The performance of kesterite thin-film solar cells is limited by a low open-circuit voltage due to defect-mediated electron-hole recombination. We calculate the non-radiative carrier-capture cross sections and Shockley-Read-Hall recombination coefficients of deep-level point defects in Cu 2 ZnSnS 4 (CZTS) from first-principles. While the oxidation state of Sn is +4 in stoichiometric CZTS, inert lone pair (5s 2 ) formation lowers the oxidation state to +2. The stability of the lone pair suppresses the ionization of certain point defects, inducing charge transition levels deep in the band gap. We find large lattice distortions associated with the lone-pair defect centers due to the difference in ionic radii between Sn(ii) and Sn(iv). The combination of a deep trap level and large lattice distortion facilitates efficient non-radiative carrier capture, with capture cross-sections exceeding 10 -12 cm 2 . The results highlight a connection between redox active cations and 'killer' defect centres that form giant carrier traps. This lone pair effect will be relevant to other emerging photovoltaic materials containing ns 2 cations.
Bibliographical noteFunding Information:
We acknowledge support from the Royal Society, the EPSRC (Grant No. EP/K016288/1), and the EU Horizon2020 Framework (STARCELL, Grant No. 720907). We are grateful to the UK Materials and Molecular Modeling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). Via our membership of the UK's HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202), this work used the ARCHER UK National Supercomputing Service (http:// www.archer.ac.uk). This work was also supported by a National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (No. 2018R1C1B6008728).
All Science Journal Classification (ASJC) codes
- Renewable Energy, Sustainability and the Environment
- Materials Science(all)