Hydrophobicity, Freezing Delay, and Morphology of Laser-Treated Aluminum Surfaces.

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 CF x 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 CF x coatings, affects wetting and ice formation behaviors and might be an efficient procedure to mitigate icing problems on metal surfaces.

3D Organic Nanofabrics: Plasma-Assisted Synthesis and Antifreezing Behavior of Superhydrophobic and Lubricant-Infused Slippery Surfaces.

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.

In Situ Determination of the Water Condensation Mechanisms on Superhydrophobic and Superhydrophilic Titanium Dioxide Nanotubes.

One-dimensional (1D) nanostructured surfaces based on high-density arrays of nanowires and nanotubes of photoactive titanium dioxide (TiO2) present a tunable wetting behavior from superhydrophobic to superhydrophilic states. These situations are depicted in a reversible way by simply irradiating with ultraviolet light (superhydrophobic to superhydrophilic) and storage in dark. In this article, we combine in situ environmental scanning electron microscopy (ESEM) and near ambient pressure photoemission analysis (NAPP) to understand this transition. These experiments reveal complementary information at microscopic and atomic level reflecting the surface wettability and chemical state modifications experienced by these 1D surfaces upon irradiation. We pay special attention to the role of the water condensation mechanisms and try to elucidate the relationship between apparent water contact angles of sessile drops under ambient conditions at the macroscale with the formation of droplets by water condensation at low temperature and increasing humidity on the nanotubes' surfaces. Thus, for the as-grown nanotubes, we reveal a metastable and superhydrophobic Cassie state for sessile drops that tunes toward water dropwise condensation at the microscale compatible with a partial hydrophobic Wenzel state. For the UV-irradiated surfaces, a filmwise wetting behavior is observed for both condensed water and sessile droplets. NAPP analyses show a hydroxyl accumulation on the as-grown nanotubes surfaces during the exposure to water condensation conditions, whereas the water filmwise condensation on a previously hydroxyl enriched surface is proved for the superhydrophilic counterpart.

Ultraviolet Pretreatment of Titanium Dioxide and Tin-Doped Indium Oxide Surfaces as a Promoter of the Adsorption of Organic Molecules in Dry Deposition Processes: Light Patterning of Organic Nanowires.

In this article we present the preactivation of TiO2 and ITO by UV irradiation under ambient conditions as a tool to enhance the incorporation of organic molecules on these oxides by evaporation at low pressures. The deposition of π-stacked molecules on TiO2 and ITO at controlled substrate temperature and in the presence of Ar is thoroughly followed by SEM, UV-vis, XRD, RBS, and photoluminescence spectroscopy, and the effect is exploited for the patterning formation of small-molecule organic nanowires (ONWs). X-ray photoelectron spectroscopy (XPS) in situ experiments and molecular dynamics simulations add critical information to fully elucidate the mechanism behind the increase in the number of adsorption centers for the organic molecules. Finally, the formation of hybrid organic/inorganic semiconductors is also explored as a result of the controlled vacuum sublimation of organic molecules on the open thin film microstructure of mesoporous TiO2.

Mechanisms of electron transport and recombination in ZnO nanostructures for dye-sensitized solar cells.

ZnO is an attractive material for applications in dye-sensitized solar cells and related devices. This material has excellent electron-transport properties in the bulk but its electron diffusion coefficient is much smaller in mesoporous films. In this work the electron-transport properties of two different kinds of dye-sensitized ZnO nanostructures are investigated by small-perturbation electrochemical techniques. For nanoparticulate ZnO photoanodes prepared via a wet-chemistry technique, the diffusion coefficient is found to reproduce the typical behavior predicted by the multiple-trapping and the hopping models, with an exponential increase with respect to the applied bias. In contrast, in ZnO nanostructured thin films of controlled texture and crystallinity prepared via a plasma chemical vapor deposition method, the diffusion coefficient is found to be independent of the electrochemical bias. This observation suggests a different transport mechanism not controlled by trapping and electron accumulation. In spite of the quite different transport features, the recombination kinetics, the electron-collection efficiency and the photoconversion efficiency are very similar for both kinds of photoanodes, an observation that indicates that surface properties rather than electron transport is the main efficiency-determining factor in solar cells based on ZnO nanostructured photoanodes.

Conformal TiO2 Aerogel-Like Films by Plasma Deposition: from Omniphobic Antireflective Coatings to Perovskite Solar Cell Photoelectrodes.

