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The morphology of numerous nanocolumnar thin films deposited by the magnetron sputtering technique at oblique geometries and at relatively low temperatures has been analyzed for materials as different as Au, Pt, Ti, Cr, TiO, Al, HfN, Mo, V, WO and W. Despite similar deposition conditions, two characteristic nanostructures have been identified depending on the material: a first one defined by highly tilted and symmetric nanocolumnar structures with a relatively high film density, and a second one characterized by rather vertical and asymmetric nanocolumns, with a much lower film density. With the help of a model, the two characteristic nanostructures have been linked to different growth dynamics and, specifically, to different surface relaxation mechanisms upon the incorporation of gaseous species with kinetic energies above the surface binding energy. Moreover, in the case of Ti, a smooth structural transition between the two types of growths has been found when varying the value of the power used to maintain the plasma discharge. Based on these results, the existence of different surface relaxation mechanisms is proposed, which quantitatively explains numerous experimental results under the same conceptual framework.

Near infrared laser ablation of metals, specifically aluminum, has been systematically applied to generate surface roughness. Very high laser fluences may even lead to a so called “explosive” ablation regime where roughness becomes dramatically enhanced. In the present work we have developed an alternative methodology that, utilizing milder laser irradiation conditions (i.e. laser fluences from 0.37 to 0.72 J/cm2), renders aluminum surfaces with a dual-scale roughness character and Sp parameter values twice or even trice the value found in reference samples. This has been possible for aluminum substrates coated with a highly transparent aluminum oxynitride capping layer. The resulting surfaces, consisting of very rough partially oxidized aluminum with negligible amounts of nitrogen species, resulted highly hydrophobic and depicted long icing delay times as required for anti-icing applications. A correlation has been found between the wetting and anti-icing behaviors, the use of a capping layer and the laser irradiation conditions. To account for this exalted roughening phenomenon, we propose that the transparent capping layer confines the laser energy within the aluminum shallow zones, delays the formation of the plasma plume and produces an enhancement in the aluminum ablation, even at relatively low laser fluences.

Icing has become a hot topic both in academia and in the industry given its implications in transport, wind turbines, photovoltaics, and telecommunications. Recently proposed de-icing solutions involving the propagation of acoustic waves (AWs) at suitable substrates may open the path for a sustainable alternative to standard de-icing or anti-icing procedures. Herein, the fundamental interactions are unraveled that contribute to the de-icing and/or hinder the icing on AW-activated substrates. The response toward icing of a reliable model system consisting of a piezoelectric plate activated by extended electrodes is characterized at a laboratory scale and in an icing wind tunnel under realistic conditions. Experiments show that surface modification with anti-icing functionalities provides a synergistic response when activated with AWs. A thoughtful analysis of the resonance frequency dependence on experimental variables such as temperature, ice formation, or wind velocity demonstrates the application of AW devices for real-time monitoring of icing processes.

The low temperature formation of monoclinic VO2crystal domains in nanocolumnar vanadium/oxygen thin films prepared by magnetron sputtering at oblique angles is analyzed. The synthesis procedure involved the deposition of amorphous nanocolumnar VO1.9thin films at room temperature and its subsequent annealing at temperatures between 250 °C and 330 °C in an oxygen atmosphere. The thermochromic transition of these films was found at a temperature of 47 °C when the annealing temperature was 270 °C and 58 °C when the annealing temperature was 280 °C and 290 °C, presenting a clear drop of the optical transmittance in the infrared region of the spectrum. The significant downshift in the temperature window to obtain VO2in comparison with compact films and other strategies in literature is explained by the particular morphology of the nanocolumnar structures, which contains numerous defects along with open and embedded porosity.

The morphology and void connectivity of thin films grown by a magnetron sputtering deposition technique at oblique geometries were studied in this paper. A well-tested thin film growth model was employed to assess the features of these layers along with experimental data taken from the literature. A strong variation in the film morphology and pore topology was found as a function of the growth conditions, which have been linked to the different collisional transport of sputtered species in the plasma gas. Four different characteristic film morphologies were identified, such as (i) highly dense and compact, (ii) compact with large, tilted mesopores, (iii) nanocolumns separated by large mesopores, and (iv) vertically aligned sponge-like coalescent nanostructures. Attending to the topology and connectivity of the voids in the film, the nanocolumnar morphology was shown to present a high pore volume and area connected with the outside by means of mesopores, with a diameter above 2 nm, while the sponge-like nanostructure presented a high pore volume and area, as well as a dense network connectivity by means of micropores, with a diameter below 2 nm. The obtained results describe the different features of the porous network in these films and explain the different performances as gas or liquid sensors in electrochromic applications or for infiltration with nanoparticles or large molecules.

