Lattice Waves at Small k
Lattice Waves Near Zone Boundary
Dispersion Relation for 3-D Lattices
Lecture 10, 11: Specific Heat of Discrete Lattice
Outline
• 2-D Lattice Waves Solutions

• Review Continuum Specific Heat Calculation
• Density of Modes
• Quantum Theory of Lattice Vibrations
• Specific Heat for Lattice
• Approximate Models
Lattice Waves in 3-D Crystals
Second order Taylor series expansion for total potential energy:
Harmonic Matrix:
Equation of motion for lattice atoms assuming ‘plane wave’ solutions:
Dynamical Matrix:
Lattice Waves in 3-D Crystals
Dimension of system is given by

(number of basis atoms) x (dimension of lattice)
Bond Stretching and Bending
Example: 1-D Diatomic Lattice with Bond Stretching and Bending
Potential Energy
M1 M2
y
x αsA αsB
Example: ‘1-D’ Diatomic Lattice with Bond Stretching and Bending
Potential Energy
M1 M2
y
x αsA αsB
Example: 2-D Lattice with Bond Stretching
Potential Energy
a1 α1
a2
α2
Elements of the Dynamical Matrix
Dynamical Matrix
Dispersion Relation
Longitudinal Waves:
Transverse Waves:
Dispersion Relations
Approach:

in each mode
Simple Harmonic Oscillator
E
ψ (x) U ( x ) = 12 mω 2 x 2
2
n=3 E 3 = 72 h ω
n=2 E 2 = 52 h ω
n =1 E1 = 32 h ω
n=0 E 0 = 12 h ω
x
Hamiltonian for Discrete Lattice
Potential energy of bonds in 3-D lattice with basis:
For single atom basis in 3-D, µ & ν denote x,y, or z direction:

Hamiltonian for Discrete Lattice
Plane Wave Expansion
The lattice wave can be represented as a superposition of plane waves

(eigenmodes) with a known dispersion relation (eigenvalues)….
σ denotes polarization
Commutation Relation for Plane Wave Displacement
…commute unless we have same polarization and k-vector

Creation and Annhilation Operators for Lattice Waves
Operators for the Lattice Displacement
We will use this for electron-phonon scattering…

Specific Heat with Continuum Model for Solid
3-D continuum density of modes in dω :

Specific Heat with Discrete Lattice
Density of Modes from Dispersion
ω
ωm
ω
ωm
Specific Heat with Discrete Lattice
Density of Modes from Dispersion
Cu
Approach:

in each mode
And we are done…

Lecture 12: Electrons in a Periodic Solid
Outline
• Review Lattice Waves

• Brillouin-Zone and Dispersion Relations
• Introduce Electronic Bandstructure Calculations
• Example: Tight-Binding Method for 1-D Crystals
Solutions of Lattice Equations of Motion
Convert to Difference Equation
Time harmonic solutions…
Plugging in, converts equation of motion into coupled difference equations:

We can guess solution of the form:
This is equivalent to taking the z-transform…

Consider Undamped Lattice Vibrations
We are going to consider the undamped vibrations of the lattice:

Dynamical Matrix
Solution of 1-D Lattice Equation of Motion

ω

This implies that the wave form of the vibrating atoms must also be identical.
Solution of 3-D Lattice Equation of Motion
Phonon Dispersion in FCC with 2 Atom Basis
http://debian.mps.krakow.pl/phonon/Public/phrefer.html
Approaches to Calculating Electronic Bandstructure
Nearly Free Electron Approximation:

• Superposition of a few plane waves
Cellular Methods (Augmented Plane Wave):
• Plane wave between outside rs

• Atomic orbital inside rs (core)
Pseudopotential Approximation:
• Superposition of plane waves
coupled by pseudopotential
k.p:
• Superposition of bandedge (k=0) wavefunctions
Tight-binding Approximation (LCAO):

• Superposition of atomic orbitals
Band Formation in 1-D Solid
Simple model for a solid: the one-dimensional solid, which consists of a single, infinitely long
line of atoms, each one having one s orbital available for forming molecular orbitals (MOs).
When the chain is extended:

Î The range of energies covered by the MOs
is spread
Î This range of energies is filled in with more
and more orbitals
Î The width of the range of energies of the
MOs is finite, while the number of molecular
orbitals is infinite: This is called a band .
4β
“s” band
Tight-binding (LCAO) Band Theory
LCAO Wavefunction
Energy for LCAO Bands
Reduced Hamiltonian Matrix: Reduced Overlap Matrix:

Reduced Overlap Matrix for 1-D Lattice
Single orbital, single atom basis
Reduced Hamiltonian Matrix for 1-D Lattice
Energy Band for 1-D Lattice
LCAO Wavefunction for 1-D Lattice
k=0
k≠0
k=π/a
k = 2πp /( Na )
remember H2 ?
lowest energy (fewest nodes)
H2
highest energy (most nodes)
Bloch’s Theorem
Translation of wavefunction by a lattice constant…
…yields the original wavefunction multiplied by a phase factor
Consistent that the probability density is equal at each lattice site

