Zhang Jing, Gu Peiyang, Long Guankui, Ganguly Rakesh, Li Yongxin, Aratani Naoki, Yamada Hiroko, Zhang Qichun
School of Materials Science and Engineering , Nanyang Technological University , Singapore . Email:
Division of Chemistry and Biological Chemistry , School of Physical and Mathematical Sciences , Nanyang Techno Logical University , Singapore.
Chem Sci. 2016 Jun 1;7(6):3851-3856. doi: 10.1039/c5sc04954g. Epub 2016 Feb 25.
Borrowing an idea from the silicon industry, where the charge-carrier's characteristics can be changed through heteroatom implantation, we believe that the charge transport nature of organic semiconductors can be switched through molecular "doping" (co-crystallization). Here, we report a novel molecule 2,7-di--butyl-10,14-di(thiophen-2-yl)phenanthro[4,5-][1,2,5]thiadiazolo[3,4-]phenazine (DTPTP), which originally is a p-type (0.3 cm V s) compound, and can be switched to an n-type semiconductor (DTPTP-TCNQ, 3 × 10 cm V s under air conditions) through tetracyanoquinodimethane (TCNQ) doping (co-crystallization). Single crystal X-ray studies revealed that TCNQ-doped DTPTP complexes (DTPTP-TCNQ) adopt a dense one-dimensional (1D) mixed π-π stacking mode with a ratio of DTPTP and TCNQ of 2 : 1, while pure DTPTP molecules utilize a herringbone-packing pattern. Interestingly, theoretical analysis suggested that there is a quasi-2D electron transport network in this host-guest system. Our research results might provide a new strategy, to switch the charge transport characteristics of an original system by appropriate molecular "doping" (co-crystal engineering).
借鉴硅产业中的一个理念，即在硅产业中载流子的特性可通过杂原子注入来改变，我们认为有机半导体的电荷传输性质可通过分子“掺杂”（共结晶）来切换。在此，我们报道了一种新型分子2,7-二-丁基-10,14-二（噻吩-2-基）菲并[4,5-][1,2,5]噻二唑并[3,4-]吩嗪（DTPTP），它原本是一种p型（0.3 cm² V⁻¹ s⁻¹）化合物，并且通过四氰基喹啉二甲烷（TCNQ）掺杂（共结晶）可切换为n型半导体（DTPTP-TCNQ，在空气条件下为3 × 10⁻² cm² V⁻¹ s⁻¹）。单晶X射线研究表明，TCNQ掺杂的DTPTP配合物（DTPTP-TCNQ）采用密集的一维（1D）混合π-π堆积模式，DTPTP与TCNQ的比例为2∶1，而纯DTPTP分子采用人字形堆积模式。有趣的是，理论分析表明在这种主客体体系中存在准二维电子传输网络。我们的研究结果可能提供一种新策略，即通过适当的分子“掺杂”（共晶工程）来切换原始体系的电荷传输特性。
