We report the growth of sheet-like nanostructured tungsten trioxide hydrate (3WO3·H2O) film on fluorine doped tin oxide (FTO) substrate via a facile crystal-seed-assisted hydrothermal method by using CH3COONH4 as capping agent. Dense thin film composed of irregular blocks with smaller surface area was obtained without the addition of CH3COONH4. X-ray diffraction (XRD) studies indicated that both films were of orthorhombic structure. The nanosheet film grown with CH3COONH4 after dehydration showed highly improved photocatalytic activities than the nanoblock one. The maximum anodic photocurrents of 1.16 mA/cm2 for oxidization of methanol and 0.5 mA/cm2 for water splitting were obtained for the nanosheet film with a highest photoconversion efficiency of about 0.3% under simulated solar illumination.

With the aid of negative dielectrophoresis (nDEP) force in conjunction with shear force and at an optimal sodium hydroxide (NaOH) concentration we demonstrated a switch-like functionality to elute immuno-bound beads from the surface. At an optimal flow rate and NaOH concentration, nDEP turned on results in bead detachment, whereas when nDEP is off, the beads remain attached. This platform offers the potential for performing a bead-based multiplexed immunoassay where in a single channel various regions are immobilized with a different antibody, each targeting a different antigen. As a proof of concept we demonstrated the ability of nDEP to provide this switching behavior in a singleplex assay for the interactions that were in the same order of magnitude in strength as typical antibody-antigen interactions.

Color-tuning of UV luminescent silicon nanocrystals (Si NCs) was successfully achieved by precise size control of non-oxidized NCs. The alkoxy-capped Si NCs was synthesized via sodium biphenylide reduction of SiCl4 encapsulated with inverse micelles, and subsequent alkoxylation of surface Si-Cl bonds. Due to the high molecular packing density of alkoxy monolayers, outermost surface of the NCs was completely protected from oxidation even under ambient conditions. Interestingly, the optical absorption and emission spectra were blueshifted with reduction of non-oxidized NC size, and we found strong light emission in the UV range when the NCs were smaller than 2.5 nm. More than 20% of PL quantum efficiencies (QYs) were estimated from those UV luminescent NCs. Monodispersed NCs without oxide can provided narrow PL spectra with 35-40 nm of line-widths, while the presence of oxidized surface region of NCs led to the broad PL spectra. In addition, the redshift of PL spectra were observed from the partially-oxidized NCs which were formed due to the lower surface molecular coverage, suggesting the significant difference in optical transition of photogenerated carriers between the non-oxidized and the partially-oxidized NCs. This can be well-illustrated by comparing decay profiles of the carriers for each sample through the time-resolved PL spectroscopic observation.

A robust processing route at low cost is an essential requirement for high-temperature materials used in automotive engines. Because of their excellent high-temperature properties, their low density, high elastic modulus as well as high specific strength, intermetallic γ-TiAl based alloys are potential candidates for application in advanced automotive turbochargers. So-called 3rd generation alloys, such as TNM™ alloys with a nominal composition of Ti-43.5Al-4Nb-1Mo-0.1B (in at%), are multi-phase alloys consisting of γ-TiAl, α2-Ti3Al and a low volume fraction of βo-TiAl phase. In this paper a novel hot-processing route, which is a combination of a one-shot hot-forging step and a controlled cooling treatment, leads to mechanical properties required for turbocharger turbine wheels. The observed strength can be attributed to the small lamellar spacing within the α2/γ colonies of the nearly lamellar microstructure. In order to analyze the microstructure and the prevailing phase fractions microscopic examinations and X-ray diffraction measurements were conducted. The mechanical properties were determined by hardness measurements as well as tensile and creep tests. The evolution of the microstructure during the hot-forming process is described and its relation to the obtained mechanical properties.

