2. P.3.

ELECTRONIC STRUCTURE OF SOLIDS

FREE ELECTRON THEORY AS A PARTICLE IN A BOX
The solid is represented by a trough of potential energy which is filled with electrons from the bottom to the top (with increasing kinetic energy): ( ) [( )]

o angular frequency of the electron o constant spatial periodicity of the wave (related to wavelength) Total energy is composed of potential and kinetic energy throughout the solid . increases with k, .

is assumed to be constant

The parameter A is the normalisation constant & depends on the size of the box: finding the electron at point x is just constant. The wave vector k is a quantum number the momentum of the electron: o o

. The probability of

, defining the state of an electron. It is proportional to .

[
( )

Velocity is proportional to the slope of the ( ) curve:

.
[
( )

The mass of the electrons depends (inversely) on the curvature of the E(k) curve:

The energy spacing between adjacent energy levels is extremely small: we talk about bands rather than discrete energy levels.

Some boundary conditions: solid is an infinite periodic structure (no surfaces), we neglect the exact positions of the ions, the electrons move freely.

THE FERMI SURFACE

Constant (Fermi) energy surface in k-space o Distribution function ( ) expresses probability of finding an electron in energy level i of energy E. o Where Represents electronic structure in k space. o For each filled electronic state: ( ) ( ) are filled; Separates occupied from empty states (inside/outside Fermi surface): definition of metal. All electronic levels with a wave vector all others are empty. Different for each metal: depends on crystal structure, electronic configuration etc. The total volume of the Fermi sphere in k-space: The number of electrons N inside the Fermi sphere is approximately: the an

( o Two allowed spin states:

The Fermi Energy is then: o

is the electron density of a material,

DENSITY-OF-SATES FUNCTIONS,
( ) is the total number of states between

( )
at the bottom of the band and the energy E. ( ( ) ( ) ) ) ( )

( ) ( ) (

) (

The DOS(E) is the number of electronic states per unit energy: ( ) ( )

In 2D the DOS is independent of E and constant:

THERMAL EXCITATION
At T>0K electrons at the Fermi level are being thermally exited and the sharp boundary between occupied and empty states is smeared out thermal broadening. ( ) o ( ) is the probability of occupation: . o At the Fermi energy the probability of finding an electron is equal to a half: ( ) ( )

SUMMARY OF KEY POINTS: FREE ELECTRON THEORY

Free electron model assumes (valence) electrons to move freely through the solid: the ion lattice is treated as uniform background charge (Free electron approximation). Electrons are regarded as independent, there are no electron/electron interactions (independent electron approximation). Based on a particle in the box model. Thermal excitation is confined to a narrow energy region around with . This leads to a small thermal broadening at for . The Fermi surface is a constant energy surface in k-space, which describes the electronic structure of a solid (and thus its electrical & optical properties). In metals it separates occupied and unoccupied states. The density of occupied states : ( ) [ ]

PROPERTIES OF FREE ELECTRON METALS

Electrons in metals do not behave as a free gas only electrons close to the Fermi level are affected by thermal excitation (instead of all delocalised electrons). o The fraction of electrons affected by thermal broadening: where . o Only about 1% of electrons in the conduction band are affected.

For the free Fermi electron gas the number of thermally excited electrons is reduced by

The internal energy of a solid also changes when energy flows into other degrees of freedom vibrations (phonons). The relative contributions depends on temperature: An electric current, I is the flow of change: . The net transport of change dependant on electric driving field and effective speed of the charge carriers. Upon application of a constant electric field a charge is accelerated, the electric field thus changes the momentum of the electron (wave vector):
( )

o o o

( )

In k space this acceleration responds to a shift of the Fermi sphere by . Electrons will eventually collide with impurities, lattice imperfections or exchange energy with lattice phonons. If the electric field acts on electrons of charge e- per unit volume, we have a current density (current per area):

Therefore electrical conductivity: with

The collision time contains all potential sources of electron collisions. For most metals at room temperature, electron/phonon scattering dominates the electrical resistivity. Contribution increases with temperature resistivity of metals increases with temperature. In terms of electron mobility: o with o
| |

Mobility is a measure for the ease with which the charge carriers (electrons/holes) can transport charge. The fundamental basis for the HALL effect is the Lorentz force which acts on a charge q moving in a perpendicular magnetic field B. Therefore the Hall Coefficient:

As e>0 then should be negative for all metals but some elements respond to the field as though they have positive net charge hole conduction. BUT electrons in a solid do not behave as electrons in a vacuum.

(SOME) FAILURES OF FREE ELECTRON THEORY

Hall Coefficients: only for alkali metals experimental & predicted values are close: for other metals neither the sign nor magnitude are correct. How does band structure emerge? Structural effects? In this theory k has no upper band predicts all elements are metals.

NEARLY FREE ELECTRON THEORY

Taken into the account the position of ions explicitly (free electron theory delocalised electrons move in a trough of constant positive background potential energy). The potential changes periodically according to the periodicity of the lattice.

