An intrinsic semiconductor has electron and hole densities , so . In a fully ionised, uncompensated n-type sample with , , , and
Thus a carrier-density ratio alone is not generally the electrical conductivity ratio. If electron mobility is unchanged and electron transport dominates the intrinsic conductivity, it reduces to ; equal electron and hole mobilities instead give . Ionised-impurity scattering can change the doped mobility.
Electron-hole symmetry 2026-10-24
Symmetry of the excitation spectrum under exchange of conduction band electrons and valence band holes, after choosing a central zero of energy. In a two-band model with equal effective masses and equal degeneracy factors, charge neutrality in an intrinsic semiconductor fixes the chemical potential at that central energy. Indeed the Fermi-Dirac distribution obeys , so excitation populations are equal at every positive energy.
Intrinsic semiconductor Created 2026-10-18 Updated 2026-10-20
An intrinsic semiconductor has equilibrium mobile electron and electron hole densities set predominantly by thermal excitation across its band gap, rather than by semiconductor doping. In the nondegenerate regime, charge neutrality gives .
Assume dilute nondegenerate electrons and electron holes, parabolic three-dimensional band edges with the stated scalar band effective masses, spin multiplicity two, one effective valley for each edge, and thermal equilibrium. Take the unchanged host ground state to have unit activity and neglect bound excitons. The effective density of states values are
For a Fermi level between the band edges,
The factors of cancel on multiplication. With , the semiconductor mass-action law is
This density-form equilibrium constant has units . A dimensionless thermodynamic constant uses a specified reference number density , giving . The dot representing the host ground state is not a freely translating gas species requiring a further gas partition function. For an intrinsic semiconductor, charge neutrality gives .
A typical intrinsic semiconductor has a nearly full valence band ending at and a nearly empty conduction band starting at , separated by
At finite temperature, the equilibrium Fermi level lies near the middle of the gap. In the nondegenerate parabolic-band approximation,
where are the two effective density of states values. Equal densities of states put it exactly at midgap; unequal masses or valley multiplicities shift it slightly. The left panel gives the requested energy-level sketch, with doped cases for comparison.
Figure 1.
Original schematic energy levels of intrinsic, donor-doped and acceptor-doped semiconductors, including the intrinsic Fermi level and band gap
. Details.
The smaller gives the valence edge a larger density-of-states prefactor than the conduction edge. If the Fermi level were exactly halfway across the gap, there would therefore be more thermally generated holes than electrons. Charge neutrality in an intrinsic semiconductor requires equal carrier densities, so the chemical potential moves upward: it suppresses holes while increasing electrons.
Explicitly, in the nondegenerate limit,
and gives the intrinsic Fermi level
Since , the Fermi level lies in the upper half of the gap at finite temperature.
The supplied inverse- density-of-states rule gives the correct ordering. Strictly, an isotropic three-dimensional parabolic band has a prefactor proportional to , rather than ; this changes the size of the displacement but not its sign. At zero temperature the limiting intrinsic expression approaches midgap; a chemical potential in a completely empty gap is not uniquely fixed by carrier neutrality alone.
Assume thermal equilibrium, nondegenerate carriers, and isotropic parabolic band dispersions, with the supplied effective masses interpreted as density-of-states masses. Take one effective valley with two electron spin states for each band; any additional valley multiplicity must instead be absorbed into the masses or explicit degeneracy factors.
Let the conduction band edge be , the valence band edge , and . The spin-summed conduction density of states per volume is
Using the nondegenerate limit of the Fermi-Dirac distribution and the substitution gives
The factor in the supplied integral produces the normalization. Counting missing valence band electrons similarly gives
Multiplication cancels the chemical potential, establishing the semiconductor mass-action law:
The result does not require an intrinsic semiconductor: semiconductor doping changes and separately while preserving this product under the stated equilibrium and nondegeneracy assumptions.
An intrinsic semiconductor has its carrier populations set primarily by thermal excitation across the band gap; in the ideal pure, neutral case its conduction-electron and hole densities are equal, . An extrinsic semiconductor has carrier populations significantly controlled by donor or acceptor impurities, producing predominantly n-type semiconductor or p-type semiconductor behavior. Chemical purity alone does not fix conductivity independently of temperature and gap size.