La técnica de pulverización catódica operada en geometría de ángulo oblicuo es bien conocida por permitir el crecimiento de películas delgadas nanocolumnares sobre sustratos planos. En otro tipo de sustratos, e.g. rugosos o litografiados, la casuística es variada, apareciendo estructuras complejas y diversas, incluso para espesores del orden de la micra. Estos resultados sugieren la existencia de una fuerte conexión entre el crecimiento de la película y la topografía del sustrato, que podría utilizarse para obtener un mayor control nanoestructural. En esta presentación se analiza teórica y experimentalmente la relación entre ambos aspectos al utilizar la técnica de pulverización catódica a ángulo oblicuo. Se demuestra la posibilidad de crecer estructuras singulares como, por ejemplo, cruces nanopilares o incluso de huecos dentro de una matriz compacta, ordenados de acuerdo a un patrón regular con distancias típicas del orden de cientos de nanómetros (ver Figura 1). Se describe, por lo tanto, el marco conceptual que permitiría que las técnicas actuales de litografía superficial se puedan utilizar como técnicas efectivas de control nanoestructural de películas delgadas. Como resultado, se demuestran varios principios que definen los diferentes estadios de la deposición que servirían como guías para el diseño inteligente del sustrato e inducir crecimientos a la carta. Estos principios se han validado experimentalmente al crecer diferentes películas delgadas sobre un total de 16 sustratos litografiados con diferentes topografías, patrones y escalas típicas por debajo de la micra, así como en otros sustratos con rugosidad intrínseca sometidos a diferentes tipos de pulido.

En un estudio preliminar [1] se determinó que los recubrimientos de Ti nanocolumnares depositados mediante pulverización catódica en ángulo oblicuo en condiciones de laboratorio [2] presentan propiedades antibacterianas mientras que mantienen la biocompatibilidad característica de este material. En este trabajo se desarrolla un nuevo enfoque y geometría para recubrir con nanocolumnas de Ti placas óseas con áreas de hasta 15 cm2, por sus dos lados de forma simultánea [3]. Estas placas se utilizan comúnmente para inmovilizar segmentos óseos, por lo que son adecuadas para su uso en el desarrollo de aplicaciones biomédicas. Para desarrollar esta nueva geometría de trabajo se ha procedido de la siguiente manera: en primer lugar, se han analizado las condiciones fundamentales que conducen a la formación de las estructuras nanocolumnares en un reactor de laboratorio, en particular, la energía y la distribución angular de las partículas pulverizadas expulsadas del blanco del magnetrón. Así, en una segunda etapa y en base a estos resultados, se propone una nueva geometría para operar en ángulos oblicuos en reactores semiindustriales, que consigue reproducir las mismas distribuciones de energía y momento en escalas espaciales mayores. Para probar la viabilidad del diseño propuesto, se han recubierto de manera homogénea y simultánea los dos lados de sustratos relativamente grandes, y se ha analizado si las funcionalidades antibacterianas eran las mismas que las obtenidas en las superficies fabricadas en un reactor de laboratorio. En particular, se realizaron dos tipos de experimentos: adhesión bacteriana y formación de biopelículas, y ensayos in vitro competitivos entre osteoblastos y bacterias.

