Cation disorder and phase transitions in the structurally complex solar cell material Cu₂ZnSnS₄

Cu₂ZnSnS₄ (CZTS) is a technologically important and complex quaternary semiconductor and a highly promising material for the absorber layer in sustainable thin film solar cells. Its photovoltaic performance is currently limited by low open-circuit voltage, thought to be due to a range of point defects such as disorder between the copper and zinc lattice sites. This is the highest-resolution neutron diffraction study reported for CZTS, which unambiguously identifies the crystal symmetry and accurately quantifies precise values for the disorder on all cation symmetry sites as a function of temperature. Two samples of CZTS were fabricated by solid state reaction and their compositions were measured by inductively-coupled plasma mass spectroscopy, which identified significant tin loss during growth, leaving the samples Sn-poor, Cu-rich and Sn-poor, Zn-rich respectively. Both samples were found exclusively to adopt the tetragonal kesterite crystal structure with significant cation disorder, which is investigated in detail over the range 4-1275 K. Importantly, and in contrast to previous reports, the 2a Wyckoff site shows disorder equal to or greater than the 2c site. The order-disorder phase transition was observed at different temperatures for the two compositions, 489 and 501 K respectively, lower than previously reported. The kesterite-sphalerite transition was observed between 1250 and 1275 K for the Sn-poor, Cu-rich sample, significantly higher than previously reported. These results provide new insights into the high levels of disorder present in CZTS and confirm that composition and cation disorder have a significant effect on the phase transition mechanism. This work will enable the development of routes to the fabrication of higher-efficiency photovoltaic devices.