The positive charge carrier mobility is the magnitude of mean drift speed per unit weak electric field. For electrons , for holes , and its SI unit is . In an isotropic relaxation-time model, .
A band effective mass characterizes how an electron wave packet accelerates in an energy band, rather than replacing its vacuum rest mass. In one dimension and its tensor generalization,
These follow by differentiating and using . Effective masses can be anisotropic and electron band curvature can be negative.
An intrinsic semiconductor has thermally generated conduction electrons and valence holes, with at equilibrium in the ideal undoped neutral material. Their abundance is controlled by its band gap, temperature and band density of states.
An extrinsic semiconductor has its mobile carrier populations substantially modified by electrically active impurities. A donor impurity can supply electrons, producing n-type material; an acceptor impurity can capture a valence electron and leave a mobile electron hole, producing p-type material. Compensation and incomplete ionization can modify these simple counts. At low temperature dopant freeze-out can occur; at sufficiently high temperature intrinsic pair production can overwhelm a fixed dopant density. Doping and the dominant transport regime are related but are not interchangeable descriptions at every temperature.
For an undoped neutral intrinsic semiconductor, . Equating the two expressions from a and taking logarithms gives
and hence the intrinsic-semiconductor chemical potential
Therefore . The logarithm is temperature-independent for fixed parabolic effective masses. The chemical potential is exactly at midgap only if the two effective density of states values coincide; for it moves above midgap. Additional valley multiplicities would add their logarithmic contribution.
Near a parabolic valence band maximum , the missing-electron effective mass is . The same two-dimensional state counting gives
Multiplication eliminates the chemical potential, giving the semiconductor mass-action law
For an intrinsic semiconductor, charge neutrality imposes , so
The intrinsic chemical potential is not exactly midgap when the two effective masses differ: . The exponential suppression still justifies the assumed nondegenerate regime here.
Equal effective masses and equal spin and valley degeneracies give electron-hole symmetry. In the intrinsic semiconductor, charge neutrality requires equal numbers of conduction band electrons and valence band holes. It therefore pins the chemical potential to the band touching point, . The Fermi-Dirac distribution gives
Measured relative to the filled valence band at zero temperature, the thermal internal energy includes both species. Removing a valence band electron at costs the positive hole energy , just as adding a conduction band electron at does. Hence
Differentiate at fixed area and fixed total electronic particle number, allowing creation of electron-hole pairs:
There is no conflict with the equipartition theorem. The normalization counts only the excited conduction band electrons, while the heat capacity includes both electrons and holes; moreover, is not fixed. In fact , and differentiating supplies another equal contribution to the heat capacity. Finally, gives occupation at the touching point, so the excitation gas is not in the classical dilute limit even though exceeds the vanishing band gap.
For the degenerate electron gas, let include both spin states. The Sommerfeld expansion gives
For the gapless symmetric intrinsic semiconductor, part (d) gave the same coefficient with . Thus for equal sample areas and equal spin and valley degeneracies,
The equality often intended in this comparison requires the same density of states. The source sets but does not explicitly equate them to the electron gas mass . Without that additional assumption the ratio is , or more generally if sample areas or degeneracy factors differ. For example, with equal areas satisfies the stated equal-effective mass condition in the semiconductor and gives ratio two. The filled Fermi sea does not add a factor : only the thermal shell near its Fermi energy contributes to its heat capacity.
Let , with the Boltzmann constant, the absolute temperature, and the common equilibrium chemical potential. The conduction band minimum and valence band maximum are and ; their separation is the band gap . The positive parameters in the supplied density of states functions are the band effective masses of electrons and electron holes, not necessarily the bare electron mass.
The electron occupation is the Fermi-Dirac distribution . The appropriate statistical factors are for electrons and for electron holes. In a nondegenerate semiconductor, and , so the Boltzmann approximation gives
For the conduction band, set and then . The supplied integral yields
For the valence band, set to obtain
The effective density of states factors include the two spin states already present in the supplied density of states functions. Multiplication cancels the chemical potential and gives the semiconductor mass-action law
Here is the intrinsic carrier concentration. Equality additionally requires an electrically neutral intrinsic semiconductor. The product law also applies to an equilibrium doped semiconductor while both populations remain nondegenerate. The derivation assumes parabolic energy bands, the stated spin degeneracy, and a single common chemical potential.
