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The built-in potential of a p-n junction is the electrostatic potential difference established when carrier diffusion exposes ionized dopants until the opposing drift and diffusion currents balance. The equilibrium electrochemical potential is constant even though the electric potential and band edges vary. In a nondegenerate homojunction with neutral-edge majority densities $p_p,n_n$, $e{V}_b=k_{B}T\log (p_p{n}_n/n_i^2)$. This is band bending within the same material, not necessarily a discontinuous offset of different materials' band edges.

For a uniformly doped p-n junction whose depleted thickness $d$ lies almost entirely on the donor side, Poisson's equation gives $dE/dx=e{N}_D/ϵ$. The minimum field obeys $E(d)=0$. Integrating the triangular electric field profile gives $V_{\mathrm{dep}}=e{N}_D{d}^2/(2ϵ)$. The external reverse bias is this total voltage minus the built-in junction potential.

Treat the $p^{+}$ strips as much more strongly doped than the $n$ bulk, so the depletion layer lies predominantly in the latter. Fully ionized donors leave uniform space charge $\rho =e{N}_D$. In one dimension,At the depletion boundary $x=d$, the minimum-bias solution has $E(d)=0$. Thus $E(x)=e{N}_D(x-d)/{ϵ}_{\mathrm{Si}}$, and the magnitude of the potential drop isFor $N_D=10^{18}{\mathrm{m}}^{-3}$, $d=300\mu \mathrm{m}$, and ${ϵ}_r=11.6$, this isThe applied reverse bias is approximately this value; more precisely the built-in junction potential contributes to the total depletion voltage and is subtracted from the required external bias. It is small on the scale of seventy volts and is not specified. Here the stated free-carrier density is used as the effective donor density of the neutral bulk before depletion.

Joining p-type and n-type regions initially allows majority carriers to diffuse across and recombine. Exposed negative acceptor charge on the p side and positive donor charge on the n side form a depletion region. Its electric field points from n to p and balances diffusion at equilibrium. The Fermi level is then spatially constant, while the conduction and valence band edges bend across the built-in potential; this equilibrium barrier cannot supply continuous power to a load.

forward bias makes p positive relative to n, reducing the barrier from $q{V}_{bi}$ to $q(V_{bi}-V)$. electrons enter p material and holes enter n material, becoming minority carriers whose diffusion and recombination sustain the current. reverse bias enlarges the barrier and leaves a much smaller minority-carrier current until breakdown. The ideal diffusion model gives $I=I_0[e^{qV/k_{B}T}-1]$, the Shockley diode equation; depletion-region recombination, series resistance and breakdown limit this approximation. Minority-carrier injection on both sides is essential to the junction theory.^[ref]

A p-n junction brings p-type and n-type regions into contact. Majority-carrier diffusion initially leaves exposed ionized acceptors and donors, producing a depletion region and a built-in potential. At thermal equilibrium the electrochemical potential is constant: drift and diffusion currents cancel. The internal barrier is not a freely extractable battery voltage.

For a nondegenerate abrupt homojunction,Here $V>0$ denotes forward bias and the depletion approximation is assumed. forward bias lowers the barrier and injects minority carriers; reverse bias widens the depleted region and suppresses ordinary majority injection. In the ideal diffusion regime,Recombination can change the ideality factor; series resistance, high-level injection, leakage and breakdown limit this simple Shockley diode equation. The original junction theory explicitly treats both electron and hole currents, which is essential to carrier injection and transistor action.^[ref]

As a rectifying diode, the junction conducts strongly in one bias direction and weakly in the other before breakdown. This permits power rectification, signal detection and electronic switching. Stored minority charge affects turn-off time, so a static exponential current-voltage relation alone does not specify switching speed. A junction capacitance $C_j\simeq {ϵ}_{s}A/W$ varies with reverse bias and can be used in a voltage-controlled capacitor; heavily doped or high-field junctions can instead exploit controlled tunnelling or avalanche breakdown.

