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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 CuInSe2 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 CuInSe2 solar cells.

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)Se2 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)Se2 is proposed based on experiments and theory. The consequences for solar cell efficiency are discussed.

The detrimental effect of tail states on the radiative and non‐radiative voltage loss has been demonstrated to be a limiting factor for the open circuit voltage (VOC) in Cu(In,Ga)Se2 solar cells. A strategy that has proven effective in reducing tail states is the addition of alkali metals, the effect of which has been associated with the passivation of charged defects at grain boundaries. Herein, tail states in Cu(In,Ga)Se2 are revisited by studying the effect of compositional variations and alkali incorporation into single‐crystal films. The results demonstrate that sodium and potassium decrease the density of tail states despite the absence of grain boundaries, suggesting that there is more to alkalis than just grain boundary effects. Moreover, an increase in doping as a result of sodium or potassium incorporation is shown to contribute to the reduced tail states, which are demonstrated to arise largely from electrostatic potential fluctuations and to be determined by grain interior properties. By analyzing the voltage loss in high‐efficiency polycrystalline and single crystalline devices, this work presents a model that explains the entirety of the voltage loss in Cu(In,Ga)Se2 based on the combined effect of doping on tail states and VOC. [ABSTRACT FROM AUTHOR]

The power conversion efficiency of solar cells strongly depends on the open‐circuit voltage VOC which, in turn, depends on the recombination activity within the device. A possible source of detrimental charge carrier recombination is band tails. An empirical linear relationship between VOC loss and the Urbach energy of the band tails has been shown in the past. Here we discuss how band tails influence the radiative recombination and the nonradiative recombination in the bulk of the absorber. First, we show through photoluminescence that the band tails can be willfully tuned in state‐of‐the‐art thin‐film Cu (In,Ga)Se2 (CIGSe) absorbers and solar cells on a 20% efficiency level and beyond through the incorporation of alkali atoms. In the second part, we compare our CIGSe results to published results from other solar cell technologies. This comparison reveals that CIGS solar cells follow the previously described empirical trend: an increase in the open‐circuit voltage with decreasing band tails. Finally, we model the influence of tail states on the radiative and nonradiative recombination losses: Radiative recombination is increased because carriers thermalize into the tail states and nonradiative recombination of free carriers in the bands is increased because of Shockley–Read–Hall recombination through the tail states. The comparison with experimental data shows that the influence of tail states is even worse than the increase in radiative and SRH recombination predicted by our model. Our results thus suggest that band tails act as one of the main remaining voltage limitations in the majority of state‐of‐the‐art solar cells. [ABSTRACT FROM AUTHOR]

We study the impact of different alkali post‐deposition treatments by thermal admittance spectroscopy and temperature‐dependent current‐voltage (IVT) characteristics of high‐efficiency Cu(In,Ga)Se2 thin‐film solar cells fabricated from low‐temperature and high‐temperature co‐evaporated absorbers. Capacitance steps observed by admittance spectroscopy for all samples agree with the widely observed N1 signature and show a clear correlation to a transport barrier evident from IVT characteristics measured in the dark, indicating that defects are likely not responsible for these capacitance steps. Activation energies extracted from capacitance spectra and IVT characteristics vary considerably between different samples but show no concise correlation to the alkali species used in the post‐deposition treatments. Numerical device simulations show that the transport barrier in our devices might be related to conduction band offsets in the absorber/buffer/window stack. We study the impact of different alkali postdeposition treatments of high‐efficiency Cu(In,Ga)Se2 thin‐film solar cells. Capacitance steps observed by admittance spectroscopy agree with the widely observed N1 signature and show a clear correlation to a transport barrier evident from temperature‐dependent current‐voltage characteristics, indicating that defects are likely not responsible for these capacitance steps. Numerical device simulations show that the transport barrier in our devices might be related to conduction band offsets in the absorber/buffer/window stack. [ABSTRACT FROM AUTHOR]

Photoluminescence (PL) measurements are performed on high-quality Cu(In,Ga)Se2 (CIGS) thin films with the intention of investigating their electronic structure. Due to the nature of the CIGS absorbers, notably their smooth surface and a graded band gap, the measured PL spectra are distorted by interference effects, limiting thus the information that one can gain. Here we show that, by varying the entrance angle of the laser light and the detection angle of the emitted PL, we are able to correct for interference effects. As a result, we receive interference-free PL spectra that enable us to determine quantities such as band gap energies and quasi-Fermi level splittings (QFLS). Furthermore, we show that it is possible to measure the QFLS even without correcting for interference effects and we compare the QFLS to the open circuit voltage for a particular sample. [ABSTRACT FROM AUTHOR]

Abstract: Cu2ZnSn(SSe)4 and CuZnSnSe4 thin film solar cells are analyzed via temperature dependent current–voltage analysis and quantum efficiency measurements in order to study the dominant recombination pathway and the temperature dependence of the series resistance. Here we show that in contrast to mixed S/Se devices, solar cells where the absorber consists of selenide only do not exhibit interface recombination and the series resistance is small in the complete investigated temperature range. The recombination path difference supports a band alignment model with a cliff for S and a spike for Se. The measurements are supplemented with secondary ion mass spectrometry measurements in order to gain insights into the physical origin of the different device characteristics. The results suggest that the high series resistance originates from a ZnS(e) secondary phase which is situated at the Cu2ZnSn(SSe)4/CdS heterojunction. [Copyright &y& Elsevier]