Doping changes the mobile carrier population by introducing controlled impurity levels. In an intrinsic semiconductor, the filled valence band is separated from the nearly empty conduction band by a band gap . Thermal excitation produces an electron-hole pair, so the electron and hole number densities obey . A electron hole represents a missing valence-band electron and behaves as a mobile positive charge carrier. For nondegenerate bands in thermal equilibrium,
Here are the effective density of states, the band edges, and denotes the chemical potential, conventionally called the Fermi level. The semiconductor mass-action law holds in this nondegenerate equilibrium regime.
In a tetrahedrally bonded elemental semiconductor such as silicon, a substitutional group-V atom has an extra outer electron relative to the host. It is a donor impurity: a shallow level just below can ionise, releasing an electron to the conduction band and leaving a fixed positively charged donor. The resulting n-type semiconductor has electrons as majority carriers and holes as minority carriers. Conversely a group-III substitution supplies one fewer bonding electron. An acceptor impurity can take an electron from the valence band, leaving a mobile electron hole and a fixed negative acceptor; the resulting p-type semiconductor has holes as majority carriers.
The impurity state is shallow because the electron or hole responds to a screened Coulomb potential and an effective mass, rather than the bare atomic potential. A simple hydrogenic donor estimate is
where is the relative permittivity. This is a useful scaling model, with real band anisotropy and central-cell effects omitted. Dopants are fixed in the lattice; their ionisation changes mobile carrier numbers without making a uniformly doped bulk sample carry a large net electric charge.
The charge neutrality condition is
When shallow dopants are almost fully ionised and , an n-type region has and . A p-type region similarly has and . Thus compensation by the opposite impurity type reduces the majority-carrier density; the total dopant concentration is not generally the mobile carrier density. At sufficiently high impurity density the degenerate semiconductor regime requires the full Fermi-Dirac distribution and these exponential approximations fail.
There are three useful temperature regimes. At low temperature, dopant freeze-out leaves many shallow levels un-ionised. In the extrinsic regime, the dopants are largely ionised and set the majority-carrier density. At high enough temperature, intrinsic pair creation dominates and approach . The Fermi level moves towards the conduction band with donor doping and towards the valence band with acceptor doping. The electrical conductivity is
Doping therefore controls conductivity and its carrier type, but ionised impurities also scatter carriers and can reduce charge carrier mobility. Carrier density and mobility must both be considered.
A p-n junction forms when p-type and n-type regions are joined within a semiconductor. Initially the concentration gradients drive diffusion current: electrons diffuse from the n region to the p region and holes in the opposite direction. Recombination removes mobile majority carriers near the join, exposing fixed positive donors on the n side and fixed negative acceptors on the p side. This forms a depletion region and an electric field directed from n to p. Its drift current opposes diffusion. At equilibrium the net current vanishes and the Fermi level is uniform, although the band edges vary spatially through band bending.
For an abrupt nondegenerate junction with fully ionised dopants, its built-in potential is
Under the depletion approximation, the space-charge densities are on a p-side width and on an n-side width . Integrating Poisson equation and imposing zero field outside gives and
Most of the depletion width therefore extends into the more lightly doped side. The schematic shows the impurity levels before contact and the resulting space charge and potential after contact; there is no externally extractable equilibrium battery voltage from the built-in field alone.
Figure 1.
Shallow donor and acceptor levels, and charge, field and potential in an equilibrium abrupt p-n junction
. Details.
A forward bias, with p positive relative to n, reduces the barrier from towards and injects minority carriers across the junction. In the ideal low-injection, diffusion-controlled regime this produces the Shockley diode equation, . Reverse bias increases the barrier and the depletion region; only a small thermally generated minority-carrier current flows before breakdown. Reverse-biased depletion regions also give a voltage-dependent junction capacitance. Real devices have recombination, leakage, series resistance and breakdown mechanisms beyond the ideal law. Controlled doping creates majority and minority carriers, and their junction produces a depletion barrier that makes rectification possible.
