“Manipulation” of Crystal Structure by Methylthiolation Enabling Ultrahigh Mobility in a Pyrene‐Based Molecular Semiconductor
“Manipulation” of Crystal Structure by Methylthiolation Enabling Ultrahigh Mobility in a Pyrene‐Based Molecular Semiconductor
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DOI：
10.1002/adma.202102914
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发表时间：
2021-07
影响因子：
29.4
通讯作者：
K. Takimiya;Kirill Bulgarevich;M. Abbas;S. Horiuchi;Takuya Ogaki;Kohsuke Kawabata;A. Ablat
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文献类型：
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作者：
K. Takimiya;Kirill Bulgarevich;M. Abbas;S. Horiuchi;Takuya Ogaki;Kohsuke Kawabata;A. Ablat
分子半导体晶体结构的控制和预测被认为具有挑战性，但它们对于合理设计优质分子半导体至关重要。据报道，通过甲硫基化，可以合理控制作为分子半导体的芘衍生物的晶体结构； 1,6-双（甲硫基）芘保持与母体芘相似的三明治人字形结构，而1,3,6,8-四（甲硫基）芘（MT-芘）则采用新型砖砌结构。这些晶体结构的这种变化可以通过甲基硫基化有效控制的分子间相互作用的改变来解释。 MT-芘单晶被评估为单晶场效应晶体管（SC-FET）中的有源半导体材料，在-5 V的漏极和栅极电压下表现出极高的迁移率（平均32 cm2 V−1 s−1）。此外，MT-芘SC-FET的带状输运和非常低的陷阱密度通过实验得到证实，证明MT-芘是用于半导体领域的最佳分子半导体之一。 SC-FET 器件。
Control and prediction of crystal structures of molecular semiconductors are considered challenging, yet they are crucial for rational design of superior molecular semiconductors. It is here reported that through methylthiolation, one can rationally control the crystal structure of pyrene derivatives as molecular semiconductors; 1,6‐bis(methylthio)pyrene keeps a similar sandwich herringbone structure to that of parent pyrene, whereas 1,3,6,8‐tetrakis(methylthio)pyrene (MT‐pyrene) takes a new type of brickwork structure. Such changes in these crystal structures are explained by the alteration of intermolecular interactions that are efficiently controlled by methylthiolation. Single crystals of MT‐pyrene are evaluated as the active semiconducting material in single‐crystal field‐effect transistors (SC‐FETs), which show extremely high mobility (32 cm2 V−1 s−1 on average) operating at the drain and gate voltages of −5 V. Moreover, the band‐like transport and very low trap density are experimentally confirmed for the MT‐pyrene SC‐FETs, testifying that the MT‐pyrene is among the best molecular semiconductors for the SC‐FET devices.