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Arsenic has five valence electrons, whereas silicon has four. A substitutional arsenic atom can therefore supply an extra electron after participating in the silicon bonding network. It acts as a shallow donor impurity, introducing a localized level $E_D$ just below the conduction band. Ionizing that donor costs much less energy than excitation across the full band gap.

At the lowest temperatures, donor electrons remain bound and the valence band is filled. Mobile-carrier populations are negligible: this is dopant freeze-out. Initial heating releases donor electrons into the conduction band, producing a rapid rise in conductivity governed by the shallow-donor energy scale. The positive ionized donor charge compensates the released electronic charge; the bulk need not acquire net charge.

At intermediate temperatures, nearly all donors are ionized but intrinsic electron–hole generation is still small. In an uncompensated sample,where $N_D$ is donor number density. The supply of donor electrons is finite, so further heating cannot keep creating them. This is the extrinsic plateau under the approximation of weakly varying mobility, and its carrier density is much larger than that of the undoped sample at the same temperature. In real material, scattering changes mobility, so donor exhaustion alone predicts a carrier-density plateau rather than guaranteeing perfectly flat conductivity.

At higher temperatures, intrinsic generation becomes comparable to and then exceeds the donor contribution. Once $n_i\gg N_D$, the populations approach $n\simeq p\simeq n_i$, and activation across the main gap causes the steeper rise. The relevant regimes are therefore freeze-out, donor exhaustion, and intrinsic excitation, not three successive types of dopant.

A direct band gap has its conduction band minimum and valence band maximum at the same crystal momentum. Near-edge absorption or emission can therefore conserve momentum with the electron and photon alone, since optical photon momentum is small on the Brillouin-zone scale. An indirect band gap has its extrema at different wavevectors and normally needs a phonon or another momentum-transfer process in addition to the photon.

Direct-gap materials are usually preferred for efficient light emission, because the radiative transition avoids the extra phonon-assisted process. Their stronger near-edge absorption also permits thinner photovoltaic absorbers. Indirect-gap materials can nevertheless make excellent solar cells: sufficiently thick optical paths, light trapping, long carrier lifetimes and suitable material quality can compensate for weaker absorption. The direct/indirect distinction alone does not rank every device.

This momentum distinction and the difference between bound exciton lines and the free-pair continuum are treated together in the primary effective-mass absorption theory.^[ref]

Three routes are donor doping, acceptor doping and above-gap illumination. All increase mobile carrier populations if the added states or excitations are effective rather than strongly trapped.

An appropriate donor impurity provides an occupied level just below the conduction band. Thermal ionization requires the smaller donor binding energy rather than the full host gap, supplying mobile electrons and n-type semiconductor behaviour. An appropriate acceptor impurity creates an available level just above the valence band; accepting a valence electron leaves a mobile hole, giving p-type semiconductor behaviour. Doping concentrations and compensation must permit useful carriers; an arbitrary impurity need not be an effective dopant.

For photoconductivity, absorbed photons with $h\nu \gtrsim E_g$ can excite valence electrons into the conduction band, producing electron–hole pairs. For the stated $2.7\mathrm{eV}$ gap, the nominal threshold is about $1240/2.7\simeq 459$ nm. Optical selection rules and absorption strength can shift the practical onset. The conductivity increase persists only while generation maintains carriers against recombination and trapping; it is not necessarily a permanent change to the material.

In each case, $\sigma =e(n{\mu }_n+p{\mu }_p)$ connects increased carrier density to conductivity. Defect-induced reductions in mobility can offset some of the gain, so the diagrams specify mechanisms rather than guarantee a numerical improvement for an unspecified preparation.

A $2.24\mathrm{eV}$ band gap is consistent with a semiconductor. In pure gallium phosphide, the valence band is essentially full and the conduction band essentially empty at low temperature; thermal or optical excitation can produce mobile electrons and electron holes.

At room temperature, $k_{B}T\approx 0.026\mathrm{eV}$ is much smaller than the band gap, so intrinsic excitation is strongly suppressed. Pure material consequently has a low intrinsic carrier density, while semiconductor doping can markedly increase its electrical conductivity.

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 $E_c$, the valence band edge $E_v$, and $E_g=E_c-E_v$. The spin-summed conduction density of states per volume isUsing the nondegenerate limit of the Fermi-Dirac distribution and the substitution $x=(E-E_c)/(k_{B}T)$ givesThe factor $\sqrt{\pi }/2$ in the supplied integral produces the normalization. Counting missing valence band electrons similarly givesMultiplication cancels the chemical potential, establishing the semiconductor mass-action law:The result does not require an intrinsic semiconductor: semiconductor doping changes $n$ and $p$ separately while preserving this product under the stated equilibrium and nondegeneracy assumptions.

