The efficiencies of solar cells based on kesterite Cu2ZnSnS4 (CZTS) and Cu2ZnSnSe4 (CZTSe) are limited by a low open-circuit voltage due to high rates of non-radiative electron-hole recombination. To probe the origin of this bottleneck, we calculate the band offset of CZTS(Se) with CdS, confirming a weak spike of 0.1 eV for CZTS/wurtzite-CdS and a strong spike of 0.4 eV for CZTSe/wurtzite-CdS. We also consider the effects of temperature on the band alignment, finding that increasing temperature significantly enhances the spike-type offset. We further resolve an outstanding discrepancy between the measured and calculated phonon frequencies for the kesterites, and use these to estimate the upper limit of electron and hole mobilities based on optic phonon Fröhlich scattering, which uncovers an intrinsic asymmetry with faster (minority carrier) electron mobility.
Bibliographical noteFunding Information:
We are grateful to the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (EP/P020194/1). The research was supported by the Royal Society and the EU Horizon2020 Framework (STARCELL, Grant No. 720907). B.M. thanks Robinson College, Cambridge, and the Cambridge Philosophical Society for a Henslow Research Fellowship. J.-S.P. thanks the Royal Society for a Shooter International Fellowship.
All Science Journal Classification (ASJC) codes
- Physics and Astronomy (miscellaneous)