Thermochromic VO2 crystalline domains have been formed in amorphous nanocolumnar VOx films by means of a low-temperature oxidation process. The oxidation of an amorphous film with [O]/[V] below 1.9 favors the formation of VO2, V3O7, and V2O5 crystalline domains in the material for temperatures as low as 260 °C, while values above 1.9 lead to the sole formation of the V2O5 phase. It is found that the absorption of oxygen also causes a relevant film volume expansion that makes pores shrink. Under some specific conditions, low-temperature oxidation causes the near disappearance of the amorphous regions, clearly improving the overall transparency and optimizing the optical and electrical modulation capabilities associated with the presence of crystalline VO2 domains. The best thermochromic performance was found when the original stoichiometry was [O]/[V] = 1.5 and the oxidation temperature was 280 °C. These conditions yield a relatively transparent coating in the visible range that presents an optical modulation in the near-infrared range of nearly 50% and a drop of electrical resistivity of more than two orders of magnitude, with a transition temperature of 50.3 °C. A tentative model based on the volume expansion experienced by the film upon oxidation is proposed, which links the structural/chemical features of the material and the formation of the crystalline domains at such relatively low temperatures.

This work addresses the fabrication of transparent glass surfaces with superior water-repellence (i.e., superhydrophobicity), and related functional properties such as omniphobicity, anti-fogging and anti-icing responses. Surfaces have been processed by means of mild femtosecond laser patterning combined with the grafting of fluorinated tethered molecules. Controlling the laser scan and ablation conditions permits the fabrication of under-design grooves with cross and lineal morphologies and separations between 10 and 500 um. These patterns provide a high transparency and repellence to liquids and ice over large areas. The best performance is obtained for cross or parallel line patterned glass with microgrooves separated by 100 um and 15 um depth thanks to 5 laser scanning repetitions. These surfaces present a stable Cassie-Baxter wetting state and very low ice-adhesion strength while keeping up to 80

Nanocolumnar thin films deposited at oblique angle (OA) by magnetron sputtering or evaporation often show common structural aspects when grown under equivalent geometrical conditions. This is the case of the column tilt angle as a function of the geometrical deposition arrangement, which coincides for some materials no matter the technique. This feature has usually been taken as a sign of a common type of growth, even though no other morphological aspects have been systematically compared. In this paper, a comparison between nanocolumnar Pt thin films grown at OA by evaporation and magnetron sputtering has been carried out, demonstrating the existence of profound differences in film density, columnar width or preferential crystalline texture, despite exhibiting the same nanocolumnar tilt. Moreover, the size distribution of voids and nanopores embedded in the nanocolumns has been specifically analyzed by means of two Positron Annihilation Spectroscopy techniques, demonstrating the existence of large variations depending on the preparation method. With the help of a growth model, these differences are discussed under the light of the atomistic processes present in evaporation and magnetron sputtering and, more specifically, on mobility processes triggered by the arrival of deposition atoms with relatively high kinetic energy.

Acoustic waves (AW) have recently emerged as an energy-efficient ice-removal procedure compatible with functional and industrial-relevant substrates. However, critical aspects at fundamental and experimental levels have yet to be disclosed to optimize their operational conditions. Identifying the processes and mechanisms by which different types of AWs induce de-icing are some of these issues. Herein, using model LiNbO3 systems and two types of interdigitated transducers, the e-icing and anti-icing efficiencies and mechanisms driven by Rayleigh surface acoustic waves (R-SAW) and Lamb waves with 120 and 510 mu m wavelengths, respectively, are analyzed. Through the experimental analysis of de-icing and active anti-icing processes and the finite element simulation of the AW generation, propagation, and interaction with small ice aggregates, it is disclosed that Lamb waves are more favorable than R-SAWs to induce de-icing and/or prevent the freezing of small ice droplets. Prospects for applications of this study are supported by proof of concept experiments, including de-icing in an icing wind tunnel, demonstrating that Lamb waves can efficiently remove ice layers covering large LN substrates. Results indicate that the de-icing mechanism may differ for Lamb waves or R-SAWs and that the wavelength must be considered as an important parameter for controlling the efficiency.

Early results on the plasma deposition of dielectric thin films on acoustic wave (AW) activated substrates revealed a densification pattern arisen from the focusing of plasma ions and their impact on specific areas of the piezoelectric substrate. Herein, we extend this methodology to tailor the plasma deposition of metals onto AW-activated LiNbO3 piezoelectric substrates. Our investigation reveals the tracking of the initial stages of nanoparticle (NP) formation and growth during the submonolayer deposition of silver. We elucidate the specific role of AW activation in reducing particle size, enhancing particle circularity, and retarding NP agglomeration and account for the physical phenomena making these processes differ from those occurring on non-activated substrates. We provide a comparative analysis of the results obtained under two representative plasma conditions: diode DC sputtering and magnetron sputtering. In the latter case, the AW activation gives rise to a 2D pattern of domains with different amounts of silver and a distinct size and circularity for the silver NPs. This difference was attributed to the specific characteristics of the plasma sheath formed onto the substrate in each case. The possibilities of tuning the plasmon resonance absorption of silver NPs by AW activation of the sputtering deposition process are discussed.