An electron hole is a missing electron in an otherwise almost filled valence band. A completely filled band has no net transport current: its velocities cancel over the Brillouin zone. Describing a few missing states as mobile excitations is therefore simpler than following almost every occupied electron state.

Near an isotropic valence maximum, write the electron dispersion as $E_v(\mathbf{k})=E_v(0)-{\hslash }^2{k}^2/(2m_h)$ with $m_h>0$. The electron curvature mass is negative there. Removing that electron creates an excitation with momentum $\hslash {\mathbf{k}}_h=-\hslash \mathbf{k}$ and energy measured upward from the filled reference,ThusThe sign refers to the positive excitation energy of a missing electron near a maximum, not to negative vacuum mass. A general maximum gives the corresponding positive hole-curvature tensor.^[ref]

Assume nondegenerate three-dimensional parabolic band edges, a fixed gap and approximately temperature-independent density-of-states effective masses. Let $\mu$ be the chemical potential, $E_c$ and $E_v$ the band edges, and $N_c,N_v$ their effective density of states. Boltzmann occupation givesFor one spin-degenerate spherical conduction extremum, direct integration of $g_c(E)\propto \sqrt{E-E_c}$ givesand similarly for the valence band with its appropriate density-of-states mass. Valley and additional band degeneracies can be included in these prefactors. The $T^{3/2}$ factor follows from the integral ${\int }_0^{\infty }\sqrt{ϵ}{e}^{-ϵ/(k_{B}T)}dϵ\propto T^{3/2}$.

Multiplication removes the chemical potential:The semiconductor mass-action law combined with intrinsic charge neutrality, $n=p$, therefore givesThe intrinsic chemical potential is not necessarily exactly midgap: ${\mu }_i=(E_c+E_v)/2+(k_{B}T/2)\ln (N_v/N_c)$. Equal effective masses are unnecessary for the displayed carrier-density law. A changing gap, effective mass or degeneracy would make the prefactor or activation law temperature dependent.

Assume thermal equilibrium, a three-dimensional nondegenerate semiconductor, one parabolic conduction extremum and one parabolic valence extremum, with two spin states in each. Use the supplied effective masses as scalar density-of-states parameters. With conduction energy $E=E_c+\epsilon$, state counting gives the per-volume density of statesSince $E_c-\mu \gg k_{B}T$, replace the Fermi-Dirac distribution by its Boltzmann factor. Using $x=\epsilon /(k_{B}T)$ and the supplied integral,The electron hole occupation is $1-f(E)$ in the valence band. Applying the same integration below $E_v$ givesTheir product cancels the chemical potential, giving the semiconductor mass-action lawThus, for masses expressed in ordinary mass units,The labels $B,C$ in this last box are exponents, unrelated to the magnetic field or Curie constant above. Valley degeneracy or multiple valence bands must be included in the effective density of states, or absorbed into suitable density-of-states effective masses, not counted twice. Real silicon has anisotropic multiple valleys, so its conductivity mass is not automatically its density-of-states mass; the numerical answers below implement the paper's supplied scalar-mass model.^[ref]

The formula is not an identity for arbitrarily degenerate carriers. For a concrete counterexample, take $\mu -E_c=10k_{B}T$ while holes remain dilute. Fermi occupation gives $n/N_c\simeq 24.1$, whereas the Boltzmann replacement would give $e^{10}\simeq 22026$; the predicted product then differs by about three orders of magnitude. Separate electron and hole quasi-Fermi levels out of equilibrium would also prevent the cancellation used above.

Near a parabolic valence band maximum $E_v$, the missing-electron effective mass is $m_h^{\ast }>0$. The same two-dimensional state counting givesMultiplication eliminates the chemical potential, giving the semiconductor mass-action lawFor an intrinsic semiconductor, charge neutrality imposes $n=p=n_i$, soThe intrinsic chemical potential is not exactly midgap when the two effective masses differ: ${\mu }_i=(E_c+E_v)/2+(k_{B}T/2)\log (m_h^{\ast }/m_e^{\ast })$. 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, $\mu =0$. The Fermi-Dirac distribution givesMeasured relative to the filled valence band at zero temperature, the thermal internal energy includes both species. Removing a valence band electron at $-E$ costs the positive hole energy $E$, just as adding a conduction band electron at $E$ does. HenceDifferentiate 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 $N_c$ counts only the excited conduction band electrons, while the heat capacity includes both electrons and holes; moreover, $N_c\propto T$ is not fixed. In fact $\Delta U/N_c={\pi }^2{k}_{B}T/(6\ln 2)$, and differentiating $N_c(T)$ supplies another equal contribution to the heat capacity. Finally, $\mu =0$ gives occupation $1/2$ at the touching point, so the excitation gas is not in the classical dilute limit even though $k_{B}T$ exceeds the vanishing band gap.

