Surface-Functionalization of Oleate-Capped Nano-Emitters for Stable Dispersion in 3D-Printable Polymers

Abstract

Two-photon polymerization (2PP) 3D printing is a well-known technique for fabricating passive micro/nanoscale structures, such as microlenses and inversely designed polarization splitters. The integration of light emitting nanoparticle (NP) dopants, such as quantum dots (QDs) and rare-earth doped nanoparticles (RENPs), into a polymer resist would enable 3D printing of active polymer micro-photonic devices, including sensors, lasers, and solid-state displays. Many NPs are stabilized with oleic acid ligands to prevent degradation, but oleate-capped NPs (oc-NPs) tend to agglomerate in nonpolar media despite the hydrophobicity of the ligand. This results in an uneven distribution of NPs in polymers and increased optical extinction properties. In this work, we propose a general approach for dispersing various oc-NPs in commercial 3D printable polymers. We achieve controlled growth of small carbon chains around the oc-NPs by functionalizing the NPs with methyl-methacrylate monomers. The proposed approach is validated on RENPs (~65 nm) and CdSe/ZnS quantum dots (~12 nm) using different commercial polymer resists (IP-Dip and IP-Visio). Dispersions of functionalized NPs (f-NPs) have improved NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. Our approach is generalizable to a variety of oc-NPs and ultimately leads to higher quality polymer-based optical and electronic devices.