Crossover from nanoscopic intergranular hopping to conventional charge transport in pyrite thin films

Pyrite FeS2 is receiving a resurgence of interest as a uniquely attractive thin film solar absorber based on abundant, low-cost, nontoxic elements. Here we address, via ex situ sulfidation synthesis, the long-standing problem of understanding conduction and doping in FeS2 films, an elusive prerequisite to successful solar cells. We find that an abrupt improvement in crystallinity at intermediate sulfidation temperatures is accompanied by unanticipated crossovers from intergranular hopping to conventional transport, and, remarkably, from hole-like to electron-like Hall coefficients. The hopping is found to occur between a small volume fraction of conductive nanoscopic sulfur-deficient grain cores (beneath our X-ray diffraction detection limits), embedded in nominally stoichiometric FeS2. In addition to placing constraints on the conditions under which useful properties can be obtained from FeS2 synthesized in diffusion-limited situations, these results also emphasize that FeS2 films are not universally p-type. Indeed, with no knowledge of the active transport mechanism we demonstrate that the Hall coefficient alone is insufficient to determine the sign of the carriers. These results elucidate the possible transport mechanisms in thin film FeS2 in addition to their influence on the deduced carrier type, an enabling advancement with respect to understanding and controlling doping in pyrite films.