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Multifunctional flexible Au electrodes based on one-dimensional (1D) arrays of plasmonic gratings are nanofabricated over large areas with an engineered variant of laser interference lithography optimized for low-cost transparent templates. Au nanostripe (NS) arrays achieve sheet resistance in the order of 20 Ohm/square on large areas (∼ cm2) and are characterized by a strong and dichroic plasmonic response which can be easily tuned across the visible (VIS) to near-infrared (NIR) spectral range by tailoring their cross-sectional morphology. Stacking vertically a second nanostripe, separated by a nanometer scale dielectric gap, we form near-field coupled Au/SiO2/Au dimers which feature hybridization of their localized plasmon resonances, strong local field-enhancements and a redshift of the resonance towards the NIR range. The possibility to combine excellent transport properties and optical transparency on the same plasmonic metasurface template is appealing in applications where low-energy photon management is mandatory like e.g., in plasmon enhanced spectroscopies or in photon harvesting for ultrathin photovoltaic devices. The remarkable lateral order of the plasmonic NS gratings provides an additional degree of freedom for tailoring the optical response of the multifunctional electrodes via the excitation of surface lattice resonances, a Fano-like coupling between the broad localised plasmonic resonances and the collective sharp Rayleigh modes.

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.

A cost effective method to tailor the optical response of large-area nanosheets of 2D materials is described. A reduced effective metalayer model is introduced to capture the key-role of the out-of-plane component of the dielectric tensor. Such a model indicates that the optical extinction of 2D materials can be strongly altered by controlling the geometry at the local (i.e., subwavelength) scale. In particular, a giant linear optical dichroism at normal incidence is demonstrated, with major features around the excitonic peaks, that can be tailored by acting on the average curvature and slope of the nanosheets. The approach is experimentally demonstrated in few-layer MoS2 grown by chemical vapor deposition on cm-scale anisotropic nanopatterned substrates prepared by a self-assembling technique, based on defocused ion beam sputtering. Major variations in the photoluminescence spectrum as a function of the average curvature and slope are also revealed. A full-vectorial numerical study beyond the effective metalayer model and comprising strain effects induced by the geometry turns out to be consistent with such a complex scenario. The results demonstrate that the extrinsic geometrical engineering definitely opens viable way to tailor the optical properties and modulate bandgap of low dimensional materials.

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 ...

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.

Substrates with engineered roughness are studied with the aim of achieving broadband and omnidirectional photon harvesting in thin film devices. Light coupling across the interfaces of a photonic device is induced by uniaxial pseudo-periodic gratings formed in a self-organised fashion via de-focused ion beam sputtering (IBS). The optical properties of the textured interfaces are assessed both experimentally and numerically using finite difference time domain (FDTD) algorithm, quantitatively demonstrating the optimal geometries which favour broadband diffuse scattering of radiation across the Vis-NIR spectral range. Thin film amorphous silicon solar cells based on the nanostructured patterns have been numerically studied via FDTD to assess absorption enhancement in comparison to flat reference devices, finding a 25% increase of short-circuit current, in good agreement with the experiment. Similar light trapping experiments performed on prototypical solar cells employing a PTB7:PC61BM organic absorber, allow to extend the general validity of the results to a relevant class of materials in the view of photovoltaic applications.

Heavy fuel oil (HFO) particulate matter (PM) emitted by marine engines is known to contain toxic heavy metals, including vanadium (V) and nickel (Ni). The toxicity of such metals will depend on the their chemical state, size distribution, and mixing state. Using online soot-particle aerosol mass spectrometry (SP-AMS), we quantified the mass of five metals (V, Ni, Fe, Na, and Ba) in HFO-PM soot particles produced by a marine diesel research engine. The in-soot metal concentrations were compared to in-PM2.5 measurements by inductively coupled plasma-optical emission spectroscopy (ICP-OES). We found that, Environmental Science & Technology, 52 (11), ISSN:0013-936X, ISSN:1520-5851

Flat-optics microfluidic sensor based on one-dimensional (1D) Au nanostrip lattices are homogeneously fabricated over large area (cm2), demonstrating a cost-effective approach able to combine scala...

Hybrid plasmonic-semiconductor assemblies are receiving considerable attention due to the possibility to achieve hot-carrier-based photodetection. In this context, 2D transition metal dichalcogenides (TMDs) coupled to metal nanostructures are very promising. However, the plasmon-to-TMD carrier injection process is extremely challenging to achieve and even to reveal in a clear-cut way. Herein, a report of multiple transient absorption ultrafast measurements, with tunable pump excitation, enabling quantitative comparison between the ultrafast behavior of metal nanostructures, TMDs, and their assembly is shown. This allows to provide the evidence of plasmon-enhanced charge injection from Au nanostripes to a rippled-shaped molybdenum disulfide (MoS2) few-layer nanosheet. Finite element method numerical simulations and modeling of the transient optical response corroborate the charge transfer mechanism, showing that the experimental data cannot be described in terms of the thermomodulational nonlinearity of gold nanostripes or by simple superposition of metal and semiconductor responses. The sample is obtained by a self-organization process on a large area; this demonstrates that plasmon-enhanced photon harvesting exploiting hot-electron injection can be achieved on a large area (approximately cm(2)) surface and provides a substantial advancement toward scalable ultrathin photodetection devices based on hot-electrons technology.