Undoped gallium arsenide is expected to be diamagnetic at zero temperature. Its valence band is filled and its conduction band empty, so there are no mobile conduction band electrons to give Pauli paramagnetism. The specified absence of localized magnetic moments removes a Curie law response and the usual mechanism for ferromagnetic ordering. The remaining induced orbital response is diamagnetism. This classification uses the ordinary weak-field band insulator picture; the band gap suppresses thermally generated carriers as $T\to 0$.

Let $\beta =1/(k_{B}T)$, with $k_B$ the Boltzmann constant, $T$ the absolute temperature, and $\mu$ the common equilibrium chemical potential. The conduction band minimum and valence band maximum are ${ϵ}_c$ and ${ϵ}_v$; their separation is the band gap $E_g={ϵ}_c-{ϵ}_v$. The positive parameters $m_e,m_h$ 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 $f(ϵ)=[e^{\beta (ϵ-\mu )}+1{]}^{-1}$. The appropriate statistical factors are $f_c=f$ for electrons and $f_v=1-f$ for electron holes. In a nondegenerate semiconductor, ${ϵ}_c-\mu \gg k_{B}T$ and $\mu -{ϵ}_v\gg k_{B}T$, so the Boltzmann approximation givesFor the conduction band, set $u=ϵ-{ϵ}_c$ and then $\xi =\beta u$. The supplied integral yieldsFor the valence band, set $u={ϵ}_v-ϵ$ to obtainThe effective density of states factors $N_c,N_v$ 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 lawHere $n_i=\sqrt{N_c{N}_v}{e}^{-E_g/(2k_{B}T)}$ is the intrinsic carrier concentration. Equality $n=p=n_i$ 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.

There are three regimes. At the lowest temperatures, most donor impurities retain their electrons; thermal ionization gives semiconductor carrier freeze-out. The result from part (b) isThis produces the approximately straight descending low-temperature tail on the logarithmic scale plot against $1/T$. The activation energy in the exponential is $E_i/2$, because the chemical potential adjusts with donor ionization.

At intermediate temperatures, the donor impurities are essentially fully ionized while intrinsic excitation remains small. Charge neutrality gives $n\simeq N_D$, producing the extrinsic plateau, roughly from $20$ to $40\mathrm{K}$ in the figure.

At higher temperatures, excitation from the valence band to the conduction band creates electron-hole pairs. The intrinsic carrier concentration grows as $n_i\propto T^{3/2}{e}^{-E_g/(2k_{B}T)}$ for constant parabolic band effective masses and constant band gap. With ionized donor impurities, charge neutrality and the semiconductor mass-action law giveThus $n\simeq n_i+N_D/2$ when $n_i\gg N_D$. This explains the renewed rapid rise and the eventual intrinsic branch; that branch is governed by the band gap, rather than the donor binding energy.

The lower curve is a valence band and the upper curve is a conduction band, separated by an indirect band gap. The readable upper curve has a minimum just inside the X boundary and slightly below the plotted chemical potential. It is therefore partially occupied, while the visible valence states lie below the chemical potential and are filled at low temperature. The sample is electron-doped, with electron pockets around the six symmetry-related conduction minima of silicon.

The full high-symmetry path and part of the lower-left dispersion are absent from the held image. Source gap: those missing path labels and curve segments cannot be read or reconstructed from this copy. The identification of the conventional six silicon valleys and the valence maximum at $\Gamma$ uses the usual silicon band model, rather than purported readings of missing pixels.

Two methods for calculating such an electronic band structure are density functional theory, solving a self-consistent periodic electronic problem, and a tight-binding model, diagonalizing a hopping Hamiltonian built from localized atomic orbitals. Neither is a measurement of the plotted dispersion relation.

