Polymer-based electronic devices are limited by slow transport and recombination of newly separated charges. Built-in electric fields, which arise from compositional gradients, are known to improve charge separation, directional charge transport, and to reduce recombination. Yet, the optimization of these fields through the rational design of polymeric materials is not prevalent. Indeed, polymers are disordered and generate nonuniform electric fields that are hard to measure, and therefore, hard to optimize. Here, we review work focusing on the intentional optimization of electric fields in polymeric systems with applications to catalysis, energy conversion, and storage. This includes chemical tuning of constituent monomers, linkers, morphology, etc. that result in stronger molecular dipoles, polarizability or crystallinity. We also review techniques to characterize electric fields in polymers and emerging processing strategies based on electric fields. These studies demonstrate the benefits of optimizing electric fields in polymers. However, rational design is often restricted to the molecular scale, deriving new pendants on, or linkers between, monomers. This does not always translate in strong electric fields at the polymer level, because they strongly depend on the monomer orientation. A better control of the morphology and monomer-to-polymer scaling relationship is therefore crucial to enhance electric fields in polymeric materials. CONTENTS 1. Introduction 13331 2. Theory 13333 3. Enhancing Electric Fields in Polymeric Materials for Electronic Devices 13336 3.1. Enhancing Electric Fields by Monomer Design 13336 3.2. Enhancing Electric Fields by Linker Design 13340 3.3. Enhancing Electric Fields by Supramolecular Architecture Tuning 13343 3.4. Opportunities for Electric Field Optimization 13344 4. Novel Polymer Classes to Enhance Electric Fields 13347 4.1.
