Thermal Scanning-Probe Lithography for Broad-Band On-Demand Plasmonic Nanostructures on Transparent Substrates.

Thermal scanning-probe lithography (t-SPL) is a high-resolution nanolithography technique that enables the nanopatterning of thermosensitive materials by means of a heated silicon tip. It does not require alignment markers and gives the possibility to assess the morphology of the sample in a noninvasive way before, during, and after the patterning. In order to exploit t-SPL at its peak performances, the writing process requires applying an electric bias between the scanning hot tip and the sample, thereby restricting its application to conductive, optically opaque, substrates.

DNA Sensing Platforms: Novel Insights into Molecular Grafting Using Low Perturbative AFM Imaging.

By using AFM as a nanografting tool, we grafted micrometer-sized DNA platforms into inert alkanethiol SAMs. Tuning the grafting conditions (surface density of grafting lines and scan rate) allowed us to tailor the molecular density of the DNA platforms. Following the nanografting process, AFM was operated in the low perturbative Quantitative Imaging (QI) mode.

Local dielectric function of hBN-encapsulated WSflakes grown by chemical vapor deposition.

Hexagonal boron nitride (hBN), sometimes referred to as white graphene, receives growing interest in the scientific community, especially when combined into van der Waals (vdW) homo- and heterostacks, in which novel and interesting phenomena may arise. hBN is also commonly used in combination with two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs). The realization of hBN-encapsulated TMDC homo- and heterostacks can indeed offer opportunities to investigate and compare TMDC excitonic properties in various stacking configurations.

Biofunctionalization of Porous Titanium Oxide through Amino Acid Coupling for Biomaterial Design.

Porous transition metal oxides are widely studied as biocompatible materials for the development of prosthetic implants. Resurfacing the oxide to improve the antibacterial properties of the material is still an open issue, as infections remain a major cause of implant failure. We investigated the functionalization of porous titanium oxide obtained by anodic oxidation with amino acids (Leucine) as a first step to couple antimicrobial peptides to the oxide surface.

In-Operando Optical Spectroscopy of Field-Effect-Gated Al-Doped ZnO.

Transparent conductive oxides (TCO) have the unique characteristics of combining optical transparency with high electrical conductivity; such a property makes them uniquely alluring for applications in visible and infrared photonics. One of their most interesting features is the large sensitivity of their optical response to the doping level. We performed the active electrical manipulation of the dielectric properties of aluminum-doped ZnO (AZO), a TCO-based on Earth-abundant elements.

Doping-Dependent Optical Response of a Hybrid Transparent Conductive Oxide/Plasmonic Medium.

Understanding the interaction between plasmonic nanoparticles and transparent conductive oxides is instrumental to the development of next-generation photovoltaic, optoelectronic, and energy-efficient solid-state lighting devices. We investigated the optical response of hybrid media composed of gold nanoparticles deposited on aluminum-doped zinc oxide thin films with varying doping concentration by spectroscopic ellipsometry. The dielectric functions of bare AZO were addressed first, revealing doping-induced effects such as the band gap shift and the appearance of free carriers.

A Two-Step Approach to Tune the Micro and Nanoscale Morphology of Porous Niobium Oxide to Promote Osteointegration.

We present a two-step surface modification process to tailor the micro and nano morphology of niobium oxide layers. Niobium was firstly anodized in spark regime in a Ca- and P-containing solution and subsequently treated by acid etching. The effects of anodizing time and applied potential on the surface morphology is investigated with SEM and AFM, complemented by XPS compositional analysis.

Local Optical Properties in CVD-Grown Monolayer WS Flakes.

Excitons dominate the light absorption and re-emission spectra of monolayer transition-metal dichalcogenides (TMD). Microscopic investigations of the excitonic response in TMD almost invariably extract information from the radiative recombination step, which only constitutes one part of the picture. Here, by exploiting imaging spectroscopic ellipsometry (ISE), we investigate the spatial dependence of the dielectric function of chemical vapor deposition (CVD)-grown WS flakes with a microscopic lateral resolution, thus providing information about the spatially varying, exciton-induced light absorption in the monolayer WS.

