Photonic Microresonators from Charge Transfer in Polymer Particles: Toward Enhanced and Tunable Two-Photon Emission

Abstract

Novel photonic microresonators with enhanced nonlinear optical (NLO) intensity are fabricated from polymer particles. As an additional advantage, they offer band gap tunability from the visible to near-infrared regions. A special protocol including (i) copolymerization of 4-(1-pyrenyl)-styrene, styrene, and 1,4-divinylbenzene, (ii) extraction of a dispersible and partly dissolvable, lightly cross-linked polymer network (PN), and (iii) treatment of the blue-emitting PN with electron acceptor (A) molecules such as 1,2,4,5-tetracyanobenzene (TCNB) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) furnishes orange- and red-emitting D–A charge-transfer (CT) complexes with the pendant pyrene units. These complexes, here named PN-TCNB and PN-TCNQ, respectively, precipitate as microparticles upon the addition of water and subsequent ultrasonication. Upon electronic excitation, these spherical microparticles act as whispering-gallery-mode resonators by displaying optical resonances in the photoluminescence (PL) spectra because of light confinement. Further, the trapped incident light increases the light–matter interaction and thereby enhances the PL intensity, including the two-photon luminescence. The described protocol for polymer-based CT microresonators with tunable NLO emissions holds promise for a myriad of photonic applications.