Mesoporous dye-doped titanium dioxide for micro-optoelectronic applications

Optically transparent, mesostructured titanium dioxide thin films were fabricated using an amphiphilic poly(alkylene oxide) block copolymer template in combination with retarded hydrolysis of a titanium isopropoxide precursor. Prior to calcination, the films displayed a stable hexagonal mesophase and high refractive indices (1.5 to 1.6) relative to mesostructured silica (1.43). After calcination, the hexagonal mesophase was retained with surface areas >300 m2 g-1. The dye Rhodamine 6G (commonly used as a laser dye) was incorporated into the copolymer micelle during the templating process. In this way, novel dye-doped mesostructured titanium dioxide films were synthesised. The copolymer not only directs the film structure, but also provides a solubilizing environment suitable for sustaining a high monomer-to-aggregate ratio at elevated dye concentrations. The dye-doped films displayed optical thresholdlike behaviour characteristic of amplified spontaneous emission. Soft lithography was successfully applied to micropattern the dye-doped films. These results pave the way for the fabrication and demonstration of novel microlaser structures and other active optical structures. This new, high-refractive index, mesostructured, dye-doped material could also find applications in areas such as optical coatings, displays and integrated photonic devices.

Sharp vibronic spectra of Cu(II) doped Cs2ZrCl6

The low temperature electronic spectrum of Cu(II) doped Cs2ZrCl6 is reported. It is found that Cu(II) is incorporated as the square planar copper tetrachloride ion, CuCl42-, which substitutes at the Zr(IV) site in the Cs2ZrCl6 lattice. There is a complete absence of axial coordination. The optical spectrum shows vibronic structure with peak widths as small as 8 cm(-1), far narrower than previously seen for this ion. The energy of the observed transitions and the Franck-Condon intensity pattern suggest that there is a substantial relaxation of the host lattice about the impurity ion. The relative intensity of the magnetic dipole component of the bands appears to be considerably greater than for pure copper(II) compounds containing the CuCl42- ion. (C) 1998 Elsevier Science B.V. All rights reserved.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

Selectively excited luminescence and magnetic circular dichroism of Cr4+-doped YAG and YGG

Site selective luminescence and magnetic circular dichroism experiments on Cr4+-doped yttrium aluminum garnet and yttrium gallium garnet have been made at low temperature. The spectral assignments for these near-IR lasing materials have been made using experimental data and ligand field calculations guided by the known geometry of the lattices. [S0163-1829(99)07003-4].

Field-swept pulsed electron paramagnetic resonance of Cr3+-doped ZBLAN fluoride glass

Field-swept pulsed electron paramagnetic resonance (EPR) spectra of a ZBLAN fluoride glass doped with a low concentration of Cr3+ are obtained using echo-detected EPR and hole-burning free induction decay detection. We review the utility of the pulsed EPR technique in generating field-swept EPR spectra, as well as some of the distorting effects that are peculiar to the pulsed detection method. The application of this technique to Cr3+-doped ZBLAN reveals that much of the broad resonance extending from g(eff) = 5.1 to g(eff) = 1.97, characteristic of X-band continuous wave EPR of Cr3+ in glasses, is absent. We attribute this largely to the variation in nutation frequencies across the spectrum that result from sites possessing large fine structure interactions. The description of the spin dynamics of such sites is complicated and we discuss some possible approaches to the simulation of the pulsed EPR spectra.

Loose abrasive truing and dressing of resin bond diamond cup wheels for grinding fibre optic connectors

A loose abrasive lapping technology was developed for truing and dressing ultrafine diamond cup wheels for grinding spherical end faces of fibre optic connectors. The relative densities of exposed grits and grit pull-outs measured from wheel surfaces prepared using the loose abrasive lapping and the bonded abrasive dressing were compared. It was found that the lapping method with loose abrasives produced wheel surfaces with more exposed grits and less grit pull-outs, especially for finer grit size wheels. For dressing ultrafine grit size wheels, the particle size of the lapping paste should be smaller than the wheel grit size to achieve a better result. It is also found that the wheels dressed using the lapping method demonstrate an excellent grinding performance. (C) 2004 Elsevier B.V.. All rights reserved.

LiI-doped N,N-dimethyl-pyrrolidinium iodide, an archetypal rotator-phase ionic conductor

N,N-Dimethyl-pyrrolidinium iodide, and the effect of doping with LiI, has been investigated using DSC, NMR, and impedance spectroscopy. It was found that the addition of a small amount of LiI enhances the ionic conductivity by LIP to 3 orders of magnitude for this ionic solid. Furthermore, a slight decrease in phase transition onset temperatures, as well as the appearance of a superimposed narrow line in the H-1 NMR spectra with dopant, suggest that the LiI facilitates the mobility of the matrix material, possibly by the introduction of vacancies within the lattice. Li-7 NMR line width measurements reveal a narrow Li line width, decreasing in width and increasing in intensity with temperature, indicating mobile Li ions.