Semiconductor doping introduces controlled impurities to alter equilibrium carrier populations and electrical conductivity. In an intrinsic semiconductor, thermally excited electrons in the conduction band and electron holes in the valence band have equal densities . A shallow donor impurity, such as phosphorus in silicon, supplies an electron from an impurity level just below the conduction-band edge. Once ionized it is positively charged, and the material is n type. An acceptor impurity, such as boron in silicon, accepts a valence electron into a level just above the valence-band edge, leaving a mobile hole and a negatively charged ionized impurity; the material is p type.
With dopant densities , charge neutrality requires
For fully ionized, nondegenerate dopants at equilibrium, the semiconductor mass-action law gives . In a substantially n-type sample, , so
The corresponding p-type result is and . The majority population grows while the minority population decreases; adding donors does not simply add equal numbers of free electrons and holes.
The Fermi energy shifts toward the conduction band for n-type material and toward the valence band for p-type material. In the nondegenerate approximation,
where are effective band-edge state densities. At very low temperature, dopants may not be ionized and carrier freeze-out occurs. At intermediate temperatures, ionized dopants dominate the carrier density; at sufficiently high temperature, intrinsic excitation can dominate. Heavy doping can produce degenerate carrier statistics, invalidating these Boltzmann expressions.
The electrical conductivity is . Doping usually raises the majority carrier density, but ionized impurity scattering can lower mobility, so conductivity need not scale indefinitely with dopant concentration. Joining p-type and n-type regions creates a p-n junction, with a depletion region and built-in electric field established by carrier diffusion and compensating drift. The fixed ionized dopants, not an absence of all charge, account for the depleted region's net charge density.
An intrinsic semiconductor has negligible electrically active impurity doping, and thermal excitation across its band gap produces equal electron and hole densities . In an extrinsic sample, semiconductor doping supplies donor impurities or acceptor impurities, so one carrier species dominates over a range of temperatures. Doping does not remove the possibility of low-temperature dopant freeze-out or high-temperature intrinsic behavior.
Assume parabolic isotropic band edges, spin degeneracy two, a single valley, thermal equilibrium and nondegenerate carriers. Write for the Fermi level, and measure conduction-band energy by . Counting momentum states gives the density of states per unit volume
The low-occupation Maxwell–Boltzmann statistics gives
The substitution and give the coefficient. Similarly and . Multiplication eliminates , proving the semiconductor mass-action law
Here the supplied effective masses are treated as the masses entering the effective density of states. A detailed multivalley silicon model would require the appropriate valley degeneracy and density-of-states masses consistently; adding an extra factor without changing the stated model would alter the requested expression.
A pentavalent arsenic impurity supplies a weakly bound excess electron. In the hydrogenic donor state approximation, dielectric screening reduces the Coulomb attraction and the band effective mass replaces the free mass. Hence the donor binding energy is
This is the effective-mass estimate, without a material-specific central-cell correction.
For the temperature plot use donor density and no acceptors. The charge neutrality with partial donor ionization model puts and includes the twofold spin degeneracy of an occupied donor:
These equations give three regimes. At low temperature, is negligible and strong dopant freeze-out gives . At intermediate temperature, the donors are almost ionized and intrinsic holes remain rare, so . At high temperature, . Thus the log-density plot against inverse temperature has a steep intrinsic segment on the left, a nearly horizontal extrinsic plateau, and a freeze-out decline on the right; the and factors give slight curvature.
Figure 1.
Carrier freeze-out, extrinsic plateau and intrinsic excitation in the specified donor model
. Original charge-neutral calculation using , constant , the supplied single-valley effective masses and donor degeneracy factor two. Dotted lines show limiting expressions where they apply; the shaded temperature interval uses a stated ten-percent plateau tolerance. Details.
To quantify “approximately constant”, require . At , the specified model gives , and . The full neutrality equations give the ten-percent plateau interval
The lower boundary is set by donor ionization and the upper boundary by intrinsic electron-hole production. The large ratio allows substantial donor ionization even when ; using only would incorrectly exclude much of the plateau. The quoted interval depends on the chosen tolerance and the constant-gap band model, rather than being an exact measured range for arsenic-doped silicon.
