Mosaic Cu I −Cu II −In III 2D Perovskites: Pressure‐Dependence of the Intervalence Charge Transfer and a Mechanochemical Alloying Method
Mosaic Cu I −Cu II −In III 2D Perovskites: Pressure‐Dependence of the Intervalence Charge Transfer and a Mechanochemical Alloying Method
复制标题
马赛克 Cu I –Cu II –In III 二维钙钛矿：压力 – 层间电荷转移的依赖性和机械化学合金化方法
DOI：
10.1002/anie.202300957
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Karunadasa, Hemamala I.
中科院分区：
文献类型：
--
作者：
Li, Jiayi;Matheu, Roc;Ke, Feng;Liu, Zhenxian;Lin, Yu;Karunadasa, Hemamala I.
钙钛矿（BA）4[CuII(CuIInIII)0.5]Cl8（1BA; BA+=丁铵）使我们能够研究混合价二维钙钛矿的高压结构、光学和输运性质。压缩可将CuI/ iii价间电荷转移的起始能量从环境压力下的1.2 eV降低到21 GPa下的0.2 eV。当压缩到20gpa时，bba的电子导电性提高了4个数量级，而传导活化能降低到0.16 eV。相比之下，cuiperov钛矿在≈50 GPa时具有相似的导电性。这些钙钛矿的溶液态合成是复杂的，含有三种不同金属离子的前驱体混合物可能产生更多不希望的副产物。为了解决这一问题，我们展示了一种有效的机械化学合成方法，通过简单地将二维cuiiiiiiiii双钙钛矿粉末粉碎在一起，扩大了具有复杂组成的卤化物钙钛矿家族。
The perovskite (BA)4[CuII(CuIInIII)0.5]Cl8(1BA; BA+=butylammonium) allows us to study the high‐pressure structural, optical, and transport properties of a mixed‐valence 2D perovskite. Compressing1BAreduces the onset energy of CuI/IIintervalence charge transfer from 1.2 eV at ambient pressure to 0.2 eV at 21 GPa. The electronic conductivity of1BAincreases by 4 orders of magnitude upon compression to 20 GPa, when the activation energy for conduction decreases to 0.16 eV. In contrast, CuIIperovskites achieve similar conductivity at ≈50 GPa. The solution‐state synthesis of these perovskites is complicated, with more undesirable side products likely from the precursor mixtures containing three different metal ions. To circumvent this problem, we demonstrate an efficient mechanochemical synthesis to expand this family of halide perovskites with complex composition by simply pulverizing together powders of 2D CuIIsingle perovskites and CuIInIIIdouble perovskites.