Crystal packing and charge transport in single crystals of chrysene derivatives: Impact of halogenation  

作　　者：NAN GuangJun LI ZeSheng 

机构地区：[1]State Key Laboratory of Urban Water Resource and Environment, Institute of Theoretical and Simulational Chemistry, Academy of Fundamental and Interdisciplinary Sciences, Harbin Institute of Technology [2]School of Chemistry, Beijing Institute of Technology

出　　处：《Science China Chemistry》2013年第2期210-221,共12页中国科学（化学英文版）

基　　金：financially supported by the Major State Basic Research Development Programs of China (2011CBA00701);the National Natural Science Foundation of China (21003030 and 20973049);the Open Project of State Key Laboratory of Urban Water Resource and Environment, Harbin Institute of Technology (HC201117);and the China Postdoctoral Science Foundation (20110490102)

摘　　要：Crystal packing has strong influence on the charge mobility for organic semiconductors, so the elucidation of the structure-property relationship is important for the design of high-performance organic semiconductors. Halogen substitution has been shown to be a promising strategy to alter the crystal structure without significantly changing the molecular size in previous reports. This paper studies the influence of halogenation on charge transport in single crystals of chrysene derivatives from a theoretical standpoint. The structure-property relationship is first rationalized by investigating the reorganization energy and electronic coupling from the density functional theory calculations. Based on the Marcus charge transfer theory, the mobilities in the molecular monolayer are then calculated with the random walk simulation technique from which the angular resolution anisotropic mobilities are obtained on the fly. It is shown that the mobilities become much larger for holes than those for electrons in the molecular monolayer when the halogenation occurs. Furthermore, the intra-layer charge transport is little influenced by the inter-layer pathways in the single crystals of the halogenated chrysene derivatives, while the opposite case is shown for the crystal of the nonhalogenated chrysene derivative. The reason for the variations of charge transport is discussed theoretically.Crystal packing has strong influence on the charge mobility for organic semiconductors, so the elucidation of the structure-property relationship is important for the design of high-performance organic semiconductors. Halogen substitution has been shown to be a promising strategy to alter the crystal structure without significantly changing the molecular size in previous reports. This paper studies the influence of halogenation on charge transport in single crystals of chrysene derivatives from a theoretical standpoint. The structure-property relationship is first rationalized by investigating the reorganization energy and electronic coupling from the density functional theory calculations. Based on the Marcus charge transfer theory, the mobilities in the molecular monolayer are then calculated with the random walk simulation technique from which the angular resolution anisotropic mobilities are obtained on the fly. It is shown that the mobilities become much larger for holes than those for electrons in the molecular monolayer when the halogenation occurs. Furthermore, the intra-layer charge transport is little influenced by the inter-layer pathways in the single crystals of the halogenated chrysene derivatives, while the opposite case is shown for the crystal of the nonhalogenated chrysene derivative. The reason for the variations of charge transport is discussed theoretically.

关 键 词：chrysene derivative organic semiconductor density functional theory Marcus charge transfer rate charge mobility 

分 类 号：TN304.5[电子电信—物理电子学]