Solar cells based on kesterite-type Cu 2 ZnSnS 4 (CZTS) were fabricated on molybdenum coated soda lime glass by evaporation using ZnS, Sn, Cu, and S sources. The coevaporation process was performed at a nominal substrate temperature of 5508C and at a sulfur partial pressure of 2-3 Â 10 À3 Pa leading to polycrystalline CZTS thin films with promising electronic properties. The CZTS absorber layers were grown copper-rich, requiring a KCN etch step to remove excess copper sulfide. The compositional ratios as determined by energy-dispersive X-ray spectroscopy (EDX) after the KCN etch are Cu/(Zn þ Sn): 1.0 and Zn/Sn: 1.0. A solar cell with an efficiency of 4.1% and an open-circuit voltage of 541 mV was obtained.
We study the sequential fabrication of Cu(In,Ga)Se2 (CIGSe) absorber layers by using an atmospheric pressure selenization with a process duration of only a few minutes and the utilization of elemental selenium vapor from independent Se sources. This technology could proof to be an industrially relevant technology for the fabrication of thin‐film solar cells. Controlling the amount of Se provided during the selenization of metal precursors is shown to be an effective measure to adjust the Ga in‐depth distribution. A reduced Se supply for CIGSe formation leads to a more homogeneous Ga distribution within the absorber. The underlying growth dynamics is investigated by interrupting the selenization at different times. At first, CIGSe formation occurs in accordance with previously suggested growth paths and Ga segregates at the Mo back contact. Between 520 and 580 °C, the growth dynamics differs distinctly, and In and Ga distribute far more uniformly within the absorber depth. We also studied the impact of the precursor architecture. The best performing precursor in terms of efficiency of the respective solar cells was a multilayer with 22 In/CuGa/In triple layers. Simple bilayers stacks lead to films of higher roughness and correlated shunting. By optimizing the precursor architecture and the Ga in‐depth distribution in the CIGSe layer, a conversion efficiency of up to 15.5% (active area) could be achieved. To our knowledge, this is the highest reported efficiency for sulfur free CIGSe‐based solar cells utilizing fast (few minutes) atmospheric processes and elemental Se vapor. Copyright © 2017 John Wiley & Sons, Ltd.
At the German Aerospace Center (DLR) in Stuttgart, a lightweight stack design for mobile applications was developed in cooperation with the automotive industry (BMW, Munich; Elring-Klinger, Dettingen; Rhodius, Weissenburg). This concept is based on the application of stamped metal sheet bipolar plates into which porous metallic substrate-supported cells (MSCs) are integrated. The paper concentrates on the one hand on the investigation of plasma sprayed button cells with a diameter of 48mm on porous metallic substrates during reduction/oxidation and thermal cycling. On the other hand, another focus lies in the electrochemical testing of short stacks in the cassette arrangement. The microstructure of the cells was characterized by optical microscopy, scanning electron microscopy (SEM), X-ray diffraction, and energy dispersive microanalysis (EDX) before and after operation. The cells and short stacks were electrochemically characterized mainly by long-term measurements (life cycle), by current-voltage measurements, and by impedance spectroscopy. In order to understand the nature of degradation mechanisms, the open-circuit voltages (OCV), the ohmic resistances, and the polarization resistances, during dynamic operation are compared and discussed. In order to distinguish between degradation effects due to the dynamic operation and usual stationary effects, these values are compared to values of noncycled cells. All of the cells investigated were able to withstand ten redox and ten thermal cycles without severe failure. Their redox- and thermal-cycling behavior are strongly dependent on their OCVs, which decrease during cycling. This proves that thermomechanical stresses in the electrolyte layer play a major role for the electrochemical performance of the cells during cycling. The improvement of the electrodes during the first 200h of operation and the ohmic resistance of the cells are not significantly influenced by the cycling. The first four-cell short stack with the cassette arrangement shows promising results with an OCV of ∼4V and an overall power of 92W at 800°C. The performances of the single cells are in the range of 180–220mW∕cm2. The differences in cell performance can be attributed to different polarization resistances of the cells in the cassettes, which might be caused by a nonuniform gas supply in the short stack.
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