Band edges and optical transitions. A direct band gap has the conduction minimum and valence maximum at the same crystal momentum. A near-edge photon then connects the two almost vertically on an energy-versus-wavevector plot, because its momentum is small on the Brillouin zone scale. An indirect band gap has the extrema at different momenta, so an additional momentum transfer, commonly supplied by phonon absorption or emission, is required for a near-edge radiative transition. This reduces its probability relative to an allowed direct transition.
Near the zone centre, an isotropic direct-gap model has and downward valence dispersions . The heavy-hole and light-hole bands are the upper branches with large and small positive hole masses: the heavy branch is flatter. In common cubic semiconductors these arise from the manifold, while spin-orbit coupling places the split-off valence band lower by . Its thermally generated hole population is suppressed by approximately relative to upper-valence holes, apart from density-of-states factors. Neglect is justified when ; it is not a universal exclusion of this band at arbitrary temperature.
Figure 1.
Original schematic direct and indirect band edges, including heavy, light and split-off hole branches
. Details.
For an indirect material such as Si, the conduction minimum need not be at . In applying the carrier-density formulae, must mean the actual minimum of the included conduction valley. The supplied scalar effective masses and densities of states constitute a simplified band-edge model; they do not specify Si's full valley anisotropy or multiplicity.
Carrier populations. Let be the Fermi-Dirac distribution. In the nondegenerate conduction tail, . Set and integrate the given density of states:
The integral is . Defining the effective density of states gives
The factor two is already included in the supplied density of states; it must not be added a second time.
A hole is an unoccupied valence state. For sufficiently below , . Substitution of gives in exactly the same way
Their product eliminates the chemical potential:
This is the semiconductor mass-action law at thermal equilibrium. In an intrinsic semiconductor, charge neutrality additionally gives
In a doped semiconductor the product still applies in this nondegenerate equilibrium model, but the two populations need not be equal.
Intrinsic chemical potential. Taking logarithms of yields the intrinsic-semiconductor chemical potential
For unequal band degeneracies, use the first form with the full . For the supplied mass ratio , the shift from midgap at is approximately , toward the valence edge.
Three temperature regimes. The original plot runs from high temperature on the left to low temperature on the right. At high temperature, thermal excitation across the gap dominates and rises rapidly with temperature. In the middle, donors and acceptors are effectively ionized, the material is extrinsic, and makes the plateau. At low temperature, dopant freeze-out binds increasing numbers of electrons to donor levels, reducing the mobile-electron population as the sample cools. Its activation scale is a donor binding energy, not the full band gap. Compensation and incomplete ionization affect that regime.
Gap estimate from the original figure. On the dashed intrinsic branch, . Hence band-gap extraction from intrinsic carrier activation uses the slope of versus . With and expressed in eV/K, two points give
The very compressed intrinsic branch is only approximately readable: near and near . These give , rather than a precision determination. Neglecting the thermal prefactor gives about from those same rough points. Thus a gap of order – is justified by this schematic plot; its resolution does not support distinguishing a few hundredths of an electronvolt. The declining freeze-out branch must not be used to infer the full gap.
Room-temperature densities. At , the supplied masses give
In the fully ionized extrinsic plateau, put . Charge neutrality and the mass-action law imply
Since , is insensitive to the imprecise gap. The minority density is much more sensitive:
Using gives and . Using instead gives and . These are explicitly conditional estimates within the stated mass model. The plot alone cannot fix a precise minority density because the uncertain gap occurs inside an exponential.
In the nondegenerate conduction band, the Fermi-Dirac distribution reduces to its Boltzmann distribution tail. Thus
Here the substitution leaves . For electron holes use the empty-state probability , not the conduction-band Boltzmann factor. This gives
The chemical potential cancels in the product. With ,
This semiconductor mass-action law holds in thermal equilibrium for nondegenerate carriers, including a doped semiconductor. Only in an intrinsic semiconductor must . The factors are the effective density of states; the factor in the final expression follows from the two spin factors already included in (a).