Lecture 16: Free Electrons (Optical Properties)

Electron bands originate from atomic levels: Three band structure scenario

Dielectrics CB Semiconductors CB Metals CB Eg > 3 eV EF Eg < 3 eV EF EF

VB VB CB: A lot of available states, no electrons VB: A lot of electrons, no states available CB: A lot of available states, no electrons at T = 0 VB: A lot of electrons, no states available CB: A lot of electrons and available states free electron model with strong conductivity

Materials Application of the Lorentz oscillator model to free electron systems: Metals Doped semiconductors Plasma reflectivity Combination: Lorentz model of dipole oscillator (No restoring force in plasma) Drude model of free electron conductivity ( - scattering time) Oscillation of a free electron induced by AC electric field E(t) of EM wave:

d 2x dx = eE (t ) = eE0 e it m0 2 + m0 dt dt x = x0 e it Damping term eE (t ) x(t ) = m0 ( 2 + i )

1/ = - mean scattering time

Macroscopic polarization: P = N(-e)x(t)

Ne 2 E D = r 0 E = 0 E + P = 0 E m0 ( 2 + i ) Ne 2 r ( ) = 1 0 m0 ( 2 + i )
Formally follows from bound e-resonace:

r ( ) = 1

2 p

( 2 + i )
1 2

Ne 2 p = m 0 0

Ne 2 1 r = 1+ 0 m0 ( 2 2 i ) j
Under j = 0 - No restoring force

p plasma frequency

In the limit 0
2 p r ( ) = 1 2 2 p 1 = 1 2 2 = 0

r
1 0

1 n= 2 1 k= 2

1 1 1 2 2 2 [1 + 1 ]2 1 + ( 1 + 2 ) = 2 1 1 1 2 2 2 [ 1 + 1 ]2 1 + ( 1 + 2 ) = 2 1 2

1 2

< p n = 0, k = 1 > p n = 1 , k = 0
p

Lecture 17: Free Electrons (Optical Properties)

Main Effects in relation to Plasma Reflectivity Model
1. High reflectivity in visible and NI regimes combined with high transmission in UV Plasma model without damping force, High R for < p,, high T for > p 2. Skin Effect at low frequencies Plasma model with damping force, Absorption for < 1/, - scattering time 3. Interband transitions in metals Quantum process in E-k band diagram, superimposed on the plasma model 4. Free carrier absorption in semiconductors Shift of p to much lower frequencies, Plasma model with damping for > p 5. Plasmons Plasma model at = p where r = 0, Restoring force due to macroscopic polarization Plasma model in relation to dipole oscillator model

r
1 0

neglecting with returning force

High reflectivity in visible and NI regimes combined with high transmission in UV

Aluminium hp =

h p = 15.8 eV

= 3.6 107 -1 m-1 = 1/ = m0/(Ne2) determines the absorption at low , as we will see below, - DC conductivity

Skin Effect at low frequencies

Model of conduction E=0

+ + + + + + + + + + + + + + + + Electron + + + Frequent collisions, but no net displacement vx + + + + + + + + +

E
+ + + +

Net displacement superimposed on the random thermal motion t vx = <t> vix v t v = <vx> = <vix> + (eE/m)<t>= (e/m)E i = eNAv= (Ne2/m)AE j = i/A = E

v = <vx> = 0

where = Ne2/m

Interband transitions in metals

Explains color of such metals as gold and copper

Inner d orbitals form narrow bands below EF Transition to half-full s band gives an absorption

Very high density of states for parallel bands Hence reflectivity dip at 1.5 eV

Free carrier absorption and reflectivity in semiconductors

Plasma frequency is reduced due to r > 1 and m* > m0:

p = (Ne2/0rm*)1/2

Control plasma frequency by varying the doping density Plasma edge in the infrared

Plasmons
Longitudinal oscillations of the electron plasma at p where r = 0

N 2e 2 d 2u Nm0 2 = NeE = u dt 0 d 2u Ne 2 + 2 m u = 0 dt 0 0

0 = (Ne / 0 m0 )
2

1 2

Metals:

h p ~3-20 eV h p ~ 10 meV hout = hin nh p

Doped demiconductors:

Measure by Raman Scattering:

Lectures 18: Interband Absorption

Direct and Indirect Absorption

The Transition Rate for Direct Absorption

Transition Rate:

2 2 W i f = M g (h ) h M = * ( r ) H ' ( r ) i ( r ) d 3 r f H E
'

The matrix element M Density of states g The first-order energy shift for a given state is the expectation value of the perturbing potential Quantum perturbation

