Architecting Layered Crystalline Organic Semiconductors Based on Unsymmetric π-Extended Thienoacenes

Abstract

Herein, we demonstrate that engineered end-cap substitution for unsymmetric extended π-cores effectively achieves well-ordered two-dimensional (2D) molecular packing and thus realizes high-performance organic semiconductors (OSCs). We developed phenyl- and decyl-substituted benzothieno­[6,5-b]­benzothieno­[3,2-b]­thiophenes (BTBTTs) as solution-processable OSCs, providing layered single-crystalline thin-film transistors with a hole mobility of up to 12 cm2 V–1 s–1. The compound formed a bilayer-type layered herringbone packing in which the unsymmetric π-core aligned unidirectionally to form the respective molecular layers, owing to the well-balanced contributions of intermolecular interactions between the π-cores and between the respective end substituents. The eventual close intralayer molecular packing afforded a small effective mass and high thermal stability. These findings will be crucial for expanding the ability to develop high-performance OSCs.

High-performance five-ring-fused organic semiconductors for field-effect transistors

“…11) with a phenyl group and an alkyl group separately located at the end of both sides. 280 The drop-cast crystalline films of Ph-BTBTT-C10 can reach a high mobility of 12.8 cm 2 V À1 s À1 . 280 Aiming at understanding the role of anti-/syn-in the charge transport properties of organic semiconductors, we have also summarized one critical review recently.…”

“…280 The drop-cast crystalline films of Ph-BTBTT-C10 can reach a high mobility of 12.8 cm 2 V À1 s À1 . 280 Aiming at understanding the role of anti-/syn-in the charge transport properties of organic semiconductors, we have also summarized one critical review recently. 286 The performance statistics of five-ring-fused organic semiconductors in Fig.…”

“…11). 100,[278][279][280] A dense intermolecular packing is observed via the introduction of SÁ Á ÁS interactions when three thiophene rings are fused together. in 1938.…”

Systematic arrangement control of functional organic molecules

“…[17][18][19][20][21][22][23][24] We previously prepared organic salts composed of disulfonic acid that contained anthracene as a functional moiety and several alkylamines as an arrangementcontrolling moiety. 25 We demonstrated that the π-stack structure of anthracene and the layered crystal structures formed by the disulfonic acid and alkylamine in the organic salts (layered crystallinity 26 ) were significantly altered depending on the type of alkylamine, without changing the structure of the functional moiety. However, to fully understand the relationship between the molecular arrangement and the functions of functional organic molecules, ideally, a method for systematically and precisely controlling their molecular arrangement without affecting the layered crystallinity is required.…”

Thermally Stable Organic Field‐Effect Transistors Based on Asymmetric BTBT Derivatives for High Performance Solar‐Blind Photodetectors

“…[1]Benzothieno[3,2‐b][1]‐benzothiophene (BTBT) derivatives, as one of the most widely studied semiconductors in outstanding organic field‐effect transistors (OFETs), [ 34 , 35 , 36 , 37 , 38 ] are of great potential in solar‐blind photodetectors due to their wide band gaps ( E g ) and high mobility. Indeed, the star molecule C8‐BTBT was reported with high mobility and excellent solar‐blind photo response performance, and was expected to boom the organic solar‐blind photodetectors, [ 7 , 39 , 40 ] yet, the poor thermal stability of C8‐BTBT limits its in‐depth applications in photodetectors.…”