The ability to control the porosity of thin oxide films is a key factor determining their properties. Despite the abundance of dry processes for synthesizing oxide porous layers, a high porosity range is typically achieved by spin-coating-based wet chemical methods. Besides, special techniques such as supercritical drying are required to replace the pore liquid with air while maintaining the porous network. In this study, we propose a new method for the fabrication of ultraporous titanium dioxide thin films at room or mild temperatures (T ≤ 120 °C) by a sequential process involving plasma deposition and etching. These films are conformal to the substrate topography even for high-aspect-ratio substrates and show percolated porosity values above 85% that are comparable to those of advanced aerogels. The films deposited at room temperature are amorphous. However, they become partly crystalline at slightly higher temperatures, presenting a distribution of anatase clusters embedded in the sponge-like open porous structure. Surprisingly, the porous structure remains after annealing the films at 450 °C in air, which increases the fraction of embedded anatase nanocrystals. The films are antireflective, omniphobic, and photoactive, becoming superhydrophilic when subjected to ultraviolet light irradiation. The supported, percolated, and nanoporous structure can be used as an electron-conducting electrode in perovskite solar cells. The properties of the cells depend on the aerogel-like film thickness, which reaches efficiencies close to those of commercial mesoporous anatase electrodes. This generic solvent-free synthesis is scalable and applicable to ultrahigh porous conformal oxides of different compositions, with potential applications in photonics, optoelectronics, energy storage, and controlled wetting.

Laser induced enhancement of dichroism in supported silver nanoparticles deposited by evaporation at glancing angles.

Silver nanoparticles (NPs) depicting well defined surface plasmon resonance (SPR) absorption were deposited on flat substrates by physical vapor deposition in a glancing angle configuration. The particles were characterized by scanning electron microscopy and atomic force microscopy and their optical properties examined by UV-vis absorption spectroscopy using linearly polarized light. It was found that, depending on the amount of deposited silver and the evaporation angle, part of the 'as-prepared' samples present NPs characterized by an anisotropic shape and a polarization dependent SPR absorption and different colors when using polarized white light at 0° and 90°. Low-power irradiation of these materials with an infrared Nd-YAG nanosecond laser in ambient conditions produced an enhancement in such dichroism. At higher powers, the dichroism was lost and the SPR bands shifted to lower wavelengths as a result of the reshaping of the silver NPs in the form of spheres. The possible factors contributing to the observed changes in dichroism are discussed.

Sensitive mutation detection in heterogeneous cancer specimens by massively parallel picoliter reactor sequencing.

The sensitivity of conventional DNA sequencing in tumor biopsies is limited by stromal contamination and by genetic heterogeneity within the cancer. Here, we show that microreactor-based pyrosequencing can detect rare cancer-associated sequence variations by independent and parallel sampling of multiple representatives of a given DNA fragment. This technology can thereby facilitate accurate molecular diagnosis of heterogeneous cancer specimens and enable patient selection for targeted cancer therapies.

Photoelectrochemical Water Splitting with ITO/WO3/BiVO4/CoPi Multishell Nanotubes Enabled by a Vacuum and Plasma Soft-Template Synthesis.

A common approach for the photoelectrochemical (PEC) splitting of water relies on the application of WO3 porous electrodes sensitized with BiVO4 acting as a visible photoanode semiconductor. In this work, we propose a new architecture of photoelectrodes consisting of supported multishell nanotubes (NTs) fabricated by a soft-template approach. These NTs are formed by a concentric layered structure of indium tin oxide (ITO), WO3, and BiVO4, together with a final thin layer of cobalt phosphate (CoPi) co-catalyst. The photoelectrode manufacturing procedure is easily implementable at a large scale and successively combines the thermal evaporation of single crystalline organic nanowires (ONWs), the magnetron sputtering deposition of ITO and WO3, and the solution dripping and electrochemical deposition of, respectively, BiVO4 and CoPi, plus the annealing in air under mild conditions. The obtained NT electrodes depict a large electrochemically active surface and outperform the efficiency of equivalent planar-layered electrodes by more than one order of magnitude. A thorough electrochemical analysis of the electrodes illuminated with blue and solar lights demonstrates that the characteristics of the WO3/BiVO4 Schottky barrier heterojunction control the NT electrode efficiency, which depended on the BiVO4 outer layer thickness and the incorporation of the CoPi electrocatalyst. These results support the high potential of the proposed soft-template methodology for the large-area fabrication of highly efficient multishell ITO/WO3/BiVO4/CoPi NT electrodes for the PEC splitting of water.