[ES] El dispositivo comprende un sustrato (2) piezoelécírico o ferroeiéctrico sobre el que se deposita hielo; unos electrodos (3), conectados al sustrato (2); un analizador de red vectorial (7), conectado a ios electrodos (3), y configurado para determinar la frecuencia de resonancia del sustrato (2); y un módulo de excitación que integra un generador de funciones (6) que comunica con el analizador de red vectorial (7) y está conectado a un amplificador (4) y este a su vez a los electrodos (3), El módulo de excitación está configurado para, mediante un interruptor automático (8), aplicar sobre los electrodos (3) una señal eléctrica AC de frecuencia coincidente con la frecuencia de resonancia medida en el analizador de red vectorial (7) y que cambia progresivamente a medida que se produce el proceso de deshielo., [EN] Disclosed is a device comprising: a piezoelectric or ferroelectric substrate (2) on which ice is deposited; electrodes (3), connected to the substrate (2); a vector network analyser (7), connected to the electrodes (3) and configured to determine the resonant frequency of the substrate (2); and an excitation module including a function generator (6) that communicates with the vector network analyser (7) and is connected to an amplifier (4), the amplifier being connected to the electrodes (3). The excitation module is configured to apply to the electrodes (3), by means of an automatic switch (8), an AC electrical signal having a frequency coinciding with the resonant frequency measured in the vector network analyser (7) and which changes gradually as the ice melts., [FR] Le dispositif comprend un substrat (2) piézoélectrique ou ferroélectrique sur lequel est déposée la glace ; des électrodes (3), reliées au substrat (2) ; un analyseur de réseau vectoriel (7), relié aux électrodes (3), et conçu pour déterminer la fréquence de résonance du substrat (2) ; et un module d'excitation qui intègre un générateur de fonctions (6) qui communique avec l'analyseur de réseau vectoriel (7) et est relié à un amplificateur (4) et ce dernier est à son tour relié aux électrodes (3). Le module d'excitation est conçu, par l'intermédiaire d'un interrupteur automatique (8), pour appliquer sur les électrodes (3) un signal électrique c.a. de fréquence correspondant avec la fréquence de résonance mesurée dans l'analyseur de réseau vectoriel (7) et qui change progressivement à mesure que se produit le processus de dégel.

We demonstrate the existence of stoichiometric variations at the nanoscale when growing nanocolumnar SiO thin films by reactive magnetron sputtering deposition at oblique angles. Results show stoichiometric variations in the range 0.3 < x < 1.3 when growing a SiO thin film. This agrees with results from a numerical growth model that obtains a shift of the stoichiometry in all nanocolumns from lower values at the side facing the Si target to higher values at the opposite side. The different momentum distribution of the gaseous reactive and sputtered species results in preferential incorporation of the latter at a particular side of the nanocolumns. The general occurrence of this mechanism during the reactive magnetron sputtering deposition of substoichiometric thin films at oblique angles is discussed.

It is demonstrated that, besides classical nanocolumnar arrays, the oblique angle geometry induces the growth of singular structures in the nanoscale when using wisely designed patterned substrates. Well-ordered array of crosses, cylindrical nanorods or hole structures arranged in square or hexagonal regular geometries are reported as examples, among others. The fundamental framework connecting substrate topography and film growth at oblique angles is presented, allowing the use of substrate patterning as a feasible thin film nanostructuring technique. A systematic analysis of the growth of TiO2 thin films on 4 different lithographic patterned substrates in 4 different scale lengths is also presented. A first conclusion is the existence of a height-based selective growth in the initial stages of the deposition, by which the film preferentially develops on top of the tallest substrate features. This behavior is maintained until the film reaches a critical thickness, the so-called Oblivion Thickness, above which the film topography becomes gradually independent of the substrate features. A general formula relating the spatial features of the pattern, the coarsening exponent and the Oblivion Thickness has been deduced.

Stainless steel (SS), widely used because of its outstanding corrosion protection properties, does not possess any particular anti-stain or anti-bacterial activity as required for household and sanitary applications. This work reports the fabrication of SS thin films that, keeping a similar corrosion resistance than the bulk material, presents hydrophobicity and anti-bacterial activity. These thin films are prepared at ambient temperature by physical vapor deposition (PVD), either electron beam evaporation (EBE) or magnetron sputtering (MS), at oblique angles (OAD). According to their scanning electron microcopy and atomic force microscopy analysis, the microstructure of the OAD-SS thin films consisted of tilted and separated nanocolumns defining a surface topology that, characterized by a high percentage of void space, varied with the deposition conditions and procedure, either EBE or MS. It has been shown that particularly the nanocolumnar MS-OAD thin films preserved and even improved the high corrosion resistance of compact SS, as determined by electrochemical analysis. Besides, all OAD-SS thin films depict hydrophobicity and a high antibacterial activity. These features, particularly remarkable for the MS-OAD thin films, have been related with their tip-like termination at the surface and the existence of large void spaces separating the nanocolumns. This topology appears to affect negatively the bacteria’s deployment onto the surface and therefore the survival rate. Differences in the corrosion and antibacterial performance between EBE and MS-OAD thin films have been related with the specificities of these two PVD methods of thin film preparation. A relatively high abrasion resistance, as determined by abrasion tests, supports the use of MS-OAD thin films for the protection of commodity materials.

