No abstract

The electronic defects in any semiconductor play a decisive role for the usability of this material in an optoelectronic device. Electronic defects determine the doping level as well as the recombination centers of a solar cell absorber. Cu(In, Ga)Se 2 is used in thin-film solar cells with high and stable efficiencies. The electronic defects in this class of materials have been studied experimentally by photoluminescence, admittance, and photocurrent spectroscopies for many decades now. The literature results are summarized and compared to new results by photoluminescence of deep defects. These observations are related to other experimental methods that investigate the physicochemical structure of defects. To finally assign the electronic defect signatures to actual physicochemical defects, a comparison with theoretical predictions is necessary. In recent years the accuracy of these calculations has greatly improved by the use of hybrid functionals. A comprehensive model of the electronic defects in Cu(In, Ga)Se 2 is proposed based on experiments and theory. The consequences for solar cell efficiency are discussed.

Copper indium gallium diselenide-based technology provides the most efficient solar energy conversion among all thin-film photovoltaic devices. This is possible due to engineered gallium depth gradients and alkali extrinsic doping. Sodium is well known to impede interdiffusion of indium and gallium in polycrystalline Cu(In,Ga)Se2 films, thus influencing the gallium depth distribution. Here, however, sodium is shown to have the opposite effect in monocrystalline gallium-free CuInSe2 grown on GaAs substrates. Gallium in-diffusion from the substrates is enhanced when sodium is incorporated into the film, leading to Cu(In,Ga)Se2 and Cu(In,Ga)3Se5 phase formation. These results show that sodium does not decrease per se indium and gallium interdiffusion. Instead, it is suggested that sodium promotes indium and gallium intragrain diffusion, while it hinders intergrain diffusion by segregating at grain boundaries. The deeper understanding of dopant-mediated atomic diffusion mechanisms should lead to more effective chemical and electrical passivation strategies, and more efficient solar cells.

The electrical and optoelectronic properties of materials are determined by the chemical potentials of their constituents. The relative density of point defects is thus controlled, allowing to craft microstructure, trap densities and doping levels. Here, we show that the chemical potentials of chalcogenide materials near the edge of their existence region are not only determined during growth but also at room temperature by post-processing. In particular, we study the generation of anion vacancies, which are critical defects in chalcogenide semiconductors and topological insulators. The example of CuInSe 2 photovoltaic semiconductor reveals that single phase material crosses the phase boundary and forms surface secondary phases upon oxidation, thereby creating anion vacancies. The arising metastable point defect population explains a common root cause of performance losses. This study shows how selective defect annihilation is attained with tailored chemical treatments that mitigate anion vacancy formation and improve the performance of CuInSe 2 solar cells.

The photoluminescence (PL) of semiconductors can be used to determine their absorption coefficient (α) using Planck's generalized law. The standard method, suitable only for self-supported thick samples, like wafers, is extended to multilayer thin films by means of the transfer-matrix method to include the effect of the substrate and optional front layers. α values measured on various thin-film solar-cell absorbers by both PL and photothermal deflection spectroscopy (PDS) show good agreement. PL measurements are extremely sensitive to the semiconductor absorption and allow us to advantageously circumvent parasitic absorption from the substrate; thus, α can be accurately determined down to very low values, allowing us to investigate deep band tails with a higher dynamic range than in any other method, including spectrophotometry and PDS.