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

Dongqing Lin,Dan Lu,Le Wang,Hongkai Hu,Wei Huang,Yongxia Wang,Yue Qian,Hang Yin,Xuefeng Guo,Linghai Xie,Jin’An Liu,Yang Li,Lei Tang,Yongxia Yan,Ying Wei,Haifeng Ling,Shasha Wang,Chaoyang Dong,Hao Zhang,Wenhua Zhang,He Zhang,Xingyu Xie ,Haixiao Hu

doi:10.34133/2022/9820585

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 (lp ≈ 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.

Highlights

The fourth-generation semiconductors have been conceived as the cornerstone of intelligent flexible electronics, which would revolute the function and morphology of integrated circuits beyond Moore’s law [1, 2]
The longer polygridization time (13~22 h) results in the formation of hyperbranched polygrids (HBPGs), suggesting that the spiro-polygridization into NPSG should be in kinetic control
A state-of-the-art ultrarigid spiro-nanopolymer has been created to explore the effect of covalent nanoscale ordering on the ultralow energy disorder and high dielectric constant

Summary

Introduction

The fourth-generation semiconductors have been conceived as the cornerstone of intelligent flexible electronics, which would revolute the function and morphology of integrated circuits beyond Moore’s law [1, 2] In this aspect, organic semiconductors [3] hold promising advantages over atomically precise synthesis, structural diversity, multifunctional integration, and high biocompatibility, in promising applications of large-area, ultrathin, and wearable optoelectronic. Gridarene-based organic nanopolymers ( called polygrids) are one-dimensional covalent nanochains with intermediate main-chain rigidity between π-conjugated polymers and carbon nanotubes (CNT). These single-bond-linked polygrids [21] with relatively large conformational entropy exhibit a limited persistence length (lp ≈ 16 nm) and disfavor covalent nanoscale ordering.

Results and Discussion

Conclusion

Materials and Methods

Conflicts of Interest