Self-Organized Plasmonic Nanowire Arrays Coated with Ultrathin TiO2 Films for Photoelectrochemical Energy Storage.

The strategic field of renewable energy production and storage requires novel nanoscale platforms that can feature competitive solar energy conversion properties. Photochemical reactions that promote energy storage, such as water splitting and oxygen-hydrogen evolution reactions, play a crucial role in this context. Here, we demonstrate a novel photoelectrochemical device based on large-area (cm2) self-organized Au nanowire (NW) arrays, uniformly coated with ultrathin TiO2 films. The NW arrays act both as transparent nanoelectrodes and as a plasmonic metasurface that resonantly enhances the very weak visible photocurrent generated by a prototype photoelectrochemical oxygen evolution reaction. We demonstrate a polarization-sensitive plasmon-enhanced photocurrent that reaches a gain of about 3.8 in the visible spectral range. This highlights the potential of our novel nanopatterned plasmonic platform in photochemistry and energy storage.

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. In this work, we show a t-SPL-based method, enabling the noninvasive high-resolution nanolithography of photonic nanostructures onto optically transparent substrates across a broad-band visible and near-infrared spectral range. This was possible by intercalating an ultrathin transparent conductive oxide film between the dielectric substrate and the sacrificial patterning layer. This way, nanolithography performances comparable with those typically observed on conventional semiconductor substrates are achieved without significant changes of the optical response of the final sample. We validated this innovative nanolithography approach by engineering periodic arrays of plasmonic nanoantennas and showing the capability to tune their plasmonic response over a broad-band visible and near-infrared spectral range. The optical properties of the obtained systems make them promising candidates for the fabrication of hybrid plasmonic metasurfaces supported onto fragile low-dimensional materials, thus enabling a variety of applications in nanophotonics, sensing, and thermoplasmonics.

Highly efficient sequestration of aqueous lead on nanostructured calcite substrates.

Following defocused ion beam sputtering, large area highly corrugated and faceted nanoripples are formed on calcite (10.4) faces in a self-organized fashion. High resolution atomic force microscopy (AFM) imaging reveals that calcite ripples are defined by facets with highly kinked (11.0) and (21¯.12) terminations.In situAFM imaging during the exposure of such modified calcite surfaces to PbCl2aqueous solution reveals that the nanostructured calcite surface promotes the uptake of Pb. In addition, we observed the progressive smoothing of the highly reactive calcite facet terminations and the formation of Pb-bearing precipitates elongated in registry with the underlying nanopattern. By SEM-EDS analysis we quantified a remarkable 500% increase of the Pb uptake rate, up to 0.5 atomic weight % per hour, on the nanorippled calcite in comparison to its freshly cleaved (10.4) surfaces. These results suggest that nanostructurated calcite surfaces can be used for developing future systems for lead sequestration from polluted waters.

Broadband Photon Harvesting in Organic Photovoltaic Devices Induced by Large-Area Nanogrooved Templates.

Thin-film organic photovoltaic (OPV) devices represent an attractive alternative to conventional silicon solar cells due to their lightweight, flexibility, and low cost. However, the relatively low optical absorption of the OPV active layers still represents an open issue in view of efficient devices that cannot be addressed by adopting conventional light coupling strategies derived from thick PV absorbers. The light coupling to thin-film solar cells can be boosted by nanostructuring the device interfaces at the subwavelength scale. Here, we demonstrate broadband and omnidirectional photon harvesting in thin-film OPV devices enabled by highly ordered one-dimensional (1D) arrays of nanogrooves. Laser interference lithography, in combination with reactive ion etching (RIE), provides the controlled tailoring of the height and periodicity of the silica grooves, enabling effective tuning of the anti-reflection properties in the active organic layer (PTB7:PCBM). With this strategy, we demonstrate a strong enhancement of the optical absorption, as high as 19% with respect to a flat device, over a broadband visible and near-infrared spectrum. The OPV device supported on these optimized nanogrooved substrates yields a 14% increase in short-circuit current over the corresponding flat device, highlighting the potential of this large-scale light-harvesting strategy in the broader context of thin-film technologies.

Flat-optics hybrid MoS2/polymer films for photochemical conversion.

