Molecular-dipole oriented universal growth of conjugated polymers into semiconducting single-crystal thin films
Chunyan Zhao, Xilin Lai, Dawei Liu, Xinrui Guo, Jiamin Tian, Zuoyuan Dong, Shaochuan Luo, Dongshan Zhou, Lang Jiang, Ru Huang, Ming He
Abstract
Precise control over crystallinity and morphology of conjugated polymers (CPs) is essential for progressing organic electronics. However, manufacturing single-crystal thin films of CPs presents substantial challenges due to their complex molecular structures, distorted chain conformations, and unbalanced crystallization kinetics. In this work, we demonstrate a universal nanoconfined molecular-dipole orientating strategy to craft high-quality single-crystal thin films for a variety of CPs, spanning from traditional thiophene- and theinothiophene-based homopolymers to diketopyrrolopyrrole- (i.e., p-type) and naphthalene-based (i.e., n-type) donor-acceptor copolymers. Central to this strategy is the synergetic manipulations of molecular dipoles, π-π stackings, and alkyl-alkyl interactions of CPs within our rationally-designed spatial-electrostatic confinement capacitor, which facilitates the rotation of conjugated backbones and the alignment of π-π stackings into microscale-sized single-crystal thin films. A minimal energetic disorder of 25 meV that below the thermal fluctuation energy kBT at room temperature, as well as an excellent transistor mobility of 15.5 cm2V−1s−1 are achieved, marking a significant step towards controllable growths of conjugated-polymer single-crystal thin films that hold a cornerstone for high-performance organic electronic devices. Precise control over the characteristics of crystalline conjugated polymers is essential for organic electronic, but this is complex. Here, the authors report a molecular dipole orienting strategy for preparation of single-crystal thin films with high transistor mobility.