Carrier Densities: Electrons

To find density of electrons in semiconductor: Find density of available states for electrons. Find probability that each of these states is occupied. Density of occupied states per unit volume and energy, n(E), is given by the product of the density of states in the conduction band, gc(E) and the Fermi-Dirac probability function, f(E).

Carrier Densities: Holes

Holes = empty states in the valence band. Probability of having a hole = probability that a particular state is not filled. Hole density per unit energy, p(E), equals:

gv(E) is the density of states in the valence band.

Carrier Densities
To obtain density of carriers, integrate the density of carriers per unit energy over all possible energies within a band. Approximate solution: use simple particle-in-a box model, where one assumes that the particle is free to move within the material.

The carrier density (electrons) in a semiconductor:

Where gc(E) is the density of states in the conduction band and f(E) is the Fermi function.

Carrier Density Integral

Density of states, gc(E), Density per unit energy, n(E), Probability of occupancy, f(E). Carrier density, no, equals the crosshatched area.

Carrier density at zero Kelvin

At T = 0 K, f(E) = 1 for all E < EF f(E) = 0 for all E > EF.

and integration yields:

This expression can be used to approximate the carrier density in heavily degenerate semiconductors provided kT << (EF - Ec) > 0

Non-degenerate Semiconductors Non-degenerate: if only a small number of donor and/or acceptor atoms have been introduced into it. Concentration of impurity atoms are small in comparison to that of the host atoms. Impurity atoms are spaced far apart from each other, such that there is no interaction among donor electrons or acceptor holes. The product of the electron and hole density of a non-degenerate semiconductor is always equal to the square of its intrinsic carrier density, whether the semiconductor is intrinsic or extrinsic.

Degenerate Semiconductors
Degenerate: one that has been doped to such high levels that the dopant atoms are an appreciable fraction of the host atoms. Impurity atoms are close enough to allow their donor electrons (or acceptor holes) to interact. Single discrete donor/acceptor energy levels will split into a band of energies due to interaction. May cause overlap with the bottom of the conduction band or top of valence band. Overlap occurs when the impurity concentration becomes comparable with the effective density of states. For donors, when the concentration of electrons in the conduction band exceeds Nc, then the Fermi level will lie within the conduction band. Overlapping in degenerate semiconductor will make it behave more like a conductor than a semiconductor.

Non-degenerate semiconductors
Non-degenerate : if EF 3kT from EC or EV. This allows the fFD(E) to be replaced by fMB(E) - a simple exponential function. The carrier density integral can then be solved analytically yielding:

Non-degenerate semiconductors

where Nc is the effective density of states in the conduction band. The Fermi energy, EF, is obtained from:

M-B distribution applies to non-interacting particles, which can be distinguished from each other. Provides the probability of occupancy for noninteracting particles at low densities, e.g. atoms in an ideal gas. The Maxwell-Boltzmann distribution function is given by:

Probability of occupancy vs energy of the F-D, B-E and M-B distribution. Assumes EF = 0

All almost equal for large E (a few kT beyond EF). F-D = 100% for E ~ a few kT below EF.

Similarly for holes, one can approximate the hole density integral as:

where Nv is the effective density of states in the valence band. The Fermi energy, EF, is obtained from:

Example: Calculate the effective densities of states in the conduction and valence bands of germanium, silicon and gallium arsenide at 300 K. The effective density of states in the conduction band of germanium equals:

where the effective mass for density of states was used (Appendix 3). Similarly one finds the effective densities for silicon and gallium arsenide and those of the valence band:

Note that the effective density of states is temperature dependent and can be obtain from: where Nc(300 K) is the effective density of states at 300 K.

Degenerate Semiconductors
A useful approximate expression of carrier density applicable to degenerate semiconductors was obtained by Joyce and Dixon and is given by: for electrons

for holes.

Intrinsic semiconductors Semiconductors which do not contain impurities. Contain electrons and holes of equal density (intrinsic carrier density, symbol ni) n = p = ni Thermal activation of an electron from the valence band to the conduction band yields a free electron in the conduction band as well as a free hole in the valence band.

Intrinsic Carrier Density

Intrinsic semiconductors - usually nondegenerate. Use expressions for the electron and hole densities in non-degenerate semiconductors. Fermi energy of intrinsic material = Ei. Relations between the intrinsic carrier density and the intrinsic Fermi energy:

Intrinsic Carrier Density

Intrinsic semiconductors
To eliminate Ei from both equations, multiply both equations and take square root. Provides expression for the intrinsic carrier density as a function of the effective density of states in the conduction and valence band, and the bandgap energy Eg = Ec - Ev.

Intrinsic semiconductors

Temperature dependence of ni is dominated by the exponential dependence on the energy bandgap. Also there is temperature dependence of the effective densities of states and that of the energy bandgap.

Intrinsic carrier density versus temperature

Mass action law

Product of electron and hole densities in a nondegenerate semiconductor equals the square of the intrinsic carrier density. This is referred to as the mass action law. It enables one to find no if po is known and vice versa. Only valid for non-degenerate semiconductors in thermal equilibrium.

