Preparation of TiO2 hollow spheres for DSSC photoanodes

High crystallinity mesoporous TiO₂ hollow spheres (MHS-TiO₂) were prepared using the mesoporous carbon hollow sphere template. The MHS-TiO₂ contains mainly nanostructured anatase. The mesopore of the MHS-TiO₂ has a pore opening in the range of 400–600 nm. The refined extended X-ray absorption fine structure spectra indicate that the MHS-TiO₂ possesses less the 1st-shell Ti–O coordination numbers than the nano-TiO₂. More surface active species (A₂ ((Ti=O)O₄)) on the MHS-TiO₂ are also observed by the component fitted X-ray absorption near edge structure spectroscopy. The MHS-TiO₂ photoanode has a better DSSC conversion efficiency than the nano-TiO₂ one by at least 40%. Note that the N3 dye molecules are accessible to the mesopores of the MHS-TiO₂, and the loading time for N3 can be reduced by at least 70% if compared with those of the nano-TiO₂.     

Local composition and carrier concentration in Pb0.7Ge0.3Te and Pb0.5Ge0.5Te alloys from Te NMR and microscopy

Pb_0.7Ge_0.3Te and Pb_0.5Ge_0.5Te alloys, (i) quenched from 923 K or (ii) quenched and annealed at 573 K for 2 h, have been studied by ¹²⁵Te NMR, X-ray diffraction, electron and optical microscopy, as well as energy dispersive spectroscopy. Depending on the composition and thermal treatment history, ¹²⁵Te NMR spectra exhibit different resonance frequencies and spin-lattice relaxation times, which can be assigned to different phases in the alloy. Quenched and annealed Pb_0.7Ge_0.3Te alloys can be considered as solid solutions but are shown by NMR to have components with various carrier concentrations. Quenched and annealed Pb_0.5Ge_0.5Te alloys contain GeTe- and PbTe-based phases with different compositions and charge carrier concentrations. Based on the analysis of non-exponential ¹²⁵Te NMR spin-lattice relaxation, the fractions and carrier concentrations of the various phases have been estimated. Our data show that alloying of PbTe with Ge results in the formation of chemically and electronically inhomogeneous systems. ¹²⁵Te NMR can be used as an efficient probe to detect the local composition in equilibrium as well as non-equilibrium states, and to determine the local carrier concentrations in complex multiphase tellurides.     

Growth of vertically aligned one-dimensional ZnO nanowire arrays on sol–gel derived ZnO thin films

Vertically aligned one-dimensional ZnO nanowire arrays have been synthesized by a hydrothermal method on sol–gel derived ZnO films. Sol–gel derived ZnO films and corresponding ZnO nanowire arrays have been characterized by X-ray diffraction and field-emission scanning electron microscopy. The effect of sol–gel derived ZnO film surface on the morphology of ZnO nanowire arrays has been investigated. The authors suggest from our investigation that sol–gel derived ZnO films affect the growth of one-dimensional ZnO nanostructures. Not only crystalline ZnO films but also amorphous ones can act as a scaffold for ZnO nucleus. Tilted ZnO micro-rods are grown on ZnO gel films, whereas vertically aligned ZnO nanowire arrays are grown on nanometer-sized ZnO grains. The average diameter of ZnO nanowire arrays are correlated strongly with the grain size of sol–gel derived ZnO films.     

Universal microstructure and conductivity relaxation of polymer-conductor composites across the percolation threshold

Micro-structural and impedance analysis of series of insulating polymer/conductor composites (PCC) as a function of frequency and volume fractions of the conductor (f_con) have been studied. Evidences of conductivity relaxation have been noticed with a correlation with the sample micro-structure. This has been understood and explained in terms of equivalent electrical circuit model of the material established through complex impedance spectroscopy (CIS) across the percolation threshold (f_c) for all the PCC. CIS analysis confirmed that PCC with f_con ≥ f_c, exhibit conductivity/interfacial relaxation due to polarization of Maxwell–Wagner–Sillars (MWS) type at f_c and the relaxation frequency increases with increase of f_con. The modulus spectroscopy analysis suggests the presence of two types of relaxations in different frequency ranges; (i) dipolar relaxation associated with the flipping of dipoles present in the pure polymer for f_con < f_c and (ii) the conductivity/interfacial relaxation due to the formation of artificial MWS dipoles at the interface of the two components. A long range dc conductivity appears at f_con ≥ f_c and Jonschers universal fractional power law is satisfied for both the regions of f_con < f_c and f_con ≥ f_c in all PCC.     

