Recent progress on synthesis, multi-scale structure, and properties of Y-Si-O oxides

Yttrium silicates (Y-Si-O oxides), including Y2Si2O7, Y2SiO5, and Y4·67(SiO4)3O apatite, have attracted wide attentions from material scientists and engineers, because of their extensive polymorphisms and important roles as grain boundary phases in improving the high-temperature mechanical/thermal properties of Si3N4and SiC ceramics. Recent interest in these materials has been renewed by their potential applications as high-temperature structural ceramics, oxidation protective coatings, and environmental barrier coatings (EBCs). The salient properties of Y-Si-O oxides are strongly related to their unique chemical bonds and microstructure features. An in-depth understanding on the synthesis - multi-scale structure-property relationships of the Y-Si-O oxides will shine a light on their performance and potential applications. In this review, recent progress of the synthesis, multi-scale structures, and properties of the Y-Si-O oxides are summarised. First, various methods for the synthesis of Y-Si-O ceramics in the forms of powders, bulks, and thin films/coatings are reviewed. Then, the crystal structures, chemical bonds, and atomic microstructures of the polymorphs in the Y-Si-O system are summarised. The third section focuses on the properties of Y-Si-O oxides, involving the mechanical, thermal, dielectric, and tribological properties, their environmental stability, and their structure-property relationships. The outlook for potential applications of Y-Si-O oxides is also highlighted.

Zr4+ doping in Li4Ti5O12 anode for lithium-ion batteries: Open Li+ diffusion paths through structural imperfection

One-dimensional nanomaterials have short Li+ diffusion paths and promising structural stability, which results in a long cycle life during Li+ insertion and extraction processes in lithium rechargeable batteries. In this study, we fabricated one-dimensional spinel Li 4Ti5O12 (LTO) nanofibers using an electrospinning technique and studied the Zr4+ doping effect on the lattice, electronic structure, and resultant electrochemical properties of Li-ion batteries (LIBs). Accommodating a small fraction of Zr4+ ions in the Ti4+ sites of the LTO structure gave rise to enhanced LIB performance, which was due to structural distortion through an increase in the average lattice constant and thereby enlarged Li+ diffusion paths rather than changes to the electronic structure. Insulating ZrO2 nanoparticles present between the LTO grains due to the low Zr4+ solubility had a negative effect on the Li+ extraction capacity, however. These results could provide key design elements for LTO anodes based on atomic level insights that can pave the way to an optimal protocol to achieve particular functionalities. Distorted lattice: Zr4+ is doped into a 1 D spinel Li4Ti5O12 (LTO) nanostructure and the resulting electrochemical properties are explored through a combined theoretical and experimental investigation. The improved electrochemical performance resulting from incorporation of Zr4+ in the LTO is due to lattice distortion and, thereby, enlarged Li+ diffusion paths rather than to a change in the electronic structure.

The oxygen migration in the apatite-type lanthanum silicate with the cation substitution

A theoretical model is proposed to determine the effects of Si substitution with Al on the oxygen diffusion in apatite-type lanthanum silicates based on density-functional theory (DFT) calculations for La10(SiO 4)4(AlO4)2O2. Substitution changes the stable configuration for excess oxygen from the split interstitial to a new cluster form with the original cluster. Al doping completely changes the migration mechanism from the interstitialcy one, which was proposed for the La9.33(SiO4)6O2 starting material, to a mechanism which contains an interstitial process. Nevertheless, the migration barrier is calculated to be 0.81 eV, which indicates small changes in oxygen conduction and is consistent with the observations. The present study indicates that the cation substitution on silicon site alone does not promise the improvement of the oxide ion conduction in the lanthanum silicate.