Intrinsic Fermi energy (Ei)

Intrinsic Fermi energy - typically close to the midgap energy, half way between the conduction and valence band edge. Ei can be obtained form equations for the intrinsic electron and hole density:

Ei can also be expressed as a function of the effective masses of the electrons and holes in the semiconductor:

Dividing above expression for electron density by the one for the intrinsic density allows to write the carrier densities as a function of the intrinsic density and the intrinsic Fermi energy, Ei, or:

Similarly,

The same relations can also be rewritten to obtain the Fermi energy from either carrier density, namely:

Doped (Extrinsic) Semiconductors

Contain impurity atoms incorporated into the crystal structure of the semiconductor. Unintentional due to lack of control during the growth of the semiconductor, or on purpose to provide free carriers in the semiconductor. Free carriers are generated when these impurities give off electrons to the conduction band in which case they are called donors. If they give off holes to the valence band, they are called acceptors.

Donor Impurity Atom donates an electron to the conduction band without creating a hole in the valence band; resulting material is an n-type semiconductor Acceptor Impurity Atom generates a hole in the valence band without generating an electron in the conduction band; resulting material is an p-type semiconductor

Dopant Atoms and Band Gap Energy Levels When dopant atoms are introduced into a semiconductor crystal, new donor and/or acceptor levels are created in the band gap. Donor level Ed and acceptor level Ea created in the band gap by doping. Electrons from impurity atoms will not be restricted to the energy levels allowed for the host atoms. Can reside in energy levels forbidden to the electrons of the host atoms. Adding impurity atoms to an intrinsic semiconductor to form an extrinsic semiconductor creates new energy levels within the band gap of the semiconductor. The new energy levels in the band gap can be occupied by extra electrons or extra holes from the impurity atoms.

Donor Energy Band Diagram

Acceptor Energy Band Diagram

Doped Semiconductors
The donor energy level is filled prior to ionization. Ionization causes the donor to be emptied, yielding an electron in the conduction band and a positively charged donor ion. The acceptor energy level is empty prior to ionization. Ionization of the acceptor corresponds to the empty acceptor level being filled by an electron from the filled valence band. This is equivalent to a hole given off by the acceptor atom to the valence band.

electron

hole

Ionization of a shallow donor Ed = Donor Ionization Energy

Ionization of a shallow acceptor Ea = Acceptor Ionization energy

A doped semiconductor will contain free carriers if the impurities are ionized. Shallow impurities - ones which require little energy to ionize (kT). Deep impurities require energies much larger than the thermal energy to ionize so that only a fraction of the impurities present in the semiconductor contribute to free carriers. Deep impurities located 5kT away from either band edge, are very unlikely to ionize. Such impurities make recombination centers called traps., in which electrons and holes fall and annihilate each other.

At room temperature: T = 300K Boltzmann constant (k): =1.380658 x 10-23 J/K = 8.617385 x 10-5 eV/K kT = 0.02586 eV ~ 25.9 meV

Ionization
A process by which a free charge carrier from an impurity atom is released in an extrinsic semiconductor. Donor impurity atoms donates electrons to the conduction band. Acceptor atom accepts an electron from the valence band. Ionization Energy: Energy needed to elevate the donor electron into the conduction band or a valence band electron to an acceptor level.

Ionization

Intrinsic Semiconductor. Impurity atoms are introduced. Creates donor and acceptor energy levels within the forbidden band. Donor levels - occupied by donor electrons from donor impurity atoms. Acceptor levels - occupied by holes from acceptor impurity atoms. If supplied with enough energy, electrons in donor level can be to jump into the conduction band and participate in conduction.

Similarly, valence band electrons can be excited to leave the valence band and jump into an acceptor level. Equivalent to a hole from the acceptor level entering the valence band. Electrons excited from the valence band into acceptor levels also contribute to conduction as moving holes in the valence band. Ionization = process of exciting an electron from the donor level to the conduction band or an electron from the valence band to an acceptor level. The energy needed is known as 'ionization energy'.

Complete Ionization
Complete ionization - When all donor or acceptor atoms in a doped semiconductor have become ionized. All donor atoms positively charged. Acceptor atoms = negatively charged. Usually occurs at room temperature.

Freeze-Out
Freeze-out: when no donor/acceptor atoms are ionized. All donor/acceptor atoms neutral. Occurs at 0 K. Between 0 K and room temperature, partial ionization. All energy states: below Ef are full, above Ef are empty.

Shallow impurities
Shallow impurities: small ionization energies. Readily ionize, free carrier density = the impurity concentration. Shallow donors: electron density = donor concentration. Shallow acceptors: hole density = acceptor concentration.

Compensated Semiconductor
Semiconductor which contains both shallow donors and shallow acceptors. Equal amounts of donor and acceptor atoms compensate each other, yielding no free carriers. Electrons given off by the donor atoms fall into the acceptor state. Ionizes the acceptor atoms without yielding a free electron or hole. Resulting carrier density in compensated material, difference between the donor and acceptor concentration.