Hybrid Metrology for Nanostructured Optical Metasurfaces.

Metasurfaces have garnered increasing research interest in recent years due to their remarkable advantages, such as efficient miniaturization and novel functionalities compared to traditional optical elements such as lenses and filters. These advantages have facilitated their rapid commercial deployment. Recent advancements in nanofabrication have enabled the reduction of optical metasurface dimensions to the nanometer scale, expanding their capabilities to cover visible wavelengths. However, the pursuit of large-scale manufacturing of metasurfaces with customizable functions presents challenges in controlling the dimensions and composition of the constituent dielectric materials. To address these challenges, the combination of block copolymer (BCP) self-assembly and sequential infiltration synthesis (SIS), offers an alternative for fabrication of high-resolution dielectric nanostructures with tailored composition and optical functionalities. However, the absence of metrological techniques capable of providing precise and reliable characterization of the refractive index of dielectric nanostructures persists. This study introduces a hybrid metrology strategy that integrates complementary synchrotron-based traceable X-ray techniques to achieve comprehensive material characterization for the determination of the refractive index on the nanoscale. To establish correlations between material functionality and their underlying chemical, compositional and dimensional properties, TiO2 nanostructures model systems were fabricated by SIS of BCPs. The results from synchrotron-based analyses were integrated into physical models, serving as a validation scheme for laboratory-scale measurements to determine effective refractive indices of the nanoscale dielectric materials.

Developing Quantitative Nondestructive Characterization of Nanomaterials: A Case Study on Sequential Infiltration Synthesis of Block Copolymers.

The sequential infiltration synthesis (SIS) of inorganic materials in nanostructured block copolymer templates has rapidly progressed in the last few years to develop functional nanomaterials with controllable properties. To assist this rapid evolution, expanding the capabilities of nondestructive methods for quantitative characterization of the materials properties is required. In this paper, we characterize the SIS process on three model polymers with different infiltration profiles through ex situ quantification by reference-free grazing incidence X-ray fluorescence. More qualitative depth distribution results were validated by means of X-ray photoelectron spectroscopy and scanning transmission electron microscopy combined with energy-dispersive X-ray spectroscopy.

Zn- and Ti-Doped SnO2 for Enhanced Electroreduction of Carbon Dioxide.

The electrocatalytic reduction of CO2 into useful fuels, exploiting rationally designed, inexpensive, active, and selective catalysts, produced through easy, quick, and scalable routes, represents a promising approach to face today's climate challenges and energy crisis. This work presents a facile strategy for the preparation of doped SnO2 as an efficient electrocatalyst for the CO2 reduction reaction to formic acid and carbon monoxide. Zn or Ti doping was introduced into a mesoporous SnO2 matrix via wet impregnation and atomic layer deposition. It was found that doping of SnO2 generates an increased amount of oxygen vacancies, which are believed to contribute to the CO2 conversion efficiency, and among others, Zn wet impregnation resulted the most efficient process, as confirmed by X-ray photoelectron spectroscopy analysis. Electrochemical characterization and active surface area evaluation show an increase of availability of surface active sites. In particular, the introduction of Zn elemental doping results in enhanced performance for formic acid formation, in comparison to un-doped SnO2 and other doped SnO2 catalysts. At -0.99 V versus reversible hydrogen electrode, the total faradaic efficiency for CO2 conversion reaches 80%, while the partial current density is 10.3 mA cm-2. These represent a 10% and a threefold increases for faradaic efficiency and current density, respectively, with respect to the reference un-doped sample. The enhancement of these characteristics relates to the improved charge transfer and conductivity with respect to bare SnO2.

TEM Nanostructural Investigation of Ag-Conductive Filaments in Polycrystalline ZnO-Based Resistive Switching Devices.

Memristive devices based on a resistive switching mechanism are considered very promising for nonvolatile memory and unconventional computing applications, even though many details of the switching mechanisms are not yet fully understood. Here, we report a nanostructural study by means of high-resolution transmission electron microscopy and spectroscopy techniques of a Ag/ZnO/Pt memristive device. To ease the localization of the filament position for its characterization, we propose to use the guiding effect of regular perturbation arrays obtained by FIB technology to assist the filament formation. HRTEM and EDX were used to identify the composition and crystalline structure of the so-obtained conductive filaments and surrounding regions. It was determined that the conducting paths are composed mainly of monocrystalline Ag, which remains polycrystalline in some circumstances, including the zone where the switching occurs and at secondary filaments created at the grain boundaries of the polycrystalline ZnO matrix. We also observed that the ZnO matrix shows a degraded quality in the switching zone, while it remains unaltered in the rest of the memristive device.

A multi-level memristor based on atomic layer deposition of iron oxide.

This work reports the fabrication of memristive devices based on iron oxide (Fe2O3) thin films grown by atomic layer deposition (ALD) using ferrocene as iron precursor and ozone as oxidant. An excellent control of the ALD process was achieved by using an experimental procedure based on a sequence of micro-pulses, which provided long residence time and homogeneous diffusion of precursors, allowing ALD of thin films with smooth morphology and crystallinity which was found to increase with layer thickness, at temperatures as low as 250 °C. The resistive switching of symmetric Pt/Fe2O3/Pt thin film devices exhibited bipolar mode with good stability and endurance. Multi-level switching was achieved via current and voltage control. It was proved that the ON state regime can be tuned by changing the current compliance while the OFF state can be changed to intermediate levels by decreasing the maximum voltage during RESET. The structural analysis of the switched oxide layer revealed the presence of nano-sized crystalline domains corresponding to different iron oxide phases, suggesting that Joule heating effects during I-V cycling are responsible for a crystallization process of the pristine amorphous layer.

Memristive behaviour in poly-acrylic acid coated TiO2 nanotube arrays.

This work investigates titanium dioxide nanotube arrays (TiO2-NTA) grown by anodic oxidation as an active material for memristive applications. In particular, metal-insulator-metal structures made of vertically oriented amorphous TiO2-NTA grown on titanium foil were exploited in Ti/TiO2-NTA/Pt devices. The deposition of a polymeric thin film between NTA and top electrodes significantly improved the stability of the devices and increased by more than double the off/on resistance ratio. The resistive switching of TiO2-NTA samples crystallised by thermal annealing was also studied. Such devices displayed nonlinear I-V curves characterised by a smooth rectifying behaviour, without any evident resistive switching (RS). Also in this case, the interposition of the polymeric layer enhanced the RS behaviour of TiO2-NTA samples, remarkably increasing the devices' off/on ratio and endurance. The rise of high resistance states can be simply related to the addition of the polymer as resistance in series, while the variation of the low resistance states is here attributed to the occurrence of surface chemical reactions between polymer functional groups and the metal oxide, which increase the charge carriers available for conduction.

SERS active silver nanoparticles synthesized by inkjet printing on mesoporous silicon.

Inkjet printing technique is exploited for the synthesis of Ag nanoparticles (NPs) patterned on electrochemically etched silicon-based substrates. The nanostructure morphology, here analyzed by scanning electron microscopy, is dictated by the ink composition and the printing parameters. Under suitable excitation conditions, resonant surface-enhanced Raman scattering (SERS) performed on such metal-dielectric nanostructures can approach single-molecule detection as recently demonstrated on silvered porous silicon synthesized by immersion plating. PACS: 78.67.Bf; 78.30.-j.