Effect of indium doping on the electrical switching behaviour of Ge-Te glasses

Bulk Ge15Te85-xInx (1 <= x <= 11) series of glasses have been found to exhibit a threshold switching behaviour for an input current of 2 mA. An initial decrease is seen in the switching voltages (V-T) with the addition of indium, which is due to the higher metallicity of indium. An increase is seen in V-T above 3 at.% of indium, which proceeds until 8 at.%, with a change in slope (lower to higher) seen around 7 at.%. Beyond x = 8, a reversal in trend is exhibited in the variation of V-T, with a well-defined minimum around x = 9 at.%. Based on the composition dependence of V-T, it is proposed that Ge15Te85-xInx glasses exhibit an extended rigidity percolation threshold. The composition, x = 3, at which the V-T starts to increase and the composition, x = 7, at which a slope change is exhibited correspond to the onset and completion, respectively, of the extended stiffness transition. Thermal studies and photoconductivity e85-xInx glasses. In addition, the minimum seen in V-T at x = 9 is associated with the chemical threshold (CT) of this glassy system.

Electrical switching and in situ Raman scattering studies on the set-reset processes in Ge-Te-Si glass

Bulk Ge15Te83Si2 glass has been found to exhibit memory-type switching for 1 mA current with a threshold electric field of 7.3 kV/cm. The electrical set and reset processes have been achieved with triangular and rectangular pulses, respectively, of 1 mA amplitude. In situ Raman scattering studies indicate that the degree of disorder in Ge15Te83Si2 glass is reduced from off to set state. The local structure of the sample under reset condition is similar to that in the off state. The Raman results are consistent with the switching results which indicate that the Ge15Te83Si2 glass can be set and reset easily. (C) 2007 American Institute of Physics.

Enhanced dielectric response of ZrO2 upon Ti doping and introduction of O vacancies

We determine the electronic properties and dielectric response of zirconia (ZrO2) with oxygen vacancies (O vacancies) and Ti doping using first-principles density functional theory calculations based on pseudopotentials and a plane wave basis. We find significantly enhanced static dielectric response in zirconia with Ti doping and introduction of oxygen vacancies. Softening of phonon modes are responsible for the enhanced dielectric response of doped samples compared to pure zirconia.

Evidence for a thermally reversing window in bulk Ge-Te-Si glasses revealed by alternating differential scanning calorimetry

Experiments on Ge15Tc85-xSix glasses (2 <= x <= 12) using alternating differential scanning calorimetry (ADSC) indicate that these glasses exhibit one glass transition and two crystallization reactions upon heating. The glass transition temperature has been found to increase almost linearly with silicon content, in the entire composition tie-line. The first crystallization temperature (T-cl) exhibits an increase with silicon content for x<5; T-cl remains almost a constant in the composition range 5 < x <= 10 and it increases comparatively more sharply with silicon content thereafter. The specific heat change (Delta C-p) is found to decrease with an increase in silicon content, exhibiting a minimum at x=5 (average coordination number, (r) = 2.4); a continuous increase is seen in Delta C-p with silicon concentration above x = 5. The effects seen in the variation with composition of T-cl and Delta C-p at x=5, are the specific signatures of the mean-field stiffness threshold at (r) = 2.4. Furthermore, a broad trough is seen in the enthalpy change (Delta H-NR), which is indicative of a thermally reversing window in Ge15Te85-xSix glasses in the composition range 2 <= x <= 6 (2.34 <= (r) <= 2.42).

Influence of sintering conditions and doping on the dielectric relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics

Detailed investigations into the dielectric dispersion phenomenon in the giant dielectric constant material CaCu3Ti4O12 (CCTO) around room temperature revealed the existence of two successive dielectric relaxations. In the temperature domain, a new dielectric relaxation was clearly observed around 250K, in addition to the well-investigated dielectric relaxation close to 100K. The effect of sintering and doping (La3+) on the strength of these dielectric relaxations were studied in detail. The sintering temperature as well as its duration was found to have tremendous influence on the dielectric relaxation that was encountered around 250 K. This Maxwell-Wagner (M-W) type of relaxation was found to be originating from the surface layer containing the Cu-rich phase, which was ascribed to the difference in the oxygen content between the surface and the interior of the sample. Interestingly, this particular additional relaxation was not observed in La2/3Cu3Ti4O12, a low dielectric constant member of the CCTO family, in which the segregation of Cu-rich phase on the surface was absent. Indeed the correlation between the new relaxation and the presence of Cu-rich phase in CCTO ceramics was further corroborated by the absence of the same after removing the top and bottom layers. (C) 2007 Elsevier Ltd. All rights reserved.