Until recently, superhydrophobicity was considered as a hint to predict surface icephobicity, an association of concepts that is by no means universal and that has been proven to depend on different experimental factors and material properties, including the actual morphology and chemical state of surfaces. This work presents a systematic study of the wetting and freezing properties of aluminum Al6061, a common material widely used in aviation, after being subjected to nanosecond pulsed IR laser treatments to modify its surface roughness and morphology. All treated samples, independent of their surface finishing state, presented initially an unstable hydrophilic wetting behavior that naturally evolved with time to reach hydrophobicity or even superhydrophobicity. To stabilize the surface state and to bestow the samples with a permanent and stable hydrophobic character, laser-treated surfaces were covered with a thin layer of CFx prepared by plasma-enhanced chemical vapor deposition. A systematic comparison between freezing delay (FD) and wetting properties of water droplets onto these plasma-/polymer-modified laser-treated surfaces that, under conditions where a heterogeneous nucleation mechanism prevails, surface morphology rather than the actual value of the surface roughness parameter the key feature for long FD times. In particular, it is found that surface morphologies rendering a Cassie–Baxter wetting regime longer FDs than those characterized by a Wenzel-like wetting state. It is that laser treatment, with or without additional coverage with thin CFx coatings, affects wetting and ice formation behaviors and might be an efficient procedure to mitigate icing problems on metal surfaces.

A checklist of lichens and lichenicolous fungi of Sierra Nevada (Granada, southeast Spain) is presented, fruit of the collecting field trip carried out by the Spanish Lichen Society (SEL), complemented with literature references. The authors identified 194 taxa (171 lichens and 23 lichenicolous fungi). As a result of these identifications, 46 lichens and nine lichenicolous fungi are reported for the first time in Sierra Nevada. To date, the catalogue includes 551 taxa (528 lichens and 23 lichenicolous fungi). We confirm both the scarce presence of terricolous lichens in the cryoromediterranean belt and the absence of alpine belt terricolous lichens., Se presenta el catalogo de líquenes y hongos liquenícolas de Sierra Nevada (Granada, Sureste de España), fruto la prospección llevada a cabo por la Sociedad Española de Liquenología (SEL), complementada por la recopilación bibliográfica. Los autores identificaron un total de 194 taxones (171 líquenes y 23 hongos liquenícolas). Como resultado de esas identificaciones, se han encontrado 46 líquenes y 9 hongos liquenícolas que son nuevas citas para Sierra Nevada. Hasta la fecha, el catálogo incluye 551 taxones (528 líquenes y 23 hongos liquenícolas). Se confirma tanto la escasa presencia de líquenes terrícolas en el piso crioromediterráneo como la ausencia de líquenes terrícolas del piso alpino.

A pulsed laser ablation backwriting technique with high repetitive rates is implemented for the fabrication of silver coatings on glass surfaces. This method enables geometrical constraint-free deposition of metallic coatings. These exhibit sufficiently low electrical resistance to be used as electrodes in dielectric barrier discharge (DBD) plasma elements. Ambient air deposition of metallic silver electrodes on standard glass slides is explored using a sub-ns UV laser source, combined with hybrid beam scanning methods. The green nature of the overall deposition process includes a preliminary irradiation scan to homogenise the target surface before the subsequent backwriting step. Metal transfer is achieved by combining two phenomena within a simple beam scanning process: LIRT (laserinduced reverse transfer) of silver from the target to the glass, with a partial and secondary LIFT (Laser-Induced Forward Transfer) of silver from the glass to the target. Appropriate selection of pulse energy and pulse repetition rates, beam scanning velocities and target motion enable the growth of sufficiently thick Ag deposits on glass with the required low electrical resistivity and nearly 2D constraint-free geometry. This method avoids the use of vacuum and liquids, resulting in a cheap, facile and green methodology for the deposition of silver electrodes onto transparent substrate surfaces.

Nanostructuration and 2D patterning of thin films are common strategies to fabricate biomimetic surfaces and components for microfluidic, microelectronic or photonic applications. This work presents the fundamentals of a surface nanotechnology procedure for laterally tailoring the nanostructure and crystalline structure of thin films that are plasma deposited onto acoustically excited piezoelectric substrates. Using magnetron sputtering as plasma technique and TiO2 as case example, it is demonstrated that the deposited films depict a sub-millimetre 2D pattern that, characterized by large lateral differences in nanostructure, density (up to 50%), thickness, and physical properties between porous and dense zones, reproduces the wave features distribution of the generated acoustic waves (AW). Simulation modelling of the AW propagation and deposition experiments carried out without plasma and under alternative experimental conditions reveal that patterning is not driven by the collision of ad-species with mechanically excited lattice atoms of the substrate, but emerges from their interaction with plasma sheath ions locally accelerated by the AW-induced electrical polarization field developed at the substrate surface and growing film. The possibilities of the AW activation as a general approach for the tailored control of nanostructure, pattern size, and properties of thin films are demonstrated through the systematic variation of deposition conditions and the adjustment of AW operating parameters.

