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BenzoylHalides as Alternative Precursors for theColloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals

机译:苯甲酰卤化物作为替代品的前体铅基卤化物钙钛矿纳米晶体的胶体合成

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摘要

We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic–inorganic lead halide perovskite nanocrystals (NCs). The main limitation of the protocols that are currently in use, such as the hot injection and the ligand-assisted reprecipitation routes, is that they employ PbX2 (X = Cl, Br, or I) salts as both lead and halide precursors. This imposes restrictions on being able to precisely tune the amount of reaction species and, consequently, on being able to regulate the composition of the final NCs. In order to overcome this issue, we show here that benzoyl halides can be efficiently used as halide sources to be injected in a solution of metal cations (mainly in the form of metal carboxylates) for the synthesis of APbX3 NCs (in which A = Cs+, CH3NH3+, or CH(NH2)2+). In this way, it is possible to independently tune the amount of both cations and halide precursors in the synthesis. The APbX3 NCs that were prepared with our protocol show excellent optical properties, such as high photoluminescence quantum yields, low amplified spontaneous emission thresholds, and enhancedstability in air. It is noteworthy that CsPbI3 NCs, whichcrystallize in the cubic α phase, are stable in air for weekswithout any postsynthesis treatment. The improved properties of ourCsPbX3 perovskite NCs can be ascribed to the formationof lead halide terminated surfaces, in which Cs cations are replacedby alkylammonium ions.
机译:我们在这里提出一种用于合成全无机和有机-无机杂化卤化钙钛矿纳米晶体(NCs)的新胶体方法。当前使用的方案(例如热注射和配体辅助的再沉淀路线)的主要局限性在于它们采用PbX2(X = Cl,Br或I)盐作为铅和卤化物的前体。这对能够精确调节反应物种的数量以及因此能够调节最终NC的组成施加了限制。为了克服这个问题,我们在这里表明,可以将苯甲酰卤有效地用作卤化物源,注入到金属阳离子溶液中(主要以金属羧酸盐的形式)以合成APbX3 NCs(其中A = Cs + ,CH3NH3 + 或CH(NH2)2 + )。以这种方式,有可能独立地调节合成中阳离子和卤化物前体的量。使用我们的协议制备的APbX3 NC具有出色的光学性能,例如高的光致发光量子产率,低的放大的自发发射阈值和增强的空气中的稳定性。值得注意的是CsPbI3 NC在立方α相中结晶,在空气中稳定数周无需任何后期合成处理。我们的改进性能CsPbX3钙钛矿NCs可归因于地层卤化铅终止的表面,其中取代了Cs阳离子通过烷基铵离子。

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