Favorable Bonding and Band Structures of Cu2ZnSnS4 and CdS Films and Their Photovoltaic Interfaces

Thin-film photovoltaic cells using Cu2ZnSnS4 (CZTS, p-type) have many advantages, such as high photoconversion, low cost, and great tunability with earth-abundant, nontoxic elements, all of which are necessary to be long-term contributors to next-generation solar energy harvesting. Accurate measurements of bonding and band structures of both the thin-film materials and their interfaces are paramount to designing the solar devices layer-by-layer. Here, finely tuned 1 μm thick CZTS films, 50 nm thick CdS layers (n-type), and their 1 μm/2 nm p-n junction were fabricated inexpensively using our previously studied methods and investigated extensively for maximizing the key interface in the CZTS solar devices. Synthesized bulk CZTS and CdS were analyzed for structural deviations and crystal defects using synchrotron-based (SR) X-ray absorption fine structure (XAFS) along with simulated XAFS patterns. The structural properties of the two materials were designed to favor photovoltaic activity. Interface valence band structures of the CZTS/CdS p-n junction were measured through SR X-ray photoelectron spectroscopy (SR-XPS) and compared with the ones simulated using density functional theory. A full band diagram was constructed from XPS of the bulk films and SR-XPS of the interface, providing guidelines in optimizing charge-carrier extraction from the CZTS absorber to CdS buffer layer. It turns out that a small spike-like interface in the conduction band overlap was formed, maintaining a strong internal bias, while favoring a small energy barrier to prevent large-scale recombination from occurring. A large open-circuit voltage was obtained in the preliminary solar cell devices built on the small spike-like interface.