( ) o The perturbation should be small compared to ( ) ( ) ( ) ( ) . ( Using the Block Function:

) ) where ( ) is a function with the

periodicity of the crystal lattice. Assume: ions forms a regular 3D lattice, ions are at rest, and electrons are waves. If ions were moving they could only do so collectively: phonons can interact via scattering which is the main source of ohomic resistance. Scatting of electrons travelling in a periodic lattice is ions, where the angle of incidence is . According to Braggs law, reflection occurs at: Reflection condition Electrons with are no longer free electrons, but reflected at the ion cores. They form standing waves of different energy, where electrons have similar kinetic, but different potential energies. Its wavefunction is a super position of waves. ( o ) [ ( )] [ ( )] A = B since the reflection condition implies that the total wavefunction is composed of equal contributions of travelling waves. ( ) ( )( : ( ) ( )

Where: ( ) ( ) Under reflection the probability distribution, ( ))

o o o

Independent of time standing waves. Normalisation: ( ) The freely travelling electron can be shown to have a constant probability of of the maximum for the

fully reflected waves. Band gaps appear in the dispersion relation ( ) a consequence of the interaction of the electrons with the periodic lattice. At the bottom of a band electrons behave free electron-like deviations become more pronounced towards the top of a band. In a band gap, there are no allowed electronic states. Electrons for which are in the first Brillouin zone.

THE EFFECTIVE MASS CONCEPT

The effective mass: o o o ( ) Effective mass of an electron depends on the curvature of ( ) Different for electrons at the top & bottom of the band the effective mass of an electron at the top of the band can be negative. Electrons behave like free electrons at the bottom of the band:

If changes sign, the acceleration of the electron in an applied filed changes direction (at constant E). Charge carriers are holes with a positive mass, their charge being of the opposite sign: +e. Charge transport in a nearly filled band is described in terms of hole transport/conduction. o Holes are vacancies in a sea of electrons under the influence of an electric field these holes move towards the negatively charge electrode. o The magnitude of the effective mass can also vary affecting the band width. Cyclotron Frequency to measure effective mass of particles -

o Sample bought into a strong state magnetic field of strength B. o Lorentz force causes electrons to spiral such that spiral axis is parallel to B. o Angular frequency of depends on the . o Alternating electric field of variable frequency perpendicular to sample is applied. o When the electron resonates with external field power from this driving field is absorbed. Effective mass of particles in solids varies do not necessarily have to be equal: generally .

BAND STRUCTURE & LCAO

Consider a chain of equally space hydrogen atoms this is not stable and will form such a distortion of a regular lattice to minimise energy is a Peierls distortion (=Jhan Teller effect). Therefore assuming: o Distance a between the atoms remains constant o Both ends of the chain are connected to avoid edge effects (cyclic boundary conditions). Obtaining the total wavefunction as the sum of all atomic orbitals: these can be inphase or out of phase. Introducing a periodic function that reflects the structure of the lattice Bloch function (symmetry adapted LCAO). The free electron function has a particular wavelength and associated wave vector, , expressed in terms of the lattice spacing a. ( ) o ( ) ( )

The periodic function ( ) modulates the local amplitude of the AO: ( ) ( ) Benefits of applying LCAO: chemical perspective,

BAND STRUCTURES FOR 3D SOLIDS & DOS

Metals Overlapping bands Broad s-level band resembles parabolic form of the free electron gas Flat-d band with low dispersion (narrow bandwidth) due to strong localisation of d electrons. No energy gap with all states occupied. Non-Metals Forbidden region occurs (energy gap) No available k-states. Valence band is full, conduction band is empty Band gap is relatively small .

SEMI-CONDUCTORS & INSULATORS

Solids with a band gap larger then are usually considered to be insulators. In pure semiconductor crystals electrons are excited thermally from a completely valence band into an initially empty conduction band: intrinsic semiconductors. Doping deliberate addition of impurity atoms: additional electronic levels either empty (acceptor) and filled (donor) which contribute to the total number of charge carriers (holes/electrons) extrinsic. o Electron deficient p type o Excess electrons n type The higher the temperature, the larger the number of charge carriers and the higher the conductivity of the semiconductor. For intrinsic semi-conductors the number of charge carriers in the conduction band: .

Electrons sill follow the Fermi distribution function: ( )

, there Fermi energy

is still the energy

where ( ) o Fermi energy is in the centre of the band gap no energy levels that could be populated. The probability of finding an electron in the conduction band is dependent on . The carrier concentration ( ), for the conduction band: : ( ) o o The energy of electrons in the conduction band relative to the conduction band edge

is:

Using the DOS(E) ( ) ( ) ( ) ] ( ) ( ) ( )

n is the density of electrons in the conduction [ ( )

concentration of electrons. ( ( ) ) ( ). )

o the same holds true for the holes in the valence band: To get the equilibrium relation: ( ) ( : ( ) ( ( o o If If then then and and ) ) )

For an intrinsic semi-conductor, n=p where

is above the centre of the gap is below the centre of the gap.