Wavefunction Normalization
Using periodic boundary conditione for a crystal

with N lattice sites between boundaries…
Counting Number of States in a Band
Combining periodic boundary condition…
…with Bloch’s theorem…
…yields a discrete set of k-vectors
Within the 1st Brillouin Zone there are N states or 2N electrons

Tight-binding and Lattice Wave Formalism
Electrons (LCAO) Lattice Waves

Outline
• Review Electronic Bandstructure Calculations

• Example: 1-D Crystals with Two Atomic Functions
• Example: 1-D Crystals with Two Atom Basis
Overview
2N electrons each
for px,py,pz
2N electrons
Tight-binding and Lattice Wave Formalism
Electrons (LCAO) Lattice Waves

Reduced Hamiltonian Matrix: Reduced Overlap Matrix:

Reduced Overlap Matrix for 1-D Lattice
Reduced Hamiltonian Matrix for 1-D Lattice
k=0
k≠0
k=π/a
k = 2πp /( Na )
Two orbital, single atom basis
2N electrons each
for px,py,pz
2N electrons
Reduced Hamiltonian and Overlap Matrices:

Hamiltonian Matrix
Overlap Matrix
Solutions
At k=0:
pure s
pure p
Solutions
At k=π/a:
pure s
pure p
For k away from zone center and zone boundary, bands are mixture of s and p
but will have a dominant s-like or p-like character….
At high symmetry points tight-binding returns pure orbitals…

Solutions
Single orbital, two atom basis
At k=0:
At k=π/a:
Outline
• Review LCAO for 1-D Crystals

• Preview Problem for 2-D Crystal
• 2-D and 3-D Tight-binding
• Example: 2-D Crystal, single atom basis, 4 orbitals
highest energy (most nodes)
lowest energy (fewest nodes)

Es= - 12 eV, Ep= - 6 eV, Vssσ= - 1 eV, Vppσ = Vppπ = + 1 eV

Es= - 0.9 eV, Vs,a= - 0.4 eV, Vs,a-d = - 0.2 eV

Hamiltonian Matrix
Preview Problem: 2D Monatomic Square Crystals
LCAO Basis for FCC Crystals
Ga: [Ar]3d10 4s2 4p1

As: [Ar]3d10 4s2 4p3
Tight-binding for 3-D Crystals
Best estimate for energy with LCAO basis….
Hamiltonian matrix….
Overlap matrix….
Since the probability of finding electrons at each lattice site is equal…
Consequently…
Orbital Overlaps for 3-D Crystals
distance from positive to negative lobe of p-orbital

Diamond and Zincblende
2D Monatomic Square Crystals
Es= - 10.11 eV
Ep= - 4.86 eV
a = 5.5 A
W
Γ X
X Γ W
Dispersion Relations at Γ=0
Dispersion Relations at Γ=0
Variations with Lattice Constant
W
X Γ W
Γ X
a = 8.3 A
X Γ W
a = 5.5 A
W
X Γ W
Γ X
a = 2.8 A
X Γ W
Fermi Energy
How many states per band ?
where n is the areal density of atoms
To estimate Fermi energy we need to know the number of

outermost valence electrons each atom has…
I II III IV V VI VII VIII

11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
a = 5.5 A
conductor Al
Mg
insulator
W
conductor
Γ Na
X

11 12 13 14 15 16 17 18
Reducing a, makes Mg a conductor ! Na Mg Al Si P S Cl Ar
Name: __________________
Matrix element (s-px) _________________________
Matrix element (s-py) _________________________
Matrix element (px -px) _________________________
Matrix element (px - py) _________________________

Outline
• Review 2-D Tight-binding

• 3-D Tight-binding
• Semiconductor Fermi Energy
• Silicon Bandstructure
Es= - 10.11 eV
Ep= - 4.86 eV
a = 5.5 A
W
Γ X
X Γ W
W
X Γ W
Γ X
a = 8.3 A
X Γ W
a = 5.5 A
W
X Γ W
Γ X
a = 2.8 A
X Γ W
Fermi Energy
How many states per band ?
where n is the areal density of atoms
To estimate Fermi energy we need to know the number of

outermost valence electrons each atom has…

11 12 13 14 15 16 17 18
a = 5.5 A
conductor Al
Mg
insulator
W
conductor
Γ Na
X

Reducing a, makes Mg a 11 12 13 14 15 16 17 18
conductor (semimetal) ! Na Mg Al Si P S Cl Ar
LCAO Basis for FCC Crystals
Ga: [Ar]3d10 4s2 4p1

As: [Ar]3d10 4s2 4p3
Best estimate for energy with LCAO basis….
Hamiltonian matrix….
Overlap matrix….
Since the probability of finding electrons at each lattice site is equal…
Consequently…
Hamiltonian Matrix
- + +
- -
= + +
= +
+ -
- + -
- +
- +
= -
+ + +
= +
109o
Zincblende LCAO Bands
Reduced Hamiltonian Matrix
Nearest Neighbors
Reduced Hamiltonian Matrix
Silicon Bandstructure
Si: [Ne] 3s2 3p2

