Influence of Different Defects in Vertically Aligned Carbon Nanotubes on TiO2 Nanoparticle Formation through Atomic Layer Deposition.

The chemical inertness of carbon nanotubes (CNT) requires some degree of "defect engineering" for controlled deposition of metal oxides through atomic layer deposition (ALD). The type, quantity, and distribution of such defects rules the deposition rate and defines the growth behavior. In this work, we employed ALD to grow titanium oxide (TiO2) on vertically aligned carbon nanotubes (VACNT). The effects of nitrogen doping and oxygen plasma pretreatment of the CNT on the morphology and total amount of TiO2 were systematically studied using transmission electron microscopy, Raman spectroscopy, and thermogravimetric analysis. The induced chemical changes for each functionalization route were identified by X-ray photoelectron and Raman spectroscopies. The TiO2 mass fraction deposited with the same number of cycles for the pristine CNT, nitrogen-doped CNT, and plasma-treated CNT were 8, 47, and 80%, respectively. We demonstrate that TiO2 nucleation is dependent mainly on surface incorporation of heteroatoms and their distribution rather than structural defects that govern the growth behavior. Therefore, selecting the best way to functionalize CNT will allow us to tailor TiO2 distribution and hence fabricate complex heterostructures.

Superomniphobic and easily repairable coatings on copper substrates based on simple immersion or spray processes.

Textures that resemble typical fern or bracken plant species (dendrite structures) were fabricated for liquid repellency by dipping copper substrates in a single-step process in solutions containing AgNO3 or by a simple spray liquid application. Superhydrophobic surfaces were produced using a solution containing AgNO3 and trimethoxypropylsilane (TMPSi), and superomniphobic surfaces were produced by a two-step procedure, immersing the copper substrate in a AgNO3 solution and, after that, in a solution containing 1H,1H,2H,2H-perfluorodecyltriethoxysilane (PFDTES). The simple functionalization processes can also be used when the superomniphobic surfaces were destroyed by mechanical stress. By immersion of the wrecked surfaces in the above solutions or by the spray method and soft heating, the copper substrates could be easily repaired, regenerating the surfaces' superrepellency to liquids. The micro- and nanoroughness structures generated on copper surfaces by the deposition of silver dendrites functionalized with TMPSi presented apparent contact angles greater than 150° with a contact angle hysteresis lower than 10° when water was used as the test liquid. To avoid total wettability with very low surface tension liquids, such as rapeseed oil and hexadecane, a thin perfluorinated coating of poly(tetrafluoroethylene) (PTFE), produced by physical vapor deposition, was used. A more efficient perfluorinated coating was obtained when PFDTES was used. The superomniphobic surfaces produced apparent contact angles above 150° with all of the tested liquids, including hexadecane, although the contact angle hysteresis with this liquid was above 10°. The coupling of dendritic structures with TMPSi/PTFE or directly by PFDTES coatings was responsible for the superrepellency of the as-prepared surfaces. These simple, fast, and reliable procedures allow the large area, and cost-effective scale fabrication of superrepellent surfaces on copper substrates for various industrial applications with the advantage of easy recovery of the surface repellency after damage.

Anisotropic effective medium properties from interacting Ag nanoparticles in silicon dioxide.

Films containing a layer of Ag nanoparticles embedded in silicon dioxide were produced by RF magnetron sputtering. Optical transmittance measurements at several angles of incidence (from normal to 75°) revealed two surface plasmon resonance (SPR) peaks, which depend on electric field direction: one in the ultraviolet and another red-shifted from the dilute Ag/SiO2 system resonance at 410 nm. In order to investigate the origin of this anisotropic behavior, the structural properties were determined by transmission electron microscopy, revealing the bidimensional plane distribution of Ag nanoparticles with nearly spherical shape as well as the filling factor of metal in the composite. A simple model linked to these experimental parameters allowed description of the most relevant features of the SPR positions, which, depending on the field direction, were distinctly affected by the coupling of oscillations between close nanoparticles, as described by a modified Drude-Lorentz dielectric function introduced into the Maxwell-Garnett relation. This approach allowed prediction of the resonance for light at 75° incidence from the SPR position for light at normal incidence, in good agreement with experimental observation.

Multi-scale structured, superhydrophobic and wide-angle, antireflective coating in the near-infrared region.

Superhydrophobic self-cleaning surfaces were produced with simultaneous wide-angle optical transmittance in the near-infrared region and antireflection properties from combination of multi-scale surface topology based on silica nanoparticles, index grading and interference.

Micro and nano-texturization of intermetallic oxide alloys by a single anodization step: preparation of artificial self-cleaning surfaces.