Novel light harvesting platforms and strategies are crucial to develop renewable photon to energy conversion technologies that overcome the current global energy and environmental challenges. Two-dimensional (2D) transition metal dichalcogenide (TMD) semiconductor layers are particularly attractive for photoconversion applications but new ultra-compact photon harvesting schemes are urgently required to mitigate their poor photon absorption properties. Here, we propose a flat-optics scheme based on nanogrooved ultra-thin MoS2 layers conformally grown onto large area (cm2 scale) nanopatterned templates. The subwavelength re-shaping of the 2D-TMD layers promotes the excitation of photonic Rayleigh anomaly (RA) modes, uniquely boosting a strong in-plane electromagnetic confinement. By tailoring the illumination conditions, we demonstrate effective tuning of the photonic anomalies over a broadband visible spectrum across the absorption band of relevant polluting dye molecules. Thanks to the strong photonic in-plane confinement, we achieve a resonant enhancement of the photodissociation rate of methylene blue (MB) molecules, well above a factor of 2. These results highlight the potential of flat-optics photon harvesting schemes for boosting photoconversion efficiency in large-scale hybrid 2D-TMD/polymer layers, with a strong impact in various applications ranging from new-generation photonics to waste water remediation and renewable energy storage.

Omnidirectional and broadband photon harvesting in self-organized Ge columnar nanovoids.

Highly porous Germanium surfaces with uniformly distributed columnar nanovoid structures are fabricated over a large area (wafer scale) by large fluence Sn+irradiation through a thin silicon nitride layer. The latter represents a one-step highly reproducible approach with no material loss to strongly increase photon harvesting into a semiconductor active layer by exploiting the moth-eye antireflection effect. The ion implantation through the nitride cap layer allows fabricating porous nanostructures with high aspect ratio, which can be tailored by varying ion fluence. By comparing the reflectivity of nanoporous Ge films with a flat reference we demonstrate a strong and omnidirectional reduction in the optical reflectivity by a factor of 96% in the selected spectral regions around 960 nm and by a factor of 67.1% averaged over the broad spectral range from 350 to 1800 nm. Such highly anti-reflective nanostructured Ge films prepared over large-areas with a self-organized maskless approach have the potential to impact real world applications aiming at energy harvesting.

Broadband and Tunable Light Harvesting in Nanorippled MoS2 Ultrathin Films.

Nanofabrication of flat optic silica gratings conformally layered with two-dimensional (2D) MoS2 is demonstrated over large area (cm2), achieving a strong amplification of the photon absorption in the active 2D layer. The anisotropic subwavelength silica gratings induce a highly ordered periodic modulation of the MoS2 layer, promoting the excitation of Guided Mode Anomalies (GMA) at the interfaces of the 2D layer. We show the capability to achieve a broadband tuning of these lattice modes from the visible (VIS) to the near-infrared (NIR) by simply tailoring the illumination conditions and/or the period of the lattice. Remarkably, we demonstrate the possibility to strongly confine resonant and nonresonant light into the 2D MoS2 layers via GMA excitation, leading to a strong absorption enhancement as high as 240% relative to a flat continuous MoS2 film. Due to their broadband and tunable photon harvesting capabilities, these large area 2D MoS2 metastructures represent an ideal scalable platform for new generation devices in nanophotonics, photo- detection and -conversion, and quantum technologies.

Ultra-broadband photon harvesting in large-area few-layer MoS2 nanostripe gratings.

Flat optics nanoarrays based on few-layer MoS2 are homogeneously fabricated over large-area (cm2) transparent templates, demonstrating effective tailoring of the photon absorption in two-dimensional (2D) transition-metal dichalcogenide (TMD) layers. The subwavelength subtractive re-shaping of the few-layer MoS2 film into a one-dimensional (1D) nanostripe array results in a pronounced photonic anomaly, tunable in a broadband spectral range by simply changing the illumination conditions (or the lattice periodicity). This scheme promotes efficient coupling of light to the 2D TMD layers via resonant interaction between the MoS2 excitons and the photonic lattice, with subsequent enhancement of absorption exceeding 400% relative to the flat layer. In parallel, an ultra-broadband absorption amplification in the whole visible spectrum is achieved, thanks to the non-resonant excitation of substrate guided modes promoted by MoS2 nanoarrays. These results highlight the potential of nanoscale re-shaped 2D TMD layers for large-area photon harvesting in layered nanophotonics, quantum technologies and new-generation photovoltaics.

Color Routing via Cross-Polarized Detuned Plasmonic Nanoantennas in Large-Area Metasurfaces.

Bidirectional nanoantennas are of key relevance for advanced functionalities to be implemented at the nanoscale and, in particular, for color routing in an ultracompact flat-optics configuration. Here we demonstrate a novel approach avoiding complex collective geometries and/or restrictive morphological parameters based on cross-polarized detuned plasmonic nanoantennas in a uniaxial (quasi-1D) bimetallic configuration. The nanofabrication of such a flat-optics system is controlled over a large area (cm2) by a novel self-organized technique exploiting ion-induced nanoscale wrinkling instability on glass templates to engineer tilted bimetallic nanostrip dimers. These nanoantennas feature broadband color routing with superior light scattering directivity figures, which are well described by numerical simulations and turn out to be competitive with the response of lithographic nanoantennas. These results demonstrate that our large-area self-organized metasurfaces can be implemented in real-world applications of flat-optics color routing from telecom photonics to optical nanosensing.