4 e- per silicon atom
2 silicon atoms per lattice site
total: 8 electrons at each site
Silicon and Germanium Bandstructure
Si: [Ne] 3s2 3p2 Ge: [Ar]3d10 4s2 4p2

LCAO and Nearly Free Electron Bandstructure
Lecture 16: Nearly Free Electron Bands
Outline
• Fun: Application of 1-D Tight Binding

• Free Electron in Reduced Zone Representation
• Nearly Free Electron Bands
• Labeling Eigenvectors
B. Ethene and frontier orbitals Ethene: CH2=CH2
Within the Hückel approximation, the secular determinant becomes:
D E E
D E 2 E 2 0
E D E
E- = D - E energy of the Lowest Unoccupied Molecular Orbital (LUMO)
E+ = D + E energy of the Highest Occupied Molecular Orbital (HOMO)
S D E + -
LUMO= 2S*
- +
&S &S
2|E|
+ +
S DE - -
HOMO= 1S
Sketch Calculated (Hartree-Fock level)
Î HOMO and LUMO are the frontier orbitals of a molecule.
Î those are important orbitals because they are largely responsible for many chemical and
optical properties of the molecule.
Courtesy of &ULVSLQ;DYLHU'HSWRI3K\VLFV Note: The S orbitals together give rise to an cylindrical
/LQNçSLQJ8QLYHUVLW\ distribution of charge. Electrons can circulate around this torus
can create magnetic effect detected in NMR
Free Electron Dispersion Relation
S/a S/a S/a S/a

k
Nearly Free Electron Dispersion Relation
For weak lattice potentials, E vs k is still approximately correct…
Dispersion relation must be periodic….
S/a S/a S/a S/a

k

Expect all solutions to be represented within the Brillouin Zone (reduced zone)
S/a S/a S/a S/a

k

S/a S/a S/a S/a

k

S/a S/a S/a S/a

k
Extension to 3-D requires, translation by reciprocal lattice vectors
in all directions…
Ge
E
S/a S/a S/a S/a

k
Ge
E
S/a S/a S/a S/a

k
Finite Basis Set Expansion with Plane Waves
Fourier series expansion of Bloch function
Basis functions in expansion are…

Hamiltonian Matrix
Basis functions are exactly orthogonal…overlaps are all zero.

Hamiltonian Matrix
Fourier Series coefficients for the lattice potential…

Hamiltonian Matrix
Infinite Basis Set Expansion with Plane Waves
Hamiltonian Matrix
Hamiltonian Matrix
Eigenvectors for Nearly Free Electron Bands
Fourier transform
Sample eigenvector…
Lecture 17: Nearly Free Electron Bands (Part III)
Outline
• Free Electron Bands

• Nearly Free Electron Bands
• Approximate Solution of Nearly Free Electron Bands
• Bloch’s Theorem
• Properties of Bloch Functions
Free Electron Dispersion Relation
−3π/a −π/a π/a 3π/a

k
For weak lattice potentials, E vs k is still approximately correct…

k


k


k


k
Ge
E

k
Ge
E

k
Fourier series expansion of Bloch function
Basis functions in expansion are…

Hamiltonian Matrix
Fourier Series coefficients for the lattice potential…

Hamiltonian Matrix
Why Is Lattice Potential Important Near Crossing Points ?
Let’s consider lattice potential to be a perturbation on free electrons….
Periodic Perturbation of Free Electron Bands
Energy up to second-order in perturbation expansion….
Matrix elements for periodic potential…

If the potential is sufficiently weak, this is a small perturbation on the

free electron bands, unless
Since these are free electron energies, we can relate this easily to
the wave vectors…
, when k is at edge of B-Z

If only two bands cross…

Solutions
Eigen-values…
Eigen-vectors…
Solutions
low energy solution

high energy solution
Plots are for a potential of the form…

Bloch’s Theorem
‘When I started to think about it, I felt that the

main problem was to explain how the electrons
could sneak by all the ions in a metal….
By straight Fourier analysis I found to my delight
that the wave differed from the plane wave of free
electrons only by a periodic modulation’
F. BLOCH
For wavefunctions that are eigenenergy states in a periodic potential…
or
Proof of Bloch’s Theorem
Step 1: Translation operator commutes with Hamiltonain…
so they share the same eigenstates.
Translation and periodic Hamiltonian commute…
Therefore,
Step 2: Translations along different vectors add…

so the eigenvalues of translation operator are exponentials
Normalization of Bloch Functions
Conventional (A&M) choice of Bloch amplitude…
6.730 choice of Bloch amplitude…
Normalization of Bloch amplitude…

Momentum and Crystal Momentum
where the Bloch amplitude is normalized…
Physical momentum is not equal to crystal momentum
So how do we figure out the velocity and trajectory in real space of electrons ?
Lecture 18: Properties of Bloch Functions
Outline
• Momentum and Crystal Momentum