Micro- and nanostructures of Ti-γCu (γ = 0, 30, 50, 70, and 100 wt %) intermetallic alloys were produced through a single anodization step. It was found that the original alloy composition influences the final oxide morphology obtained after anodization which presented formation of a microstructure with nanotubes, nanoparticles or nanopillars on the surface. Pure Ti and Cu oxide metals and their alloys presented hydrophilic or superhydrophilic properties immediately after anodization. When the anodized pure metal and/or Ti-γCu surfaces were functionalized with trimethoxypropylsilane (TPMSi), by dipping and coating with a thin perfluorinated layer, the treated substrates became in all cases superhydrophobic (water contact angles in the range of 152-166°), showing excellent self-cleaning properties with hysteresis below 3°. These results can be explained by a combination of nanomicro morphologies with low surface energy compounds in the topmost monolayers. The decrease in hysteresis was associated with a higher M-OH bond concentration on the anodized surfaces, which allowed for more complete TMPSi coating coverage. This study also indicates that easy and effective fabrication of superhydrophobic surfaces in pure metals and alloys is possible without involving traditional multistep processes.

Glass window coatings for sunlight heat reflection and co-utilization.

Buildings that simultaneously provide natural illumination and thermal comfort for all seasons have met with increasing demand as conventional resource limitations are realized. In this context, organic and metal-dielectric coatings are tested, and a simple, coated double-glazed window with solar blinds is conceived that includes passive infrared (IR) reflection, active illumination control, and integration to the building envelope. As a result, a proper spectrally selective coating is applied to produce a low-emissivity solar window with climate-adaptive co-utilization of the reflected IR.

Simple modeling of plasmon resonances in Ag/SiO2 nanocomposite monolayers.

Normal incidence transmittance and reflectance spectra of sputtered nanocomposite monolayer films of Ag in SiO2, buried and unburied, showed significant redshifted plasmon resonances from 410 to 455 nm, which could be well interpreted with a simple model that starts from the Maxwell Garnett theory and the Kreibig extension of the Drude-Lorentz equation, but with a further extension related to the dipolar interaction between the metal particles distributed on a surface.

Spectral polarimetry technique as a complementary tool to ellipsometry of dielectric films.

Ellipsometry is a highly sensitive optical technique for coating characterization but usually presents multiple solutions in many cases. To prevent these, a method with addition of a spectral polarimetric technique is proposed. An initial film dispersion curve, independently of its physical thickness, is then provided using the same setup as spectral ellipsometry and at the same sample position, which later is used for thickness determination and dispersion refinement with increase of reliability of results. Characterization of thin TiO2 films with one and two ellipsometric solutions is shown to corroborate the validity of the proposed method.

Analysis of dip coating processing parameters by double optical monitoring.

Double optical monitoring is applied to determine the influence of main process parameters on the formation of sulfated zirconia and self-assembled mesoporous silica solgel films by dip coating. In addition, we analyze, for the first time to the best of our knowledge, the influence of withdrawal speed, temperature, and relative humidity on refractive-index and physical thickness variations (uncertainties of +/-0.005 and +/-7 nm) during the process. Results provide insight into controlled production of single and multilayer films from complex fluids by dip coating.

Double optical monitoring of dip coating with a time-varying refractive index.

A brief overview of optical monitoring for vacuum and wet-bench film-deposition processes is presented. Interferometric and polarimetric measurements are combined with regard to simultaneous monitoring of refractive index and physical thickness in real time. Monitoring stability and accuracy are verified during dip coating with a transparent oil standard. This double optical technique is applied to dip coating with a multicomponent zirconyl chloride aqueous solution, whose resulting temporal refractive-index and physical-thickness curves indicate good reproducibility as well as significant sensitivity to changes of film-flow properties during the dip-coating process.

Optically monitored dip coating as a contactless viscometry method for liquid films.

Real-time interferometric monitoring of the dip coating process is applied to the study of properties of flowing liquids. Nonvolatile Newtonian oils are considered, allowing validity of a simple model after the steady state is reached where film physical thickness depends on time as t(-1/2). Measurement of two distinct mineral oil standards, under several withdrawing speeds, resulted in kinematic viscosities of 1.17+/-0.03 and 9.9+/-0.2 S (1S = 1 cm2/s). Agreement of these results with nominal values from the manufacturer suggests that interferometric monitoring of dip coating may become a valuable method for accurate, contactless viscometry of liquid films. Advantages and present limitations are discussed.

Interferometric monitoring of dip coating.

Dip-coated films, which are widely used in the coating industry, are usually measured by capacitive methods with micrometric precision. For the first time to our knowledge, we have applied an interferometric determination of the evolution of thickness in real time to nonvolatile Newtonian mineral oils with several viscosities and distinct dip withdrawing speeds. The evolution of film thickness during the process depends on time as t(-1/2), in accordance with a simple model. Comparison with measured results with an uncertainty of +/- 0.007 microm) showed good agreement after the initial steps of the process had been completed.

Simple polarimetric approach to direct measurement of the near-surface refractive index in graded-index films.

In the standard M-line method for the characterization of graded-index film, an analytical curve is fitted to the waveguide mode measurements and extrapolated to provide the refractive index in the zero-depth limit. Here we review our polarimetric approach to a direct near-surface measurement, which complements the M-line method. Also, we present its new and more straightforward version, which is applicable to existing samples and does not require masking before ion exchange.