In a thermodynamic treatment electromagnetic radiation of any kind is described. The difference between thermal and non-thermal radiation is accounted for by introducing the chemical potential of photons. Instead of an effective temperature all kinds of radiation have the real temperature of the emitting material. As a result Planck's law for thermal radiation is extended to radiation of any kind. The concept of the chemical potential of radiation is discussed in detail in conjunction with light-emitting diodes, two-level systems, and lasers. It allows the calculation of absorption coefficients, of emission spectra of luminescent materials, and of radiative recombination lifetimes of electrons and holes in semiconductors. Theoretical emission spectra are compared with experimental data on GaAs light-emitting diodes and excellent agreement is obtained.

A system for solar energy conversion using the up-conversion of sub-band-gap photons to increase the maximum efficiency of a single-junction conventional, bifacial solar cell is discussed. An up-converter is located behind a solar cell and absorbs transmitted sub-band-gap photons via sequential ground state absorption/excited state absorption processes in a three-level system. This generates an excited state in the up-converter from which photons are emitted which are subsequently absorbed in the solar cell and generate electron-hole pairs. The solar energy conversion efficiency of this system in the radiative limit is calculated for different cell geometries and different illumination conditions using a detailed balance model. It is shown that in contrast to an impurity photovoltaic solar cell the conditions of photon selectivity and of complete absorption of high-energy photons can be met simultaneously in this system by restricting the widths of the bands in the up-converter. The upper limit of the energy conversion efficiency of the system is found to be 63.2% for concentrated sunlight and 47.6% for nonconcentrated sunlight.

One of the major loss mechanisms leading to low energy conversion efficiencies of solar cells is the thermalization of charge carriers generated by the absorption of high-energy photons. These losses can largely be reduced in a solar cell if more than one electron–hole pair can be generated per incident photon. A method to realize multiple electron–hole pair generation per incident photon is proposed in this article. Incident photons with energies larger than twice the band gap of the solar cell are absorbed by a luminescence converter, which transforms them into two or more lower energy photons. The theoretical efficiency limit of this system for nonconcentrated sunlight is determined as a function of the solar cell’s band gap using detailed balance calculations. It is shown that a maximum conversion efficiency of 39.63% can be achieved for a 6000 K blackbody spectrum and for a luminescence converter with one intermediate level. This is a substantial improvement over the limiting efficiency of 30.9%, which a solar cell exposed directly to nonconcentrated radiation may have under the same assumption of radiative recombination only.

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The selective transport of electrons and holes to the two terminals of a solar cell is often attributed to an electric field, although well-known physics states that they are driven by gradients of quasi-Fermi energies. However, in an illuminated semiconductor, these forces are not selective, and they drive both charge carriers toward both contacts. This paper shows that the necessary selectivity is achieved by differences in the conductivities of electrons and holes in two distinct regions of the device, which, for one charge carrier, allows transport to one contact and block transport to the other contact.To clarify the physics, we perform numerical simulations of three different solar cell structures with asymmetric carrier conductivities. Two of them achieve the ideal conversion efficiency limit, despite the fact that the charge carriers flow against an internal electric field, proving that the latter cannot explain carrier separation. A third, i.e., conceptual structure, has no electric field at all but still works ideally as a solar cell. In conclusion, the different conductivities of electrons and holes in two regions of the device can be identified as the essential ingredient for charge carrier separation in solar cells, regardless of the existence of an electric field.