In order to characterize the microstructure of oxide layers formed on Zircaloy-4 tubes during the breakaway transition, oxidation tests in a flowing steam environment were performed at 1000°C with a different oxidation time. It was found that breakaway oxidation occurred after the oxidation time of 3000s, and zirconium dioxide layers existed in two mixed crystallographic forms of the tetragonal and monoclinic phase in all samples. The zirconium oxide layers showed enhanced crystallinity, increase in grain size, and fine pores at the grain boundary after breakaway oxidation. We found that the initiation of breakaway-oxidation instability originated from these microstructural changes.

We produce four distinct ZnO nanorod diode structures that are based on ZnO nanorods produced at pH 6 and pH 11 and have the p-type material PEDOT:PSS (hybrid device) or CuSCN (all inorganic device). After testing the performance of the diodes we show a rectification of 1050 at ±1V in the dark for the inorganic device. The device also exhibits good UV photodetection showing a rapid ca0.1ms turn on and off to a source of illumination. The hybrid devices performed as previously reported with a rectification of 25 at ±1V in both dark and under illumination. We ascribe the performance of the devices to the differences in morphology in the ZnO brought about by the processing conditions and the way in which the p-type layer coats the nanostructure.

We have developed the tactile sensor using the microcantilevers with strain gauge film which can detect normal and shear forces simultaneously. In this work, the tactile sensor and the IC amplifier have been integrated heterogeneously to shorten the wire length by chip-on-chip stacking and reduce the noise in the output voltage. Standard deviation of the noise can be reduced from 27.6 mV to 3.3 mV by heterogeneous integration of the tactile sensor and the IC amplifier using Au wire bonding. By this heterogeneous integration, the device size and wiring numbers can be reduced, and installation of more sensors is allowed on fingertips of the robot. Moreover, through-silicon-via (TSV) holes were fabricated to mount an IC amplifier on the backside of the sensor chip, instead of using Au wires. Although TSV can be fabricated successfully, resistance to sacrificial etching process is problem. As a result, Si3N4 used instead of SiO2 has improved insulation between TSVs.

ZnO bulk crystals can be grown by several methods. 1) From the gas phase, usually by chemical vapor transport. Such CVT crystals may have high chemical purity, as the growth is performed without contact to foreign material. The crystallographic quality is often very high (free growth). 2) From melt fluxes such as alkaline hydroxides or other oxides (MoO3, V2O5, P2O5, PbO) and salts (PbCl2, PbF2). Melt fluxes offer the possibility to grow bulk ZnO under mild conditions (<1000°C, atmospheric pressure), but the crystals always contain traces of solvent. The limited purity is a severe drawback, especially for electronic applications. 3) From hydrothermal fluxes, usually alkaline (KOH, LiOH) aqueous solutions beyond the critical point. Due to the amphoteric character of ZnO, the supercritical bases can dissolve it up to several per cent of mass. The technical requirements for this growth technology are generally hard, but this did not hinder its development as the basic technique for the growth of α-quartz, and meanwhile also of zinc oxide, during the last decades. 4) From pure melts, which is the preferred technology for numerous substances applied whenever possible, e.g. for the growth of silicon, gallium arsenide, sapphire, YAG. The benefits of melt growth are (i) the high growth rate and (ii) the absence of solvent related impurities. In the case of ZnO, however, it is difficult to find container materials that are compatible from the thermal (fusion point T f = 1975°C) and chemical (required oxygen partial pressure) point of view. Either cold crucible (skull melting) or Bridgman (with reactive atmosphere) techniques were shown to overcome the problems that are inherent to melt growth. Reactive atmospheres allow to grow not only bulk ZnO single crystals, but also other TCOs such as β-Ga2O3 and In2O3.

The phase transition of VO2 grown on sapphire having different crystallographic growth planes is examined experimentally. Measurements of electrical resistivity are compared with spectroscopic ellipsometry studies, to obtain complex index of refraction and plasma frequency, and transmission in the terahertz frequency range, each as a function of temperature.