Identification of hydrocarbons and crude oils is typically carried out with samples that, taken from natural sources or refineries, must be brought to the laboratory for their analysis with rather sophisticated instruments. Alternatively, “in situ” procedures have been also developed for this purpose. In this work, we propose the use of a series of several sensor systems based on photonic transducers in the form of chips for the identification and classification of crude oils and hydrocarbons through the determination of their refractive index in the visible and absorption in the near infrared regions of the electromagnetic spectrum. Two of the photonic transducers rely on modifications of a Bragg microcavity and they monitor the changes in visible light interference phenomena that occur in response to the variation of the refractive index of oils. The third one, in the form of a dielectric mirror, monitors the near infrared absorption of crude oils and hydrocarbons through the recording of a transflectance spectrum. The capacity of these transducers for crude oil identification is proved by the analysis of a series of oils and distilled fractions that have been properly identified and classified as a function of their density and partition of long hydrocarbon chains. The three photonic transducers are operated with optical fibers and can be used in static and dynamic modes, this latter under conditions that are especially well-suited for “insitu” analysis of oil streams in real facilities. The proved resistance of the chips to high pressure and temperature conditions supports their suitability to withstand harsh working environments as those existing in extraction wells.

Infusion of low surface tension liquids in nanostructured surfaces is currently used to promote an anti-icing response, although the long term stability of these systems is often jeopardized by losses of the infused liquid. In this work, we propose an alternative to the infusion procedure to induce a more effective and long lasting anti-icing capacity. The method consists of a combination of surface nanostructuration with the chemical grafting of fluorocarbon molecules. Al6061 substrates have been subjected to laser roughening and further modified with a nanostructured AlO thin film to achieve a dual roughness and porous surface state. These surfaces have been subjected to a grafting treatment with perfluorooctyltriethoxysilane (PFOTES) vapor or, for comparative purposes, infused with a low surface tension liquid. A comparative analysis of the wetting, water condensation and anti-icing properties of these two systems showed an outstandingly better performance for the grafted surfaces with respect to the infused ones. Grafted surfaces were markedly superhydrophobic and required higher water vapor pressures to induce condensation. When looking for their anti-icing capacity, they presented quite long freezing delay times for supercooled water droplets (i.e. almost four hours) and exhibited a notably low ice accretion in a wind tunnel test. The high aging resistance and durability of these grafted surfaces and the reproducibility of the results obtained when subjected to successive ice accretion cycles show that molecular grafting is an efficient anti-icing methodology that, in aggressive media, may outperform the classical infusion procedures. The role of the fluorocarbon chains anchored on the surface in inducing an anti-icing functionality is discussed.

Addressing the problem of infection from the very first stage, i.e. inhibiting the formation of the bacterial biofilm, is a crucial step to prevent implant rejection. Nanocolumnar coatings exhibiting antibacterial properties have been fabricated by oblique deposition with magnetron sputtering [1]. The formation of nanocolumns (Fig.1) is the result of the effects of atomic shadowing when the atoms reach the surface along an inclined direction [2]. This technique is environmentally friendly: it is carried out at RT and does not involve chemical products (no recycling problems). Such methodology have been tested in a semiindustrial scale reactor, successfully coating in a single step the two sides of fixation plates for bone fractures [3]. Several in vitro experiments have been performed: analysis of bacterial adhesion and biofilm formation, analysis of osteoblast proliferation and mitochondrial activity, and osteoblasts–bacteria competitive growth scenarios, the latter also named “Race for the Surface” competition. In all these cases, the coatings show an opposite behavior toward osteoblast and bacterial proliferation [1,3]. Moreover, they are effective against Gram positive (S. aureus) and Gram negative (E. coli) bacteria [4]. Finally, when a synergic route is followed and the coatings are functionalized with Te nanorods, the antibacterial properties are enhanced, since Te adds contact-killing (Fig. 2), i.e. bactericidal effect, whilst the biocompatibility is preserved [4].