We report on the optical photomodulation properties of all-polymer planar microcavities in which the photochromic poly((4-pentyloxy-3’-methyl-4’-(6-methacryloxyhexyloxy))azobenzene) (PMA4) acts as photoresponsive cavity layer. We induce the trans-cis isomerization process of the azobenzene group by polarized 405 nm CW-laser irradiation, while the backward process is driven by unpolarized CW-laser irradiation at 442 nm. The all-optical photoisomerization process induces a remarkable in-plane anisotropic spectral shift of the cavity modes for the first and second order photonic band gaps. The spectral and intensity modulation effects for these flexible all-polymer microcavities are discussed with respect to those so far reported in literature for analogous systems.

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.

Pentacene is known to grow on isotropic silicon oxide surfaces in a substrate-induced phase with fiber textured crystallites. This growth study reports on the growth of pentacene crystallites on uniaxially oriented surfaces. Silica substrates have been treated by ion beam sputtering so that ripples with a lateral corrugation length of 38 nm and a surface roughness of 1.3 nm are formed. Pentacene thin films with a nominal thickness in the range from 20 nm up to 300 nm are deposited on top of the rippled surfaces. The films are characterized by atomic force microscopy and grazing incidence X-ray diffraction. Bi-axially oriented crystals are formed due to the grooves of the substrate surface opening up the possibility of a defined in-plane alignment of the crystals. In a first stage of thin film growth, the thin film phase (TFP) of pentacene is formed, while in the later stage the bulk crystal structure (C, Campbell phase) also appears. Due to the bi-axial alignment of the crystallites the transition from the thin film phase to the bulk crystal structure can be directly investigated. An epitaxial relationship with (1 2 0)TFP || (2 1 0)C and [−2 1 0]TFP ||[1 −2 0]C is observed which can be explained by an adaption of the herringbone layers of both crystal structures. This work reveals one possible microscopic mechanism for the transition from the metastable substrate-induced phase of pentacene to its equilibrium bulk structure.

MoS2 and generally speaking, the wide family of transition-metal dichalcogenides represents a solid nanotechnology platform on which to engineer a wealth of new and outperforming applications involving 2D materials. An even richer flexibility can be gained by extrinsically inducing an in-plane shape anisotropy of the nanosheets. Here, the synthesis of anisotropic MoS2 nanosheets is proposed as a prototypical example in this respect starting from a highly conformal chemical vapor deposition on prepatterend substrates and aiming at the more general purpose of tailoring anisotropy of 2D nanosheets by design. This is envisioned to be a suitable configuration for strain engineering as far as strain can be spatially redistributed in morphologically different regions. With a similar approach, both the optical and electronic properties of the 2D transition-metal dichalcogenides can be tailored over macroscopic sample areas in a self-organized fashion, thus paving the way for new applications in the field of optical metasurfaces, light harvesting, and catalysis.

Two-dimensional transition metal dichalcogenide (MX 2 ) are receiving lot of attention in recent years due to their excellent electronic and optical properties which make them feasible for advanced photonics applications [1]. In particular Molybdenum-Disulfide (MoS 2 ) has shown large exciton binding energy, strong spin-orbit interaction, and high carrier mobilities.

We present a self-organizedmethod based on defocused ion beamsputtering for nanostructuring glass substrates which feature antireflective and light trapping effects. By irradiating the substrate, capped with a thin gold (Au) film, a self-organized Au nanowire stencil mask is firstly created. The morphology of the mask is then transferred to the glass surface by further irradiating the substrate, finally producing high aspect ratio, uniaxial ripple-like nanostructures whose morphological parameters can be tailored by varying the ion fluence. The effect of a Ti adhesion layer, interposed between glass and Au with the role of inhibiting nanowire dewetting, has also been investigated in order to achieve an improved morphological tunability of the templates. Morphological and optical characterization have been carried out, revealing remarkable light trapping performance for the largest ion fluences. The photon harvesting capability of the nanostructured glass has been tested for different preparation conditions by fabricating thin film amorphous Si solar cells. The comparison of devices grown on textured and flat substrates reveals a relative increase of the short circuit current up to 25%. However, a detrimental impact on the electrical performance is observed with the rougher morphologies endowed with steep v-shaped grooves. We finally demonstrate that post-growth ion beam restructuring of the glass template represents a viable approach toward improved electrical performance. © 2017 by the authors.

We study the optical properties of Molybdenum Disulphide nanosheets deposited by chemical vapor deposition onto a nanopatterned substrate endowed with a uniaxial corrugation. The uniaxial nanocorrugation leads to a polarization dependence in steady state and an anisotropic relaxation around the C resonance. Finite element numerical simulations allow to better disclose the scenario. Our findings point towards new possibilities for the manipulation of the optical properties of two-dimensional transition metal dichalcogenides via substrate nanopatterning.

