Polarization-controlled anisotropy in hybrid plasmonic nanoparticles

Anisotropy has played a critical role in many material systems, but its controllable creation and modulation have been a long-lasting challenge for the scientific communities. Polarization-addressed anisotropy appears more attractive among all approaches due to its excellent controllability, simplicity, and accuracy, but only a limited number of material systems are applicable for such a concept, which are largely focused on oriented growth. Here, we establish a polarization-dependent anisotropic etching system made of Au@oligomer core–shell nanoparticles (NPs). As the oligomer coatings can be photochemically degraded via two-photon photolithography, the plasmonic near-field enhancement supported by the Au NP cores renders much faster degradation of the oligomer shells along the polarization, resulting in anisotropic Au@oligomer hybrid NPs. Such shape anisotropy leads to polarization-dependent photoluminescence with embedded dyes of methylene blue, which can be used as single-particle-based polarization detector. The oligomer lobes capped at the sides of the Au NP can also function as a protection agent for anisotropic photochemical growth of Au NPs, which evolve into Au nanorods and mushrooms with controlled irradiation time. Such polarization-directed etching of oligomer shells has unique advantages of high local-selectivity, controllability, and versatility for on-chip nanofabrication, which opens many new opportunities for integrated nanophotonic devices.