Herz Laura M
Department of Physics, University of Oxford, OX1 3PU Oxford, United Kingdom; email:
Annu Rev Phys Chem. 2016 May 27;67:65-89. doi: 10.1146/annurev-physchem-040215-112222. Epub 2016 Feb 26.
Hybrid organic-inorganic metal halide perovskites have recently emerged as exciting new light-harvesting and charge-transporting materials for efficient photovoltaic devices. Yet knowledge of the nature of the photogenerated excitations and their subsequent dynamics is only just emerging. This article reviews the current state of the field, focusing first on a description of the crystal and electronic band structure that give rise to the strong optical transitions that enable light harvesting. An overview is presented of the numerous experimental approaches toward determining values for exciton binding energies, which appear to be small (a few milli-electron volts to a few tens of milli-electron volts) and depend significantly on temperature because of associated changes in the dielectric function. Experimental evidence for charge-carrier relaxation dynamics within the first few picoseconds after excitation is discussed in terms of thermalization, cooling, and many-body effects. Charge-carrier recombination mechanisms are reviewed, encompassing trap-assisted nonradiative recombination that is highly specific to processing conditions, radiative bimolecular (electron-hole) recombination, and nonradiative many-body (Auger) mechanisms.
有机-无机杂化金属卤化物钙钛矿最近已成为用于高效光伏器件的令人兴奋的新型光捕获和电荷传输材料。然而,关于光生激发的性质及其后续动力学的认识才刚刚开始出现。本文综述了该领域的当前状态,首先着重描述了产生能够实现光捕获的强光学跃迁的晶体和电子能带结构。概述了确定激子结合能值的众多实验方法,激子结合能似乎很小(几毫电子伏特到几十毫电子伏特),并且由于介电函数的相关变化而显著依赖于温度。从热化、冷却和多体效应的角度讨论了激发后最初几皮秒内电荷载流子弛豫动力学的实验证据。综述了电荷载流子复合机制,包括高度依赖于加工条件的陷阱辅助非辐射复合、辐射双分子(电子-空穴)复合和非辐射多体(俄歇)机制。