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, TiO2, Al, HfN, Mo, V, WO3and 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.

Early results on the plasma deposition of dielectric thin films on acoustic wave (AW) activated substrates revealed a densification pattern arisen from the focusing of plasma ions and their impact on specific areas of the piezoelectric substrate. Herein, we extend this methodology to tailor the plasma deposition of metals onto AW-activated LiNbO3 piezoelectric substrates. Our investigation reveals the tracking of the initial stages of nanoparticle (NP) formation and growth during the submonolayer deposition of silver. We elucidate the specific role of AW activation in reducing particle size, enhancing particle circularity, and retarding NP agglomeration and account for the physical phenomena making these processes differ from those occurring on non-activated substrates. We provide a comparative analysis of the results obtained under two representative plasma conditions: diode DC sputtering and magnetron sputtering. In the latter case, the AW activation gives rise to a 2D pattern of domains with different amounts of silver and a distinct size and circularity for the silver NPs. This difference was attributed to the specific characteristics of the plasma sheath formed onto the substrate in each case. The possibilities of tuning the plasmon resonance absorption of silver NPs by AW activation of the sputtering deposition process are discussed.

Stainless steel (SS) alloys are prevalent in many industries, household appliances or other commodities, where a strict control of surface properties is required to tailor their interaction with the environment. In this work we report a new procedure of stainless steel surface processing that provides a multifunctional response including superhydrophobicity, omniphobicity, self-cleaning, anti-fouling and effective anti-icing capacity, while still preserving a corrosion resistance similar to that of this material in compact form. The method consisted of a first nanostructuration step followed by a low fluorination. The nanostructured surfaces presented a dual scale roughness of hierarchical character. The liquid free approach developed in this work to get this singular surface nanostructuration consisted of a first laser treatment of stainless steel flat substrates, followed by the deposition of a nanostructured thin layer of this material by electron beam evaporation in an oblique angle configuration. The resulting hierarchical surfaces were subjected to fluorination by: i) the plasma-assisted deposition of a thin Teflon-like coating or ii) the grafting of fluorinated molecules. The self-cleanable, anti-adherent and ice repellent character of the resulting low fluorinated surfaces outperformed the behaviour of classical slippery surfaces obtained by the infusion of high amounts of fluorinated liquids. These hierarchical SS surfaces withstood mild abrasion tests and the effect of water jets. Moreover, the corrosion behaviour of the fluorinated surfaces determined through their potentiodynamic analysis revealed a similar corrosion resistance than flat SS substrates. Outstandingly, after these corrosion tests, the fluorinated samples obtained by grafting preserved their surface functionalities without significant degradation. The high mechanical and chemical stability of these low fluorinated samples support their use for a large variety of applications.

Icing has become a hot topic both in academia and in the industry given its implications in strategic sectors such as transport, robotics, wind turbines, photovoltaics, and electricity supply. 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 protocols. Herein we experimentally unravel some of the basic interactions that contribute to the de-icing and/or hinder the icing (ice accretion) on AW-activated substrates. The response toward icing of a model substrate system consisting of a piezoelectric LiNbO3 plate AW activated by radio-frequency (rf) signaling to planar electrodes has been characterized both at a laboratory scale and in an icing wind tunnel under forced convection conditions. Main features related to de-icing mechanisms, a decrease of ice adhesion, or the avoidance of ice accretion have been disclosed by this holistic investigation. Furthermore, additional experiments have shown that the piezoelectric substrate surfaces modified with a fluorinated ZnO thin film or a ZnO/CFx bilayer present anti-icing functionality and a synergistic response when activated with AWs. A careful analysis of the dependence of resonance frequency of the piezoelectric substrates on experimental variables such as temperature, ice formation, or wind velocity shows that this parameter can be used as an internal control procedure for real-time monitoring of icing processes onto AW-activated devices

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, uti-lizing 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.

The low temperature formation of monoclinic VO 2 crystal 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 VO 1.9 thin 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 VO 2 in 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.