Crack free lead zirconate titanate (PZT) films for piezoelectric based MEMS devices have been prepared by a multiple coating sol gel process on platinized silicon (100) substrates. Rapid thermal annealing and Conventional furnace annealing were used for densification and crystallization of the amorphous PZT films. Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) and Atomic force microscopy (AFM) were used to observe surface film morphology and grain growth. The phase content of the films was analyzed using X-ray diffraction. The role of intermetallics formed during the heat treatment in the growth of different orientations has also been observed. Film aging critical for device performance has been observed and methods to revert aging effects have been examined and discussed.

The generation of terminal N-Hydroxyl substituents in p-phenylene ethynylene based compounds is presented. P-phenylene ethynylene derivatives were synthesized in a Sonogashira coupling reaction. N-Hydroxyl groups could be introduced by lithiation of iodine moieties and subsequent reaction with the 2-methyl-2-nitrosopropane generated by the cleavage of its dimer. The synthesis by lithiation was found to be more effective compared to the reaction with the Grignard reagent and the chloro-derivative. The resulting compounds were characterized by 1H NMR, UV and PL spectroscopy and were shown to be sensitive towards oxidation. This new approach of introducing additional charge carriers by nitroxyl endgroups might enable conjugated polymers with enhanced conductivity.

Epitaixal Ba0.5Sr0.5TiO3 (BST) thin films were grown on SrTiO3 (STO) and DyScO3 substrates by radio-frequency magnetron sputtering system using three-step method which involves a relatively low-temperature (573-773 K) growth of a BST interlayer sandwiched between two BST layers deposited at a high substrate temperature of 1068 K. X-ray diffraction measurement showed different strains on the films with interlayers grown at different temperatures. Post-growth thermal treatment reduced film strain to a great extent (the film strain of a tri-layer film with a 773 K grown interlayer is only -0.001). Comparing with the control films grown at high temperature, three-step technique improved the dielectric properties, especially increased dielectric constant by 60% for BST/STO and 31% for BST/DyScO3, respectively. High dielectric constant of 1631.4 and its tuning of 36.7% were achieved on the BST/STO with an interlayer grown on 773 K.

GaN nanowires and nanorods have been successfully synthesized on Si (111) substrates by magnetron sputtering through ammoniating Ga2O3/Nb thin films and the effects of ammoniation temperatures on growth of GaN nanowires and nanorods were analyzed in detail. X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy, and photoluminescence spectra were carried out to characterize microstructures, morphologies, and optical properties of GaN samples. The results demonstrate that sample after ammoniation at 950 °C is single crystal GaN with hexagonal wurtzite structure and high crystalline quality, having the size of 30 - 80 nm in diameter. After ammoniation at 1000 °C, GaN nanorods appear with smooth and clean surface and more than 100 nm in diameter. The optical properties of GaN nanowires grown at 950 °C and nanorods grown at 1000 °C are best with strong emission intensities.

In recent years, first-principle electronic structure calculations have been carried out to investigate such diverse phenomena as charge transport in molecular wires, optical properties of quantum structures and in photonics. However, at this time the prohibitive computational cost does not allow for such calculations to be easily carried out on nano-scale device structures comprising thousands of atoms. In addition, there are issues relating to the applicability of these approaches to describing the excitations that ought to be involved in charge transport.

Self-consistent extended Huckel theory (SC-EHT) has proved very effective in describing the band alignment at semiconductor interfaces, and optical properties of partially covered surfaces, as well as being employed in studying the electronic states of large molecules. We have developed a non-equilibrium Greens function (NEGF) SC-EHT code that may be applied to study charge transport through molecular wires. We study the transmission of a porphyrin molecule attached via thiol linkers to gold electrodes, compare our results with those obtained from density functional theory (DFT). We have studied the influence the thiol position on the Au substrate has on the conduction and the dependence of the electron transmission on the molecular conformation. In addition, we also report on the results of some preliminary investigations studying the influence of water on the conduction pathways.

