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A Direct Bandgap Copper–Antimony Halide Perovskite

Vargas, Brenda, Ramos, Estrella, Pérez-Gutiérrez, Enrique, Alonso, Juan Carlos, Solis-Ibarra, Diego
Journal of the American Chemical Society 2017 v.139 no.27 pp. 9116-9119
copper, geometry, humidity, lead, oxidation, semiconductors, solar cells, thermal stability
Since the establishment of perovskite solar cells (PSCs), there has been an intense search for alternative materials to replace lead and improve their stability toward moisture and light. As single-metal perovskite structures have yielded unsatisfactory performances, an alternative is the use of double perovskites that incorporate a combination of metals. To this day, only a handful of these compounds have been synthesized, but most of them have indirect bandgaps and/or do not have bandgaps energies well-suited for photovoltaic applications. Here we report the synthesis and characterization of a unique mixed metal ⟨111⟩-oriented layered perovskite, Cs₄CuSb₂Cl₁₂ (1), that incorporates Cu²⁺ and Sb³⁺ into layers that are three octahedra thick (n = 3). In addition to being made of abundant and nontoxic elements, we show that this material behaves as a semiconductor with a direct bandgap of 1.0 eV and its conductivity is 1 order of magnitude greater than that of MAPbI₃ (MA = methylammonium). Furthermore, 1 has high photo- and thermal-stability and is tolerant to humidity. We conclude that 1 is a promising material for photovoltaic applications and represents a new type of layered perovskite structure that incorporates metals in 2+ and 3+ oxidation states, thus significantly widening the possible combinations of metals to replace lead in PSCs.