The electrical conductivity depends on two factors: o Carrier concentration (n/p) increases with T (fermi distribution). o Carrier mobility proportional to collision time, which decreases with increasing T (collisions with thermal phonons). | |

At room temperature the collision time depends on T increases in carrier concentration govern T dependence: the conductivity of semiconductors increases with temperature due to increasing carrier concentration. o Metals o Semi-conductors o Insulators at this scale Conductivity of a semiconductor can be increased by the deliberate addition of impurity atoms providing excess electrons (n-doping) or are electron deficient (p-doping). Impurity atoms are built into the lattice - .e.g. substituted into place of regular atoms. Compared to the neighbouring Si atoms, As carriers one nuclear charge more excess electron described as though it revolved around hydrogen like single charged nucleus. Bohrs model of the H atom: o Excess charge is screened by the solid of dielectric constant

o o

Excess charge has an effective mass Ionization means excitation to the bottom of the conduction band (not to infinity).

Total energy of the system: .

Ionization energy: transition from n=1 (ground state) to

(conduction band delocalised over lattice):

Binding energy for the electron moving from the conduction band into the donor state:

Binding energy is negative energy level must be below the conduction band edge. Thermal excitation into the conduction band now occurs from the donor levels. For p-type doping excitation of the electrons from the valence band into the acceptor levels. o B carries one nuclear charge less. The missing electron as positively charged hole revolving around an effectively negatively charged nucleus. o Binding energy is now relative to the top of the valence band: o

Thermal excitation into the acceptor levels occurs from the valence band. We assume low doping levels: o Low T: fermi level between and charge carrier concentration and conductivity increase with T. o Saturation Regime: fermi level moves towards the centre of the band carrier concentration constant as doped levels are depleted of electrons. o Intrinsic Regime: donor levels no longer important for carrier concentration fermi level in the centre of the band gap carrier concentration rises with T. o

OPTICAL PROPERTIES OF SEMI-CONDUCTORS

Absorption of photons can cause the excitation of electrons and the formation of electron/hole pairs excitons. For thermal excitation the (thermal) band gap was considered to be the minimum energy difference between valence and conduction band, irrespective of k value. For the absorption of photons the instantaneous transition, momentum must be conserved. o The wavelength of the incoming photon is large compared to the wavelength of the electron in the solid: . Conservation of momentum implies: For an optical transition to be allowed, the selection rule: Optical transitions are therefore vertical in the ( ) diagram, occur between Bloch functions with the same wave vector, k. o Photons can also be absorbed during the excitation process formally forbidden much less likely to occur & less intense. Band gap determined via T-dependant conductivity or optical spectroscopy (PES): o DIRECT: lowest energy transition does not require a change in k. o INDIRECT: lowest energy transition does require a change in k. o o o Indirect Band Gap Lowest energy transition occurs at Inefficient absorption/emission of light Poor material for optoelectronic devices Used for electronic devices

Direct Band Gap Lowest energy transition occurs at Efficient absorption/emission of light Good material for optoelectronic devices

Thermal excitation between bands does not require conservation of k.

ELECTRON/HOLE PAIRS EXCITONS

On creation of excitons electron and hole are initially close together. Because they have opposite charge, they will experience an attractive interaction, which will decrease with distance. ( ) Cannot regard either of the particles as fixed they are both of comparable mass rotate around the centre of mass: [ ]. & , along with the reduced

We have a force balance and angular momentum: mass: .

The energy levels allowed for the electron/hole system (attractive): o o o

If we ignored the existence of excitons, the minimum energy required to create an electron/hole pair (intrinsic semi-conductor) would be the band gap . Because the interaction is favourable the energy is reduced by:

At energies just below we can create excitons at very specific frequencies of incoming light. Located at the inset of light absorption due to the excitation of valence electrons into the conduction band.

SURFACES & INTERFACES

The Work function W is the minimum energy required to take an electron from the inside of a (neutral) solid into a vacuum. Typical values for metals: some correlation with IE ~ elements with a small IE have a low work function. When 2 pieces of metal are joined they have different fermi energies and work functions. Upon contact, electrons flow from the metal with the higher fermi energy/lower work function to the one with lower Fermi energy/higher work function. In equilibrium the potential V is equal to the difference in work function: Photoelectric Effect: high energy photons collide with electrons in the metal. If the photon energy exceeds a threshold, electrons are being emitted. o By measuring their kinetic energy (counteracting voltage applied) as a function of photon energy, the minimum energy required can be determined, the work function, W.
( ) ( )

INTERFACE BETWEEN TWO (DOPED) SEMICONDUCTORS: P/N JUNCTIONS

Semiconductor crystal that is doped p-type in one region & n-type in another.

Consider motion of electrons in CB under applied bias voltage, V:

Photo detector: photons can be used to excite electrons from the VB to the CB leading to an increase in conductivity photo conductivity.

Light emitting diode (LEDs): emission of light occurs when conduction electron recombines with a hole. Requires direct gap semi-conductor material.