The nano-porosity embedded into the tilted and separated nanocolumns characteristic of the microstructure of evaporated thin films at oblique angles has been critically assessed by various variants of the positron annihilation spectroscopy. This technique represents a powerful tool for the analysis of porosity, defects and internal interfaces of materials, and has been applied to different as-deposited SiO and TiO thin films as well as SiO/TiO multilayers prepared by electron beam evaporation at 70° and 85° zenithal angles. It is shown that, under same deposition conditions, the concentration of internal nano-pores in SiO is higher than in TiO nanocolumns, while the situation is closer to this latter in TiO/SiO multilayers. These features have been compared with the predictions of a Monte Carlo simulation of the film growth and explained by considering the influence of the chemical composition on the growth mechanism and, ultimately, on the structure of the films.

Ceramic tiles are widely used as construction materials because of their outstanding mechanical properties (high strength, hardness, toughness and abrasion resistance), chemical inertness and aesthetic appearance. Concomitantly, a variety of new functionalities have been demonstrated during recent years, by developing appropriate frit and glaze compositions. Laser processing has been intensively utilized to improve surface characteristics, either applying ablative laser regimes or intense mid-IR emission beams that enable high temperature surface melting. In this context, in addition to the numerous thermal annealing procedures reported in the literature and applied to industry to modify the surface properties of ceramics, a novel Laser Furnace (LF) method has been recently patented. It enables modifying the surface finish of solids by inducing high temperature (1500-3000 °C) reactions at surfaces and interfaces, while maintaining volume temperatures at relatively low values (i.e. below 1200 °C). This paper deals with the application of this laser technology to the coloring of ceramic tiles previously deposited with either metal and oxide precursor thin films, or, alternatively with noble metal-organic layers. These layer/tile systems have been treated both, with nIR ns pulsed lasers and by cw CO2 lasers with emission in the mid-IR. The latter were coupled into a roller furnace to induce chemical processes which result in a variety of coloring effects.

Herein, we present the development of supported organic nanofabrics formed by a conformal polymer-like interconnection of small-molecule organic nanowires and nanotrees. These organic nanostructures are fabricated by a combination of vacuum and plasma-assisted deposition techniques to generate step by step, single-crystalline organic nanowires forming one-dimensional building blocks, organic nanotrees applied as three-dimensional templates, and the polymer-like shell that produces the final fabric. The complete procedure is carried out at low temperatures and is compatible with an ample variety of substrates (polymers, metal, ceramics; either planar or in the form of meshes) yielding flexible and low solid-fraction three-dimensional nanostructures. The systematic investigation of this progressively complex organic nanomaterial delivers key clues relating their wetting, nonwetting, and anti-icing properties with their specific morphology and outer surface composition. Water contact angles higher than 150° are attainable as a function of the nanofabric shell thickness with outstanding freezing-delay times (FDT) longer than 2 h at −5 °C. The role of the extremely low roughness of the shell surface is settled as a critical feature for such an achievement. In addition, the characteristic interconnected microstructure of the nanofabrics is demonstrated as ideal for the fabrication of slippery liquid-infused porous surfaces (SLIPS). We present the straightforward deposition of the nanofabric on laser patterns and the knowledge of how this approach provides SLIPS with FDTs longer than 5 h at −5 °C and 1 h at −15 °C.

Unlike topography patterning, widely used for numerous applications and produced by means of different technologies, there are no simple procedures to achieve surface compositional patterning at nanometric scales. In this work we have developed a simple method for 2D patterning the composition of thin films. The method relies on the magnetron sputtering deposition at oblique angles onto patterned substrates made by laser induced periodic surface structures (LIPSS). The method feasibility has been demonstrated by depositing SiOx thin films onto LIPSS structures generated in Cr layers. A heterogeneous and aligned distribution of O/Si ratios (and different Sin+ chemical states) along the LIPSS structure in length scales of some hundreds nm's has been proven by angle resolved X-ray photoelectron spectroscopy and a patterned arrangement of composition monitored by atomic force microscopy-Raman analysis. The obtained results are explained by the predictions of a Monte Carlo simulation of this deposition process and open the way for the tailored one-step fabrication of surface devices with patterned compositions.