Quantitative Ultrafast Electron-Temperature Dynamics in Photo-Excited Au Nanoparticles.

The femtosecond evolution of the electronic temperature of laser-excited gold nanoparticles is measured, by means of ultrafast time-resolved photoemission spectroscopy induced by extreme-ultraviolet radiation pulses. The temperature of the electron gas is deduced by recording and fitting high-resolution photo emission spectra around the Fermi edge of gold nanoparticles providing a direct, unambiguous picture of the ultrafast electron-gas dynamics. These results will be instrumental to the refinement of existing models of femtosecond processes in laterally-confined and bulk condensed-matter systems, and for understanding more deeply the role of hot electrons in technological applications.

Structural and Spectroscopic Properties of Benzoylpyridine-Based Hydrazones.

Photochromic hydrazones are attracting the attention in the field of photochromic systems especially due to their P-type character. To understand the structural features and their correlation with the spectroscopic data, UV-Vis, vibrational and ellipsometry spectroscopic techniques are employed with the support of density functional theory (DFT) calculations to three hydrazone derivatives based on benzoylpyridine. Interestingly, analysis of the structure shows the presence of two distinct rotamers around the pyridine ring with different energy and the well-defined conjugation path that changes due to E to Z isomerization especially in the hydrazone -C=N-NH part of the skeleton.

High response photochromic films based on D-A diarylethenes and their application in holography.

A set of photochromic dithienylethenes bearing amino and nitro groups are synthesised and embedded at high concentrations in a polymer matrix (Cellulose Acetate Butyrate, CAB) to produce films showing a large reversible modulation of the complex refractive index in the Vis-NIR spectral range, thanks to an interesting combination of remarkable response at the molecular level and very high load capability in the chosen matrix. The photochromic derivatives are characterized in solution and in CAB films by means of electronic and vibrational spectroscopy, complemented by DFT calculations. Both the real and imaginary part of the refractive index are determined by spectroscopic ellipsometry.

Morphological and Mechanical Characterization of DNA SAMs Combining Nanolithography with AFM and Optical Methods.

The morphological and mechanical properties of thiolated ssDNA films self-assembled at different ionic strength on flat gold surfaces have been investigated using Atomic Force Microscopy (AFM). AFM nanoshaving experiments, performed in hard tapping mode, allowed selectively removing molecules from micro-sized regions. To image the shaved areas, in addition to the soft contact mode, we explored the use of the Quantitative Imaging (QI) mode.

Observation of a Correlation Between Internal friction and Urbach Energy in Amorphous Oxides Thin Films.

We have investigated by spectroscopic ellipsometry (SE, 190-1700 nm) the optical properties of uniform, amorphous thin films of TaO and NbO as deposited and after annealing, and after so-called "doping" with Ti atoms which leads to mixed oxides. TaO and Ti:TaO are currently used as high-index components in Bragg reflectors for Gravitational Wave Detectors. Parallel to the optical investigation, we measured the mechanical energy dissipation of the same coatings, through the so-called "loss angle" ϕ = Q, which quantifies the energy loss in materials.

Functionalizing gold with single strand DNA: novel insight into optical properties via combined spectroscopic ellipsometry and nanolithography measurements.

We have studied the self-assembly of 22-base oligonucleotides bound by a short alkyl thiol linker (C6-ssDNA) on flat Au films. The self-assembled monolayer (SAM) was modified by addition of a spacer (mercaptohexanol, MCH). Molecular depositions were monitored in situ by spectroscopic ellipsometry (SE).

Plasmonics of Au nanoparticles in a hot thermodynamic bath.

Electromagnetically-heated metal nanoparticles can be exploited as efficient heat sources at the nanoscale. The assessment of their temperature is, however, often performed indirectly by modelling their temperature-dependent dielectric response. Direct measurements of the optical properties of metallic nanoparticles in equilibrium with a thermodynamic bath provide a calibration of their thermo-optical response, to be exploited for refining current thermoplasmonic models or whenever direct temperature assessments are practically unfeasible.

Electronic properties of single-layer tungsten disulfide on epitaxial graphene on silicon carbide.