In a photodiode, absorbed photons generate electron-hole pairs and the depleted-region field assists collection. reverse bias widens the collecting region and can improve speed, but adds dark-current noise and breakdown constraints. In a solar cell, the same carrier generation supplies current against an external voltage. An ideal illuminated characteristic is $I=I_s(e^{qV/(k_{B}T)}-1)-I_{\mathrm{ph}}$: at open circuit the forward diode current balances photocurrent, while useful power is taken at an intermediate operating point. Neither short circuit nor open circuit delivers power to a load.

A forward-biased light-emitting diode injects electrons and holes that can recombine radiatively. Efficient emission favors suitable direct-gap materials and carrier confinement; the characteristic photon energy is near the semiconductor band gap. nonradiative recombination, escape losses, series resistance and heating limit efficiency. Two coupled junctions also form a bipolar junction transistor: an emitter injects minority carriers through a thin base, and a reverse-biased collector collects them. Useful current gain depends on efficient injection and limited base recombination, not simply on joining any three arbitrary regions.

These functions are experimentally distinguished by measuring dark and illuminated current-voltage curves, bias-dependent capacitance, transient switching or optical emission, with controlled temperature and current limits. The common mechanism is bias-controlled carrier injection or collection at a depletion barrier; the device geometry and operating mode determine which function is useful.

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.

A direct band gap has its conduction minimum and valence maximum at the same crystal momentum. A photon can then connect the band-edge states with negligible momentum change. An indirect band gap requires an additional phonon to supply or remove momentum, making radiative recombination much less probable. Direct-gap materials such as gallium arsenide or gallium nitride are therefore usually better for a light-emitting diode than silicon.

For the graded junction, let $q=|e|>0$, ${\epsilon }_s={\epsilon }_0{\epsilon }_r$, and use electrostatic potential $\phi$ with $E_x=-{\phi }^{\prime }$. Fully ionized dopants have charge density $\rho =q(N_D-N_A)=q\alpha x$, so Poisson's equation is ${\phi }^{\prime \prime }=-q\alpha x/{\epsilon }_s$. The paper's displayed plus sign corresponds to using the negative potential $V=-\phi$, or a signed electron charge in that formula. The positive barrier magnitude and charge magnitude must be used consistently in the width below.

The intended compensation point is $x=0$, where $N_D=N_A$ and the net doping changes sign. A locally neutral model with comparable electron and hole mobilities has its lowest carrier conductivity near there. The depletion approximation neglects mobile-carrier conductivity throughout the layer, so it does not by itself locate an exact conductivity minimum; unequal mobilities or asymmetric carrier profiles can shift it.

Let the depletion edges be $x=\pm d$. With zero exterior field, integrating $E_x^{\prime }=\rho /{\epsilon }_s$ and imposing $E_x(\pm d)=0$ gives the linearly graded p-n junction fieldIts integral gives $\phi (x)=\phi (0)+q\alpha (d^{2}x-x^3/3)/(2{\epsilon }_s)$, so the electric potential increases toward the n-type side while the electron band edges $E_c,E_v$ bend downward together. Their separation is the local band gap, and the equilibrium electrochemical potential is flat. The built-in potential arises when carrier diffusion exposes ionized dopants until the opposing field balances further diffusion.

Finally the positive barrier isWith total width $w=2d$, this yields the linearly graded junction depletion widthHere $\alpha >0$ labels p-to-n progression with increasing $x$; otherwise use its magnitude in the width formula.

A solar cell uses the photovoltaic effect to turn photon energy into electrical work. In a semiconductor, above-gap photon absorption generates an electron in the conduction band and an electron hole in the valence band. A p-n junction, together with selective electrical contacts, collects the two carrier species at opposite terminals. Carrier diffusion and the built-in electric field help separate them before electron-hole recombination. Illumination maintains different quasi-Fermi levels for electrons and electron holes; their splitting, divided by $e$, sets the available terminal voltage in an ideal device. The equilibrium built-in potential alone cannot continuously deliver work.

