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ChemSusChem. 2017 Oct 9;10(19):3754-3759. doi: 10.1002/cssc.201700980. Epub 2017 Jul 6.

Photovoltaic Rudorffites: Lead-Free Silver Bismuth Halides Alternative to Hybrid Lead Halide Perovskites.

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Chemical Materials Evaluation and Research Base (CEREBA), Higashi 1-1-1, AIST Central 5-2, Tsukuba, Ibaraki, 305-8565, Japan.
National Institute of Advanced Industrial Science and Technology, Higashi 1-1-1, AIST Central 2, Tsukuba, Ibaraki, 305-8565, Japan.
Department of Applied Molecular Chemistry, Nihon University, Izumi-cho 1-2-1, Narashino, Chiba, 275-8575, Japan.


Hybrid CPbX3 (C: Cs, CH3 NH3 ; X: Br, I) perovskites possess excellent photovoltaic properties but are highly toxic, which hinders their practical application. Unfortunately, all Pb-free alternatives based on Sn and Ge are extremely unstable. Although stable and non-toxic C2 ABX6 double perovskites based on alternating corner-shared AX6 and BX6 octahedra (A=Ag, Cu; B=Bi, Sb) are possible, they have indirect and wide band gaps of over 2 eV. However, is it necessary to keep the corner-shared perovskite structure to retain good photovoltaic properties? Here, we demonstrate another family of photovoltaic halides based on edge-shared AX6 and BX6 octahedra with the general formula Aa Bb Xx (x=a+3 b) such as Ag3 BiI6 , Ag2 BiI5 , AgBiI4 , AgBi2 I7 . As perovskites were named after their prototype oxide CaTiO3 discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO2 . We studied structural and optoelectronic properties of several highly stable and promising Ag-Bi-I photovoltaic rudorffites that feature direct band gaps in the range of 1.79-1.83 eV and demonstrated a proof-of-concept FTO/c-m-TiO2 /Ag3 BiI6 /PTAA/Au (FTO: fluorine-doped tin oxide, PTAA: poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], c: compact, m: mesoporous) solar cell with photoconversion efficiency of 4.3 %.


halides; iodobismuthate; lead-free; photovoltaics; solar cells

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