Determination of the SERS enhancement factor through the challenging measurement of the molecular surface density by reference-free X-ray fluorescence.

Controlling the location and the distribution of hot spots is a crucial aspect in the fabrication of surface-enhanced Raman spectroscopy (SERS) substrates for bio-analytical applications. The choice of a suitable method to tailor the dimensions and the position of plasmonic nanostructures becomes fundamental to provide SERS substrates with significant signal enhancement, homogeneity and reproducibility. In the present work, we studied the influence of the long-range ordering of different flexible gold-coated Si nanowires arrays on the SERS activity. The substrates are made by nanosphere lithography and metal-assisted chemical etching. The degree of order is quantitatively evaluated through the correlation length (ξ) as a function of the nanosphere spin-coating speed. Our findings showed a linear increase of the SERS signal for increasing values of ξ, coherently with a more ordered and dense distribution of hot spots on the surface. The substrate with the largest ξ of 1100 nm showed an enhancement factor of 2.6 · 10³ and remarkable homogeneity over square-millimetres area. The variability of the signal across the substrate was also investigated by means of a 2D chemical imaging approach and a standard methodology for its practical calculation is proposed for a coherent comparison among the data reported in literature.

In the continuous downscaling of device features, the microelectronics industry is facing the intrinsic limits of conventional lithographic techniques. The development of new synthetic approaches for large-scale nanopatterned materials with enhanced performances is therefore required in the pursuit of the fabrication of next-generation devices. Self-assembled materials as block copolymers (BCPs) provide great control on the definition of nanopatterns, promising to be ideal candidates as templates for the selective incorporation of a variety of inorganic materials when combined with sequential infiltration synthesis (SIS). In this review, we report the latest advances in nanostructured inorganic materials synthesized by infiltration of self-assembled BCPs. We report a comprehensive description of the chemical and physical characterization techniques used for in situ studies of the process mechanism and ex situ measurements of the resulting properties of infiltrated polymers. Finally, emerging optical and electrical properties of such materials are discussed.

Porous materials display enhanced scattering mechanisms that greatly influence their transport properties. Metal-assisted chemical etching (MACE) enables fabrication of porous silicon nanowires starting from a doped Si wafer by using a metal template that catalyzes the etching process. Here, we report on the low thermal conductivity (κ) of individual porous Si nanowires (NWs) prepared from MACE, with values as low as 0.87 W·m⁻¹·K⁻¹ for 90 nm diameter wires with 35–40% porosity. Despite the strong suppression of long mean free path phonons in porous materials, we find a linear correlation of κ with the NW diameter. We ascribe this dependence to the anisotropic porous structure that arises during chemical etching and modifies the phonon percolation pathway in the center and outer regions of the nanowire. The inner microstructure of the NWs is visualized by means of electron tomography. In addition, we have used molecular dynamics simulations to provide guidance for how a porosity gradient influences phonon transport along the axis of the NW. Our findings are important towards the rational design of porous materials with tailored thermal and electronic properties for improved thermoelectric devices.

In this work, we performed a systematic study on the effect of the geometry of pre-patterned templates and spin-coating conditions on the self-assembling process of colloidal nanospheres. To achieve this goal, large-scale templates, with different size and shape, were generated by direct laser-writer lithography over square millimetre areas. When deposited over patterned templates, the ordering dynamics of the self-assembled nanospheres exhibits an inverse trend with respect to that observed for the maximisation of the correlation length $\xi$ on a flat surface. Furthermore, the self-assembly process was found to be strongly dependent on the height (H) of the template sidewalls. In particular, we observed that, when H is 0.6 times the nanospheres diameter and spinning speed 2500 rpm, the formation of a confined and well ordered monolayer is promoted. To unveil the defects generation inside the templates, a systematic assessment of the directed self-assembly quality was performed by a novel method based on Delaunay triangulation. As a result of this study, we found that, in the best deposition conditions, the self-assembly process leads to well-ordered monolayer that extended for tens of micrometres within the linear templates, where 96.2% of them is aligned with the template sidewalls.