Department of Chemistry, Stanford University, Stanford, CA 94305, USA.
Current address: Institut de Recerca de Química Teòrica i Computacional, Departament de Química Inorgànica i Orgànica, Universitat de Barcelona, 08007, Barcelona, Spain.
Angew Chem Int Ed Engl. 2023 May 8;62(20):e202300957. doi: 10.1002/anie.202300957. Epub 2023 Apr 12.
The perovskite (BA) [Cu (Cu In ) ]Cl (1 ; BA =butylammonium) allows us to study the high-pressure structural, optical, and transport properties of a mixed-valence 2D perovskite. Compressing 1 reduces the onset energy of Cu intervalence charge transfer from 1.2 eV at ambient pressure to 0.2 eV at 21 GPa. The electronic conductivity of 1 increases by 4 orders of magnitude upon compression to 20 GPa, when the activation energy for conduction decreases to 0.16 eV. In contrast, Cu perovskites 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 Cu single perovskites and Cu In double perovskites.
钙钛矿（BA）[Cu（Cu In ）]Cl（1；BA = 丁基铵）允许我们研究混合价二维钙钛矿的高压结构、光学和输运性质。压缩 1 将 Cu 价间电荷转移的起始能量从常压下的 1.2 eV 降低到 21 GPa 下的 0.2 eV。在压缩到 20 GPa 时，1 的电子电导率增加了 4 个数量级，此时传导的激活能降低至 0.16 eV。相比之下，Cu 钙钛矿在 ≈50 GPa 时达到类似的电导率。这些钙钛矿的溶液态合成较为复杂，由于含有三种不同金属离子的前体混合物，可能会产生更多不理想的副产物。为了解决这个问题，我们通过简单地将二维 Cu 单钙钛矿和 Cu In 双钙钛矿粉末粉碎在一起，展示了一种高效的机械化学合成方法，从而扩展了具有复杂成分的卤化物钙钛矿家族。
