True Vapor-Liquid-Solid Process Suppresses Unintentional Carrier Doping of Single Crystalline Metal Oxide Nanowires.

Single crystalline nanowires composed of semiconducting metal oxides formed via a vapor-liquid-solid (VLS) process exhibit an electrical conductivity even without an intentional carrier doping, although these stoichiometric metal oxides are ideally insulators. Suppressing this unintentional doping effect has been a challenging issue not only for metal oxide nanowires but also for various nanostructured metal oxides toward their semiconductor applications. Here we demonstrate that a pure VLS crystal growth, which occurs only at liquid-solid (LS) interface, substantially suppresses an unintentional doping of single crystalline SnO2 nanowires. By strictly tailoring the crystal growth interface of VLS process, we found the gigantic difference of electrical conduction (up to 7 orders of magnitude) between nanowires formed only at LS interface and those formed at both LS and vapor-solid (VS) interfaces. On the basis of investigations with spatially resolved single nanowire electrical measurements, plane-view electron energy-loss spectroscopy, and molecular dynamics simulations, we reveal the gigantic suppression of unintentional carrier doping only for the crystal grown at LS interface due to the higher annealing effect at LS interface compared with that grown at VS interface. These implications will be a foundation to design the semiconducting properties of various nanostructured metal oxides.

Suppressing Structural Colors of Photocatalytic Optical Coatings on Glass: The Critical Role of SiO2.

The appearance of structural colors on coated-glass is a critical esthetical drawback toward industrialization of photocatalytic coatings on windows for architecture or automobile. Herein we describe a rational approach to suppress the structural color of mesoporous TiO2-based coatings preserving photoactivity and mechanical stiffness. Addition of SiO2 as third component is discussed. TixSi(1-x)O2 mesoporous coatings were fabricated by one-step liquid deposition process through the evaporation induced self-assembling and characterized by GI-SAXS, GI-WAXS, electron microscopies, and in situ Environmental Ellipsometry Porosimetry. Guided by optical simulation, we investigated the critical role of SiO2 on the optical responses of the films but also on the structural, mechanical, and photocatalytic properties, important requirements to go toward real applications. We demonstrate that adding SiO2 to porous TiO2 allows tuning and suppression of structural colors through refractive index matching and up to 160% increase in mechanical stiffening of the films. This study leads us to demonstrate an example of "invisible" coating, in which the light reflection is angle- and thickness-independent, and exhibiting high porosity, mechanical stiffness, and photoactivity.

Rational Concept for Reducing Growth Temperature in Vapor-Liquid-Solid Process of Metal Oxide Nanowires.

Vapor-liquid-solid (VLS) growth process of single crystalline metal oxide nanowires has proven the excellent ability to tailor the nanostructures. However, the VLS process of metal oxides in general requires relatively high growth temperatures, which essentially limits the application range. Here we propose a rational concept to reduce the growth temperature in VLS growth process of various metal oxide nanowires. Molecular dynamics (MD) simulation theoretically predicts that it is possible to reduce the growth temperature in VLS process of metal oxide nanowires by precisely controlling the vapor flux. This concept is based on the temperature dependent "material flux window" that the appropriate vapor flux for VLS process of nanowire growth decreases with decreasing the growth temperature. Experimentally, we found the applicability of this concept for reducing the growth temperature of VLS processes for various metal oxides including MgO, SnO2, and ZnO. In addition, we show the successful applications of this concept to VLS nanowire growths of metal oxides onto tin-doped indium oxide (ITO) glass and polyimide (PI) substrates, which require relatively low growth temperatures.

Converting Water Adsorption and Capillary Condensation in Usable Forces with Simple Porous Inorganic Thin Films.

