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

Abstract Two‐photon polymerization 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 contain 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 nanoparticle distribution and increased optical extinction. In this work, a general approach is proposed for dispersing oc‐NPs in commercial 3D printable polymers. Controlled growth of small carbon chains around the oc‐NPs is achieved by functionalizing them with methyl‐methacrylate monomers. The proposed approach is validated on RENPs (≈65 nm) and CdSe/ZnS quantum dots (≈12 nm) using commercial polymer resists (IP‐Dip and IP‐Visio). Dispersions of functionalized NPs (f‐NPs) have improved the NP density by an order of magnitude and are shown to be stable for several weeks with minimal impact on printing quality. The approach is generalizable to other oc‐NPs, enabling synthesis of functional resins for high‐quality polymer‐based optical and electronic devices.