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An indirect band gap separates a valence band maximum and a conduction band minimum at different values of crystal momentum. A near-edge radiative transition then usually needs a phonon or another momentum-transfer process in addition to the photon, whose momentum is small on the Brillouin zone scale. A direct band gap has the extrema at the same crystal momentum and more readily supports efficient band-edge light emission. A material can have direct transitions at higher energy while its smallest gap is indirect.

Suppose a model replaces a set of free-electron boundary energies $E^{(0)}$ by lower and upper edges $E^{(0)}-V$ and $E^{(0)}+V$, with $V>0$. If these are the relevant global band edges, the indirect band gap is $(E_{\min }^{(0)}+V)-(E_{\max }^{(0)}-V)$, giving the displayed expression. A positive direct gap $2V$ at each crossing need not be enough: a band insulator needs $2V>E_{\max }^{(0)}-E_{\min }^{(0)}$. This is a band-edge estimate, not a general three-dimensional nearly-free-electron theorem; multiple Bragg planes at a corner can require a larger coupling matrix.

An optical interband transition that requires another momentum source, commonly a phonon, to connect initial and final electronic wavevectors. Near an indirect band gap, phonon emission gives a threshold photon energy $E_g+\hslash \Omega$, while phonon absorption gives $E_g-\hslash \Omega$ and requires an occupied phonon mode. The temperature dependence of the absorption therefore contains phonon-population information in addition to electronic occupations.

An interband transition moves an electron between distinct energy bands. A direct optical transition approximately conserves crystal momentum because optical photon momentum is small compared with a reciprocal lattice vector. A phonon-assisted transition can supply the momentum difference needed near an indirect band gap. Transition energies alone do not fix their optical intensities, which also depend on matrix elements and occupations.

Consider a noninteracting band model in which all states of one energy band would be occupied and the next energy band empty. Define the global indirect band gapIf ${\Delta }_{\mathrm{ind}}>0$, this filling can have a positive bulk excitation gap. If ${\Delta }_{\mathrm{ind}}<0$, transferring an electron from the highest occupied states of the lower energy band to sufficiently low states of the upper energy band lowers the total energy. The nominal complete-band filling is not the equilibrium state: electron and electron hole populations can occupy the overlapping bands, precluding a gapped band insulator at that filling.

The equality case requires care. At ${\Delta }_{\mathrm{ind}}=0$, the excitation gap closes, but contact only at isolated wavevectors need not create finite-volume carrier pockets or a finite carrier density at zero temperature. It is therefore incorrect to infer strictly energy-lowering redistribution or partially occupied pockets merely from a band touching. Electron interactions and symmetry breaking can alter this single-particle description.

In weak-probe optical absorption, Fermi's golden rule creates an electron-hole pair, with negligible population depletion. Negligible photon momentum makes a direct band gap transition nearly vertical in crystal momentum:For allowed transitions between three-dimensional parabolic bands, the joint density of states yields $\alpha \propto \sqrt{\hslash \omega -E_g}/\omega$ above the gap. Selection rules and polarization enter the dipole matrix element. An indirect band gap needs an additional phonon to conserve crystal momentum, with phonon absorption/emission weights and shifted thresholds.

Electron-hole attraction produces Wannier excitons below the continuum, approximately $E_n=E_g-R^{\ast }/n^2$, with bright $s$-state oscillator strength decreasing as $n^{-3}$. It also enhances the continuum edge. Screening, disorder and phonons broaden these features; heavy/light valence bands can create distinct series. This linear-response picture includes Coulomb binding but excludes a resolved coherent photon–exciton anticrossing: that would require a strong light–matter coupling treatment. “Weak coupling” here is distinguished from neglecting the electron-hole interaction altogether.

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]

At equilibrium, electrons initially diffuse from the n side and holes from the p side. Recombination leaves ionized donors and acceptors in a depletion region, producing an internal electric field and band bending. The Fermi level is constant across the equilibrium p-n junction. With p material on the left, both band edges lie higher on the p side, as in the left panel.

Forward bias, with the p side positive relative to n, reduces the injection barrier. Electrons and holes enter the junction region and can recombine radiatively, emitting photons with energy close to the band gap. Under bias, separate electron and hole quasi-Fermi levels replace a single equilibrium Fermi level.