In this paper, light absorption enhancement in thin film solar cell (SC) is reported and analyzed. The suggested design is based on a nanostructured pattern that increases the diffuse scattered component of radiation and hence the absorption through the active layer. An ion beam sputtering (IBS) approach is used to texture large areas of the glass substrate with high aspect-ratio ripples in order to increase light scattering. Then, thin film SC supported on the textured glass is simulated and analyzed using 3D finite difference time domain (FDTD) method. The suggested SC can offer an ultimate efficiency of 19.26% with short circuit current of 15.76 mA/cm2 with an enhancement of 31.435% over the SC without texturing surface.

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.

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 MoS

We investigate the scattering properties of novel kinds of nano-textured substrates, fabricated in a self-organized fashion by defocused ion beam sputtering. These substrates provide strong and broadband scattering of light and can be useful for applications in thin-film solar cells. In particular, we characterize the transmitted light in terms of haze and angle-resolved scattering, and we compare our results with those obtained for the commonly employed Asahi-U texture. The results indicate that the novel substrate has better scattering properties compared to reference Asahi-U substrates. We observe super-Lambertian light scattering behavior in selected spectral and angular regions due to the peculiar morphology of the nano-textured interface, which combines high aspect ratio pseudo random structures with a one-dimensional periodic pattern. The enhancement of light absorption observed in a prototype thin film semiconductor absorber grown on nano-textured glass with respect to an Asahi-U substrate further confirms the superior light trapping properties of the novel substrate.

We have investigated the growth and stability of molecular ultra-thin films, consisting of rod-like semiconducting para-hexaphenyl (6P) molecules vapor deposited on ion beam modified TiO2(110) surfaces. The ion bombarded TiO2(110) surfaces served as growth templates exhibiting nm-scale anisotropic ripple patterns with controllable parameters, like ripple depth and length. In turn, by varying the ripple depth one can tailor the average local slope angle and the local step density/terrace width of the stepped surface. Here, we distinguish three types of substrates: shallow, medium, and deep rippled surfaces. On these substrates, 6P sub-monolayer deposition was carried out in ultra-high vacuum by organic molecular beam evaporation (OMBE) at room temperature leading to the formation of islands consisting of upright standing 6P molecules, which could be imaged by scanning electron microscopy and atomic force microscopy (AFM). It has been found that the local slope and terrace width of the TiO2 template strongly influences the stability of OMBE deposited 6P islands formed on the differently rippled substrates. This effect is demonstrated by means of tapping mode AFM, where an oscillating tip was used as a probe for testing the stability of the organic structures. We conclude that by increasing the local slope of the TiO2(110) surface the bonding strength between the nearest neighbor standing molecules is weakened due to the presence of vertical displacement in the molecular layer in correspondence to the TiO2 atomic step height.

Here we report on the potentiality of the self-organised nanopatterning in view of broadband photon harvesting in thin film amorphous silicon (a-Si) solar cells. Self-organised pattern formation of glass, semiconductor and TCO interfaces is achieved recurring to low-energy Ion Beam Sputtering (IBS).

Self-organized nanowire arrays are confined by glancing-angle Au deposition on nanopatterned glass templates prepared by ion beam sputtering. The semi-transparent 1D nanowire arrays are extended over large cm2 areas and are endowed with excellent electrical conductivity competitive with the best transparent conductive oxides (sheet resistance in the range of 5-20 Ohm sq-1). In addition, the nanowires support localized surface plasmon (LSP) resonances, which are easily tunable into the visible and near infrared spectrum and are selectively excited with incident light polarized perpendicularly to the wires. Such substrates, thus, behave as multifunctional nanoelectrodes, which combine good optoelectronic performance with dichroic plasmonic excitation. The electrical percolation process of the Au nanoelectrodes was monitored in situ during growth at glancing angle, both on flat and nanopatterned glass templates. In the first case, we observed a universal scaling of the differential percolation rate, independently of the glancing deposition angle, while deviations from the universal scaling were observed when Au was confined on nanopatterned templates. In the latter case, the pronounced shadowing effect promotes the growth of locally connected 1D Au nanosticks on the 'illuminated' ripple ridges, thus, introducing strong anisotropies with respect to the case of a 2D percolating network.

We report on the formation of high aspect ratio anisotropic nanopatterns on crystalline GaAs (100) and Si (100) substrates exploiting defocused Ion Beam Sputtering assisted by a sacrificial self-organised Au stencil mask. The tailored optical properties of the substrates are characterised in terms of total reflectivity and haze by means of integrating sphere measurements as a function of the morphological modification at increasing ion fluence. Refractive index grading from sub-wavelength surface features induces polarisation dependent anti-reflection behaviour in the visible-near infrared (VIS-NIR) range, while light scattering at off-specular angles from larger structures leads to very high values of the haze functions in reflection. The results, obtained for an important class of technologically relevant materials, are appealing in view of photovoltaic and photonic applications aiming at photon harvesting in ultrathin crystalline solar cells.