= pe E

photon

photon

( r ) = E 0 e i kr
i kr

H ' ( r ) = e E 0 re

1 i (r ) = u i ( r ) e ik i r V 1 ik f r f (r ) = u f (r )e V

Continuing

e * ik r M = u f (r )e f (E 0 re ikr )ui (r )e ik ir d 3r V hk f hk i = hk Required for the integral to be non zero M ~ kf = ki 1 2m* 1 2 E2 g (E) = 2 2 h
3 2 unit _ cell

ui* (r ) xu f (r )d 3r

For x-polarized light M electric dipole moment of the transition

Obtained previously in 3-D case, m* instead of m

Atomic Physics of Semiconductors

m = -1, 0, +1 l = 1 ms = 0

Ge: 4s24p2

Bonding and Antibonding Modes in Bispherical Atoms

Illustrated by coupled Whispering Gallery Modes in Dielectric Bispheres Antibonding Bonding

Due to different fractions in high (dielectric spheres) and low (air) index media these modes have different energy anticrossing splitting

Lectures 19: Interband Absorption (Continue)

GaAs Band Structure

Four-Band Model

Joint Density of States

Eg < 3 eV

EF

1 1 = *+ * me mh h 2k 2 h 2k 2 h 2k 2 + = Eg + h = E g + * * 2me 2mh 2 For _ h < E g , _ g (h ) = 0

1 1 2 For _ h > E g , _ g (h ) = 2 (h E g )2 2 h 3 2

VB

InAs Band Edge Absorption

The Franz-Keldysh Effect

At the classical turning points A and B, change from oscillatory to decaying: ~ ukeikx, where k is imaginary With increase of E the distance AB decreases and the overlap of increases First effect Second Effect In the absence of photons AB = d = Eg/qE For h < Eg AB = d = (Eg - h)/qE tunneling barrier is reduced absorption The frequency dependence of is given:

4 2m* 3 e (Eg h )2 (h ) ~ exp 3 e hEel

Transmission coefficient through a triangular barrier

For h > Eg displays Franz-Keldysh oscillations

Magneto-Absorption in Germanium

Cyclotron Motion
Application in particle physics:

F = qvB = mar = mv2/r rcyc = mv/(qB) fcyc = v/2r = qB/(2m) cyc is independent of the particle speed Each time traversing the gap the particle gains kinetic energy eV

cyc = qB/m

Magneto-Optics in Semiconductors
In quantum physics the energy is quantized. In can be shown that this problem can be formally reduced to a harmonic oscillator potential: U = kx2/2 En = (n+1/2)c - Landau Levels The ground state E0 = c/2 is explained by the uncertainty principle: px~ (x) 2(x) H = p2/2m + kx2/2

Band Edge Absorption in a Magnetic Field

1 ehB h 2 k z2 e En ( k z ) = E g + n + * + * 2 me 2me 1 ehB h 2 k z2 h En (k z ) = n + * * 2 mh 2me

It can be shown that the Landau level number n does not change in transition:

1 ehB h 2 k z2 e h h = E n ( k z ) E n ( k z ) = E g + n + + 2 2 1 ehB h = E g + n + 2
In a 1-D system the density of states is peaked at kz=0 Explains a series of equally spaced peaks Blue shift of the absorption edge by eB/2

Lectures 20: Interband Absorption (Continue)

Direct Versus Indirect Absorption

Indirect transitions:

E f = Ei + h h hk f = hki hq

Energy conservation Momentum conservation

Initial state: (Ei, ki) Final state: (Ef, kf)

Germanium Band Structure

Germanium Band Edge Absorption

Silicon Absorption

Band Structure

Absorption Spectroscopy

Photodetectors

p-i-n Diodes

Lectures 21: Excitons

Theory: Frenkel 1931 (Ioffe Institute) exciton is small and tightly bound Mott and Wannier exciton is large and weakly bound Experimental discovery (1951) of hydrogen-like exciton optical spectrum in semiconductor crystals of cuprous oxide, E.F. Gross (Ioffe Institute)

An electron and a hole may be bounded together by their attractive coulomb interaction, just as an electron is bound to a proton to form a hydrogen atom.

Properties
An exciton can move through the crystal and transport energy

It does not transport charge because it is electrically neutral Excitons can be formed by photon absorption at any critical point, for if kv = kc the group velocities for electrons and holes are equal and they can be bounded. In direct band gap semiconductors the excitons can be formed at k = 0 corresponding to energy Eg When the band gap is indirect, excitons near the direct gap can be unstable with respect to decay into a free electron and free hole. The energy of the exciton formation in a direct transition at k = 0 is Rx less the binding energy due to the Coulomb interaction: En = Eg Rx /n2, where Rx exciton binding energy

Exciton Levels
Conduction Band, me Exciton Levels Eg Eb Eg-Eb Energy Gap, Eg Valence Band, mh An excition can have translational kinetic energy Excitions can recombine rediatively Conduction Band Continuum Exciton Levels Exciton Binding Energy