Flory-Huggins Photonic Sensors for the Optical Assessment of Molecular Diffusion Coefficients in Polymers.

The lack of cost-effective systems for the assessment of air pollutants is a concern for health and safety in urban and industrial areas. The use of polymer thin films as label-free colorimetric sensors featuring specific interactions with pollutants would then represent a paradigm shift in environmental monitoring and packaging technologies, allowing to assess air quality, formation of byproducts in closed environment, and the barrier properties of the polymers. To this end, all-polymer distributed Bragg reflectors represent a promising approach toward a reliable and cost-effective transduction of chemical stimuli and effective colorimetric label-free selective detectors. We show selectivity attained by specific interactions between the polymer and analytes. Such interactions drive the analyte intercalation through the polymer structure and its kinetics, converting it in a dynamic optical response which is at the basis of the Flory-Huggins photonic sensors. The multivariate analyses of the response kinetics also allow distinguishing binary mixtures. Additionally, we demonstrate that such optical responses can be used to esteem the diffusion coefficients of small molecules within polymer media via simple UV-vis spectroscopy retrieving data comparable to those obtained with state-of-the-art gravimetric procedures. Last, we assess the figures of merit of the sensors in terms of lower detection limit, sensitivity, and reversibility, demonstrating that such devices can pave the way to an innovative, simple, and low-cost detection method integrable to in situ assessment of barrier polymers used for the encapsulation of optoelectronic devices, food packaging, and goods storage in general.

Anisotropic MoS2 Nanosheets Grown on Self-Organized Nanopatterned Substrates.

Manipulating the anisotropy in 2D nanosheets is a promising way to tune or trigger functional properties at the nanoscale. Here, a novel approach is presented to introduce a one-directional anisotropy in MoS2 nanosheets via chemical vapor deposition (CVD) onto rippled patterns prepared on ion-sputtered SiO2 /Si substrates. The optoelectronic properties of MoS2 are dramatically affected by the rippled MoS2 morphology both at the macro- and the nanoscale. In particular, strongly anisotropic phonon modes are observed depending on the polarization orientation with respect to the ripple axis. Moreover, the rippled morphology induces localization of strain and charge doping at the nanoscale, thus causing substantial redshifts of the phonon mode frequencies and a topography-dependent modulation of the MoS2 workfunction, respectively. This study paves the way to a controllable tuning of the anisotropy via substrate pattern engineering in CVD-grown 2D nanosheets.

SERS Amplification from Self-Organized Arrays of Plasmonic Nanocrescents.

We report on the surface-enhanced Raman scattering (SERS) efficiency of self-organized arrays of Au nanocrescents confined on monolayers of polystyrene nanospheres. A dichroic SERS emission in the visible spectrum is observed due to the selective excitation of a localized surface plasmon (LSP) resonance along the "short axis" of the Au nanocrescents. Under these conditions SERS signal amplifications in the range of 10(3) have been observed with respect to a flat reference Au film. The far field and near field plasmonic response of Au nanocrescent arrays have been investigated as a function of the metal dose deposited onto the polymeric spheres. In this way, we show the possibility of simply tailoring the SERS emission by engineering the morphology of the plasmonic nanocrescents. We highlight the SERS activity of chains of satellite nanoclusters that decorate the border of each connected crescent and sustain isotropic high energy LSP resonances in the visible spectrum.

Optical properties of biaxial nanopatterned gold plasmonic nanowired grid polarizer.

Gold nanoparticles deposited on self-organized nano-ripple quartz substrates have been studied by spectroscopic Mueller matrix ellipsometry. The surface was found to have biaxial anisotropic optical properties. For electric field components normal to the ripples the periodic and disconnected nature of the in plane nanowires gives rise to an optical response dominated by the localized plasmon resonance. In the direction parallel to the ripples the gold nanoparticles are aligned closely leading to localized plasmon resonances in the infrared. As Au was deposited at an angle oblique to the surface normal, the gold nanoparticles were formed on the side of the ripples facing the incoming evaporation flux. This makes the gold particles slightly inclined, correspondingly the principal coordinate system of the biaxial dielectric tensor results tilted. The anisotropic plasmonic optical response results in a strong polarizing effect, making it suitable as a plasmonic nanowired grid polarizer.

