Turkevych Ivan, Kazaoui Said, Ito Eisuke, Urano Toshiyuki, Yamada Koji, Tomiyasu Hiroshi, Yamagishi Hideo, Kondo Michio, Aramaki Shinji
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.
ChemSusChem. 2017 Oct 9;10(19):3754-3759. doi: 10.1002/cssc.201700980. Epub 2017 Jul 6.
Hybrid CPbX (C: Cs, CH NH ; 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 C ABX double perovskites based on alternating corner-shared AX and BX 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 AX and BX octahedra with the general formula A B X (x=a+3 b) such as Ag BiI , Ag BiI , AgBiI , AgBi I . As perovskites were named after their prototype oxide CaTiO discovered by Lev Perovski, we propose to name these new ABX halides as rudorffites after Walter Rüdorff, who discovered their prototype oxide NaVO . 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-TiO /Ag BiI /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 %.
混合CPbX（C：Cs，CH₃NH₃；X：Br，I）钙钛矿具有优异的光伏性能，但毒性很强，这阻碍了它们的实际应用。不幸的是，所有基于Sn和Ge的无铅替代品都极其不稳定。尽管基于交替角共享AX和BX八面体（A = Ag，Cu；B = Bi，Sb）的稳定且无毒的CABX双钙钛矿是可能的，但它们具有间接且大于2 eV的宽带隙。然而，是否有必要保持角共享钙钛矿结构以保留良好的光伏性能呢？在这里，我们展示了另一类基于边共享AX和BX八面体的光伏卤化物，其通式为A₂B₃X₉（x = a + 3b），例如Ag₂BiI₉、Ag₃BiI₉、AgBiI₃、Ag₅BiI₈。由于钙钛矿是以Lev Perovski发现的原型氧化物CaTiO₃命名的，我们提议以发现其原型氧化物NaVO₃的Walter Rüdorff将这些新的ABX卤化物命名为鲁多夫矿。我们研究了几种高度稳定且有前景的Ag - Bi - I光伏鲁多夫矿的结构和光电性能，其特征在于直接带隙在1.79 - 1.83 eV范围内，并展示了一个概念验证的FTO/c - m - TiO₂/Ag₂BiI₃/PTAA/Au（FTO：氟掺杂氧化锡，PTAA：聚[双（4 - 苯基）（2,4,6 - 三甲基苯基）胺]，c：致密，m：介孔）太阳能电池，其光转换效率为4.3%。