Ferromagnetism, paramagnetism, and a Curie-Weiss metal in an electron-doped Hubbard model on a triangular lattice

Motivated by the unconventional properties and rich phase diagram of NaxCoO2 we consider the electronic and magnetic properties of a two-dimensional Hubbard model on an isotropic triangular lattice doped with electrons away from half-filling. Dynamical mean-field theory (DMFT) calculations predict that for negative intersite hopping amplitudes (t < 0) and an on-site Coulomb repulsion, U, comparable to the bandwidth, the system displays properties typical of a weakly correlated metal. In contrast, for t > 0 a large enhancement of the effective mass, itinerant ferromagnetism, and a metallic phase with a Curie-Weiss magnetic susceptibility are found in a broad electron doping range. The different behavior encountered is a consequence of the larger noninteracting density of states (DOS) at the Fermi level for t > 0 than for t < 0, which effectively enhances the mass and the scattering amplitude of the quasiparticles. The shape of the DOS is crucial for the occurrence of ferromagnetism as for t > 0 the energy cost of polarizing the system is much smaller than for t < 0. Our observation of Nagaoka ferromagnetism is consistent with the A-type antiferromagnetism (i.e., ferromagnetic layers stacked antiferromagnetically) observed in neutron scattering experiments on NaxCoO2. The transport and magnetic properties measured in NaxCoO2 are consistent with DMFT predictions of a metal close to the Mott insulator and we discuss the role of Na ordering in driving the system towards the Mott transition. We propose that the Curie-Weiss metal phase observed in NaxCoO2 is a consequence of the crossover from a bad metal with incoherent quasiparticles at temperatures T > T-* and Fermi liquid behavior with enhanced parameters below T-*, where T-* is a low energy coherence scale induced by strong local Coulomb electron correlations. Our analysis also shows that the one band Hubbard model on a triangular lattice is not enough to describe the unusual properties of NaxCoO2 and is used to identify the simplest relevant model that captures the essential physics in NaxCoO2. We propose a model which allows for the Na ordering phenomena observed in the system which, we propose, drives the system close to the Mott insulating phase even at large dopings.

Electron paramagnetic resonance of Ni(II) doped tris(ethylenediamine)zinc(II) dinitrate

Variable temperature electron paramagnetic resonance spectra of tris(ethylenediamine)zinc(II) dinitrate single crystals doped with NI(II) have been measured. The host crystal undergoes a trigonal to monoclinic phase transition at 146 K. Above the transition temperature the zero field splitting tensor is axially symmetric with D = -0.831 cm(-1) and below it becomes rhombic with D = -0.785 cm(-1), E = -0.088 cm(-1). The low temperature spectrum is characterised by the pattern repeating every 60 degrees when the crystal is rotated about the high temperature c axis. The analysis shows that the Zn(II) site retains a C-2 symmetry axis and that the distortion away from the D-3 site symmetry observed for high temperatures is small, the principal axes being tilted by 2.6 degrees. This implies that the phase transition involves the flipping of the C-C backbone in one of the ethylenediamine ligands of the complex, resulting in a A delta delta delta to Lambda delta delta lambda type conformational change.

Ni(II)-doped CsCdBrCl2: Variation of spectral and structural properties via mixed-halide coordination

A new addition to the family of single-molecule magnets is reported: an Fete cage stabilized with benzoate and pyridonate ligands. Monte Carlo methods have been used to derive exchange parameters within the cage, and hence model susceptibility behavior.

A critical comparison of the external and internal boron requirements for contrasting species in boron-buffered solution culture

Despite reports that boron (B) requirements differ among plant species there is a shortage of critical evidence to demonstrate unequivocally whether species differ in internal or external B requirements or both. The present research was conducted to establish the external and internal B requirements of three contrasting species, a woody dicot (marri), an herbaceous dicot (sunflower) and a monocot (wheat) using B-buffered solution culture. Boron-buffered solution culture provided satisfactory control of external B concentrations ranging from 0.04 to 30 muM throughout the 20- (sunflower and wheat) or 40-day (marri) growth period. At low external B concentrations (less than or equal to 0.13 muM), the growth of marri and sunflower was severely depressed but by contrast the vegetative growth of wheat plants was satisfactory and free of B deficiency symptoms. Marri and sunflower plants achieved total maximum shoot growth at greater than or equal to1.2 muM B in solutions while wheat plants did so at greater than or equal to 0.6 muM B. The critical B concentrations (mg kg(-1) dry matter) in the youngest open leaf blades of marri, sunflower and wheat plants were 17.9, 19.7 and 1.2 on 20, 10 and 10 days after transplanting (DAT), respectively. Lower internal and external B requirements of wheat were matched by a lower uptake rate of B compared to marri and sunflower.

