Transport Evidence for Sulfur Vacancies as the Origin of Unintentional n-Type Doping in Pyrite FeS₂

Pyrite FeS2 has long been considered a potential earth-abundant low-cost photovoltaic material for thin-film solar cells but has been plagued by low power conversion efficiencies and open-circuit voltages. Recent efforts have identified a lack of understanding and control of doping, as well as uncontrolled surface conduction, as key roadblocks to the development of pyrite photovoltaics. In particular, while n-type bulk behavior in unintentionally doped single crystals and thin films is speculated to arise from sulfur vacancies (VS), proof remains elusive. Here, we provide strong evidence, from extensive electronic transport measurements on high-quality crystals, that VS are deep donors in bulk pyrite. Otherwise identical crystals grown via chemical vapor transport under varied S vapor pressures are thoroughly characterized structurally and chemically, and shown to exhibit systematically different electronic transport. Decreased S vapor pressure during growth leads to reduced bulk resistivity, increased bulk Hall electron density, reduced transport activation energy, onset of positive temperature coefficient of resistivity, and approach to an insulator–metal transition, all as would be expected from increased VS donor density. Impurity analyses show that these trends are uncorrelated with metal impurity concentration and that extracted donor densities significantly exceed total impurity concentrations, directly evidencing a native defect. Well-controlled, wide-range n-doping of pyrite is thus achieved via the control of VS concentration, with substantial implications for photovoltaic and other applications. The location of the VS state within the gap, the influence of specific impurities, unusual aspects to the insulator–metal transition, and the influence of doping on surface conduction are also discussed.