Cross-Scale Synthesis of Organic High- k Semiconductors Based on Spiro-Gridized Nanopolymers

Dongqing Lin; Wenhua Zhang; Hang Yin; Haixia Hu; Yang Li; He Zhang; Le Wang; Xinmiao Xie; Hongkai Hu; Yongxia Yan; Haifeng Ling; Jin'an Liu; Yue Qian; Lei Tang; Yongxia Wang; Chaoyang Dong; Linghai Xie; Hao Zhang; Shasha Wang; Ying Wei; Xuefeng Guo; Dan Lu; Wei Huang

doi:10.34133/2022/9820585

Cross-Scale Synthesis of Organic High- k Semiconductors Based on Spiro-Gridized Nanopolymers

Research (Wash D C). 2022 Jan 12:2022:9820585. doi: 10.34133/2022/9820585. eCollection 2022.

Authors

Dongqing Lin¹, Wenhua Zhang², Hang Yin³, Haixia Hu³, Yang Li¹, He Zhang¹, Le Wang¹, Xinmiao Xie^{1

4}, Hongkai Hu¹, Yongxia Yan¹, Haifeng Ling¹, Jin'an Liu¹, Yue Qian¹, Lei Tang¹, Yongxia Wang¹, Chaoyang Dong¹, Linghai Xie^{1

5}, Hao Zhang⁶, Shasha Wang¹, Ying Wei¹, Xuefeng Guo⁴, Dan Lu⁶, Wei Huang^{1

5}

Affiliations

¹ Centre for Molecular Systems and Organic Devices (CMSOD), State Key Laboratory of Organic Electronics and Information Displays & Institute of Advanced Materials (IAM), Nanjing University of Posts & Telecommunications, 9 Wenyuan Road, Nanjing 210023, China.
² National Synchrotron Radiation Laboratory, Anhui Provincial Engineering Laboratory of Advanced Functional Polymer Film, CAS Key Laboratory of Soft Matter Chemistry, University of Science and Technology of China, Hefei 230026, China.
³ School of Physics, State Key Laboratory of Crystal Materials, Shandong University, Jinan, Shandong 250100, China.
⁴ Beijing National Laboratory for Molecular Sciences, National Biomedical Imaging Center, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.
⁵ Frontiers Science Center for Flexible Electronics (FSCFE), MIIT Key Laboratory of Flexible Electronics (KLoFE), Northwestern Polytechnical University, Xi'an 710072, China.
⁶ State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, 2699 Qianjin Avenue, Changchun 130012, China.

Abstract

High dielectric constants in organic semiconductors have been identified as a central challenge for the improvement in not only piezoelectric, pyroelectric, and ferroelectric effects but also photoelectric conversion efficiency in OPVs, carrier mobility in OFETs, and charge density in charge-trapping memories. Herein, we report an ultralong persistence length (l _p ≈ 41 nm) effect of spiro-fused organic nanopolymers on dielectric properties, together with excitonic and charge carrier behaviors. The state-of-the-art nanopolymers, namely, nanopolyspirogrids (NPSGs), are synthesized via the simple cross-scale Friedel-Crafts polygridization of A₂B₂-type nanomonomers. The high dielectric constant (k = 8.43) of NPSG is firstly achieved by locking spiro-polygridization effect that results in the enhancement of dipole polarization. When doping into a polystyrene-based dielectric layer, such a high-k feature of NPSG increases the field-effect carrier mobility from 0.20 to 0.90 cm² V^-1 s^-1 in pentacene OFET devices. Meanwhile, amorphous NPSG film exhibits an ultralow energy disorder (<50 meV) for an excellent zero-field hole mobility of 3.94 × 10^-3 cm² V^-1 s^-1, surpassing most of the amorphous π-conjugated polymers. Organic nanopolymers with high dielectric constants open a new way to break through the bottleneck of efficiency and multifunctionality in the blueprint of the fourth-generation semiconductors.