Dynamic Behavior of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion in Cu2+ doped Cs-2[Zn(H2O)(6)](ZrF6)(2) and the crystal structure of the host lattice

The temperature dependence of the X- and Q-band EPR spectra of Cs-2[Zn(H2O)(6)](ZrF6)(2) containing similar to1% Cu2+ is reported. All three molecular g-values vary with temperature, and their behavior is interpreted using a model in which the potential surface of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion is perturbed by an orthorhombic strain induced by interactions with the surrounding lattice. The strain parameters are significantly smaller than those reported previously for the Cu(H2O)(6)(2+) ion in similar lattices. The temperature dependence of the two higher g-values suggests that in the present compound the lattice interactions change slightly with temperature. The crystal structure of the Cs-2[Zn(H2O)(6)](ZrF6)(2) host is reported, and the geometry of the Zn(H2O)(6)(2+) ion is correlated with lattice strain parameters derived from the EPR spectrum of the guest Cu2+ complex.

Dry matter production and boron concentrations of vegetative and reproductive tissues of canola and sunflower plants grown in nutrient solution

Canola (Brassica napus L.) and sunflower (Helianthus annuus L.), two important oilseed crops, are sensitive to low boron (B) supply. Symptoms of B deficiency are often more severe during the reproductive stage, but it is not known if this is due to a decreased external B supply with time or an increased sensitivity to low B during this stage. Canola and sunflower were grown for 75 days after transplanting (DAT) in two solution culture experiments using Amberlite (IRA-743) B-specific resin to maintain constant B concentration in solution over the range 0.6 - 53 muM. Initially, the vegetative growth of both crops was good in all treatments. With the onset of the reproductive stage, however, severe B deficiency symptoms developed and growth of canola and sunflower was reduced with less than or equal to 0.9 and less than or equal to 0.7 muM B, respectively. At these concentrations, reproductive parts failed to develop. The critical B concentration (i.e. 90% of maximum shoot dry matter yield) in the youngest opened leaf was 18 mg kg(-1) in canola and 25 mg kg(-1) in sunflower at 75 DAT. The results of this study indicate that the reproductive stage of these two oilseed crops is more sensitive than the vegetative stage to low B supply.

Effect of Co addition on the lattice parameter, electrical conductivity and sintering of gadolinia-doped ceria

Co-sintering aid has been added to Ce1.9Gd0.1O1.95 (CGO) by treating a commercial powder with Co(NO3)(2) (COCGO), X-ray diffraction (XRD) measurements of lattice parameter indicated that the Co was located on the CGO particle surface after calcination at 650 degreesC. After heat treatment at temperatures above 650 degreesC, the room temperature lattice parameter of CGO was found to increase, indicating redistribution of the Gd. Compared to CGO, the lattice parameter of CGO + 2 cation% Co (2CoCGO) was lower for a given temperature (650-1100 degreesC), A.C. impedance revealed that the lattice conductivity of 2CoCGO was enhanced when densified at lower temperatures, Transmission electron microscopy (TEM) showed that, even after sintering for 4 h at 980 degreesC, most of the Co was located at grain boundaries. (C) 2002 Published by Elsevier Science B.V.

Oxide ionic conductivity and microstructures of Sm- or La-doped CeO2-based systems

The concept of crystallographic index termed the effective index is suggested and applied to the design of ceria (CeO2)-based electrolytes to maximize oxide ionic conductivity. The suggested index considers the fluorite structure, and combines the expected oxygen vacancy level with the ionic radius mismatch between host and dopant cations. Using this approach, oxide ionic conductivity of Sm- or La-doped CeO2-based system has been optimized and tested under operating conditions of a solid oxide fuel cell. In the observation of microstructure in atomic scale, both Sm-doped CeO2 and La-doped CeO2 electrolytes had large micro-domains over 10 nm in the lattice. On the other hand, Sm or La and alkaline earth co-doped CeO2-based electrolytes with high effective index had small micro-domains around 1-3 nm in the microstructure. The large micro-domain would prevent oxide ion from passing through the lattice. Therefore, it is concluded that the improvement of ionic conductivity is reflected in changes of microstructure in atomic scale. (C) 2002 Elsevier Science B.V. All rights reserved.