This article presents a systematic study on the electronic transport mechanisms of CuGaSe2-based thin film solar cells. A variety of samples with different types of stoichiometry deviations, substrates and buffer layers is investigated. We propose two transport models, namely tunneling enhanced volume recombination and tunneling enhanced interface recombination, which allow to explain the observed features for all devices under consideration. The doping level of the absorber layer turns out to be the most decisive parameter for the electronic loss mechanism. The doping is influenced by the type of stoichiometry deviation as well as by the Na content of the substrate. High doping levels result in tunnel assisted recombination. The best solar cells display the lowest tunneling rates. For these devices treatments of the absorber surface by air-annealing and/or the deposition temperature of the CdS buffer layer are decisive for the final device performance. We use the investigation of the open-circuit voltage relaxation to verify the assumptions on the dominant loss mechanism in the different devices.
Stability aspects of the Mo/Cu(In,Ga)Se 2 /CdS/ZnO solar cell are reviewed and assessed. These include (i) the chemical stability of the various interfaces present in the device, (ii) the long-term behavior of metastable defects found in the Cu(In,Ga)Se 2 (CIGS) compound, and (iii) the impact of Cu migration on device performance and lifetime. We find that (i) all interfaces within the structure are chemically stable, (ii) metastable defects have a beneficial effect on performance, and (iii) Cu migration effects are reversible and their possible detrimental effects are eclipsed by the beneficial effect of the metastable states. Moreover, Cu out-diffusion from the CIGS layer is absent in photovoltaic-quality CIGS. Finally, we propose a model that explains the exceptional radiation hardness and impurity tolerance of CIGS-based devices, based on the synergetic effect of copper migration and point defect reactions.
We investigate irradiation-induced defects in high-efficiency Cu(In,Ga)Se2/CdS/ZnO heterojunction solar cells after electron irradiation with energies of 0.5, 1, and 3 MeV and after 4 MeV proton irradiation. We use electron and proton fluences of more than 1018 cm−2 and up to 1014 cm−2, respectively. The reduction of the solar cell efficiency in all experiments is predominantly caused by a loss ΔVOC of the open circuit voltage VOC. An analytical model describes ΔVOC in terms of radiation-induced defects enhancing recombination in the Cu(In,Ga)Se2 absorber material. From our model, we extract defect introduction rates for recombination centers in Cu(In,Ga)Se2 for the respective particles and energies. We directly monitor the defect generation of these radiation-induced defects by admittance spectroscopy. The decrease of effective doping density in the Cu(In,Ga)Se2 absorber layer under particle irradiation is analyzed with capacitance voltage measurements at low temperatures. Furthermore, data on the relative damage coefficients for high-energy electron irradiation in Cu(In,Ga)Se2 solar cells are presented. All data, from electron as well as proton irradiations, merge to a single characteristic degradation curve.
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