Review of Semiconductors

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Review of Semiconductors
Origin of Band Gaps and Band Diagrams Direct and Indirect Band Gaps Carrier Concentration
The Fermi-Dirac Distribution Density of States Carrier Population in a Band

Intrinsic Material Doping of Semiconductors Generation and Recombination Carrier Transport

In Electric Field Due to Diffusion

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Energy of Electrons
In free space electrons can take on any energy and form a continuum The electrons each have a momentum associated with its energy which means the mass of the electron is related to the energy also

more generally Call this the effective mass Becomes important later

As does this

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Energy of Electrons
In real world electrons are almost never free In atoms there is a Coulombic attraction between the protons (+ve) in the nucleus and the electrons (-ve)

V=

q is electronic charge (constant) and r is distance to nucleus, 0 is free space permittivity

When we apply quantum mechanics and solve the Schrdinger equation we get a series of possible values for the energy (orbitals)
s p

Energy spectrum

Classical view of orbitals

Actual

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Band Gaps
When atoms are put together (e.g. a crystal) the splitting of the single energy levels form bands of allowed and forbidden energies Outermost forbidden gap between non-conducting and conducting bands is referred to as the band gap of the material Size of band gap determines whether material is a conductor (0 band gap), semiconductor ( <4 eV) or insulator (> 4eV)

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Metal, Semiconductor, Insulator?

Classification depends on band gap and the number of electrons in outer most band (conduction) In a metal the bands can overlap or be partially filled so electrons available for conduction is high

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Energy Dispersion Curve

When Schrdinger equation is solved for a crystal get a complex series of allowed energy states according to k the crystal momentum Electrons can only occupy energy states on the E-k curves all other energy states are forbidden Band gap is minimum difference in energy between two outermost bands Using symmetry energy states can be folded into reduced zone Near maxima and minima, curves are parabolic approximate as free Each band has its own curvature and hence effective mass Effective mass varies as a function of k
Actual
ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Simplification

Real Crystals
In reality the E-k curves for crystals are complex with bands varying in three dimensions Means that band gap can vary in different directions of the crystal Conduction between bands is more complex than the picture given in the simplified scheme must be aware of this Top of Valence Band and bottom of Conduction Band dont always align this has massive impact on properties of crystal

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Direct Band Gap

Direct alignment of Conduction Band minima and Valence Band maxima Two requirements for transition between bands 1. The energy supplied is greater than band gap and 2. the momentum is conserved In direct band gap 2. is always satisfied near the zone centre and so only need energy Generally means absorption of light is greater Materials such as GaAs, InP, InAs are examples of direct semiconductors used in optoelectronics Transition sees an electron move from VB to CB leaves behind a hole refer to electrons and holes as carriers
ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Indirect Band Gap

CB minima and VB maxima do not align Transition requires the addition or subtraction of momentum in order to satisfy conservation condition Require interaction with a third particle with momentum phonon Three particle transition less likely hence lower light absorption Examples include Si, Ge as well as III-V materials such as AlAs Arent solar cells made of Si ? What gives?

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Electron Population in Bands

Electrons are in constant random (Brownian) motion and are in thermal equilibrium with each other and the crystal lattice At absolute zero (0 K) the electrons all occupy the lowest possible energies with no excess energy We cannot know the precise energy of a particular electron but we can know the average energy (given by the temperature) which should remain the same Since the electrons have a temperature there will be empty lower energy states and occupied higher energy states. The electrons in the higher energy states will relax down to the lower energy states with the excess energy given off to other electrons which can then occupy the higher energy states This is a dynamic equilibrium, on average it doesnt change but individual electrons do change their states

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Free Electrons
We are interested only in electrons that are able to participate in conduction or are able to change their energy When a semiconductor (or insulator) is at 0 K the valence band will be completely full and the conduction band will be completely empty For conduction, electrons must be able to move to another physical location and gain energy
Electrons in a full band cannot participate in conduction

When an electron receives enough energy to cross the band gap it requires an empty state in the conduction band to be available also leaves behind an empty state in the valence band

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

The holes left behind in the valence band can be thought of as particles themselves in fact it is a lot easier to do so Holes conduct just as much as electrons do, so we are interested in not just the electron population but also the corresponding hole population Holes have their own properties like effective mass that are very different to electrons

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Carrier Concentration
Need to know carrier concentration as well as allowed energy states Require the following information:
number of states available for the carriers, referred to as the density of states the probability a carrier will be in that state, this is given by the distribution function

Distribution function depends on what type of particle we are looking at, there are two broad types:
Bosons, where the particles can all fill the same energy level. Important examples include photons and phonons. Fermions, where two particles can NEVER occupy the same energy state. Important examples include electrons and holes.

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Fermi distribution
Probability distribution function tells us the probability that a particle occupies a given energy state. To find this we need to determine the number of possible arrangements for the particles where the number and the total energy remains a constant. Mathematically this involves counting up the different arrangements using probability theory Result is that lower energy states are most probable to be occupied whilst higher energies are least likely Remember that only one particle can occupy an energy state at one time

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Fermi Distribution
Fermi-Dirac distribution is result:

Note that it only takes into account the number of carriers and the energy of the system doesnt know about allowed or forbidden states Depends on temperature of system. At 0K the lowest available arrangement is for all low energy states to be filled hence FD is square As temperature increases the probability a higher energy state is occupied increases

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Fermi Distribution
Fermi-Dirac distribution is result:

FD distribution is symmetric when a carrier is placed in a higher energy state it is removed from a lower energy state As temperature increases the FD distribution is smeared out Since it is symmetric the energy for which the probability of occupation is half doesnt change this is called the Fermi energy or level

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Fermi Level
Fermi level (energy) EF is defined by:

Assuming that the number of carriers does not change with temperature EF remains the same for all temperatures EF relates to the number of carriers in the system when at 0K the Fermi level is the highest energy of carriers in the system since all states below are occupied it gives us information on the number of carriers

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Fermi Level
FD probability for a hole is fh = 1-f(E)e since it is the probability that a state is not occupied by an electron Fermi level is interpreted as the average energy of the free carriers in the system
In equilibrium the average energy must stay the same by definition so EF must be constant

Also tells us the filling level of electrons (and holes) in a system and so therefore is an indicator of the carrier concentration

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Approximating the FD Dist.