Both GaN polymorphs have a direct band gap, so a conduction-band electron and valence-band hole can recombine without a large crystal-momentum change. Silicon and germanium have indirect band gaps, requiring phonon assistance for near-edge radiative recombination, which makes efficient band-edge light emission much harder. A direct gap enables the process; defects, carrier confinement and competing nonradiative channels still determine device efficiency.

With spin degeneracy, each energy band contains two electrons per primitive unit cell. Divalency therefore permits a filled first band, but only if its maximum lies below the second band's minimum. With negligible ionic periodic potential, the circular Fermi surface and the rectangular zone have equal enclosed area, not equal shape. Electrons occupy some states outside the first zone while some higher-energy first-zone states remain empty. Folded bands overlap, and the material is a metal.

A periodic potential mixes plane waves differing by a reciprocal lattice vector. At a two-wave Bragg point, the nearly-free electron model gives a direct gap $2|V_{\mathbf{G}}|$. Increasing appropriate Fourier coefficients can remove the band overlap. With the first band filled, the system is then a band insulator, provided the temperature is small compared with the insulating band gap in energy units.

The rectangular free-electron band-overlap scale follows from two different points in reciprocal space. Put $C={\hslash }^2/(2m_e)$. Before gap opening, the highest first-zone energy is at the corner, while the lowest second-zone energy is at the midpoint of the nearer face:Thus the downward shift ${\delta }_v$ of the first-band maximum plus the upward shift ${\delta }_c$ of the second-band minimum must overcomeIn a rigid-splitting estimate, an opening $\Delta$ lowers the first band by $\Delta /2$ and raises the second by $\Delta /2$, giving the familiar threshold $\Delta >{\hslash }^2{\pi }^2/(2m_e{b}^2)$. Equality is only band touching, not a positive insulating gap. This expression is the overlap that must be removed, under that explicit band-shift approximation.

Positive direct gaps can coexist with band overlap: a local direct splitting and the global indirect band gap are not interchangeable. The shape and Fourier coefficients of the ionic potential are unspecified, so there is no universal exact critical direct-gap width determined by $a,b$ alone. For a concrete demonstration, a separable potential $2V_x\cos (2Kx)+2V_y\cos (2Ly)$ has axial direct gaps ${\Delta }_x=2|V_x|$ and ${\Delta }_y=2|V_y|$. To first order, the corner's lowest level is $C(K^2+L^2)-|V_x|-|V_y|$, and the two candidate second-band minima are $C{K}^2+|V_x|$ and $C{L}^2+|V_y|$. Therefore, within this model and neglecting higher-order band shifts, nonoverlap requiresEqual axial gaps would give the first-order estimate $\Delta >2C{L}^2/3$, rather than the rigid-splitting estimate. Such a large opening can exceed the quantitative range of weak-potential perturbation theory, but the example identifies the missing model assumption: corner levels feel both couplings. The exact general answer is the positive indirect-gap criterion above; a geometry-only direct-gap threshold would claim more than the supplied potential information supports.

There are two electrons per primitive unit cell; a spin-degenerate energy band accommodates exactly that number. A semiconductor results when the first band is full and does not overlap the second. In the leading two-wave/four-wave approximation, compare the first-band maximum at $M$ with the second-band minimum at $X$:This is an indirect band gap; a nonzero local splitting at $X$ alone is insufficient. At the onset,With $a=0.3\mathrm{nm}$, ${\hslash }^2/(2m_e)=0.03810\mathrm{eV}\mathrm{n}{\mathrm{m}}^2$ gives $E_X\simeq 4.178\mathrm{eV}$, henceFor $V_{10}$ more negative than this value the estimated indirect band gap is positive; at equality the bands just touch. This is the onset estimate within the source's nearly-free electron model truncation, not an exact critical potential after coupling all plane waves.

A semiconductor has a filled valence band and an empty conduction band at zero temperature in the intrinsic idealisation, separated by a modest band gap. Thermal excitation or deliberately introduced impurities can create mobile electrons and electron holes. Its conductivity is consequently very sensitive to temperature and doping. A metal has available electronic states at the occupied energy boundary, through a partly filled band or overlapping bands, and need not thermally excite carriers across a gap.

For a direct band gap, the conduction-band minimum and valence-band maximum occur at the same crystal momentum. An electron can recombine with a hole near these extrema and emit a photon while conserving crystal momentum, since optical photon momentum is small on the lattice scale. For an indirect band gap, the extrema lie at different crystal momenta. A band-edge radiative transition then ordinarily needs a phonon as well, making it less probable and allowing nonradiative processes to compete more effectively.

gallium arsenide has a direct fundamental gap, while silicon has an indirect one. This makes efficient band-edge emission and hence a light-emitting diode easier to obtain from gallium arsenide. It does not mean silicon has no optical transitions or that every direct-gap sample emits efficiently: defects, surfaces and carrier confinement also matter.

