Rapid in situ photochemical synthesis of carbon dots in polymer coating by infrared CO₂ laser writing for color tunable fluorescent patterning

Abstract

The significant in situ multicolored patterning without changing printing tools nor substrate media still remains challenging, especially toward practical applications for anti-counterfeiting. This research invented a unique universal approach for the laser-induced in situ synthesis of colorful fluorescent patterns (from blue: CIE 0.15, 0.18 to red orange: CIE 0.36, 0.39) through the controlled formation of N, S doped carbon dots (CDs) in solid composite polymer films or hydrogel with a hierarchical and physically unclonable microsurface architecture for anti-counterfeiting. The in situ patterning approach, coupled with multi-layer technique, yielding designable blue, yellow, orange, and red orange color under 365 nm in the same pattern. A 5 cm² colorful pattern can be efficiently finished within 5 min without changing the substrate and the line width accuracy can be up to 300 μm. The absolute quantum efficiency of the blue pattern reached as high as 23%. The fluorescent patterns can be survived at indoor for 24 months. The hydrogen bonding interactions between the CDs precursor and polymer facilitated the generation, uniform dispersion and stabilization of CDs during the laser irradiation. The hypothesis that laser irradiation induced photochemical reactions of CD precursors within a polymer matrix was supported by thermodynamic assessments. The universality of in situ fluorescent patterning strategy was demonstrated by developing fluorescent patterns on both solid polymer films, hydrogel, pharmaceutical packaging and textile.