Highly Absorbing Lead-Free Semiconductor Cu₂AgBiI₆ for Photovoltaic Applications from the Quaternary CuI-AgI-BiI₃...

Since the emergence of lead halide perovskites for photovoltaic research, there has been mounting effort in the search for alternative compounds with improved or complementary physical, chemical, or optoelectronic properties. Here, we report the discovery of Cu₂AgBiI₆: a stable, inorganic, lead-free wide-band-gap semiconductor, well suited for use in lead-free tandem photovoltaics. We measure a very high absorption coefficient of 1.0 × 10⁵ cm^-1 near the absorption onset, several times that of CH₃NH₃PbI₃. Solution-processed Cu₂AgBiI₆ thin films show a direct band gap of 2.06(1) eV, an exciton binding energy of 25 meV, a substantial charge-carrier mobility (1.7 cm² V^-1 s^-1), a long photoluminescence lifetime (33 ns), and a relatively small Stokes shift between absorption and emission. Crucially, we solve the structure of the first quaternary compound in the phase space among CuI, AgI and BiI₃. The structure includes both tetrahedral and octahedral species which are open to compositional tuning and chemical substitution to further enhance properties. Since the proposed double-perovskite Cs₂AgBiI₆ thin films have not been synthesized to date, Cu₂AgBiI₆ is a valuable example of a stable Ag⁺/Bi³⁺ octahedral motif in a close-packed iodide sublattice that is accessed via the enhanced chemical diversity of the quaternary phase space.