High pressure studies on the electrical resistivity of As-Te-bond Si glasses and the effect of network topological thresholds

The variation of resistivity in an amorphous As30Te70-xSix system of glasses with high pressure has been studied for pressures up to 8 GPa. It is found that the electrical resistivity and the conduction activation energy decrease continuously with increase in pressure, and samples become metallic in the pressure range 1.0-2.0 GPa. Temperature variation studies carried out at a pressure of 0.92 GPa show that the activation energies lie in the range 0.16-0.18eV. Studies on the composition/average co-ordination number (r) dependence of normalized electrical resistivity at different pressures indicate that rigidity percolation is extended, the onset of the intermediate phase is around (r) = 2.44, and completion at (r) = 2.56, respectively, while the chemical threshold is at (r) = 2.67. These results compare favorably with those obtained from electrical switching and differential scanning calorimetric studies.

Si, CdTe and CdZnTe radiation detectors for imaging applications

The structure and operation of CdTe, CdZnTe and Si pixel detectors based on crystalline semiconductors, bump bonding and CMOS technology and developed mainly at Oy Simage Ltd. And Oy Ajat Ltd., Finland for X- and gamma ray imaging are presented. This detector technology evolved from the development of Si strip detectors at the Finnish Research Institute for High Energy Physics (SEFT) which later merged with other physics research units to form the Helsinki Institute of Physics (HIP). General issues of X-ray imaging such as the benefits of the method of direct conversion of X-rays to signal charge in comparison to the indirect method and the pros and cons of photon counting vs. charge integration are discussed. A novel design of Si and CdTe pixel detectors and the analysis of their imaging performance in terms of SNR, MTF, DQE and dynamic range are presented in detail. The analysis shows that directly converting crystalline semiconductor pixel detectors operated in the charge integration mode can be used in X-ray imaging very close to the theoretical performance limits in terms of efficiency and resolution. Examples of the application of the developed imaging technology to dental intra oral and panoramic and to real time X-ray imaging are given. A CdTe photon counting gamma imager is introduced. A physical model to calculate the photo peak efficiency of photon counting CdTe pixel detectors is developed and described in detail. Simulation results indicates that the charge sharing phenomenon due to diffusion of signal charge carriers limits the pixel size of photon counting detectors to about 250 μm. Radiation hardness issues related to gamma and X-ray imaging detectors are discussed.

The effect of pressure and W-doping on the properties of ZnO thin films for NO2 gas sensing

Pure and W-doped ZnO thin films were obtained using magnetron sputtering at working pressures of 0.4 Pa and 1.33 Pa. The films were deposited on glass and alumina substrates at room temperature and subsequently annealed at 400oC for 1 hour in air. The effects of pressure and W-doping on the structure, chemical, optical and electronic properties of the ZnO films for gas sensing were examined. From AFM, the doped film deposited at higher pressure (1.33 Pa) has spiky morphology with much lower grain density and porosity compared to the doped film deposited at 0.4 Pa. The average gain size and roughness of the annealed films were estimated to be 65 nm and 2.2 nm, respectively with slightly larger grain size and roughness appeared in the doped films. From XPS the films deposited at 1.33 Pa favored the formation of adsorbed oxygen on the film surface and this has been more pronounced in the doped film which created active sites for OH adsorption. As a consequence the W-doped film deposited at 1.33 Pa was found to have lower oxidation state of W (35.1 eV) than the doped film deposited at 0.4 Pa (35.9 eV). Raman spectra indicated that doping modified the properties of the ZnO film and induced free-carrier defects. The transmittance of the samples also reveals an enhanced free-carrier density in the W-doped films. The refractive index of the pure film was also found to increase from 1.7 to 2.2 after W-doping whereas the optical band gap only slightly increased. The W-doped ZnO film deposited at 0.4 Pa appeared to have favorable properties for enhanced gas sensing. This film showed significantly higher sensing performance towards 5-10 ppm NO2 at lower operating temperature of 150oC most dominantly due to increased free-carrier defects achieved by W-doping.