• k.p Hamiltonian
• Velocity of Electrons in Bloch States
Bloch’s Theorem
‘When I started to think about it, I felt that the

main problem was to explain how the electrons
could sneak by all the ions in a metal….
By straight Fourier analysis I found to my delight
that the wave differed from the plane wave of free
electrons only by a periodic modulation’
F. BLOCH
For wavefunctions that are eigenenergy states in a periodic potential…
or
Therefore,

Normalization of Bloch Functions
Conventional (A&M) choice of Bloch amplitude…
6.730 choice of Bloch amplitude…
Normalization of Bloch amplitude…

where the Bloch amplitude is normalized…
Physical momentum is not equal to crystal momentum
So how do we figure out the velocity and trajectory in real space of electrons ?
canceling exponentials from both sides
A useful identity, for the action of the momentum operator

on the Bloch amplitude….
Leads us to, the action of the Hamiltonian on the Bloch amplitude….

k.p Hamiltonian
(in our case q.p)
If we know energies as k we can extend this to calculate energies at k+q

for small q…
k.p Hamiltonian
Taylor Series expansion of energies…
Matching terms to first order in q…

Velocity of an Electron in a Bloch Eigenstate
Electron Wavepacket in Periodic Potential
Wavepacket in a dispersive media…
So long as the wavefunction has the same short range periodicity as the
underlying potential, the electron can experience smooth uniform motion
at a constant velocity.
Energy Surface for 2-D Crystal
In 2-D, circular energy contours result in parallel to

In general, for higher lying energies is not parallel to

4 conduction bands 4 valence bands




Semiclassical Equation of Motion
Ehrenfest’s Theorem:
Consider some external force that perturbs the electron in the lattice…
An elegant derivation can be made if we consider the equation

of motion for the lattice translation operator
Since the lattice translation and Hamiltonian commute with each other…
Lets consider a specific external force…an external uniform electric field…
Equation of motion for translation operator becomes…
Can evaluate the commutation relation in the position basis…

Plugging in this commutation relation into the equation of motion…
Solving the simple differential equation…
From Bloch’s Thm. We know the

eigenvalues of TR…
Electron Motion in a Uniform Electric Field
2-D Crystal
http://www.physics.cornell.edu/sss/ziman/ziman.html
Lecture 19: Motion of Electronic Wavepackets
Outline
• Review of Last Time

• Detailed Look at the Translation Operator
• Electronic Wavepackets
• Effective Mass Theorem
Therefore,


k.p Hamiltonian
(in our case q.p)

for small q…
k.p Hamiltonian

In 2-D, circular energy contours result in parallel to

In general, for higher lying energies is not parallel to


2-D Crystal
Properties of the Translation Operator
Definition of the translation operator…
Bloch functions are eigenfunctions of the lattice translation operator…
Lattice translation operator commutes with the lattice Hamiltonian (Vext=0)
The translation operator commutes with other translation operators…

Lets see what the action of the following operator is…
This is just the translation operator…

Another Look at Electronic Bandstructure

k
As we will see, it is often convenient to represent the bandstructure by
its inverse Fourier series expansion…
Translation Operator and Lattice Hamiltonian
From before, the eigenvalue equation for the translation operator is….
If we multiply this by the Fourier coefficients of the bandstructure…
…and sum over all possible lattice translations…
…we see that the eigenvalue on the left is just the bandstructure (energy)
This suggests the operator on the left is just the crystal Hamiltonian !
No wonder
Electron Wavepacket in Periodic Potential
Wavepacket in a dispersive media…
So long as the wavefunction has the same short range periodicity as the
underlying potential, the electron can experience smooth uniform motion
at a constant velocity.
Wavefunction of Electronic Wavepacket
The eigenfunction for k~k0 are approximately…
A wavepacket can therefore be constructed from Bloch states as follows…
G is a slowly varying function…

Since we construct wavepacket from a small set of k’s…
…the envelope function must vary slowly…wavepacket must be large…

Action of Crystal Hamiltonian on Wavepacket
It appears that the Hamiltonian only acts on the slowly varying amplitude…
Effective Mass Theorem
If we can consider an external potential (eg. electric field) on the crystal…
The influence of the external field on the wavepacket…
We can solve Schrodinger’s equation just for the envelope functions…

Normalization of the Envelope Function
Since the envelope is slowly varying…it is nearly constant over the

volume of one primitive cell…
What is the Position of Wavepacket ?
Proof that…
What is the Momentum of Wavepacket
Summary
Without explicitly knowing the Bloch functions, we can solve
for the envelope functions…
Bandstructure shows up in here…
The envelope functions are sufficient to determine the

expectation of position and crystal momentum for the
system…
Lecture 20: Impurity States
Outline
• Semiclassical Equations of Motion

• Review of Last Time: Effective Mass Hamiltonian
• Example: Impurity States
k.p Hamiltonian


2-D Crystal
Definition of the translation operator…
Bloch functions are eigenfunctions of the lattice translation operator…
Lattice translation operator commutes with the lattice Hamiltonian (Vext=0)
The translation operator commutes with other translation operators…

Lets see what the action of the following operator is…
This is just the translation operator…

