Formation of one-dimensional capped ZnO nanoparticle assemblies at the air/water interface

The self-assembling behavior and microscopic structure of zinc oxide nanoparticle Langmuir-Blodgett monolayer films were investigated for the case of zinc oxide nanoparticles coated with a hydrophobic layer of dodecanethiol. Evolution of nanoparticle film structure as a function of surface pressure (π) at the air-water interface was monitored in situ using Brewster’s angle microscopy, where it was determined that π=16 mN/m produced near-defect-free monolayer films. Transmission electron micrographs of drop-cast and Langmuir-Schaefer deposited films of the dodecanethiol-coated zinc oxide nanoparticles revealed that the nanoparticle preparation method yielded a microscopic structure that consisted of one-dimensional rodlike assemblies of nanoparticles with typical dimensions of 25 x 400 nm, encased in the organic dodecanethiol layer. These nanoparticle-containing rodlike micelles were aligned into ordered arrangements of parallel rods using the Langmuir-Blodgett technique.

ZnO nanostructures grown on epitaxial GaN

Presented is the growth of zinc oxide nanorod/nanowire arrays on gallium nitride epitaxial layers. A hierarchical zinc oxide morphology comprising of different scale zinc oxide nanostructures was observed. The first tier of the surface comprised of typical zinc oxide nanorods, with most bridging to adjacent nanorods. While the second tier comprised of smaller zinc oxide nanowires approximately 30 nm in width often growing atop the aforementioned bridges. Samples were analysed via scanning electron microscopy, as well as, cross-sectional and high resolution transmission electron microscopy to elucidate the detailed growth and structural elements of the heterostructure. © 2009 Elsevier B.V. All rights reserved.

Facet-controlled Self-assembly of ZnO Nanocrystals by Non-Hydrolytic Aminolysis and their Photodegradation Activities

We report a method for controlling the exposed facets and hence the dimensionality and shape of ZnO nanocrystals using a non-hydrolytic aminolysis synthesis route. The effects of changes to reaction conditions on ZnO formation were investigated and possible self-assembly mechanisms proposed. The crystal facet growth and hence morphologies of the ZnO nanocrystals were controlled by varying reaction temperature and the reactant ratio. Four distinct ZnO nanocrystal types were produced (nanocones, nanobullets, nanorods and nanoplates). The relative photocatalytic activities of the exposed facets of these ZnO nanostructures were also examined, which showed the activities obviously depended on the reactivity of exposed crystal facets in the order: {1011}>>{0001}, {1010}.

Non-aqueous synthesis of hexagonal ZnO nanopyramids : gas sensing properties

Zinc oxide (ZnO) nanopyramids were synthesized by a one-pot route in a non-aqueous and surfactantfree environment. The synthesized metal oxide was characterized using SEM, XRD, and TEM to investigate the surface morphology and crystallographic phase of the nanostructures. It was observed that the ZnO nanopyramids were of uniform size and symmetrical, with a hexagonal base and height of ∼100 nm. Gas sensing characterization of the ZnO nanopyramids when deposited as thin-film onto conductometric transducers were performed towards NOx and C2H5OH vapor of different concentrations over a temperature range of 22–350 ◦C. It was observed that the sensors responded towards NO2 (10 ppm) and C2H5OH(250 ppm) analytes best at temperatures of 200 and 260 ◦C with a sensor response of 14.5 and 5.72, respectively. The sensors showed satisfactory sensitivity, repeatability as well as fast response and recovery towards both the oxidizing and the reducing analyte. The good performance was attributed to the low amount of organic impurities, large surface-to-volume ratio and high crystallinity of the solvothermally synthesized ZnO nanopyramids.

Pt/ZnO/SiC thin film for hydrogen gas sensing

Zinc oxide (ZnO) is one of the most promising electronic and photonic materials to date. In this work, we present an enhanced ZnO Schottky gas sensor deposited on SiC substrates in comparison to those reported previously in literature. The performance of ZnO/SiC based Schottky thin film gas sensors produced a forward lateral voltage shift of 12.99mV and 111.87mV in response to concentrations of hydrogen gas at 0.06% and 1% in air at optimum temperature of 330 ºC. The maximum change in barrier height was calculated as 37.9 meV for 1% H2 sensing operation at the optimum temperature.

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO2 catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO2 and H2 on ZnO/SiO2 catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO2 and H2 with Cu/ZnO/SiO2 catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism

Characterization of precursors to methanol synthesis catalysts Cu/ZnO system

The composition of a series of hydroxycarbonate precursors to copper/zinc oxide methanol synthesis catalysts prepared under conditions reported as optimum for catalytic activity has been studied. Techniques employed included thermogravimetry (TG), temperature-programmed decomposition (TPD), X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), and Raman and FTIR spectroscopies. Evidence was obtained for various structural phases including hydrozincite, copper hydrozincite, aurichalcite, zincian malachite and malachite (the concentrations of which depended upon the exact Cu/Zn ratio used). Significantly, previously reported phases such as gerhardite and rosasite were not identified when catalysts were synthesized at optimum solution pH and temperature values, and after appropriate aging periods. Calcination of the hydroxycarbonate precursors resulted in the formation of catalysts containing an intimate mixture of copper and zinc oxides. Temperature-programmed reduction (TPR) revealed that a number of discrete copper oxide species were present in the catalyst, the precise concentrations of which were determined to be related to the structure of the catalyst precursor. Copper hydrozincite decomposed to give zinc oxide particles decorated by highly dispersed, small copper oxide species. Aurichalcite appeared to result ultimately in the most intimately mixed catalyst structure whereas zincian malachite decomposed to produce larger copper oxide and zinc oxide grains. The reason for the stabilization of small copper oxide and zinc oxide clusters by aurichalcite was investigated by using carefully selected calcination temperatures. It was concluded that the unique formation of an 'anion-modified' oxide resulting from the initial decomposition stage of aurichalcite was responsible for the 'binding' of copper species to zinc moieties.