Effect of alumina addition on the microstructure and grain boundary resistance of magnesia partially-stabilized zirconia

The electrical properties of 9 mol% MgO–ZrO₂ (Mg-PSZ) with 1 mol% Al₂O₃ and the mechanisms for electrical degradation were investigated using structural, morphological, and electrochemical analyses. The addition of Al₂O₃ caused an increase in both the monoclinic and the Mg-rich phases at the grain boundaries in the Mg-PSZ. Coarse grains larger than 20 μm and an intergranular layer composed of the Mg-rich phase were identified in a specimen sintered at 1600 °C. This specimen exhibited a minimum of ionic conductivity (4.98 × 10⁻⁴ S cm⁻¹ at 700 °C) due to the grain boundary resistance (245 Ω cm²), which dominated the overall resistance. A similar trend was observed over the entire temperature range (600–1500 °C). An intergranular siliceous impurity (SiO₂) was present in conjunction with the Mg-rich phase. This impurity and the Mg-rich phase acted as a barrier layer for oxygen ion diffusion. The presence of the intergranular phases (i.e. the monoclinic and Mg-rich phases) contributed to the degradation of the ionic conductivity in Mg-PSZ with an Al₂O₃ addition.     

Measuring small compartments with relatively weak gradients by angular double-pulsed-field-gradient NMR

NMR diffusion–diffraction patterns observed in compartments in which restricted diffusion occurs are a useful tool for direct extraction of compartment sizes. Such diffusion–diffraction patterns may be observed when the signal intensity E_(q,?) is plotted against the wave-vector q (when q = (2π)^− 1γδG). However, the smaller the compartment sizes are, the higher are the q-values needed to observe such diffractions. Moreover, these q-values should be achieved using short gradient pulses requiring extremely strong gradient systems. The angular double-pulsed-field gradient (d-PFG) NMR methodology has been proposed as a tool to extract compartment sizes using relatively low q-values. In this study, we have used single-PFG (s-PFG) NMR and angular d-PFG NMR to characterize the size of microcapillaries of about 2 ± 1 μm in diameter. We found that these microcapillaries are characterized by relatively strong background gradients that completely masked the effects of the microscopic anisotropy (μA) of the sample, resulting in a completely unexpected E(φ) profile in the angular d-PFG NMR experiments. We also show that bipolar angular d-PFG NMR experiments can largely suppress the effect of these background gradients resulting in the expected E(φ) profile from which the compartment dimensions could be obtained with relatively weak gradient pulses. These results demonstrate that the above methodology provides a quick, reliable, non-invasive means for estimating small pore sizes with relatively weak gradients in the presence of large magnetic susceptibility.     

Growth behavior and microstructure of Ge self-assembled islands on nanometer-scale patterned Si substrate

We investigate the growth behavior and microstructure of Ge self-assembled islands of nanometer dimension on Si (0 0 1) substrate patterned with hexagonally ordered holes of 25 nm depth, 30 nm diameter, and 7×10¹⁰ cm⁻² density. At 9 Å Ge coverage and 650 °C growth temperature, Ge islands preferentially nucleate inside the holes, starting at the bottom perimeter. Approximately 14% of the holes are filled by Ge islands. Moiré fringe analysis reveals partial strain relaxation of about 72% on average, which is not uniform even within a single island. Crystalline defects such as dislocation are observed from islands smaller than 30 nm. Increased Ge coverage to 70 Å forms larger aggregates of many interconnected islands with slightly increased filling factor of about 17% of the holes. Reducing the growth temperature to 280 °C results in much higher density of islands with a filling factor of about 80% and with some aggregates. The results described in this report represent a potential approach for fabricating semiconductor quantum dots via epitaxy with higher than 10¹⁰ cm⁻² density.     

Aurivillius-type ceramics, a class of high temperature piezoelectric materials: Drawbacks, advantages and trends

The obtention of reliable and high performance piezoelectric ceramics for uses at high temperatures is still an open issue in the field of electroceramics. The materials used nowadays for such applications present limitations due to different causes: low piezoelectric coefficients, difficulties in processing that lead to the necessary use of single crystals, high cost of raw materials and more. In this sense, an increasing interest in materials with the so-called Aurivillius-type structure has occurred during recent years, due to their relatively high piezoelectric coefficients and high ferro–paraelectric phase transition temperature. However, some difficulties must be overcome, such as processing for obtaining highly dense ceramics and determining their real piezoelectric behaviour at high temperature. In this work, a review of the processing and properties of ceramics with this structure is shown. Effects of the use of precursors obtained by an alternative route mechanical activation on the microstructure are explained. A complete piezoelectric characterization at working temperatures (>300 °C), barely found in the literature, is also shown. The effects of trapped charges in the dielectric permittivity and in the piezoelectric radial resonance are also discussed.