We experimentally analyze different growth regimes of Ti thin films associated to the existence of kinetic energy-induced relaxation mechanisms in the material's network when operating at oblique geometries. For this purpose, we have deposited different films by evaporation and magnetron sputtering under similar geometrical arrangements and at low temperatures. With the help of a well-established growth model we have found three different growth regimes: (i) low energy deposition, exemplified by the evaporation technique, carried out by species with typical energies in the thermal range, where the morphology and density of the film can be explained by solely considering surface shadowing processes, (ii) magnetron sputtering under weak plasma conditions, where the film growth is mediated by surface shadowing mechanisms and kinetic-energy-induced relaxation processes, and (iii) magnetron sputtering under intense plasma conditions, where the film growth is highly influenced by the plasma, and whose morphology is defined by nanocolumns with similar tilt than evaporated films, but with much higher density. The existence of these three regimes explains the variety of morphologies of nanocolumnar Ti thin films grown at oblique angles under similar conditions in the literature.

Based on an already tested laboratory procedure, a new magnetron sputtering methodology to simultaneously coat two-sides of large area implants (up to ~15 cm2) with Ti nanocolumns in industrial reactors has been developed. By analyzing the required growth conditions in a laboratory setup, a new geometry and methodology have been proposed and tested in a semi-industrial scale reactor. A bone plate (DePuy Synthes) and a pseudo-rectangular bone plate extracted from a patient were coated following the new methodology, obtaining that their osteoblast proliferation efficiency and antibacterial functionality were equivalent to the coatings grown in the laboratory reactor on small areas. In particular, two kinds of experiments were performed: Analysis of bacterial adhesion and biofilm formation, and osteoblasts–bacteria competitive in vitro growth scenarios. In all these cases, the coatings show an opposite behavior toward osteoblast and bacterial proliferation, demonstrating that the proposed methodology represents a valid approach for industrial production and practical application of nanostructured titanium coatings.

Traditionally porous silicon based photonic structures have been prepared by electrochemically etching of silicon. In this work, porous multilayers of nanocolumnar SiOx and SiO2 thin films acting as near infrared (NIR) 1D-photonic nanostructures are prepared by magnetron sputtering deposition at oblique angles (MS-OA). Simultaneous control of porosity and stoichiometry of the stacked films is achieved by adjusting the deposition angle and oxygen partial pressure according to a parametric formula. This new methodologoy is proved for the synthesis of SiOx thin films with x close to 0.4, 0.8, 1.2, 1.6 and nanostructures varying from compact (at 0° deposition angle) to highly porous and nanocolumnar (at 70° and 85° deposition angles). The strict control of composition, structure and nanostructure provided by this technique permits a fine tuning of the absorption edge and refraction index at 1500 nm of the porous films and their manufacturing in the form of SiOx-SiO2 porous multilayers acting as near infrared (NIR) 1D-photonic structures with well-defined optofluidic responses. Liquid tunable NIR Bragg mirrors and Bragg microcavities for liquid sensing applications are presented as proof of concept of the possibilities of this MS-OA manufacturing method as an alternative to the conventional electrochemical fabrication of silicon based photonic structures.

This paper reports a new methodology for the coloring of glazed ceramic tiles consisting of the near infrared pulsed laser processing of copper containing oxide coatings prepared by magnetron sputtering. As a second approach, the employ for the same purpose of a novel laser furnace technique is also described. Changing the laser parameters and using the laser furnace to treat the tiles at high temperature during irradiation has resulted in a wide color palette. The optical characterization of the modified tiles by UV‐Vis spectroscopy has been complemented with their microstructural and compositional analysis by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), and Time Of Flight Secondary Ion Mass Spectrometry (TOF‐SIMS). The chemical composition of the surface was obtained by X‐ray Photoemission Spectroscopy (XPS) and its structure determined by X?ray diffraction (XRD). The chemical resistance was characterized by several tests following the norm ISO 10545‐13. Color changes have been attributed to surface microstructural and chemical transformations that have been accounted for by simple models involving different ablation, melting, diffusion, and segregation/agglomeration phenomena depending on the laser treatments employed.

The influence of one dimensional substrate patterns on the nanocolumnar growth of thin films deposited by magnetron sputtering at oblique angles is theoretically and experimentally studied. A well-established growth model has been used to study the interplay between the substrate topography and the thin film morphology. A critical thickness has been defined, below which the columnar growth is modulated by the substrate topography, while for thicknesses above, the impact of substrate features is progressively lost in two stages; first columns grown on taller features take over neighboring ones, and later the film morphology evolves independently of substrate features. These results have been experimentally tested by analyzing the nanocolumnar growth of SiO thin films on ion-induced patterned substrates.