Controlled synthesis of inorganic semiconductor nanocrystals and their applications

This thesis is a comprehensive study of the synthesis of nanomaterials. It explores the synthetic methods on the control of the size, shape and phase of semiconductor nanocrystals. A number of important conclusions, including the mechanism behind crystal growth and the structure-relationship, have been drawn through the experimental and theoretical investigation. The synthesized nanocrystals have been tested for applications in gas sensing, photocatalysis and solar cells, which exhibit considerable commercialization potential.

The anodized crystalline WO3 nanoporous network with enhanced electrochromic properties

We demonstrate that a three dimensional (3D) crystalline tungsten trioxide (WO3) nanoporous network, directly grown on a transparent conductive oxide (TCO) substrate, is a suitable working electrode material for high performance electrochromic devices. This nanostructure, with achievable thicknesses of up to 2 μm, is prepared at room temperature by the electrochemical anodization of a RF-sputtered tungsten film deposited on a fluoride doped tin oxide (FTO) conductive glass, under low applied anodic voltages and mild chemical dissolution conditions. For the crystalline nanoporous network with thicknesses ranging from 0.6 to 1 μm, impressive coloration efficiencies of up to 141.5 cm2 C−1 are achieved by applying a low coloration voltage of −0.25 V. It is also observed that there is no significant degradation of the electrochromic properties of the porous film after 2000 continuous coloration–bleaching cycles. The remarkable electrochromic characteristics of this crystalline and nanoporous WO3 are mainly ascribed to the combination of a large surface area, facilitating increased intercalation of protons, as well as excellent continuous and directional paths for charge transfer and proton migration in the highly crystalline material.

Electrodeposited α- and β-phase MoO3 films and investigation of their gasochromic properties

α- and β-Phase MoO3 are synthesized using an electrodeposition method on fluorine-doped tin oxide (FTO) glass substrates from sodium-molybdate (Na2MoO4) solutions. We show that it is possible to obtain both α- and β-MoO3 by manipulating the cyclic voltammetry (CV) parameters during electrodeposition. Raman spectroscopy, X-ray diffraction, and scanning electron microscopy indicate that the applied potential range and sweep rate are strongly influential on the phase obtained and the surface morphology of the electrodeposited thin films. Gasochromic measurements were carried out on the annealed samples by exposing them to H2 gas. It was revealed that α-MoO3 thin films provided better response to H2 interaction than β-MoO3 films did. Additionally, porous films provided significantly larger responses than smooth films.

Engineering electrodeposited ZnO films and their memristive switching performance

We report the influence of zinc oxide (ZnO) seed layers on the performance of ZnO-based memristive devices fabricated using an electrodeposition approach. The memristive element is based on a sandwich structure using Ag and Pt electrodes. The ZnO seed layer is employed to tune the morphology of the electrodeposited ZnO films in order to increase the grain boundary density as well as construct highly ordered arrangements of grain boundaries. Additionally, the seed layer also assists in optimizing the concentration of oxygen vacancies in the films. The fabricated devices exhibit memristive switching behaviour with symmetrical and asymmetrical hysteresis loops in the absence and presence of ZnO seed layers, respectively. A modest concentration of oxygen vacancy in electrodeposited ZnO films as well as an increase in the ordered arrangement of grain boundaries leads to higher switching ratios in Ag/ZnO/Pt devices.

Hexagon platinum Schottky contact with ZnO thin film for hydrogen sensing

This paper reports on the study of the effect on adding total peripheries and sharp edges to the Schottky contact as a hydrogen sensor. Schottky contact was successfully designed and fabricated as hexagon-shape. The contact was integrated together with zinc oxide thin film and tested towards 1% hydrogen gas. Simulations of the design were conducted using COMSOL Multiphysics to observe the electric field characteristic at the contact layer. The simulation results show higher electric field induced at sharp edges with 4.18×104 V/m. Current-voltage characteristic shows 0.27 V voltage shift at 40 μA biased current.

Colloidal semiconductor nanocrystals : controlled synthesis and surface chemistry in organic media

Colloidal semiconductor nanocrystals (CS-NCs) possess compelling benefits of low-cost, large-scale solution processing, and tunable optoelectronic properties through controlled synthesis and surface chemistry engineering. These merits make them promising candidates for a variety of applications. This review focuses on the general strategies and recent developments of the controlled synthesis of CS-NCs in terms of crystalline structure, particle size, dominant exposed facet, and their surface passivation. Highlighted are the organic-media based synthesis of metal chalcogenide (including cadmium, lead, and copper chalcogenide) and metal oxide (including titanium oxide and zinc oxide) nanocrystals. Current challenges and thus future opportunities are also pointed out in this review.

Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.