For a nondegenerate band $E(\mathbf{k})$, define the reciprocal effective mass tensor byIt is the curvature tensor of the energy band. Near an extremum, $E\simeq E_0+{\hslash }^2\delta {\mathbf{k}}^T{M}^{-1}\delta \mathbf{k}/2$, so positive principal curvatures give positive electron effective masses. Together with the group velocity $\mathbf{v}={\hslash }^{-1}{\nabla }_{\mathbf{k}}E$ and $\hslash \dot{\mathbf{k}}=\mathbf{F}$, it yields ${\dot{v}}_i=(M^{-1}{)}_{ij}{F}_j$. Negative electron curvature at a valence band maximum is conventionally recast as a positive band effective mass for missing electrons.

For $\mathbf{B}\parallel [111]$, its squared projection onto the long axis of every valley is $1/3$. All six valleys therefore have the same cyclotron effective mass:At the fixed photon energy,Thus the two-peak spectrum is replaced by one peak near $1.4\mathrm{T}$. The source does not determine the linewidth or absolute oscillator strength for the new direction; the sketch below shows only a normalized illustrative line at the computed position.

For the electron-doped sample, sketch six closed ellipsoids centred on the $\Gamma$--X axes, just inside the six square faces of the face-centred-cubic first Brillouin zone, with long axes pointing radially toward X. In the parabolic approximation,The radial-to-transverse semiaxis ratio is $\sqrt{m_2/m_1}\simeq 2.2$. The readable conduction minimum near X and its crossing of $\mu$ support these electron Fermi surface pockets. The two $[001]$ cyclotron resonance fields arise from the two distinct orientations of the six ellipsoids, rather than two unrelated carrier species. The left panel of the original sketch includes axes, $\Gamma$, and the three positive-axis X points; the negative-axis X points are symmetry-equivalent.

The surviving valence maximum lies roughly $1.2\mathrm{eV}$ below the original $\mu$. Lowering $\mu$ by $1.5\mathrm{eV}$ therefore places it in the upper valence band in the conventional silicon band interpretation. The electron pockets disappear and one sketches a hole pocket centred at $\Gamma$, as in the middle panel. Detailed valence-band warping and the number of spin-orbit-resolved sheets cannot be extracted from the damaged figure, and the single drawn surface is schematic rather than a claim that all such sheets coincide.

A discriminating physical property is the Hall coefficient: electron-dominated transport gives a negative value, whereas hole-dominated transport gives a positive value in the ordinary single-dominant-carrier regime. One should not infer a numerical resistivity change without the carrier densities and mobilities.

Assume equal excess electron and electron hole number densities $N_t$, with no additional doping imbalance. At zero temperature, both occupied carrier spheres have the same Fermi wavevector $k_F$ because their spin counting is the same:For $k<k_F$, the conduction band is occupied and the valence band has electron holes, so $f_c-f_v=1$. Beyond $k_F$ the occupations reverse and the medium absorbs. Thus the upper edge of the positive-optical gain interval is the supremumEquivalently $E_{\mathrm{Fc}}=E_g+{\hslash }^2{k}_F^2/(2m_c^{\ast })$ and $E_{\mathrm{Fv}}=-{\hslash }^2{k}_F^2/(2m_v^{\ast })$. With the supplied effective masses,Using the vacuum wavelength $\lambda =hc/(\hslash \omega )$ reverses the endpoints:These boundaries are idealized and open: the lower-energy edge has zero joint density of states, and the upper edge is the zero-temperature occupation discontinuity, not a finite-width gain peak. The calculation gives positive material optical gain, not the stronger requirement of exceeding the losses at laser threshold.

A double heterostructure laser sandwiches a narrow-band gap active layer between wider-band gap cladding layers. In a type-I band alignment, the conduction band edge is lower and the valence band edge higher in the active layer. Electrons therefore see an energy well, and electron holes also see a well because their excitation energy increases when the valence band edge decreases. Both carrier populations remain concentrated where stimulated emission occurs.

The active layer also normally has the higher refractive index, forming an optical waveguide. The optical normal mode overlaps the injected carriers strongly, and the wider-band gap cladding has less interband absorption at the emitted photon energy. Carrier confinement reduces leakage, while optical confinement reduces the required pump current and hence heating.

Writing $\Gamma$ for the fraction of the optical normal mode overlapping the active layer, the threshold condition is $\Gamma g={\alpha }_i+{\alpha }_m$, with internal and mirror losses ${\alpha }_i,{\alpha }_m$. A larger overlap and a higher carrier number density at a given current both lower the threshold current. The figure shows composition-induced offsets; a working junction also has band bending under bias, which is omitted to make the confinement mechanism visible.

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]