Several national programs for geological disposal of higher activity radioactive waste will initiate siting via a call for volunteers. This is probably furthest advanced in Japan (NUMO) and the UK (NDA RWMD). In both these cases, rather than focusing on a reference repository concept, a catalogue of options has been developed. This requires a process to tailor design options to sites and compare particular design/site combinations as part of the site selection process. As has been noted in the longer-running Japanese program, the assessment of options must be as realistic as possible, rather than conservative, as in past nominating approaches to siting. Past demonstration work has focused on feasibility, showing that it is possible to implement a design. Determining practicality, which incorporates many more complex factors, is more difficult. Extensive desk studies can form a basis for such analysis but these must be rigorously tested, which makes full-scale tests in Underground Rock Laboratories (URLs) an essential component of any program. This paper highlights the importance of such demonstration projects and illustrates how they are vital in both improving understanding of the engineered barrier system and stakeholder engagement.

To establish a promising method for the purification of air containing volatile organic compounds, TiO2 nanoparticles with interesting physicochemical properties were prepared by the sol-gel method to perform the photocatalytic decomposition of acetaldehyde. The obtained samples were characterized by the x-ray diffraction -Rietveld refinement, transmission electron microscopy (TEM) and the Brunauer, Emmet and Teller (BET) model. According to the results, the sample that presented the highest activity (96.4%) in the photocatalytic oxidation of acetaldehyde was the one annealed at 200 °C. This material showed the presence of a mixture of the anatase (higher proportion) and brookite phases, nanometric crystal size (7.03 nm) and high surface area (189 m2g-1). The physicochemical properties present in the TiO2-P-200°C nanoparticles suggest that they may establish a photoassisted reaction process for air purification, in which volatile organic compounds are photocatalitically decomposed.

We prepared the type-I Ba8Aux Si46-x (x=5.5, 5.4 and 5.33) clathrates with p-type conduction by arc-melting and subsequent annealing. The Seebeck coefficients of all as-synthesized samples were negative. After annealing, in the case of x=5.4 and 5.5, the Seebeck coefficients changed to positive, and in the case of x=5.33, this value was negative for the annealed sample. The chemical composition revealed that Au content in the Ba8Aux Si46-x clathrates increased after the annealing process. The backscattered electron images showed that there were many Au-excess regions which were not clathrate structure in the as-synthesized samples, and these regions decreased and even disappeared after the annealing process. The disappearing of Au-excess regions can be explained by the diffusion of Au atoms from the Au-excess regions into the clathrates. Based on these results, annealing treatment can be used to tune the carrier conduction by controlling the content of Au for type-I Ba8Aux Si46-x clathrates.

In many deep repository concepts spent nuclear fuel (SNF) will be disposed in canisters containing large amounts of iron. Intrusion of groundwater in a failed canister may occur under the presence of hydrogen, expected to be produced by the anoxic corrosion of iron. Compelling evidence now exists that hydrogen inhibits oxidative dissolution of SNF, the mechanism is however not fully understood. Hydrogen generally requires a catalyst in order to operate as a reductant. The metallic inclusions (ε-particles) present in SNF are a likely catalyst for this process due to their noble metal content. There is also evidence that the SNF UO2 matrix or doping of the UO2 with fission products can activate hydrogen. In most spent fuel experiments carried out under hydrogen, a decrease in concentration of all redox sensitive nuclides originating from a pre-oxidized layer is observed. Given their low concentrations and abundance in the fuel, it has however been difficult to detect any reductive precipitation on the fuel surfaces.

In this study, Cr(VI) oxyanions were employed as a redox sensitive marker, as Cr(VI) is expected to precipitate as Cr(III) oxide on the catalyst that activates hydrogen.

In the experiments PWR spent fuel (43 MWd/kgU) was leached in simulated groundwater (10 mM NaCl, 2 mM NaHCO3) at 25 and 70 ◦C under 5 MPa of hydrogen and dissolved Cr(VI). Dark green, Cr(III)-oxide was found to precipitate; mapping by electron microscopy (SEM-WDS) evidenced a Cr rich layer covering the fuel, suggesting that the whole fuel surface is catalyzing the reduction of chromium.