Structural, ferroelectric and optical properties of Bi2VO5.5 thin films deposited on platinized silicon {(100) Pt/TiO2/SiO2/Si} substrates

Bismuth vanadate (Bi2VO5.5, BVO) thin films have been deposited by a pulsed laser ablation technique on platinized silicon substrates. The surface morphology of the BVO thin films has been studied by atomic force microscopy (AFM). The optical properties of the BVO thin films were investigated using spectroscopic ellipsometric measurements in the 300–820 nm wavelength range. The refractive index (n), extinction coefficient (k) and thickness of the BVO thin films have been obtained by fitting the ellipsometric experimental data in a four-phase model (air/BVOrough/BVO/Pt). The values of the optical constants n and k that were determined through multilayer analysis at 600 nm were 2.31 and 0.056, respectively. For fitting the ellipsometric data and to interpret the optical constants, the unknown dielectric function of the BVO films was constructed using a Lorentz model. The roughness of the films was modeled in the Brugmann effective medium approximation and the results were compared with the AFM observations.

Structure and bonding of MCB5H7 and its sandwiched dimer CB5H6M–MCB5H6 (M = Si, Ge, Sn): Isomer stability and preference for slip distorted structure

We find sandwiched metal dimers CB5H6M–MCB5H6 (M = Si, Ge, Sn) which are minima in the potential energy surface with a characteristic M–M single bond. The NBO analysis and the M–M distances (Å) (2.3, 2.44 and 2.81 for M = Si, Ge, Sn) indicate substantial M–M bonding. Formal generation of CB5H6M–MCB5H6 has been studied theoretically. Consecutive substitution of two boron atoms in B7H−27 by M (Si, Ge, Sn) and carbon, respectively followed by dehydrogenation may lead to our desired CB5H6M–MCB5H6. We find that the slip distorted geometry is preferred for MCB5H7 and its dehydrogenated dimer CB5H6M–MCB5H6. The slip-distortion of M–M bond in CB5H6M–MCB5H6 is more than the slip distortion of M–H bond in MCB5H7. Molecular orbital analysis has been done to understand the slip distortion. Larger M–M bending (CB5H6M–MCB5H6) in comparison with M–H bending (MCB5H7) is suspected to be encouraged by stabilization of one of the M–M π bonding MO’s. Preference of M to occupy the apex of pentagonal skeleton of MCB5H7 over its icosahedral analogue MCB10H11 has been observed.

Theory of the unusual doping and temperature dependence of photoemission spectra in manganites

A recent, major, puzzle in the core-level photoemission spectra of doped manganites is the observation of a 1–2 eV wide shoulder with intensity varying with temperature T as the square of the magnetization over a T scale of order 200 K, an order of magnitude less than electronic energies. This is addressed and resolved here, by extending a recently proposed two-fluid polaron–mobile electron model for these systems to include core-hole effects. The position of the shoulder is found to be determined by Coulomb and Jahn-Teller energies, while its spectral weight is determined by the mobile electron energetics which is strongly T and doping dependent, due to annealed disorder scattering from the polarons and the t2g core spins. Our theory accounts quantitatively for the observed T dependence of the difference spectra, and furthermore, explains the observed correspondence between spectral changes due to increasing doping and decreasing T.