Valence Band Continuum

Energy levels of an exciton created in a direct process

Bohr model of hydrogenic atoms

Bohr Postulates: 1. Angular momentum is quantized (stationary orbits): mvr = nh/2 (1) 2. Transitions at h = E E Let us consider nuclear charge Ze, electron e, radius r. Coulomb Force = Centrifugal Force

( CGS ) _ units : Ze 2 mv 2 = _ Combined _ with _( 1 ) : 2 r r 1 n 2h 2 2 Ze 2 r = _ and _ v = 2 2 hn 4 Ze m 1 2 2 e 4 Z 2 m Ze 2 = The _ energy : _ E = mv 2 2 r h 2n 2

Weakly Bound (Wannier-Mott) Excitons

For Z = 1 E 0 n=2 R

e m0 = 13.6eV Rydberg _ Const 2 2h h2 a= = 5.29 10 9 cm 0.5 m0 e 2 R=

n=1

For an exciton in a solid the Rydberg Constant can be calculated taking into account polarization of lattice (r) and effective mass (). Such a Rydberg Constant is the exciton binding energy Rx.

Rx = R m0 r2 r m0 ax = a

For Ge, Si and AIIIBV (GaAs) and AIIBVI semiconductors:

= memh/(me + mh) ~ me~0.1m0, r ~ 10

Rx ~ 10 meV << Eg , ax ~ 10 nm >> Lattice Constant

More detailed data on Rx and ax

As Eg increases

Rx increases and ax decreases

This can be explained by decreasing r and increasing for larger Eg Rx is smaller than kT at Eg room temperature for all semiconductors In insulators Eg 5 eV ax is comparable to the lattice constant Wannier-Mott model is no longer valid

Frenkel Excitons
A Frenkel exciton is essentially an excited state of a single atom, but the excitation can hop from one atom to another by virtue of the coupling between neighbors. Can be present in extremely wide band gap materials. Stable at room temperature Phenomenological Treatment Based on interaction constant (T), see Kittel

g = u1u2 u N 1u N j = u1u2 u j 1v j u j +1 u N
H j = E j + T ( j 1 + j +1 )

Consider a crystal of N noninteracting atoms Describe a single excited atom and N-1 atoms If there is an interaction between excited atom and its close neighbors when T measures the rate of transfer of the excitation. Here E is the free atom excitation energy. If T = 0 when the solution is j. If T 0 when use a Bloch form

k = exp(ijka) j
j

H k = eijka H j = eijka E j + T ( j 1 + j +1 )
j j

Let H operate on k

Rearrange the right-hand side to obtain:

H k = eijka E + T (eika + e ika ) j =( E + 2T cos ka) k

j

Ek = E + 2T cos ka

So, the energy eigenvalues are found

1 1 1 k = 2s / Na, _ s = N , N + 1, N 1 2 2 2
Large Eg: Rare Gas Crystals Ne, Ar, Kr, Xe Alkali halides: KI, KBr, KCl , KF NaI, Molecular thin films and organic crystals

Lectures 22: Excitons

Free Exciton Absorption

Excitons in Bulk GaAs

The dominating mechanisms of exciton broadening are impurity scattering (low T) and scattering on LO phonons (high T). Since ELO = 35 meV>>kT the occupancy of LO phonons is small collisional broadening is small even at high temperatures.

Field Ionization in GaAs

Excitonic effects do not play a large part in the physics of bulk semiconductor diodes. The dominant effect is Franz-Keldysh effect. This however is not true for QWs!

Magnetic Fields

hc = h

eB

c exciton cyclotron frequency - reduced electron-hole effective mass

Weak Field Limit

RX >> c The magnetic field is a perturbation on excitons. For a ground state (n=1) it will be a diamagnetic shift:

Strong Field Limit RX << c

Landay Levels for individual electron and holes Coulomb interaction is a small perturbation In GaAs the transition occurs at T ~ 2T for n=1

e E = rn2 B 2 12
Induced magnetic moment

Free Excitons at High Densities

Exciton-Exciton interaction
Exciton-exciton interactions are controlled by their concentration The excitons wavefunction overlap occurs when their separation is equal to ax. Mott density:

N Mott

1 4 3 rn 3

rn radius for the excitons in the n-th quantum state. For excitons in GaAs for the n=1 states NMott = 1.1 1023 m-3

Screening by an electron-hole plasma

Electron-hole pairs generated either directly or in the cause of excitons collisions screen the excitons broadening and weakening of the excitonic feature

Excitons against hydrogen atoms

Exctions Biexcitons Electron-hole droplets
Bound state of two atoms Gaseous phase Atoms condense to form a liquid

Hydrogen atoms H2 molecule Liquid hydrogen

Bose-Einstein statistics: the occupancy factors are unlimited. At low T system of N atoms switches into coherent state. Criterion: Atomic de Broglie wavelength is comparable with the interparticle separation

mk T N = 2.612 B 2c 2h
Bose-Einsten condensate in a solid

3 2

Bose-Einsten condensate in a trap