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.

Different measurements reveal different aspects of electronic band structure; a convincing determination combines their constraints.

Angle-resolved photoemission. In angle-resolved photoemission spectroscopy, photons of known energy eject occupied electrons. Measuring their kinetic energy and emission angle reconstructs binding energy and the component of crystal momentum parallel to the surface:Here $\Phi$ is the sample work function when kinetic energy is referenced to the nearby vacuum; an analyzer energy scale requires its own work-function calibration. Momentum is conserved modulo a surface reciprocal lattice vector, neglecting photon momentum. Tracking the peaks maps occupied dispersion relations and the Fermi surface. The measured intensity also contains the matrix element, the Fermi-Dirac distribution and the spectral function, so an absent bright feature does not establish an absent band. For a three-dimensional solid, the perpendicular momentum requires a final-state model. Inverse photoemission spectroscopy probes unoccupied states by injecting electrons and detecting emitted photons.

Optical spectroscopy. Photon absorption and ellipsometry measure interband transitions, optical selection rules and the complex dielectric response. Because optical photon momentum is small on the scale of the Brillouin zone, direct transitions approximately preserve crystal momentum. Their onset constrains a direct band gap; a threshold involving a phonon can reveal an indirect band gap. Peak positions constrain energy differences between bands, but the response also depends on the joint density of states and optical matrix elements, so it does not uniquely determine every $E_n(\mathbf{k})$.

Quantum oscillations and cyclotron resonance. In clean samples at low temperature, the de Haas-van Alphen effect measures oscillations in magnetization and the Shubnikov-de Haas effect measures oscillations in electrical resistivity as the inverse magnetic field is varied. Their period in inverse magnetic field is $1/F$, where Onsager quantization relates $F$ to an extremal Fermi-surface area perpendicular to the field:Rotating the magnetic field maps the geometry of extremal orbits. The thermal damping determines the cyclotron effective mass,with the appropriate magnitude for a hole orbit. Cyclotron resonance supplies the corresponding dynamical mass through ${\omega }_c=eB/m_c$. These are detailed probes near the Fermi level, rather than measurements of all occupied bands. Diffraction supplies the reciprocal lattice needed to label the measured momenta, but diffraction by itself is not a measurement of electronic dispersion.

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 a semiconductor, a conduction electron fills a vacant valence state and emits a photon. In a simple nondegenerate model the recombination rate is $Bnp$, while the equilibrium reverse generation rate is $B{n}_i^2$; their difference gives the displayed net pair-loss rate. This subtraction enforces detailed balance at thermal equilibrium. Photon momentum is small on the scale of a Brillouin zone, so a direct band gap permits a direct transition while an indirect band gap generally requires a phonon or another source of momentum.

For rectangular real-space periods $a>b$, the free first-zone corner has energy ${\hslash }^2{\pi }^2(a^{-2}+b^{-2})/(2m)$, whereas the free second-zone minimum is ${\hslash }^2{\pi }^2/(2m{a}^2)$. Their difference is the displayed overlap. A divalent spin-degenerate system is a band insulator only when the actual first-band maximum lies below the second-band minimum. A rigid symmetric splitting $\Delta$ removes the overlap if $\Delta >{\Delta }_{\mathrm{overlap}}$, but an arbitrary periodic potential does not shift every corner and face by the same amount. The exact criterion uses the indirect band gap, not a geometry-only local direct-gap width.

For a divalent square Bravais lattice, let $E_X={\hslash }^2{\pi }^2/(2m_e{a}^2)$ and real periodic potential coefficients $V_{10}<V_{11}<0$. The leading two-wave edge levels are $E_X\pm V_{10}$. The four-wave corner levels are $2E_X+V_{11}\pm 2V_{10}$ and a doublet at $2E_X-V_{11}$. Comparing the lowest corner level with the upper edge level gives the displayed indirect band gap. The first spin-degenerate energy band can hold the two electrons per primitive unit cell; it becomes isolated when $-E_X-V_{11}-3V_{10}>0$ in this truncation. This follows from resonant degenerate perturbation theory, and higher plane waves can shift the threshold.