Thermal ice protection systems (IPS) are used extensively in aeronautics. They are tailored according to the aircraft characteristics or flight envelope and can be used in different modes, anti-icing to avoid ice accretion or de-icing to remove the ice once accreted. A relevant issue by this application is the runback icing, caused by the downstream flow of melted or running water to unprotected areas, where activation is not possible in terms of energy consumption. Passive systems are being explored to complement or replace active systems, although, up to now, solutions have not been reported with the required performance for real-life applications.One of the most commonly reported anti-icing strategy relays on superhydrophobicity, i.e., it is based on the water roll-off capacity of Cassie-Baxter superhydrophobic surfaces (CB-SHP). Precisely, running wet phenomena, where liquid water is flowing on the surface, could be an appropiate application field for this type of materials. Herein, we have explored the behavior and limitations of a stable, newly developed, CB-SHP material to protect a runback section under icing conditions (temperature, air speed, liquid water content, droplet size distribution, and angle of attack) closer to those encountered in a wing airfoil.Two icing mechanisms, running-wet and direct impingement of supercooled microdroplets, have been evaluated for short (2 minutes) and long (10 minutes) period tests. It is found that the tested SHP material improved the performance of reference polyurethane (PU) paints, avoiding any ice accretion at low air speeds and low angles of attack.

In this work, piezoelectric AWs and plasmas have been brought together during the growth of a thin film as a novel methodology of plasma-assisted thin film structuration. The ensuing effects have been investigated on a model system where SiO2 and SiOx (x<2) thin films have been deposited by magnetron sputtering at oblique angles (MS-OAD) on an electro-acoustically excited LiNbO3 piezoelectric substrate under resonant conditions. The microstructure of the resulting films was 2D patterned and depicted submillimeter size intermingled zones with different optical characteristics, compositions (SiO2 and SiOx) and porosity, from highly porous to dense and compact regions. The 2D nanostructural pattern mimics the AW distribution and has been accounted for by means of a specific simulation model. It is concluded that the morphological and chemical film pattern replicates the distribution of polarization potential on the surface of the AW activated substrate immersed in the plasma. Moreover, we show that the main mechanism responsible for the appearance of domains with different morphology and chemical composition is the focused impingement of Ar+plasma ions on certain regions of the substrate. The general character of this patterning process, the underlying physics and its possibilities to tailor the composition and microstructure of dielectric thin film materials are discussed.

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.

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.

Light trapping effects are known to boost the photocatalytic degradation of organic molecules in 3D photonic structures of anatase titania (a-TiO2) with an inverse opal configuration. In the present work, we show that photocatalytic activity can also be enhanced in a-TiO2 thin films if they are incorporated within a nanoporous 1D optical resonant microcavity. We have designed and manufactured multilayer systems that, presenting a high open porosity to enable a straightforward diffusion of photodegradable molecules, provide light confinement effects at wavelengths around the absorption edge of photoactive a-TiO2. In brief, we have observed that a nanoporous 1D Bragg microcavity prepared by electron beam evaporation at oblique angles comprising a central defect layer of nanoporous a-TiO2 boosts the photocatalytic degradation of nitrobenzene and methyl orange dye solutions. The multilayer structure of the microcavity was designed to ensure the appearance of optical resonances at the a-TiO2 layer location and wavelengths around the absorption onset of this semiconductor. In this porous 1D Bragg microcavity, the diffusion constraints of molecules through the capping layers covering the a-TiO2 are effectively compensated by an increase in the photocatalytic activity due to the light confinement phenomena. We also report that the absorption coefficient of methyl orange dye solution infiltrated within the pore structure of the microcavity is exalted at the wavelengths of the corresponding optical resonances. This effect gives rise to a small but non-negligible visible light photodegradation of dye molecules. The possibilities of tailoring the design of 1D photonic systems to boost the photocatalytic activity of a-TiO2 are discussed.

In this work, piezoelectric AWs and plasmas have been brought together during the growth of a thin film as a novel methodology of plasma-assisted thin film structuration. The ensuing effects have been investigated on a model system where SiO2 and SiOx (x<2) thin films have been deposited by magnetron sputtering oblique angles (MS-OAD) on an electro-acoustically excited LiNbO3 substrate under resonant conditions. The resulting films were 2D patterned and depicted submillimeter size intermingled zones with different optical characteristics, compositions (SiO2 and SiOx) and porosity, from highly porous to dense and compact regions. The 2D nanostructural pattern mimics the AW distribution and its origin has been analized by means of a specifically developed simulation model. It is concluded that the morphological and chemical pattern replicates the polarization potential pattern generated at the surface of the AW activated substrate immersed in the plasma. Moreover, we show that the main mechanism responsible for the appearance of the different morphological and chemical composition domains is the local impingement of Ar+ plasma ions on certain polarized regions of the substrate. The general character of this patterning process, the underlying physics and its possibilities to tailor the processing of thin film materials are discussed in relation with the control of composition of dielectric thin films and/or their 2D structuration at micro and larger scales.

We demonstrate the existence of stoichiometric variations at the nanoscale when growing nanocolumnar SiOx 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 SiO0.5 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.