Advanced Cellulose-Nanocarbon Composite Films for High-Performance Triboelectric and Piezoelectric Nanogenerators.

Natural polymers such as cellulose have interesting tribo- and piezoelectric properties for paper-based energy harvesters, but their low performance in providing sufficient output power is still an impediment to a wider deployment for IoT and other low-power applications. In this study, different types of celluloses were combined with nanosized carbon fillers to investigate their effect on the enhancement of the electrical properties in the final nanogenerator devices. Cellulose pulp (CP), microcrystalline cellulose (MCC) and cellulose nanofibers (CNFs) were blended with carbon black (CB), carbon nanotubes (CNTs) and graphene nanoplatelets (GNPs). The microstructure of the nanocomposite films was characterized by scanning electron and probe microscopies, and the electrical properties were measured macroscopically and at the local scale by piezoresponse force microscopy. The highest generated output voltage in triboelectric mode was obtained from MCC films with CNTs and CB, while the highest piezoelectric voltage was produced in CNF-CNT films. The obtained electrical responses were discussed in relation to the material properties. Analysis of the microscopic response shows that pulp has a higher local piezoelectric d33 coefficient (145 pC/N) than CNF (14 pC/N), while the macroscopic response is greatly influenced by the excitation mode and the effective orientation of the crystals relative to the mechanical stress. The increased electricity produced from cellulose nanocomposites may lead to more efficient and biodegradable nanogenerators.

Following the wetting of one-dimensional photoactive surfaces.

This article aims toward a full description of the wetting conversion from superhydrophobicity to superhydrophilicity under illumination with UV light of high-density ZnO nanorods surfaces by (i) following the evolution of the clusters and superstructures formed by the nanocarpet effect as a function of the water contact angle (WCA); (ii) characterization of the superhydrophobic and superhydrophilic states with an environmental scanning electron microscope (ESEM); and (iii) using the nanocarpet effect as a footprint of both local and apparent water contact angles. Thus, the main objective of the article is to provide a general vision of the wettability of 1D photoactive surfaces. In parallel, the nanocarpet (NC) formation by clustering of vertically aligned ZnO nanorods (NR) when water is dripped on their surface and then dried is studied for the first time by taking advantage of the possibility of tuning the surface water contact angle of the ZnO NR structure under UV preillumination. As a result, we demonstrate the feasibility of controlling the size and other morphological characteristics of the NCs. Moreover, a strong anisotropic wetting behavior, characterized by a Δθ = θ(parallel) - θ(perpendicular) = 30°, is shown on an asymmetrically aligned NC surface resulting from arrays of tilted NRs. The study of the condensation/evaporation of water on/from an as-prepared (superhydrophobic) or a preilluminated (superhydrophilic) NR surface examined by an environmental scanning electron microscope has evidenced the formation of supported water droplets with polygonal shapes in the first case and the complete filling of the inter-NR space in the latter. The long-term stability of the NC clusters has been utilized as a footprint to track the penetration depth of water within the inter-NR space in the three borderline regions of water droplets. This analysis has shown that for moderately hydrophobic surfaces (i.e., water contact angles lower than 130°) water droplets do not present a well-defined borderline trace but a spreading region where water penetrates differently with the NR interspace. The transition from a Cassie-Baxter to a modified Cassie-Baxter to finish in a Wenzel wetting state is found on these surfaces depending on the UV preillumination time and is explained with a model where water interaction with the NR units is the critical factor determining the macroscopic wetting behavior of these surfaces.

Vertical and tilted Ag-NPs@ZnO nanorods by plasma-enhanced chemical vapour deposition.

Supported ZnO nanorods have been prepared at 405 K by plasma-enhanced chemical vapour deposition (PECVD) using diethylzinc as precursor, oxygen plasma and silver as the promotion layer. The nanorods are characterized by a hollow and porous microstructure where partially percolated silver nanoparticles are located. By changing different deposition parameters like the thickness of the silver layer, the type of oxidation pretreatment or the geometry of the deposition set-up, the length, the width and the tilting angle of the nanorods with respect to the substrate can be modified. Other nanostructures like nanobushes, zigzag linear structures and stacked bilayers with nanocolumns of TiO(2) can also be prepared by adjusting the deposition conditions. A phenomenological model relying on the assessment of the diverse nanostructure morphologies and the evidence provided by an in situ x-ray photoelectron spectroscopy (XPS) experiment has been proposed to describe their formation mechanism. From this analysis it is deduced that the effect of the electrical field of the plasma sheath, the high mobility of silver and silver oxide, and the diffusion of the precursor molecules are some of the critical factors that must converge by the formation of the nanorods.

