Optimized Synthesis of Solution‐Processable Crystalline Poly(Triazine Imide) with Minimized Defects for OLED Application

Poly(triazine imide) (PTI) is a highly crystalline semiconductor, and though no techniques exist that enable synthesis of macroscopic monolayers of PTI, it is possible to study it in thin layer device applications that are compatible with its polycrystalline, nanoscale morphology. We find that the by‐product of conventional PTI synthesis is a C−C carbon‐rich phase that is detrimental for charge transport and photoluminescence. An optimized synthetic protocol yields a PTI material with an increased quantum yield, enabled photocurrent and electroluminescence. We report that protonation of the PTI structure happens preferentially at the pyridinic N atoms of the triazine rings, is accompanied by exfoliation of PTI layers, and contributes to increases in quantum yield and exciton lifetimes. This study describes structure–property relationships in PTI that link the nature of defects, their formation, and how to avoid them with the optical and electronic performance of PTI. On the basis of our findings, we create an OLED prototype with PTI as the active, metal‐free material.