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The effective density of states of a parabolic semiconductor band is its density of states integrated against a thermal Boltzmann factor measured from its edge. For one spin-degenerate valley,These quantities have units of number per volume, unlike the energy-resolved density of states. In a nondegenerate semiconductor, $n=N_c{e}^{-(E_c-\mu )/(k_{B}T)}$ and $p=N_v{e}^{-(\mu -E_v)/(k_{B}T)}$; multiple equivalent valleys add their contributions.

For nondegenerate bands separated by $E_g$, the intrinsic carrier concentration is $n_i=\sqrt{N_c{N}_v}{e}^{-E_g/(2k_{B}T)}$, using the effective density of states $N_c,N_v$. For fixed parabolic band effective masses and fixed gap, $n_i\propto T^{3/2}{e}^{-E_g/(2k_{B}T)}$.

In a nondegenerate parabolic-band semiconductor with fixed density-of-states mass, $n(T)=C{T}^{3/2}{e}^{-\Delta (T)/(k_{B}T)}$, where $\Delta (T)=E_c(T)-\mu (T)$. ThusA single measured value of $\Delta$ does not determine its temperature dependence. A fixed-gap intrinsic model instead has $n_i=C_i{T}^{3/2}{e}^{-E_g/(2k_{B}T)}$, with the two effective density of states factors in $C_i$. Identifying a crossover by $n_i(T_c)\simeq n_{\mathrm{ext}}$ gives an order-of-magnitude dopant-density estimate once that activation law is specified. At exact charge neutrality with $n_i=n_{\mathrm{ext}}$, the total mobile-electron density is $(1+\sqrt{5})n_{\mathrm{ext}}/2$, so a crossover is not a sharp equality of every density definition.

For nondegenerate conduction bands and valence bands, charge neutrality gives $N_c{e}^{-(E_c-{\mu }_i)/(k_{B}T)}=N_v{e}^{-({\mu }_i-E_v)/(k_{B}T)}$. Taking logarithms yieldsFor single spin-degenerate parabolic extrema this becomes $(E_c+E_v)/2+(3k_{B}T/4)\ln (m_h^{\ast }/m_e^{\ast })$. Valley multiplicities or additional hole bands belong in $N_c,N_v$ and change the logarithm. The intrinsic chemical potential lies exactly at midgap only when the two effective density of states values agree.

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 $E_g$. Thermal excitation produces an electron-hole pair, so the Electron and hole number densities obey $n=p=n_i$. A electron hole represents a missing valence-band Electron and behaves as a mobile positive charge carrier. For nondegenerate bands in thermal equilibrium,Here $N_C,N_V$ are the effective density of states, $E_C,E_V$ the band edges, and $E_F$ 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 $E_C$ 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 iswhere ${ϵ}_r$ 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 isWhen shallow dopants are almost fully ionised and $N_D-N_A\gg n_i$, an n-type region has $n\simeq N_D-N_A$ and $p\simeq n_i^2/n$. A p-type region similarly has $p\simeq N_A-N_D$ and $n\simeq n_i^2/p$. 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 $n,p$ approach $n_i$. The Fermi level moves towards the conduction band with donor doping and towards the valence band with acceptor doping. The electrical conductivity isDoping 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 isUnder the depletion approximation, the space-charge densities are $-e{N}_A$ on a p-side width $w_p$ and $+e{N}_D$ on an n-side width $w_n$. Integrating Poisson equation and imposing zero field outside gives $N_A{w}_p=N_D{w}_n$ andMost 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.

A forward bias, with p positive relative to n, reduces the barrier from $V_{\mathrm{bi}}$ towards $V_{\mathrm{bi}}-V$ and injects minority carriers across the junction. In the ideal low-injection, diffusion-controlled regime this produces the Shockley diode equation, $I=I_s[e^{eV/(k_{B}T)}-1]$. 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.

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 $E_c(k)=E_c+{\hslash }^2{k}^2/(2m_e^{\ast })$ and downward valence dispersions $E_{v,j}(k)=E_v-{\hslash }^2{k}^2/(2m_{h,j}^{\ast })$. 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 $j=3/2$ manifold, while spin-orbit coupling places the $j=1/2$ split-off valence band lower by ${\Delta }_{\mathrm{so}}$. Its thermally generated hole population is suppressed by approximately $e^{-{\Delta }_{\mathrm{so}}/(k_{B}T)}$ relative to upper-valence holes, apart from density-of-states factors. Neglect is justified when ${\Delta }_{\mathrm{so}}\gg k_{B}T$; it is not a universal exclusion of this band at arbitrary temperature.

