Hybrid Au-Si microspheres produced by laser ablation in liquid (LAL) for temperature-feedback optical nano-sensing and anti-counterfeit labeling

Abstract: Recent progress in hybrid nanomaterials composed of dissimilar constituents permitted to improve performance and functionality of novel devices developed for optoelectronics, catalysis, medical diagnostic and sensing. However, the rational combination of such contrasting materials as noble metals and semiconductors within individual hybrid nanostructures $via$ a ready-to-use and lithography-free fabrication approach is still a standing challenge. Here, we report on a two-step synthesis of Au-Si microspheres generated by laser ablation of silicon in isopropanol followed by laser irradiation of the produced Si nanoparticles in presence of HAuCl$_4$. Thermal reduction of [AuCl$_4$]$^-$ species to metallic gold phase, along with its subsequent mixing with silicon under laser irradiation creates a nanostructured material with a unique composition and morphology revealed by electron microscopy, tomography and elemental analysis. Combination of such basic plasmonic and nanophotonic materials as gold and silicon within a single microsphere allows for efficient light-to-heat conversion, as well as single-particle SERS sensing with temperature feedback modality and expanded functionality. Moreover, the characteristic Raman signal and hot-electron induced nonlinear photoluminescence coexisting within Au-Si hybrids, as well as commonly criticized randomness of the nanomaterials prepared by laser ablation in liquid, were proved useful for realization of anti-counterfeiting labels based on physically unclonable function approach.