High‐Security Plastic with Integrated Holographic and Phosphorescent Images

Organic room temperature phosphorescence (ORTP) polymer materials have sparked considerable research interests in recent years, but their optical function is still limited for multi-mode optical imaging. Herein, a feasible and universal approach is proposed to endow ORTP polymer materials with periodic refractive index modulation functions by holographic patterning. The key to this approach is to design a two-stage stepwise crosslinking. Stage-1, with low crosslinking density (≤0.75 mol L^-1), is phosphorescence-silent but can provide greater free volume for monomer diffusion and thus facilitate the patterning of refractive index modulated holograms via photopolymerization-induced phase separation. The dense crosslinking at stage-2 can turn on phosphorescence with the intensity rising by 144% when the crosslinking density increases from 3.77 to 4.12 mol L^-1. The enhanced phosphorescence is primarily ascribed to the increase of conformational distortion and spin-orbit coupling of organic phosphors based on theoretical calculations. Eventually, the first example is demonstrated of holographic plastic with the unique capability of independently displaying holographic andphosphorescent images. This work not only provides a novel paradigm to impart added optical functions to ORTP polymer materials but also paves the way for the development of high-security optical materials to combat counterfeiting.