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

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 ( ≈ 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 AB-type nanomonomers. The high dielectric constant ( = 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- feature of NPSG increases the field-effect carrier mobility from 0.20 to 0.90 cm V s 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 cm V s, surpassing most of the amorphous -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.