This work reports an innovative humidity-driven actuation concept based on conversion of chemical energy of adsorption/desorption using simple nanoporous sol-gel silica thin films as humidity-responsive materials. Bilayer-shaped actuators, consisting of a humidity-sensitive active nanostructured silica film deposited on a polymeric substrate (Kapton), were demonstrated as an original mean to convert water molecule adsorption and capillary condensation in usable mechanical work. Reversible solvation stress changes in silica micropores by water adsorption and energy produced by the rigid silica film contraction, induced by water capillary condensation in mesopores, were finely controlled and used as energy sources. The influence of the film nanostructure (microporosity, mesoporosity) and thickness and the polymeric substrate thickness on actuation force, on movement speed and on displacement amplitude are clearly evidenced and discussed. We show that the global mechanical response of such silica-based actuators can easily be adjusted to fabricate tailor-made actuation systems triggered by humidity variation. This study provides insight into hard ceramic stimulus-responsive materials that seem to be a promising alternative to traditional soft organic materials for surface-chemistry-driven actuation systems.

Tailoring Nucleation at Two Interfaces Enables Single Crystalline NiO Nanowires via Vapor-Liquid-Solid Route.

Here we show a rational strategy to fabricate single crystalline NiO nanowires via a vapor-liquid-solid (VLS) route, which essentially allows us to tailor the diameter and the spatial position. Our strategy is based on the suppression of the nucleation at vapor-solid (VS) interface, which promotes nucleation only at the liquid-solid (LS) interface. Manipulating both the supplied material fluxes (oxygen and metal) and the growth temperature enables enhancement of the nucleation only at the LS interface. Furthermore, this strategy allows us to reduce the growth temperature of single crystalline NiO nanowires down to 550 °C, which is the lowest growth temperature so far reported.

Nanostructuration of PEDOT in Porous Coordination Polymers for Tunable Porosity and Conductivity.

A series of conductive porous composites were obtained by the polymerization of 3,4-ethylenedioxythiophene (EDOT) in the cavities of MIL-101(Cr). By controlling the amount of EDOT loaded into the host framework, it was possible to modulate the conductivity as well as the porosity of the composite. This approach yields materials with a reasonable electronic conductivity (1.1 × 10(-3) S·cm(-1)) while maintaining high porosity (SBET = 803 m(2)/g). This serves as a promising strategy for obtaining highly nanotextured conductive polymers with very high accessibility for small gas molecules, which are beneficial to the fabrication of a chemiresistive sensor for the detection of NO2.

Engineering functionality gradients by dip coating process in acceleration mode.

In this work, unique functional devices exhibiting controlled gradients of properties are fabricated by dip-coating process in acceleration mode. Through this new approach, thin films with "on-demand" thickness graded profiles at the submillimeter scale are prepared in an easy and versatile way, compatible for large-scale production. The technique is adapted to several relevant materials, including sol-gel dense and mesoporous metal oxides, block copolymers, metal-organic framework colloids, and commercial photoresists. In the first part of the Article, an investigation on the effect of the dip coating speed variation on the thickness profiles is reported together with the critical roles played by the evaporation rate and by the viscosity on the fluid draining-induced film formation. In the second part, dip-coating in acceleration mode is used to induce controlled variation of functionalities by playing on structural, chemical, or dimensional variations in nano- and microsystems. In order to demonstrate the full potentiality and versatility of the technique, original graded functional devices are made including optical interferometry mirrors with bidirectional gradients, one-dimensional photonic crystals with a stop-band gradient, graded microfluidic channels, and wetting gradient to induce droplet motion.

Structural transitions in asymmetric poly(styrene)-block-poly(lactide) thin films induced by solvent vapor exposure.

Successive structural transitions in thin films of asymmetric poly(styrene)-block-poly(lactide) (PS-PLA) block copolymer samples upon exposure to tetrahydrofuran (THF) vapors have been monitored using atomic force microscopy (AFM) and both in situ and ex situ grazing incidence small-angle X-ray scattering (GISAXS). A direct link was established between the structure in the swollen state and the morphology formed in the dried state post solvent evaporation. This was related to the high incompatibility between the constituting blocks of the copolymer that thwarted the system from reaching the homogeneous disordered state in the swollen state under the specific conditions utilized in this study. Upon rapid solvent removal, the morphologies formed in the swollen state were trapped due the fast evaporation kinetics. This work provides a better understanding of the mechanisms associated with block copolymer thin film morphology changes induced by solvent vapor annealing.