Resonant Laser PrintingAll-dielectric and semiconductor-based optical antennas are intensively investigated as promising substrates for surface enhanced Raman scattering (SERS). 1 This emerging interest stems from several factors. One is the possibility to exploit a rich variety of opportunities to tune the Raman response. For example, the chemical enhancement can be widely modulated by controlling charge transfer and adsorption-induced changes of the molecular polarizability of a given analyte.In parallel, the electromagnetic enhancement can take advantage of Mie-type resonances, light trapping and related optical effects to increase sensitivity and selectivity of the Raman response.Further major benefits of non-plasmonic SERS are low-invasiveness (plasmonic heating and plasmon-driven catalysis are avoided) 2-6 and high reproducibility, which make dielectrics more advantageous than metals for many types of Raman analysis, including the real-time monitoring of chemical reactions. These hallmarks are ultimately related to the lossless nature of dielectrics, which avoids the generation of strong local heating under light irradiation. Among the different types of dielectrics and semiconductors that have been proposed so far, SiO 2 /TiO 2 core/shell beads (T-rex) 7 demonstrated unique performances in sensing environmental pollutants and biomarkers.
6-10In particular, micron-sized beads can be individually visualized by optical microscopy and exploited as Mie resonators able to act as all-in-one colloidal platforms combining SERS, mass spectrometry and optical sensing. 11 As the SERS efficiency of these resonators is closely related to the refractive index contrast between core and shell, the replacement of the TiO 2 with a higher index material could further improve the performance of these systems. 12 In this regard, Si represents a natural choice in terms of high refractive index (n∼4 at the most common Raman exciting wavelengths) and compatibility with sensing devices. [13][14][15] Maier and co-workers demonstrated that dimers of spheres and nanodisks, either made of GaP or Si, are able to produce a good near-field enhancement, yet with minimal heating losses if compared with the analogous gold counterparts. (100) substrates by rf-magnetron sputtering and selected for the study (details in Supporting Information, SI 1 and SI 2). The laser spot size of the three wavelengths is commensurate with the 2 µm-sized beads, which enables a geometrically efficient light in-coupling. On the other hand, the laser spot size is about 1/3 of that of the whole sphere in the case of∼ 6.5 µm-sized cores. Both single beads and three-dimensional (3D) colloidal crystals were analysed. ) Raman spectra of the samples before (blue) and after (red) 500s of exposure to an exciting laser beam (laser wavelength: 633 nm, power: 5mW); c) 6_Si100 and d) 2_Si100 samples: e) Raman intensity ratio (IαSi/IcSi) as function of time respectively for 6_Si100 (pink) and for 2_Si100 (light blue); f) Threshold laser power as function of shell thickness...