For an indirect material such as Si, the conduction minimum need not be at $\Gamma$. In applying the carrier-density formulae, $E_c$ 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 $f(E)$ be the Fermi-Dirac distribution. In the nondegenerate conduction tail, $f(E)\simeq e^{-(E-\mu )/(k_{B}T)}$. Set $x=E-E_c$ and integrate the given density of states:The integral is $\Gamma (3/2)(k_{B}T{)}^{3/2}=\sqrt{\pi }(k_{B}T{)}^{3/2}/2$. Defining the effective density of states givesThe 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 $E$ sufficiently below $\mu$, $1-f(E)\simeq e^{(E-\mu )/(k_{B}T)}$. Substitution of $x=E_v-E$ gives in exactly the same wayTheir product eliminates the chemical potential:This is the semiconductor mass-action law at thermal equilibrium. In an intrinsic semiconductor, charge neutrality additionally givesIn 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 $n=p$ yields the intrinsic-semiconductor chemical potentialFor unequal band degeneracies, use the first form with the full $N_c,N_v$. For the supplied mass ratio $m_h^{\ast }/m_e^{\ast }=1/2$, the shift from midgap at $300\mathrm{K}$ is approximately $-13.4\mathrm{meV}$, 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 $n\simeq p\simeq n_i$ rises rapidly with temperature. In the middle, donors and acceptors are effectively ionized, the material is extrinsic, and $n\simeq N_D-N_A$ 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, $n_i=C{T}^{3/2}{e}^{-E_g/(2k_{B}T)}$. Hence band-gap extraction from intrinsic carrier activation uses the slope of $\ln (n_i/T^{3/2})$ versus $1/T$. With $x=1000\mathrm{K}/T$ and $k_B$ expressed in eV/K, two points giveThe very compressed intrinsic branch is only approximately readable: $n_i\sim 10^{15}\mathrm{c}{\mathrm{m}}^{-3}$ near $x\sim 1.8$ and $n_i\sim 10^{13}\mathrm{c}{\mathrm{m}}^{-3}$ near $x\sim 2.5$. These give $E_g\sim 1.0\mathrm{eV}$, rather than a precision determination. Neglecting the thermal prefactor gives about $1.13\mathrm{eV}$ from those same rough points. Thus a gap of order $1$–$1.1\mathrm{eV}$ 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 $300\mathrm{K}$, the supplied masses giveIn the fully ionized extrinsic plateau, put $N=N_D-N_A=10^{15}\mathrm{c}{\mathrm{m}}^{-3}$. Charge neutrality and the mass-action law implySince $n_i\ll N$, $n\simeq 10^{15}\mathrm{c}{\mathrm{m}}^{-3}$ is insensitive to the imprecise gap. The minority density is much more sensitive:Using $E_g=1.0\mathrm{eV}$ gives $n_i\simeq 5.8\times 10^{10}\mathrm{c}{\mathrm{m}}^{-3}$ and $p\simeq 3.3\times 10^6\mathrm{c}{\mathrm{m}}^{-3}$. Using $1.1\mathrm{eV}$ instead gives $n_i\simeq 8.3\times 10^9\mathrm{c}{\mathrm{m}}^{-3}$ and $p\simeq 7.0\times 10^4\mathrm{c}{\mathrm{m}}^{-3}$. 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. ThusHere the substitution $x=(ϵ-{ϵ}_c)/(k_{B}T)$ leaves ${\int }_0^{\infty }{x}^{1/2}{e}^{-x}dx=\sqrt{\pi }/2$. For electron holes use the empty-state probability $1-f(ϵ)\simeq e^{(ϵ-\mu )/(k_{B}T)}$, not the conduction-band Boltzmann factor. This givesThe chemical potential cancels in the product. With $E_g={ϵ}_c-{ϵ}_v$,This semiconductor mass-action law holds in thermal equilibrium for nondegenerate carriers, including a doped semiconductor. Only in an intrinsic semiconductor must $n=p=n_i$. The factors $N_c,N_v$ are the effective density of states; the factor $1/2$ in the final expression follows from the two spin factors already included in (a).

Spin-orbit coupling separates the $j=1/2$ valence states from the upper $j=3/2$ manifold at the zone centre in common cubic semiconductors. If its maximum lies ${\Delta }_{\mathrm{so}}>0$ below the upper valence band edge, its thermal electron hole population is suppressed by $e^{-{\Delta }_{\mathrm{so}}/(k_{B}T)}$ apart from effective density of states factors. Neglect requires $k_{B}T\ll {\Delta }_{\mathrm{so}}$; it is not valid at every temperature or in every material.