Another Look at Electronic Bandstructure

k
As we will see, it is often convenient to represent the bandstructure by
its inverse Fourier series expansion…
The eigenfunction for k~k0 are approximately…
A wavepacket can therefore be constructed from Bloch states as follows…
Since we construct wavepacket from a small set of k’s…
…the envelope function must vary slowly…wavepacket must be large…

Summary of Last Time
Without explicitly knowing the Bloch functions, we can solve

for the envelope functions…
The envelope functions are sufficient to determine the

expectation of position and crystal momentum for the
system…
Using Bandstructure in Effective Mass Hamiltonian
where
For example…
Donor Impurity States
Example of Effective Mass Approximation
Replace silicon (IV) with group V atom…

This is a central potential problem, like the hydrogen atom…

Hydrogenic wavefunction with an equivalent Bohr radius..
n-type Si
Donor ionization energy… EC
ED
Egap~ 1 eV
EV
When there are Nd donor impurities…
E
Acceptor Impurity States
Replace silicon (IV) with group III atom…

Another central potential problem…

Hydrogenic wavefunction with an equivalent Bohr radius..
Acceptor ionization energy… EC
EA
EV
p-type Si
Lecture 21:
Outline
• Dynamical Effective Mass

• Fermi Surfaces
• Electrons and Holes
Semiclassical Equations of Motion
Lets try to put these equations together….
Looks like Newton’s Law if we define the mass as follows…
dynamical effective mass
mass changes with k…so it changes with time according to k

Dynamical Effective Mass (3D)
Extension to 3-D requires some care,

F and a don’t necessarily point in the same direction
where
Ellipsoidal Energy Surfaces
Fortunately, energy surfaces can often be approximate as…

a = 5.5 A
conductor Al
‘Mg’
insulator
W
conductor
Γ Na
X

11 12 13 14 15 16 17 18
4 conduction bands
Si: [Ne] 3s2 3p2
4 e- per silicon atom
2 silicon atoms per lattice site
total: 8 electrons at each site
4 valence bands
Finite Temperatures
Free Electron Fermi Surfaces (2D)
T=0
For free electrons energy surfaces are simple spheres (circles)…
Valence (# of electrons) determines radius of energy surface… 1st zone
2nd zone
3rd zone
Fermi Surfaces (3D)
2D
When k near to BZ boundary:
E contours become distorted
Fermi Surfaces (3D)
Ne = 1 monovalent metals, e.g. Na, Cu, with values ~ f.e. theory
other cases, e.g. Be (Ne=2), Al (Ne=3), there are serious differences

Finite Temperatures
Overview of Electron Distributions
Metal Insulator Semi- n-Doped

or Conductor Semi-
Semiconductor T=0 Conductor
T=0
Electron Distributions in Doped Semiconductors
+1 e-
n-type Si
EC
ED
Semi- n-Doped
Conductor Semi-
T=0 Conductor Egap~ 1 eV
EV
Electron and Holes
Electrons in conduction band
Holes in valence band
Semi-
Conductor
T=0
Motion of Valence Electrons
electrons have negative charge
k-space
Valence electrons (and vacancy) all move in the positive kx direction…

valence electrons have negative mass !
Real space
Vacancy ends up moving in the direction of the
electric field as if it had a positive charge
Hole is a quasi-particle with positive charge and positive mass…

Hole is a quasi-particle with

positive charge and positive
mass…
k-space
hole dispersion
Lecture 23: Effective Mass
Outline
• Review of Last Time

• A Closer Look at Valence Bands
• k.p and Effective Mass
Lets try to put these equations together….
Looks like Newton’s Law if we define the mass as follows…
dynamical effective mass
mass changes with k…so it changes with time according to k

Extension to 3-D requires some care,

F and a don’t necessarily point in the same direction
where
Ellipsoidal Energy Surfaces
Fortunately, energy surfaces can often be approximate as…

Motion of Valence Electrons (and Holes)
valence electrons have negative mass !
Real space
Vacancy ends up moving in the direction of the
electric field as if it had a positive charge
Hole is a quasi-particle with positive charge and positive mass…

Increasing the orbital overlap, reduces the effective mass…

W
X Γ W
Γ X
a = 8.3 A
X Γ W

a = 5.5 A
W
X Γ W
Γ X
a = 2.8 A
X Γ W

3D Band Structures
Lighter effective mass Larger overlap between orbitals
basis
orbital
a a a
light heavy heavy

mass mass mass
Bandstructure of GaAs
s like -orbital
(k)
p-like orbital
What is this split-off band ?