Re-radiation enhancement in polarized surface-enhanced resonant Raman scattering of randomly oriented molecules on self-organized gold nanowires.

We explore the effect of re-radiation in surface-enhanced Raman scattering (SERS) through polarization-sensitive experiments on self-organized gold nanowires on which randomly oriented Methylene Blue molecules are adsorbed. We provide the exact laws ruling the polarized, unpolarized, and parallel- and cross-polarized SERS intensity as a function of the field polarizations. We show that SERS is polarized along the wire-to-wire nanocavity axis, independently from the excitation polarization. This proves the selective enhancement of the Raman dipole component parallel to the nanocavity at the single molecule level. Introducing a field enhancement tensor to account for the anisotropic polarization response of the nanowires, we work out a model that correctly predicts the experimental results for any excitation/detection polarization and goes beyond the E(4) approximation. We also show how polarization-sensitive SERS experiments permit one to evaluate independently the excitation and the re-radiation enhancement factors accessing the orientation-averaged non-diagonal components of the molecular Raman polarizability tensor.

Tailored second harmonic generation from self-organized metal nano-wires arrays.

Here we report the second harmonic emission properties of self-organized gold nanowires arrays supported on dielectric substrates with a sub-wavelength periodic pattern. The peculiar morphology of the nanowires, which are locally tilted with respect to the average plane of the substrate, allows to generate maximum second harmonic signal at normal incidence with a polarization direction driven by the orientation of the wires (perpendicular to the wires). The generation efficiency was increased by tailoring the growth process in order to tune the metal plasmon resonance close to the pump field frequency and also by increasing the local tilt of the nanowires.

Unexpected behavior of the surface composition of PtRh alloys during chemical reaction.

The changes in the surface composition of a Pt(50)Rh(50)(100) alloy due to an ongoing 2H(2) + O(2)-->2H(2)O chemical reaction have been studied in situ. Exploiting the high-energy resolution and surface sensitivity of synchrotron radiation core-level spectroscopy it was possible to monitor the population of the two transitions metals atoms at the gas-surface interface. Sequences of fast high-resolution core-level spectra of the Rh3d(5/2), Pt4f(7/2), and O1s core levels showed a continuous exchange of atoms between the first and subsurface layers. An unexpected Pt surface enrichement was found under slightly oxidizing conditions, opposite to what found in a highly oxidizing atmosphere.

Adatom ascending at step edges and faceting on fcc metal (110) surfaces.

Using first-principles total-energy calculations, we show that an adatom can easily climb up at monatomic-layer-high steps on several representative fcc metal (110) surfaces via a place exchange mechanism. Inclusion of such novel adatom ascending processes in kinetic Monte Carlo simulations of Al(110) homoepitaxy as a prototypical model system can lead to the existence of an intriguing faceting instability, whose dynamical evolution and kinetic nature are explored in comparison with experimental observations.

Nanocrystal formation and faceting instability in Al(110) homoepitaxy: true upward adatom diffusion at step edges and island corners.

Using atomic force microscopy and spot-profile analyzing low energy electron diffraction, we have observed the existence of a striking faceting instability in Al(110) homoepitaxy, characterized by the formation of nanocrystals with well-defined facets. These hut-shaped nanocrystals are over tenfold higher than the total film coverage, and coexist in a bimodal growth mode with much shallower and more populous surface mounds. We further use density functional theory calculations to elucidate the microscopic origin of the faceting instability, induced by surprisingly low activation barriers for adatom ascent at step edges and island corners.

The contact mechanics of fractal surfaces.

The role of surface roughness in contact mechanics is relevant to processes ranging from adhesion to friction, wear and lubrication. It also promises to have a deep impact on applied science, including coatings technology and design of microelectromechanical systems. Despite the considerable results achieved by indentation experiments, particularly in the measurement of bulk hardness on nanometre scales, the contact behaviour of realistic surfaces, showing random multiscale roughness, remains largely unknown. Here we report experimental results concerning the mechanical response of self-affine thin films indented by a micrometric flat probe. The specimens, made of cluster-assembled carbon or of sexithienyl, an organic molecular material, were chosen as prototype systems for the broad class of self-affine fractal interfaces, today including surfaces grown under non-equilibrium conditions, fractures, manufactured metal surfaces and solidified liquid fronts. We observe that a regime exists in which roughness drives the contact mechanics: in this range surface stiffness varies by a few orders of magnitude on small but significant changes of fractal parameters. As a consequence, we demonstrate that soft solid interfaces can be appreciably strengthened by reducing both fractal dimension and surface roughness. This indicates a general route for tailoring the mechanical properties of solid bodies.