Correlation lengths, porosity and water adsorption in TiO2 thin films prepared by glancing angle deposition.

This paper reports a thorough microstructural characterization of glancing angle deposited (GLAD) TiO(2) thin films. Atomic force microscopy (afm), grazing-incidence small-angle x-ray scattering (GISAXS) and water adsorption isotherms have been used to determine the evolution of porosity and the existence of some correlation distances between the nanocolumns constituting the basic elements of the film's nanostructure. It is found that the deposition angle and, to a lesser extent, the film thickness are the most important parameters controlling properties of the thin film. The importance of porosity and some critical dimensions encountered in the investigated GLAD thin films is highlighted in relation to the analysis of their optical properties when utilized as antireflective coatings or as hosts and templates for the development of new composite materials.

Highly Anisotropic Organometal Halide Perovskite Nanowalls Grown by Glancing-Angle Deposition.

Polarizers are ubiquitous components in current optoelectronic devices as displays or photographic cameras. Yet, control over light polarization is an unsolved challenge, since the main drawback of the existing display technologies is the significant optical losses. In such a context, organometal halide perovskites (OMHP) can play a decisive role given their flexible synthesis with tunable optical properties such as bandgap and photoluminescence, and excellent light emission with a low non-radiative recombination rate. Therefore, along with their outstanding electrical properties have elevated hybrid perovskites as the material of choice in photovoltaics and optoelectronics. Among the different OMHP nanostructures, nanowires and nanorods have lately arisen as key players in the control of light polarization for lighting or detector applications. Herein, the fabrication of highly aligned and anisotropic methylammonium lead iodide perovskite nanowalls by glancing-angle deposition, which is compatible with most substrates, is presented. Their high alignment degree provides the samples with anisotropic optical properties such as light absorption and photoluminescence. Furthermore, their implementation in photovoltaic devices provides them with a polarization-sensitive response. This facile vacuum-based approach embodies a milestone in the development of last-generation polarization-sensitive perovskite-based optoelectronic devices such as lighting appliances or self-powered photodetectors.

Enhanced photoactivity in bilayer films with buried rutile-anatase heterojunctions.

Herein, we study the photoactivity of anatase-rutile bilayer thin films consisting of an anatase overlayer of variable thickness from some tenths to some hundred nanometers deposited onto a rutile thin film. As references single anatase layers of equivalent thickness were deposited onto silicon. All the films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. The photoactivity of the samples was assessed by following the evolution with the UV illumination time of both the wetting angle on the thin film surface and the decoloration of a dye in a water solution. While a similar efficiency is found for the first type of experiments irrespective of the anatase thickness, in the second type a maximum in the photoactivity is found for a thickness of the anatase layer of about 130 nm. This enhanced photoactivity in bilayer systems with a buried anatase-rutile heterojunction is related to the formation of different Schottky potential barriers in the anatase layer, depending on its thickness and the substrate (i.e. rutile or SiO(2)) where it is deposited.

Mechanically Switchable Wetting Petal Effect in Self-Patterned Nanocolumnar Films on Poly(dimethylsiloxane).

Switchable mechanically induced changes in the wetting behavior of surfaces are of paramount importance for advanced microfluidic, self-cleaning and biomedical applications. In this work we show that the well-known polydimethylsiloxane (PDMS) elastomer develops self-patterning when it is coated with nanostructured TiO2 films prepared by physical vapor deposition at glancing angles and subsequently subjected to a mechanical deformation. Thus, unlike the disordered wrinkled surfaces typically created by deformation of the bare elastomer, well-ordered and aligned micro-scaled grooves form on TiO2/PDMS after the first post-deposition bending or stretching event. These regularly patterned surfaces can be reversibly modified by mechanical deformation, thereby inducing a switchable and reversible wetting petal effect and the sliding of liquid droplets. When performed in a dynamic way, this mechanical actuation produces a unique capacity of liquid droplets (water and diiodomethane) transport and tweezing, this latter through their selective capture and release depending on their volume and chemical characteristics. Scanning electron and atomic force microscopy studies of the strained samples showed that a dual-scale roughness, a parallel alignment of patterned grooves and their reversible widening upon deformation, are critical factors controlling this singular sliding behavior and the possibility to tailor their response by the appropriate manufacturing of surface structures.