Spin-orbit Coupling Wavefunctions
heavy hole charge distribution light hole charge distribution

Orbital Angular Momentum
Angular momentum for quantum state with l = 2:
l=2 z
m=2
55º
m=1
24º
m=0
m = −1
m = −2
Spin-Orbit Coupling
L, Bl
+Zq
-q +Zq
-q
The effective current from the motion of a nucleus in a circular orbit…
…generates an effective magnetic field…

Spin-Orbit Splitting
L, Bl µs L, Bl
-q +Zq +Zq
S S -q
µs
Spin up: Spin down:
High Energy Low Energy
2P3/2
2P B L S J = L + S = 3/2
2P1/2
B L S J = L + S = 1/2
1S
Spin-Orbit Splitting in Hydrogen
L, Bl
-q +Zq
S
µs
Spin up:
High Energy
µs L, Bl
+Zq
S -q
Spin down:
Low Energy
Angular Momentum Addition Rules
Vectors Quantum Numbers
Example: l = 1, s = ½
j = 3/2 j = 1/2
Spin-orbit Coupling Wavefunctions
heavy hole charge distribution light hole charge distribution
heavy mass (along kz) light mass (along kz)

Bandstructure of GaAs
Spin-orbit
splitting
Another Approach to Bandstructure: k.p
Often it is easier to know the energies at a particular point (ex. Bandgap)

than it is to measure the effecitve mass
k.p is a way to relate your knowledge of energy levels at k to the effective

mass…using perturbation theory

k.p Hamiltonian
(in our case q.p)

for small q…
k.p Effective Mass
Second-order perturbation theory…

k.p Effective Mass
k.p Effective Mass
Example
Lets only consider two bands (valence and conduction) and assume
they are spherical…
k.p Effective Mass
Example
Level repulsion causes bands to curve as bandgap is reduceed…

Effective Mass and Bandgap
Experimental Data
Courtesy of Jasprit Singh; Used with Permission http://www.eecs.umich.edu/~singh/semi.html
(see "Semiconductor Bandstructure")

Lecture 24: Chemical Potential and Equilibrium
Outline
• Microstates and Counting

• System and Reservoir Microstates
• Constants in Equilibrium
Temperature & Chemical Potential
• Fermi Integrals and Approximations
Microstates and Counting
Ensemble of 3 ‘2-level’ Systems
Total Energy # of Microstates

E=0 g=1
E=1 g=3
E=2 g=3
E=3 g=1
As we shall see, g is related to the entropy of the system…

E=2 Microstates and Counting
Ensemble of 4 ‘2-level’ Systems
Total Energy # of Microstates

E=0 g=1
E=1 g=4
E=2 g=6
E=3 g=4
E=4 g=1
E=2
Microstates and Counting
The larger the systems, the stronger the dependence on E
For most mesoscopic and macroscopic systems, g is a monotonically

increasing function of E
System + Reservoir Microstates
Gibb’s Postulate = all microstates are equally likely
reservoir
system
Example
Consider a system of 3 ‘2-levels’ + a reservoir of 10 ‘2-levels’
Probability of finding: Es = 0 45/78

Es = 1 30/78
Es = 2 3/78
Most electrons are in the ground state so reservoir entropy is maximized !
System + Reservoir Microstates
reservoir
system
For sufficiently large reservoirs….
…we only care about the most likely microstate for S+R
Now we have a tool to look at equilibrium…

System + Reservoir in Equilibrium
reservoir
system
Equilibrium is when we are sitting in this max entropy (g) state…
is the same for two systems in equilibrium

reservoir
system
We observe that two systems in equilibrium have the same

temperature, so we hypothesize that…
This microscopic definition of temperature is a central result of stat. mech.

Boltzmann Distributions
S is the thermodynamic entropy of a system
Boltzmann observed that…
and
…so he hypothesized that

Boltzmann Distributions
reservoir controls
system distribution
Now we allow system and reservoir to

exchange particles as well as energy…
reservoir
system
reservoir
system
Entropy of reservoir can be expanded for each case…
Difference in entropy of the two configurations is…
..where µ is the electrochemical potential

Chemical potential is change in energy of system if one particle is added

without changing entropy
Example: Fermi-Dirac Statistics
Consider that the system is a single energy level which can either be…
occupied:
unoccupied:
Normalized probability…
Two Systems in Equilibrium
reservoir
system 1 system 2
Particles flow from 1 to 2…
Particles flow from 2 to 1…
In equilibrium…
Counting and Fermi Integrals
3-D Conduction Electron Density
3-D Hole Density
Exact solution !
Lecture 25: Chemical Potential and Non-equilibrium
Outline
• Fermi Integrals and Approximations

• Rate Equations for Non-equilibrium Electrons
• Quasi-Fermi Levels
3-D Hole Density
Boltzmann Approximation
Boltzmann Approximation:
Approximations for Fermi Integrals
3-D Carrier Densities
Sommerfeld Approximation:
Unger Approximation:
where
Approximations for Fermi Integrals
3-D Carrier Densities
Approximations for Inverse Fermi Integrals
Inverse First-order Sommerfeld Approximation:
for 0.04 error
Inverse Second-order Unger Approximation:
for 0.04 error

Near Equilibrium Electron Distributions
Optical Excitation
E1 E1
E2 E2
E3 E3
Intraband scattering: electron-electron

electron-acoustic phonon
Interband scattering: electron-hole

electron-phonon with defects
What are f1, f2, & f3 under illumination (non-equilibrium) ?