This work reports an electronic and micro-structural study of an appealing system for optoelectronics: tungsten disulfide (WS) on epitaxial graphene (EG) on SiC(0001). The WS is grown via chemical vapor deposition (CVD) onto the EG. Low-energy electron diffraction (LEED) measurements assign the zero-degree orientation as the preferential azimuthal alignment for WS/EG.

Photochromic Polyurethanes Showing a Strong Change of Transparency and Refractive Index.

Photochromic polymers have been studied as rewritable systems for optical elements with tunable transparency in the visible and refractive index in the NIR. Six diarylethene monomers have been synthesized to give thin films of photochromic polyurethanes. The absorption properties of the monomers in solution and of the corresponding polymeric films have been evaluated showing that a transparency contrast in the visible spectrum of the order of 10 3 can be obtained by a suitable choice of the chemical structure and illumination wavelength.

Morphological modulation of graphene-mediated hybridization in plasmonic systems.

We investigated the plasmonic response of a 2-dimensional ordered array of closely spaced (few-nm apart) Au nanoparticles covered by a large-area single-layer graphene sheet. The array consisted of coherently aligned nanoparticle chains, endowed with a characteristic uniaxial anisotropy. The joint effect of such a morphology and of the very small particle size and spacing led to a corresponding uniaxial wrinkling of graphene in the absence of detectable strain.

Investigating organic multilayers by spectroscopic ellipsometry: specific and non-specific interactions of polyhistidine with NTA self-assembled monolayers.

Background: A versatile strategy for protein-surface coupling in biochips exploits the affinity for polyhistidine of the nitrilotriacetic acid (NTA) group loaded with Ni(II). Methods based on optical reflectivity measurements such as spectroscopic ellipsometry (SE) allow for label-free, non-invasive monitoring of molecule adsorption/desorption at surfaces.

Results: This paper describes a SE study about the interaction of hexahistidine (His6) on gold substrates functionalized with a thiolate self-assembled monolayer bearing the NTA end group.

Plasmonic Color-Graded Nanosystems with Achromatic Subwavelength Architectures for Light Filtering and Advanced SERS Detection.

Plasmonic color-graded systems are devices featuring a spatially variable plasmonic response over their surface. They are widely used as nanoscale color filters; their typical size is small enough to allow integration with miniaturized electronic circuits, paving the way to realize novel nanophotonic devices. Currently, most plasmonic color-graded systems are intrinsically discrete because their chromatic response exploits the tailored plasmon resonance of microarchitectures characterized by different size or geometry for each target color.

Spectroscopic ellipsometry meets AFM nanolithography: about hydration of bio-inert oligo(ethylene glycol)-terminated self assembled monolayers on gold.

For the first time, to our knowledge, spectroscopic ellipsometry (SE) has been combined with state-of-the-art AFM differential height measurements conducted after shaving nano-lithography of ultrathin, soft-matter films for thickness determination. We investigated self-assembled monolayers of SH-(CH2)11-EGn-OH molecules on gold, where EG is ethylene glycol units and n = 3 and 6, a prototypical non-fouling system. We performed SE measurements (245-1200 nm) focusing on the changes induced by the formation of the film (difference spectra).

Pushing the high-energy limit of plasmonics.

The localized surface plasmon resonance of metal nanoparticles allows confining the eletromagnetic field in nanosized volumes, creating high-field "hot spots", most useful for enhanced nonlinear optical spectroscopies. The commonly employed metals, Au and Ag, yield plasmon resonances only spanning the visible/near-infrared range. Stretching upward, the useful energy range of plasmonics requires exploiting different materials.

Spectroscopic ellipsometry of self assembled monolayers: interface effects. The case of phenyl selenide SAMs on gold.

This work focuses on the quantitative application of spectroscopic ellipsometry to the study of optical properties and thickness of self assembled monolayers (SAMs) of phenyl selenide deposited from the liquid phase on gold. STM, XPS and cyclic voltammetry measurements provide additional chemical and morphological characterization of the SAMs. While routine ellipsometry analysis of SAMs often relies on the film-induced δΔ change in the Δ ellipsometric angle and discards SAM-substrate interface effects, the present data show a distinctive behaviour of the δΨ data that we assign to interface effects, stronger than those previously found for densely packed alkanethiol SAMs.