A radial polarization converter is a super-structured optical retarder that converts a conventional linearly polarized light beam into a structured beam with radial or azimuthal polarization. We present a new type of these sophisticated optical elements, which is made of porous nanostructured sculptured single thin films or multilayers prepared by physical vapor deposition at an oblique angle. They are bestowed with an axisymmetric retardation activity (with the fast axis in a radial configuration). In particular, a Bragg microcavity multilayer that exhibits a tunable transmission peak in the visible range with a retardance of up to 0.35 rad has been fabricated using this methodology. Owing to the highly porous structure of this type of thin films and multilayers, their retardance could be switched off by liquid infiltration. These results prove the possibility of developing wavelength dependent (through multilayer optical design) and switchable (through vapor condensation or liquid infiltration within the pore structure) radial polarization converters by means of oblique angle physical vapor deposition.

This work reports about the performance of a Ni/Cu-modified screen printed electrodes (SPE/Ni/Cu), prepared by physical vapor deposition (PVD) in an oblique angle configuration (OAD), for non-enzymatic glucose sensing applications. SPE/Ni/Cu electrodes showed an excellent reversibility and a catalytic behavior for detection of glucose that were controlled by the diffusion of reactants up to the active sites at the electrode surface. The study with a flow injection analysis (FIA) setup of the main experimental variables affecting the detection process has shown that the developed electrode system had an excellent glucose sensitivity of 1.04 AM1cm2 (R2:0.999), a linear response up to 1 mM, a limit of detection of 0.33 mM and a time of analysis of ca. 30 s per sample. The selectivity of the sensor was checked against various interferences, including ascorbic acid, uric acid, acetaminophen and other sugars, in all cases with excellent results. The feasibility of using this sensor for practical applications was successfully confirmed by determining the glucose concentration in different commercial beverages.

The use of lasers to achieve transformations at interfaces, either on solids under air, controlled atmospheres or a diversity of liquid environments, is evolving at a fast pace and in-line with recent advances in photonic technologies. The singular properties of lasers, which provide a choice of emission parameters, such as emission wavelength, pulsed or cw mode and pulse width, together with the use of optomechanical means to scan in beam or line fashion, are ideal in order to trigger physico-chemical phenomena which are not available with alternative methods and are, at large, based on thermally activated processes. Recently developed methods in our Laboratories include those that are based, on the one hand, on strongly photothermal interactions; on the other, on mixed type interactions, where photothermal, photophysical and, in some cases, photochemical types may cohexist. In the former case, a solid may melt and, with the controled laser movement, directionally solidify into a material with controlled microstructure. In the latter case, an ablation process with extreme physical or chemical consequences may be triggered and be localised at the irradiated interface. A brief description of the phenomena behind laser-solid interactions will be presented, along with results obtained with the Laser Ablation Backwriting (LAB) method and applied to surface modification of glass. This has been recently developed in order to modify physico-chemical and functional properties of glass surfaces at large, based on this fully scaleable method. In particular, selective metallization of glass surfaces will be addressed in this talk.

The selective incorporation of deposition species with preferential directionality is analyzed during the growth of TiO thin films by magnetron sputtering. Using wisely-designed collimators, tilted nanocolumnar morphologies are grown in a ballistic deposition regime, i.e. when most deposition species arrive at the film surface along well-defined preferential directions, and also in a thermalized deposition regime, when these species follow an isotropic momentum distribution in the plasma gas. The obtained results suggest that the use of particle collimators may promote the growth of porous thin films even in the classical magnetron sputtering configuration, when the target and the substrate are parallel. General insights are given on this approach and, as a proof of concept, its principles applied for the synthesis of nanostructured films in a laboratory-size reactor.

In this article we show for the first time the formation of magnetic supported organic nanowires (ONWs) driven by self-assembly of a nonplanar Fe(III) phthalocyanine chloride (FePcCl) molecule. The ONWs grow by a crystallization mechanism on roughness-tailored substrates. The growth methodology consists of a vapor deposition under low vacuum and mild temperature conditions. The structure, microstructure, and chemical composition of the FePcCl NWs are thoroughly elucidated and compared with those of Fe(II) phthalocyanine NWs by a consistent and complementary combination of advanced electron microscopies and X-ray spectroscopies. In a further step, we vertically align the NWs by conformal deposition of a SiO2 shell. Such orientation is critical to analyze the magnetic properties of the FePcCl and FePc supported NWs. A ferromagnetic behavior below 30 K with an easy axis perpendicular to the phthalocyanine plane was observed in the two cases with the FePcCl nanowires presenting a wider hysteresis. These results open the path to the fabrication of nanostructured one-dimensional small-molecule spintronic devices.