FD distribution is not very nice to work with as a rule Can use an approximation to the FD distribution whne the energy is away from the Fermi level, called the Boltzmann distribution:

Nice and easy to use, in general can be used without too much worry Problem when semiconductor is degenerate:

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Density of States
The density of states is the number of allowed energy states per unit volume per unit energy Want the TOTAL number of energy states, dont really care about their momentum Find two things: E-k relationship and the number of k states per volume

1 dimensional

3 dimensional

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Density of States
Remember that DOS gives the maximum number of states that can be occupied not the actual number Near the bottom of the conduction band (top of valence band) can approximate by a parabola, this is not true far away from these regions, in fact real DOS goes to zero at high energies

DOS has large effect on properties like the absorption coefficient since it determines how many carriers can be excited across the band gap

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Carrier Concentration
Find the carrier concentration simply by multiplying the number of available states by the probability of the state being occupied Note the position of the Fermi level

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Number of Carriers
Mathematically we have for electrons

And similarly for holes we have

BURN THESE INTO YOUR BRAIN!!

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Intrinsic Material
Refers to a pure semiconductor (this will be clearer in a second) For an intrinsic semiconductor we must have n = p (think about it) We denote the Fermi energy in intrinsic material as Ei this is always the same, also denote carrier concentration as ni The intrinsic level will sit roughly halfway in the band gap of the semiconductor but off a little due to differences in the density of states in the conduction and valence bands

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Law of Mass Action

ni depends on the band gap, temperature and effective masses of carriers Law of mass action relates n, p and ni Will become very important when we have a situation where n p, it ALWAYS holds in Equilibrium

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Doping
Carrier concentrations in semiconductors can be altered to desired levels - a process called doping Add small amount of material with less or more outer shell electrons The doped semiconductor is still electrically neutral it is the number of free electrons and holes that has changed Can find the modified carrier concentrations fairly easily Terminology n type added dopant has an excess of electrons p type added dopant has paucity of electrons or put another way has excess of holes

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Doping
Doping introduces energy levels into the forbidden gap of the doped semiconductor In case of n type doping, if the dopant is at energy level ED the excess electron can move to the conduction band if:
The electron has enough thermal energy There is an energy state vacant in the conduction

The remaining dopant atom is now ionized with positive charge Similarly for p type doping, the excess hole moves to the valence band with an electron moving from the valence band to the dopant which is now negatively charged

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Doping
Fermi level moves depending on type and concentration of doping
Closer to conduction band for n type Closer to valence band for p type

Can calculate carrier concentrations in similar manner to the intrinsic case

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Doped Carrier Concentrations

Take n type as example Assume full ionization of dopant so we have ND+ ND and since the doping concentration is much larger than the intrinsic concentration we also have: n ND Take the law of mass action to find the carrier concentration Recall n.p = ni2 and so it is relatively straight forward to estimate the hole concentration: ni2 __ p << n ND Terminology: in this case we refer to the electrons as the majority carrier and the holes as the minority carriers. In p type material the monikers are reversed Fermi levels: left as exercise
ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

This is fine for the electron concentration but what about the holes?

Generation and Recombination

Generation refers to any process whereby an electron moves from the valence band to the conduction band
This leaves a hole in the valence band, often refer to the process as electron-hole pair generation

Recombination refers to any process whereby any electron returns to the valence band
The term comes from the electron and hole coming together again Electron has not vanished, it is now in the valence band again

For each generation process there is an inverse recombination process

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Recombination
In thermal equilibrium the nett generation rate is zero. In order for thermally induced generation to give a nett rate would require thermal gradient across material typically only consider optical generation Each recombination process has associated with it a lifetime for that process typically labelled The presence of defects, level of doping and even whether the band gap is direct or indirect determines what types of recombination are present and which is dominant Reducing recombination processes is what photovoltaics is ultimately about

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Transport - Drift
Two important transport mechanisms are drift and diffusion Electrons are in constant random motion but if subjected to an electric field the motion of a charged particle in the electric field is superimposed on the random motion Nett effect is that the electrons (and holes) drift in the direction expected from classical electromagnetism. Electrons and holes go in opposite directions (since charge is opposite

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Drift
Mobility is a measure of how a carrier responds to an electric field Mobility of carriers depends on the mean time between scattering events

Current due to an electric field consists of both the flow of electrons and holes

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Diffusion
Diffusion occurs whenever there are concentration differences Also depends on a carriers mobility

Typically have both drift and diffusion, so can write total current for electrons and holes

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner

Other Stuff
Poisson equation div E = / mostly means for us: q (p n + N N ) dE/dx = _ D A Continuity (Book-keeping) Equations dJn 1 _ __ q dx dJp 1 __ _ q dx = R-G

= -(R-G)

We will see these again..

ELEG620: Solar Electric Systems University of Delaware, ECE Spring 2009 S. Bremner