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 and downward valence dispersions . 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 manifold, while spin-orbit coupling places the split-off valence band lower by . Its thermally generated hole population is suppressed by approximately relative to upper-valence holes, apart from density-of-states factors. Neglect is justified when ; it is not a universal exclusion of this band at arbitrary temperature.
Figure 1.
Original schematic direct and indirect band edges, including heavy, light and split-off hole branches
. Details.
For an indirect material such as Si, the conduction minimum need not be at . In applying the carrier-density formulae, 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 be the Fermi-Dirac distribution. In the nondegenerate conduction tail, . Set and integrate the given density of states:
The integral is . Defining the effective density of states gives
The 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 sufficiently below , . Substitution of gives in exactly the same way
Their product eliminates the chemical potential:
This is the semiconductor mass-action law at thermal equilibrium. In an intrinsic semiconductor, charge neutrality additionally gives
In 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 yields the intrinsic-semiconductor chemical potential
For unequal band degeneracies, use the first form with the full . For the supplied mass ratio , the shift from midgap at is approximately , 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 rises rapidly with temperature. In the middle, donors and acceptors are effectively ionized, the material is extrinsic, and 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, . Hence band-gap extraction from intrinsic carrier activation uses the slope of versus . With and expressed in eV/K, two points give
The very compressed intrinsic branch is only approximately readable: near and near . These give , rather than a precision determination. Neglecting the thermal prefactor gives about from those same rough points. Thus a gap of order – 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 , the supplied masses give
In the fully ionized extrinsic plateau, put . Charge neutrality and the mass-action law imply
Since , is insensitive to the imprecise gap. The minority density is much more sensitive:
Using gives and . Using instead gives and . 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.