Rate Equation Formalism
number of electrons = number of states x probability of occupancy
assume total number of electrons in

N1, N2, & N3 is contant
Rate Constants in Equilibrium
Detailed Balance
In equilibrium:
Detailed balance:
In equilibrium, each scattering process balances with its inverse
Rate Equations
Assume the rate constants don’t change out of equilibrium…

Steady-State Solutions
Non-equilibrium
For example when intraband scattering is much faster than interband

scattering…
Non-equilibrium
Equilibrium Fermi-Dirac Non-equilibrium Quasi-Fermi-Dirac

distribution: distribution:
Intraband states have same chemical potential

in ‘equilibrium’ with each other because of fast intraband scattering
Non-equilibrium
Interband states have different chemical potentials

unless
Counting in Non-equilibrium Semiconductors
Equilibrium Quasi-equilibrium
Lecture 26: Inhomogeneous Solids
Outline
• Last Time: Quasi-Fermi Levels

• Inhomogenous Solids in Equilibrium
• Quasi-equilibrium Transport
• Heterostructures
Near Equilibrium Electron Distributions
Optical Excitation
E1 E1
E2 E2
E3 E3
Intraband scattering: electron-electron

electron-acoustic phonon
Interband scattering: electron-hole

electron-phonon with defects
What are f1, f2, & f3 under illumination (non-equilibrium) ?

Non-equilibrium
For example when intraband scattering is much faster than interband

scattering…
Non-equilibrium
Equilibrium Fermi-Dirac Non-equilibrium Quasi-Fermi-Dirac

distribution: distribution:
Intraband states have same chemical potential

in ‘equilibrium’ with each other because of fast intraband scattering
Non-equilibrium
Interband states have different chemical potentials

unless
Counting in Non-equilibrium Semiconductors
Equilibrium Quasi-equilibrium
Inhomogeneous Semiconductors in Equilibrium
Consider a solid with a spatially varying impurity concentration…
0.06
17
1 10
Electron Concentration (cm-3)
Electrostatic Potential (V)

0.05
16
8 10
0.04
16
6 10
0.03
16
4 10 0.02
16
2 10 0.01
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Microns Microns
In equilibrium, the carrier concentration is balanced by an internal

electrostatic potential…
If electrostatic potential varies slowly compared to wavepacket…
Dividing solid into slices where φi is uniform…
…the envelope function has solutions of the form…
…therefore the eigenenergies are…

Given the modified energy levels, the 3-D DOS becomes….
…in equilibrium the carrier concentration is…
Boltzmann approx.
The slowly varying electrostatic potential can be incorporated in

Quasi-equilibrium Transport
Species of Heterjunctions
Type I
Type II
Type III
Type I
Type III
http://www.utdallas.edu/~frensley/technical/hetphys
Tight-binding Calculation of Band Alignments
LCAO internally references bandstructures to each other…
GaAs InAs
Unfortunately, this doesn’t take into account the details of the

charges and bonding at the interface…
…need a self-consistent LCAO theory…still a research topic !
Tight-binding Calculation of Band Alignments
Example GaAs/InAs
Ga: As: In:
GaAs: InAs:
GaAs InAs
GaAs/InAs: (LCAO)
(experiment)
Experimentally Determined Band Alignment
Valence Band Alignment

Energy (eV)
Courtesy of Sandip Tiwari, Cornell University; Used with Permission

Conduction Band Alignment

Energy (eV)
InAs

Energy (eV)

SimWindows Software
Self-consistent solution of modified drift-diffusion & Poisson’s Equation…
http://www-ocs.colorado.edu/SimWindows/simwin.html
Lecture 27: Scattering of Bloch Functions
Outline
• Review of Quasi-equilibrium
• Occupancy Functions
• Fermi’s Golden Rule
• Bloch electron scattering
Occupancy Functions and Quasi-Fermi Functions
E1
E2
E3
Equilibrium occupancy function…
Quasi-equilibrium occupancy function…

Properties of the Occupancy Function
Moments of f (r,k,t)
Carrier density…
Current density…
Energy density…
All the classical information about the carriers is contained in f (r,k,t)

Rate Equations for Occupancy Function
Previously we developed rate equation for model 3-level system…
E1
E2
E3
Now, generalize for the whole occupancy function…

Rate Equations for Occupancy Function
rate of scattering from k’ to k
rate of scattering from k to k’
Perturbations that cause scattering….

• Impurities or defects
• Electron-phonon scattering
• Electron-photon scattering
Use Fermi’s Golden Rule to calculate scattering between Bloch functions…

Fermi’s Golden Rule
Scattering rate from k to k ’
• For weak collisions to continuum of nearby states…
where…
• Energy conservation holds for infrequent collisions …

General Scattering Potential
We will only consider scattering potentials of the form…
We can consider each potential term separately…
…Fermi…
final state energy is greater than initial absorption
final state energy is less than initial emission

Initial and Final States for Scattering
Envelope (effective mass) approximation…
∆ is volume of primitive cell

N is numer of primitive cells in solid
are slowly varying over ∆

Normalization of Envelope Functions
Since envelope functions are slowly varying…
Normalization of envelope functions…

Matrix Elements for Bloch States
Approximation for periodic scattering potential…
Approximation for slowly varying scattering potential…

Scattering from a Slowly Varying Potential
Matrix element is just the Fourier component of the scattering

potential at
Scattering Rate Calculations
Example: 1-D Scattering from Defect
• Sharply peaked potential scatters isotropically
• Static potential scatters elastically

Example: 1-D Scattering from Traveling Wave
• Periodic potentials conserve total momentum..

