A systematic study of the variability of Cu 2 ZnSnS 4 nanoparticle hot injection synthesis Karen Stroh 1,2 , M. Szablewski 1 , and D. P. Halliday 1 1 Department of Physics, South Road, Durham University, Durham, UK, DH1 3LE, 2 Faculty of Physics, Georg-August-Universität Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen, Germany Alternatives for the next generation of suitable semiconductor materials for future thin-film solar cells are under active exploration [1] . With a focus on low cost, and earth-abundant elements, Cu 2 ZnSnS 4 (CZTS) has been identified as a promising contender [2] . However, efficiencies of CZTS devices are currently limited because of a large open circuit voltage deficit [3] . As a quaternary semiconductor system, CZTS has a large number of native point defects and charge-compensating defect complexes which alter the energy bandgap, modify carrier dynamics and PV device behaviour [4, 5] . These charge-compensating defect complexes have been found to determine the overall crystal structure and composition of CZTS limiting the composition to specific parts of the compositional phase diagram [6] . Since first developed by Guo et al . [7] , the hot injection method of synthesising CZTS films via intermediate nano-crystalline ink deposition has become a predominant method for the facile synthesis of CZTS thin films [8] . Currently CZTS devices have efficiencies of 10% [2] with scope for further improvement [3] . A key aspect of further enhancing device efficiency is effective control over fabrication routes to produce material of known composition, stoichiometry and doping level [9] . As a solution based method, the hot injection process has inherent variability. We have investigated the variability in hot injection synthesis of Cu 2 ZnSnS 4 nanoparticles by fabricating 11 batches under the same initial conditions. We found that the lattice constants of the nanocrystalline material do not change significantly. The relative concentration of the constituent elements varies by up to 4% for S and 1% for Sn. We compared compositional data from EDX and ICP-MS chemical analysis methods and we present our findings in this paper. References 1. Polman, A., M. Knight, E.C. Garnett, B. Ehrler, and W.C. Sinke,Science, 2016. 352 (6283): p.4424 2. Yan, C., J.L. Huang, K.W. Sun, S. Johnston, Y.F. Zhang, H. Sun, A.B. Pu, M.R. He, F.Y. Liu, K. Eder, L.M. Yang, J.M. Cairney, N.J. Ekins-Daukes, Z. Hameiri, J.A. Stride, S.Y. Chen, M.A. Green, and X.J. Hao,Nature Energy, 2018. 3 (9): p. 764- 772 3. Hood, S.N., A. Walsh, C. Persson, K. Iordanidou, D. Huang, M. Kumar, Z. Jehl, M. Courel, J. Lauwaert, and S. Lee, Journal of Physics: Energy, 2019. 1 (4): p. 042004 4. Chen, S.Y., A. Walsh, X.G. Gong, and S.H. Wei, Advanced Materials, 2013. 25 (11): p. 1522-1539 5. Chen, S.Y., J.H. Yang, X.G. Gong, A. Walsh, and S.H. Wei, Physical Review B, 2010. 81 (24): p. 245204 6. Bosson, C.J., M.T. Birch, D.P. Halliday, K.S. Knight, A.S. Gibbs, and P.D. Hatton, Journal of Materials Chemistry A, 2017. 5 (32): p. 16672-16680 7. Guo, Q.J., H.W. Hillhouse, and R. Agrawal, Journal of the American Chemical Society, 2009. 131 (33): p. 11672-11673 8. Wei, H., W. Guo, Y.J. Sun, Z. Yang, and Y.F. Zhang,Materials Letters, 2010. 64 (13): p. 1424-1426 9. Siebentritt, S., Solar Energy Materials and Solar Cells, 2011. 95 (6): p. 1471-1476
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