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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.

Take an abrupt equilibrium p-n junction with the p side at $x<0$ and the n side at $x>0$. In the quasi-neutral bulk, electron holes are the majority carriers on the p side and Electrons are the majority carriers on the n side. With ionized dopant densities $N_A,N_D$ and nondegenerate statistics,where $n_i$ is the intrinsic carrier concentration. The semiconductor mass-action law $np=n_i^2$ applies at equilibrium. Both mobile populations are small in the depletion region compared with the dopant densities.

The charge and carrier density of an abrupt p-n junction must distinguish mobile populations from net charge. Diffusion leaves negatively charged ionized acceptor impurities on the p side and positively charged ionized donor impurities on the n side. Under the depletion approximation,The neutral bulks have large carrier densities but nearly zero net charge density. The electric field points from the positive donor region toward the negative acceptor region, balancing diffusion at equilibrium.

The figure uses equal dopant densities only to show a simple symmetric sketch. Generally the more lightly doped side has the wider depleted interval. The carrier profiles are smooth, whereas the step-shaped net charge density is the ideal depletion approximation.

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 $n=p=n_i$. 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 $N_D,N_A$, charge neutrality requiresFor fully ionized, nondegenerate dopants at equilibrium, the semiconductor mass-action law gives $np=n_i^2$. In a substantially n-type sample, $N_D-N_A\gg n_i$, soThe corresponding p-type result is $p\simeq N_A-N_D$ and $n\simeq n_i^2/(N_A-N_D)$. 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 $N_C,N_V$ 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 $\boxed{\sigma =e(n{\mu }_e+p{\mu }_h)}$. 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.

Nondegenerate carrier product. Assume three-dimensional parabolic energy bands near their extrema, spin degeneracy two, and no additional uncounted valley multiplicity. Near the conduction edge, a Boltzmann approximation to the Fermi-Dirac distribution givesAngular integration and the Gaussian radial integral yieldFor valence electron holes, the empty-state probability is $1-f(E)\simeq e^{(E-\mu )/(k_{B}T)}$. Measuring electron hole kinetic energy downwards from $E_v$ similarly givesThe factors two count spin once in each band. Multiplying cancels the chemical potential and proves the semiconductor mass-action law:In an intrinsic neutral semiconductor, $n=p=n_i$. In a doped equilibrium semiconductor the same product holds under the stated nondegenerate assumptions, even when $n\ne p$. Extra valleys or several valence branches must be included in the effective density-of-states factors rather than counted inconsistently.

Equilibrium junction. Put the p region on the left and the n region on the right. Before contact their majority carriers are electron holes and Electrons, respectively. Diffusion initially sends Electrons from n to p and electron holes from p to n. This leaves negative ionized acceptors on the p side and positive ionized donors on the n side, creating a depletion region and an electric field directed from n to p. At equilibrium this field balances diffusion, so the net electric current vanishes.

For a homojunction the gap remains constant while the conduction band and valence band edges bend downwards from p to n by $e{V}_{\mathrm{bi}}$. The equilibrium chemical potential is flat. Since $E_{c,v}(x)=E_{c,v}^{\mathrm{ref}}-e\varphi (x)$, the electrostatic potential rises from p to n. The carrier profiles satisfyWith fully ionized nondegenerate dopants, the neutral p side has $p_p\simeq N_A$, $n_p\simeq n_i^2/N_A$, while the neutral n side has $n_n\simeq N_D$, $p_n\simeq n_i^2/N_D$. Thus the Electron concentration rises across the junction and the electron hole concentration falls, with both small relative to the far-side majority densities in much of the depleted region. The ideal depletion approximation neglects these mobile populations when calculating the fixed space electric charge, but the actual equilibrium profiles are smooth.

The built-in potential follows from these Boltzmann factors:There is no applied terminal bias; the internal electrostatic potential variation does not contradict a constant electrochemical potential.

Opposing carrier fluxes under reverse bias. Use $V>0$ for the magnitude of reverse bias and $I>0$ for reverse electric current, as in the PDF. The junction barrier increases by $eV$. The Shockley diode equation in that orientation can be writtenThe reverse-directed contribution is supplied by minority Electrons on the p side and minority electron holes on the n side. They reach the depletion edge by diffusion and are swept across by the built-in field. The opposing contribution is associated with majority carriers thermally crossing the barrier in the forward direction; reverse bias suppresses it by the Boltzmann factor. At zero bias detailed balance makes the two equal, while at large enough reverse bias the opposing flux becomes negligible.

In the ideal neutral-region diffusion model,Here $D_n,D_p$ are minority-carrier diffusion coefficients, $L_n,L_p$ their diffusion lengths, and $\mathcal{A}$ is junction area. The two terms inside this positive prefactor are the Electron and electron hole contributions; both flow in the same reverse-current direction. This separates the two carrier-species contributions from the two opposing fluxes in the Shockley diode equation. Calling the saturation term a drift current refers to its passage across the depleted region, and does not eliminate the minority-carrier diffusion needed to supply it.

Reading the measured curves. At $eV\ll k_{B}T$, the ideal equation gives $I\simeq I_{\mathrm{sat}}eV/(k_{B}T)$, initially proportional to reverse electric potential difference. At $eV\gg k_{B}T$, it approaches a plateau $I\simeq I_{\mathrm{sat}}$. The thermal electric potential differences at the three temperatures are about $21$–$26\mathrm{mV}$, consistent with a rise at small reverse biases and near saturation at larger ones. Higher temperature produces a much larger plateau because thermal electron-hole excitation raises $n_i^2$ exponentially.

The lower-temperature curve has a noticeable residual electric potential difference dependence rather than a perfectly flat plateau. Depletion-region generation, surface leakage or other departures from the ideal diffusion model can contribute. The sharp upturn at the largest reverse electric potential differences is reverse breakdown, outside the unextended Shockley diode equation; the plot alone does not identify a unique microscopic breakdown mechanism. The original horizontal axis duplicates the final decade label, so a precise breakdown electric potential difference cannot be read reliably. Neither issue prevents estimating the gap from the intermediate-bias saturation region.

Band-gap estimate. Use plateau electric currents at a common intermediate reverse bias, away from both the small-bias rise and the breakdown upturn. Approximate readings are $I_{\mathrm{sat}}(298\mathrm{K})\sim 2.5\times 10^{-6}\mathrm{A}$, $I_{\mathrm{sat}}(273\mathrm{K})\sim 1.5$–$2\times 10^{-7}\mathrm{A}$, and $I_{\mathrm{sat}}(248\mathrm{K})\sim 10^{-8}\mathrm{A}$. Kelvin temperatures are required in the activation law.

For fixed effective masses, $n_i^2\propto T^3{e}^{-E_g/(k_{B}T)}$. If the remaining transport prefactor is approximately constant, extracting a semiconductor band gap from diode saturation current therefore usesUsing the widest temperature separation and the rounded readings givesNeglecting all algebraic prefactors and fitting $\ln I_{\mathrm{sat}}$ instead gives about $0.70\mathrm{eV}$. These differ by roughly $0.07\mathrm{eV}$, a material correction on the graph's precision scale. Thus an honest graph-based conclusion isThe nonflat low-temperature plateau, rough electric current readings, unprovided temperature dependence of $D/L$, and possible gap variation prevent a more precise extraction. If depletion-region generation dominated rather than the specified $I_{\mathrm{sat}}\propto n_i^2$ mechanism, its activation slope could involve a different energy scale; the displayed estimate explicitly uses the diffusion-dominated saturation model requested here.

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).