Scattering Times
Scattering time out of state k …
…at low densities…
…relaxation time is a function of state k
We usually measure some ensemble averaged relaxation time…
…which means we have to know

Scattering Times
Relaxation time for z-directed momentum…
Relaxation time for energy…

Lecture 28: Electron-phonon Scattering
Outline
• Bloch Electron Scattering

• Deformation Potential Scattering
• LCAO Estimation of Deformation Potential
• Matrix Element for Electron-Phonon Scattering
• Energy and Momentum Conservation
final state energy is greater than initial absorption
final state energy is less than initial emission

Scattering from a Slowly Varying Potential
Matrix element is just the Fourier component of the scattering

potential at
Example: 1-D Scattering from Traveling Wave
• Periodic potentials conserve total momentum..

Overview
Step 1: Determine Scattering Potential
Step 2: Calculate Matrix Elements
Step 3: Calculate State-State Transition Rates
Step 4: Calculate State Lifetime
Step 5: Calculate Ensemble Lifetime

Electron-Phonon Scattering Potential
Beyond the Born-Oppenheimer Approximation…
• Phonons change the electron energies by changing the bond displacement

• Both shear strain and local volume changes alter the electron energy
…change in the bandstructure due to a dilatation of solid by sound wave…
Relate the phonons to local changes in the volume (lattice constant)….

Only LA phonons cause local changes in the volume (lattice constant)….

Conduction band (diamond):
Valence band (diamond):

Silicon Example
Phonon Displacement Operator
See Lecture 11…phonon displacement operator
relating mass for continuum solid and discrete lattice

Overview

Electron-Phonon Matrix Element
Phonon absorption…
Electron-Phonon Matrix Element
For long wavelength phonons, can make slowly-varying approx…

Overview

Electron-Phonon Scattering Rate
Overview

Energy and Momentum Conservation
For acoustic phonons…

Typical acoustic phonon velocity…
Velocity of typical electron (300 K)…
final inital
Maximum momentum exchange…
Maximum energy exchange…
Acoustic phonon scattering is essentially elastic for 300K electrons…

Overview

Electron-Phonon Scattering Time
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麻省理工大学固体物理课件

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１分子－简单固体（ＰＤＦ）

Lecture 1: Molecules – the Simple Solid

• Continuum Models of Solids

• Lattice (‘Atomic’) Models of Solids

• Single Electron Transport

• Statistical Theory of Electron Transport

When the chain is extended:

Before we can build models for the solid, we need to

, the wavefunction for the entire system of nuclei and electrons

Linear Combination of Atomic Orbitals (LCAO)

6.730 where E is the energy of the entire molecule

For example, if we consider 1s orbitals only…

Normalize to guarantee the probability of finding an

Lecture 2: Vibrational and Rotational States in Hydrogen

, the wavefunction for the entire system of nuclei and electrons

Linear Combination of Atomic Orbitals (LCAO)

where E is the energy of the entire molecule

Decrease of electron density

Increase of electron density

LCAO for electron

Center-of-mass and LCAO for electron

Note that R is the C-of-M coordinate now

Total energy is the sum of CM motion and relative:

If this is the total energy, where is the electron energy ?

Schrodinger equation for center-of-mass

Schrodinger equation for relative motion

Radial kinetic energy Angular kinetic energy

is the angular momentum operator

is the spherical Bessel function

For no rotation, this simplifies to…

Approximation: Born-Oppenheimer, parabolic effective potential

Assuming that the vibrational motion

Binding Vibrational Rotational Translational

H2 1.4 eV 0.5 (n + ½) eV 7.5 l (l+1) meV

O2 1.0 eV 0.1 (n + ½) eV 30 l (l +1) meV

30 THz 3-30 THz 0.3-3 THz

• The source of the binding energy is primarily the electrostatic potential

• Sharing electrons between nuclei lowers the energy of the solid.

• Exicted states exists.

• One electron energy levels

• No spin or exchange energies

• LCAO a good approximation

• Ignore motion of the nuclei

Lecture 3: Metal as a Free Electron Gas

• The source of the binding energy is primarily the electrostatic potential

• Sharing electrons between nuclei lowers the energy of the solid.

• Exicted states exists.

• One electron energy levels

• No spin or exchange energies

• LCAO a good approximation

• Ignore motion of the nuclei

Goal: Calculate electrical properties (eg. resistance) for solids

• Phenomenological model of transport: n, τ, m

• Relate parameters in phenomenological theory to electronic energy

Goal: Calculate electrical properties (eg. resistance) for solids

You will be able to relate a bandstructure to macroscopic

Why this approach ?:

Balance equation for forces on electrons:

In steady-state when B=0:

Recovering macroscopic variables:

Balance equation for energy of electrons:

In the continuum models, we assume that electron scattering is

How do we relate ∆E and T ?