For an ideal junction, the illuminated output current density isHere $J_{\mathrm{sc}}$ is the photogenerated short-circuit current density and $J_0$ the diode saturation current. The useful operating point maximizes $VJ$, rather than either current or voltage separately. With solar-cell fill factor $\mathrm{FF}=P_{\max }/(V_{\mathrm{oc}}{I}_{\mathrm{sc}})$,Series resistance, shunts, incomplete photon absorption and nonradiative recombination reduce the attainable efficiency.

The Shockley-Queisser limit removes these avoidable losses but retains the following physical constraints. There is one semiconductor junction with one band gap; each absorbed above-gap photon yields at most one collected electron-hole pair; carriers thermalize to the cell temperature; and the inverse optical process produces unavoidable radiative recombination. If ${\Phi }_{\odot }(E)$ is the incident photon flux per unit energy, ideal photon absorption givesThe same ability to absorb light requires the junction to emit it. At a forward voltage $V$, the emitted photon population has a chemical potential $eV$; in the ordinary nondegenerate limit the resulting recombination current is the exponential diode term above. Maximizing $VJ$ with this radiative $J_0$, and then choosing $E_g$, gives the limiting efficiency.

A small band gap collects many photons but gives a low voltage and large thermalization losses. A large band gap permits a larger voltage but transmits too much of the incident spectrum. Below-gap photons are lost to transmission, excess photon energy above the gap becomes heat, and radiative emission and its associated entropy loss keep $e{V}_{\mathrm{oc}}$ below $E_g$. The optimum single-junction conversion is roughly thirty percent under ordinary unconcentrated sunlight; the precise ceiling depends on spectrum, cell temperature and optical geometry. The original detailed-balance calculation gave about $30\%$ at $E_g\simeq 1.1\mathrm{eV}$ under its specified assumptions.^[ref] Multiple junctions and optical concentration change the assumptions and consequently change the bound.

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.

At equilibrium, majority electrons undergo diffusion from n to p, while majority electron holes diffuse from p to n. Their departure exposes positive donors on the n side and negative acceptors on the p side. The resulting electric field points from n to p and opposes further diffusion. Equilibrium is reached when the chemical potential is constant across the junction. The built-in potential is this electrostatic adjustment, not a discontinuity of the material's band gap.

Since electronic band energies shift by $-eV(x)$, both the conduction band and valence band undergo band bending down from p to n by $e{V}_b$ at zero applied bias. Their separation remains the same gap. In the nondegenerate thermal equilibrium limit the built-in voltage can also be expressed using neutral-edge densities as $e{V}_b=k_{B}T\log (n_n/n_p)=k_{B}T\log (n_n{p}_p/n_i^2)$.

Take the n-contact potential and its electrochemical potential as reference. Applying $V_{\mathrm{ext}}$ to the p side changes the total depletion-layer drop toThus $V_{\mathrm{ext}}<0$ is reverse bias: it increases the barrier and widens the depletion region. The bands have horizontal tangents at the neutral edges in this approximation and a smooth cubic bend within the linearly graded layer.

A biased junction is not in global thermal equilibrium. Its contact electron electrochemical potentials obeyUnder reverse bias the p-contact level is higher by $e|V_{\mathrm{ext}}|$. A single horizontal equilibrium chemical potential cannot describe this state; electron and hole quasi-Fermi levels describe the nonequilibrium populations. The sketch marks the contact levels. Detailed spatial quasi-Fermi profiles require transport and recombination information beyond the electrostatic doping profile.

The photovoltaic effect is the production of an electric potential difference or an electric current by photon absorption in a material or device. In a semiconductor, absorbed photons generate electrons and electron holes; asymmetric transport and selective collection can maintain distinct quasi-Fermi levels and deliver electrical power to a load. An equilibrium built-in potential alone supplies no continuous electrical power.