One-reactor vacuum and plasma synthesis of transparent conducting oxide nanotubes and nanotrees: from single wire conductivity to ultra-broadband perfect absorbers in the NIR.

The eventual exploitation of one-dimensional nanomaterials needs the development of scalable, high yield, homogeneous and environmentally friendly methods capable of meeting the requirements for fabrication of functional nanomaterials with properties on demand. In this article, we demonstrate a vacuum and plasma one-reactor approach for the synthesis of fundamental common elements in solar energy and optoelectronics, i.e. the transparent conducting electrode but in the form of nanotube and nanotree architectures. Although the process is generic and can be used for a variety of TCOs and wide-bandgap semiconductors, we focus herein on indium doped tin oxide (ITO) as the most previously researched in previous applications. This protocol combines widely applied deposition techniques such as thermal evaporation for the formation of organic nanowires serving as 1D and 3D soft templates, deposition of polycrystalline layers by magnetron sputtering, and removal of the templates by simply annealing under mild vacuum conditions. The process variables are tuned to control the stoichiometry, morphology, and alignment of the ITO nanotubes and nanotrees. Four-probe characterization reveals the improved lateral connectivity of the ITO nanotrees and applied on individual nanotubes shows resistivities as low as 3.5 ± 0.9 × 10-4Ω cm, a value comparable to that of single-crystalline counterparts. The assessment of diffuse reflectance and transmittance in the UV-Vis range confirms the viability of the supported ITO nanotubes as random optical media working as strong scattering layers. Their further ability to form ITO nanotrees opens a path for practical applications as ultra-broadband absorbers in the NIR. The demonstrated low resistivity and optical properties of these ITO nanostructures open a way for their use in LEDs, IR shields, energy harvesting, nanosensors, and photoelectrochemical applications.

Wetting properties of polycrystalline TiO2 surfaces: a scaling approach to the roughness factors.

This work presents a thorough study on the wettability of polycrystalline anatase TiO(2) thin films prepared at 250 °C in a microwave plasma enhanced chemical vapor deposition (MW-PECVD) reactor with Ar/O(2) plasmas. Anatase polycrystalline thin films with different microstructures, textures, and surface roughness were obtained as a function of their thickness. The water contact angle of the samples was analyzed within the assumptions of the Wenzel, Cassie, and Miwa models to ascertain the effect of roughness and other surface heterogeneities on their characteristic parameters. The roughness factors defined in the different models were calculated from the atomic force microscopy (AFM) images of the films for two different observation scales within the premises of the dynamic scaling theories. The obtained results indicate that the wetting angle of an equivalent flat anatase surface with a value of 82° can only be properly estimated for observation scales of 5 × 5 µm(2) and using the Miwa model. The analysis of the UV induced hydrophilization of the surface state of the anatase films and the posterior recovery of the partially hydrophobic character of these surfaces in the absence of UV photons suggest a clear dependence of the light induced wettability on their texture and size of crystalline domains.

One-step dry method for the synthesis of supported single-crystalline organic nanowires formed by pi-conjugated molecules.

We present for the first time a general vacuum process for the growth of supported organic nanowires formed by pi-conjugated molecules, including metalloporphyrins, metallophthalocyanines, and perylenes. This methodology consists on a one-step physical vapor deposition of the pi-conjugated molecules. The synthesis is carried out at controlled temperature on substrates with tailor morphology which allows the growth of organic nanowires in the form of squared nanofibers and nanobelts. The study of the nanowires by electron diffraction and HRTEM combining with the results of a theoretical analysis of the possible arrangement of the pi-conjugated molecules along the nanowires reveals that the nanowires show a columnar structure along the fiber axis consisting of pi-stacked molecules having a herringbone-like arrangement. The formation of these nanowires on different substrates demonstrates that the growth mechanism is independent of the substrate chemical composition. An in-depth phenomenological study of the formation of the nanowires drives us to propose a growth mechanism based on a crystallization process. Furthermore, the growth method allows the fabrication of two particular 1D heterostructures: binary and open core@shell organic nanofibers.

Air- and light-stable superhydrophobic colored surfaces based on supported organic nanowires.

In this work, we report on a new type of superhydrophobic material consisting of supported organic nanowires prepared by vacuum deposition. Different intensely colored surfaces with water contact angles as high as 180 degrees can be fabricated depending on the composition, morphology, and density of the nanowires. These surfaces are stable in air and under intense light irradiation. The wettability properties of coatings made of metalloporphyrins and metallophthalocyanines nanowires as well as other heterostructured binary and open core@shell nanowires are studied.