Usta, HakanKim, DojeonOzdemir, ResulZorlu, YunusKim, SanghyoRuiz Delgado, M. CarmenHarbuzaru, AlexandraKim, SeonhyoungDemirel, GokhanHong, JonginHa, Young-GeunCho, KilwonFacchetti, AntonioKim, Myung-Gil2021-03-232021-03-2320190897-47561520-5002https://doi.org/10.1021/acs.chemmater.9b01614https://hdl.handle.net/20.500.12573/609H.U., G.D., and R.O. acknowledge support from the Scientific and Technological Research Council of Turkey (TUBITAK) grant number 216M430. M.-G. Kim acknowledges support from the National Research Foundation of Korea (NRF) grant number 2016K2A9A1A06924256. A.F. thanks the AFOSR grant FA9550-18-1-0320. M.C.R.D. and A.H. acknowledge support from MINECO (CTQ2015-66897) and Junta de Andalucia (P09-FQM-4708) projects. The authors thankfully acknowledge the computer resources, technical expertise, and assistance provided by the SCBI (Supercomputing and Bioinformatics) center of the University of Malaga.The first example of an n-type [1]benzothieno[3,2-b][1]benzothiophene (BTBT)-based semiconductor, D-(PhFCO)-BTBT, has been realized via a two-step transition metal-free process without using chromatographic purification. Physicochemical and optoelectronic characterizations of the new semiconductor were performed in detail, and the crystal structure was accessed. The new molecule exhibits a large optical band gap (similar to 2.9 eV) and highly stabilized (Delta E-LUMO = 1.54 eV)/pi-delocalized lowest unoccupied molecular orbital (LUMO) mainly comprising the BTBT pi-core and in-plane carbonyl units. The effect of out-of-plane twisted (64 degrees) pentafluorophenyl groups on LUMO stabilization is found to be minimal. Polycrystalline D(PhFCO)-BTBT thin films prepared by physical vapor deposition exhibited large grains (similar to 2-5 mu m sizes) and "layer-by-layer" stacked edge-on oriented molecules with an in-plane herringbone packing (intermolecular distances similar to 3.25-3.46 angstrom) to favor two-dimensional (2D) source-to-drain (S -> D) charge transport. The corresponding TC/BG-OFET devices demonstrated high electron mobilities of up to similar to 0.6 cm(2)/V.s and I-on/I-off ratios over 10(7)-10(8). These results demonstrate that the large band gap BTBT pi-core is a promising candidate for high-mobility n-type organic semiconductors and, combination of very large intrinsic charge transport capabilities and optical transparency, may open a new perspective for next-generation unconventional (opto)electronics.enginfo:eu-repo/semantics/closedAccessORGANIC SEMICONDUCTORSMOLECULAR-ORBITAL METHODSCHARGE-TRANSPORT PARAMETERSTHIN-FILM TRANSISTORSarticleVolume: 311452545263