Kesterite Cu2ZnSn(S,Se)4 (CZTSSe) absorbers are considered promising alternatives to commercial thin film technologies including CdTe and Cu(In,Ga)Se2 (CIGSe) owing to the earth abundance and non-toxicity of their constituents. However, to be competitive with the existing technologies, the photovoltaic performance of CZTSSe solar cells needs to be improved beyond the current record conversion efficiency of 12.6%. In this study, nanoscale elemental mapping using Auger nanoprobe microscopy (NanoAuger) and nano secondary ion mass spectrometry (NanoSIMS) are used to provide a clear picture of the compositional variations between the grains and grain boundaries in Cu2ZnSn(S,Se)4 kesterite thin films. NanoAuger measurements revealed that the top surfaces of the grains are coated with a Zn-rich (Zn,Sn)Ox layer. While thick oxide layers were observed at the grain boundaries, their chemical compositions were found to be closer to SnOx. NanoSIMS elemental maps confirmed the presence of excess oxygen deeper within the grain boundary grooves, as a result of air annealing of the CZTSSe films.
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The information, data, or work presented herein was funded in part by the U.S. Department of Energy, Energy Efficiency and Renewable Energy Program, under Award Number DE-EE0006334. The information, data, or work presented herein was funded in part by an agency of the United States Government. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Government or any agency thereof; see the Supporting Information section of this article for more information. Part of this work was performed at the Stanford NanoShared Facility (SNSF). The CAMECA nanoSIMS 50L was supported by the National Science Foundation under award # 0922648. Special thanks to Liang-Yi Chang for supplying the CZTSSe films used in these investigations. Funding for the technique development was also provided by National Science Foundation Grant DMR 1207213.
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Sardashti, K., Paul, D., Hitzman, C. et al. Nano-scale compositional analysis of surfaces and interfaces in earth-abundant kesterite solar cells. Journal of Materials Research 31, 3473–3481 (2016). https://doi.org/10.1557/jmr.2016.389