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Title: Effect of Cd on cation redistribution and order-disorder transition in Cu2(Zn,Cd)SnS4
Authors: Hadke, Shreyash
Chen, Wei
Tan, Joel Ming Rui
Guc, Maxim
Izquierdo-Roca, Victor
Rignanese, Gian-Marco
Hautier, Geoffroy
Wong, Lydia Helena
Keywords: Engineering::Materials
Issue Date: 2019
Source: Hadke, S., Chen, W., Tan, J. M. R., Guc, M., Izquierdo-Roca, V., Rignanese, G.-M., ... Wong, L. H. (2019). Effect of Cd on cation redistribution and order-disorder transition in Cu 2 (Zn, Cd) SnS 4. Journal of Materials Chemistry A, 7(47), 26927-26933. doi:10.1039/C9TA09572A
Journal: Journal of Materials Chemistry A 
Abstract: Cation substitution has been extensively used to improve the fundamental optoelectronic properties and the photovoltaic performance of kesterite solar cells, and some of the most promising results have been obtained by substituting zinc with cadmium. Structurally, the positive effects of Cd have been attributed to the expected increase in the formation energy of defects such as CuZn + ZnCu due to the larger ionic radius of Cd2+ as compared to Zn2+. However, ab initio calculations using density functional theory (DFT) showed similar formation energies for CuZn + ZnCu in Cu2ZnSnS4 and CuCd + CdCu in Cu2CdSnS4. Further, in this report, it is shown that Cd does not directly substitute the zinc lattice sites (2d Wyckoff positions) in the Cu2ZnSnS4 structure, but rather, a two-way cation restructuring due to the continuous transformation of the structure from kesterite to stannite leads to Cu replacing Zn, and Cd occupying the Cu sites (2a Wyckoff positions) in the partially Cd-substituted Cu2Zn1−xCdxSnS4. Hence, the structural reasons for the beneficial effects of Cd need to be reinterpreted. Here, using computational model based on cluster expansion (fitted on DFT data), Monte-Carlo simulations, and differential scanning calorimetry, it is shown that Cu2CdSnS4 has less structural disorder than Cu2ZnSnS4 even if the thermodynamic point defect formation energy calculated using diluted point-defect models for disorder-inducing CuZn + ZnCu and CuCd + CdCu defects in these two materials is predicted to be similar. This difference in the structural disorder is due to a sharp order-disorder transformation in Cu2ZnSnS4 at about 530 K, and a continuous order-disorder transformation in Cu2CdSnS4 throughout the range of processing temperatures.
ISSN: 2050-7496
DOI: 10.1039/C9TA09572A
Schools: School of Materials Science and Engineering 
Interdisciplinary Graduate School (IGS) 
Research Centres: Energy Research Institute @ NTU (ERI@N) 
Rights: © 2019 Royal Society of Chemistry. All rights reserved. This paper was published in Journal of Materials Chemistry A and is made available with permission of Royal Society of Chemistry.
Fulltext Permission: open
Fulltext Availability: With Fulltext
Appears in Collections:MSE Journal Articles

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