An exciton is an electron-hole bound state and behaves approximately as a boson when the gas is dilute compared with the inverse exciton volume. A condensation experiment needs a long enough lifetime for cooling, high phase-space density and evidence of spontaneous coherence; excessive density causes ionization or a Mott transition instead.
Bulk Cu₂O offers long-lived excitons, but heating, losses and Auger recombination complicate interpretation. Spectral narrowing or anomalous transport alone is insufficient: early claims required reinterpretation. Coupled quantum wells separate electron and hole layers, increasing lifetime and enabling cold indirect-exciton gases, though disorder, trapping and nonequilibrium flow must be distinguished from condensation.[ref]
In a semiconductor microcavity, coherent strong coupling mixes an exciton with a light cavity photon to form polaritons with very small effective mass. Nonresonant pumping supplies particles without imposing the condensate's phase. The 2006 CdTe experiment reported a threshold, strong low-momentum occupation, increased temporal coherence and long-range spatial coherence. These combined signatures support an exciton-polariton condensate; a threshold or bright emission alone does not distinguish it from photon lasing. Check that strong coupling persists above threshold. Finite lifetime and pumping make this an open, driven system, so thermalization must be demonstrated rather than inferred merely from the word condensate.[ref]
Absorption generates electrons and holes in the perovskite. After relaxation toward the band edges, their nonequilibrium populations are described by separate electron and hole quasi-Fermi levels. Selective contacts collect electrons through an electron-transport layer and holes through a hole-transport layer, while suppressing the opposite carriers.
For ideal contacts at open circuit,
This quasi-Fermi-level splitting is not the band gap itself or simply the equilibrium built-in voltage. At equilibrium there is one common Fermi level and no extractable photovoltage. Under illumination at open circuit, generation is balanced by recombination while a nonzero population splitting persists.
Figure 1.
Selective extraction, quasi-Fermi splitting and recombination-limited solar-cell voltage
. Original qualitative energy diagram and stipulated illuminated diode curves. Trap-assisted and interface recombination reduce carrier splitting and open-circuit voltage. Band offsets, energy spacings and current scales are illustrative rather than fitted perovskite data. Details.
Important parasitic paths include trap-assisted Shockley-Read-Hall recombination in the bulk, at grain boundaries and at interfaces, and recombination at poorly selective contacts. They lower the steady carrier populations and their quasi-Fermi splitting. Auger recombination can matter at high carrier densities but need not dominate an ordinary one-sun device. Radiative recombination is an unavoidable detailed-balance contribution, rather than an avoidable defect loss of the same kind.
An approximate illuminated diode relation is
Increased nonradiative recombination generally increases the dark recombination current and reduces ; it can also change ideality and fill factor. Shunts add a leakage path. Series resistance mainly reduces voltage under load and fill factor: its simple drop vanishes at zero terminal current, so it should not be invoked as an automatic direct subtraction from open-circuit voltage.
Generation increases the mobile electron or hole populations; interband excitation creates an electron-hole pair. Thermal excitation and absorbed photons are important sources, and impact ionization can multiply carriers in a strong field. Ordinary single-photon interband absorption needs enough photon energy to bridge the band gap, with the required momentum balance.
Electron-hole recombination removes a pair. Radiative electron-hole recombination emits a photon, with simple rate ; trap-assisted electron-hole recombination uses localized defect levels and transfers energy to the lattice; Auger recombination transfers the electron-hole recombination energy to another carrier. The last process becomes especially important at high injection because its rate contains products such as and . The detailed band structure and available defects determine which channel dominates.
At thermal thermodynamic equilibrium, generation and electron-hole recombination continue at equal rates. For the simple radiative model the net electron-hole recombination rate is , enforcing the semiconductor mass-action law. Under weak excitation with the majority density nearly fixed, an excess minority density often decays as , defining its minority carrier lifetime.
A short light pulse followed by time-resolved electrical conductivity or luminescence measures the relaxation. Spatial diffusion, trapping and instrumental response must be separated from electron-hole recombination before identifying a single fitted decay constant with the intrinsic lifetime. These processes control photodetector response and light-emitting-device efficiency.
Let , so the initial conduction-electron kinetic energy is . In the normal momentum-conserving process with the final hole fixed at zero wavevector, the two final conduction electrons obey . Their total kinetic energy satisfies
Energy conservation for impact ionization is . Consequently , giving
The bound is attained when ; opposite spins permit the two electrons to share that wavevector. Fixing the hole momentum is essential: a mobile final hole gives a different threshold. This is the threshold for impact ionization with a hole at zero momentum.
The two hot electrons subsequently redistribute energy by electron-electron collisions and transfer it to the lattice by electron-phonon scattering. Optical-phonon emission can provide large discrete losses while the electrons are hot; acoustic phonons dominate later small energy exchanges. Electron-electron collisions alone conserve the electron system's total energy and do not cool it into the lattice. The electron-hole pair eventually recombines radiatively or through nonradiative channels, such as defect-assisted recombination or Auger recombination. Recombination is distinct from the preceding intraband cooling.