Neutron polarization analysis on the multiferroic TbMn2O5

Polycrystalline TbMn₂O₅ was prepared by the standard solid-state reaction method and characterized by powder X-ray diffraction and magnetization to assure it is of single phase. Heat capacity measurements on the compound reveal an antiferromagnetic phase transition at 45 K. A broad peak below 6 K in the heat capacity measurements corresponds to the crossover transition of Tb³⁺ ordering. To confirm these magnetic orderings, neutron powder diffractions on TbMn₂O₅ with XYZ neutron polarization analysis were performed at the diffuse neutron scattering (DNS) spectrometer, FRJ-II, by using neutron wavelength of 4.8 Å in the temperature range of 1.8–250 K. Magnetic scattering was separated from nuclear coherent and spin incoherent scattering contributions. Long-range ordered magnetic peaks were observed below 39 K which is consistent with the heat capacity results. The drastic increasing intensities below 6 K indicate the ferromagnetic transition in Tb³⁺ orderings.     

Structure and properties of the one-dimensional cobalt oxide CaCo2O4

We have studied crystal structure and transport properties of the quasi one-dimensional cobalt oxide CaCo₂O₄. The CaCo₂O₄ phase crystallizes in calcium-ferrite type structure, which consists of a corner- and edge-shared CoO₆ octahedron network including one-dimensional double chains. Large thermoelectric power (S  150 μV/K at 390 K) with metallic temperature dependence of S, moderate resistivity (ρ  2.9 × 10⁻¹ Ω cm at 390 K) with carrier localization at low temperature, and normal thermal conductivity (κ  6.3 W/Km at 390 K) were observed. The phonon mean-free path was calculated from the observed data, as a function of temperature. The long phonon mean-free path (l  24 Å at 300 K) implies that the thermal conductivity could be suppressed by impurity scattering of phonons with partial element substitution.     

Scanning tunneling microscopy/spectroscopy on multi-layered cuprate superconductor Ba2Ca5Cu6O12 (O1−x Fx)2

Scanning tunneling microscopy/spectroscopy (STM/STS) measurements on multi-layered cuprate superconductor Ba₂Ca₅Cu₆O₁₂ (O_1−x F_x)₂ are carried out. STM topographies show randomly distributed bright spot structures with a typical spot size of 0.8 nm. These bright spots are occupied about 28% per one unit cell of c-plane, which is comparable to the regular amount of apical oxygen of 20% obtained from element analysis. Tunneling spectra simultaneously show both the small and the large gap structures. These gap sizes at 4.9 K are about Δ 15 meV and 90 meV, respectively. The small gap structure disappears at the temperature close to T_C, while the large gap persists up to 200 K. Therefore, these features correspond to the superconducting gap and pseudogap, respectively. These facts give evidence for some ordered state with large energy scale even in the superconducting state. For the superconducting gap, the ratio of 2Δ/K_BT_C = 4.9 is obtained with T_C = 70 K, which is determined from temperature dependence of the tunneling spectra.     

Optical properties of GaN nanocrystals embedded into silica matrices

The purpose of this work was to obtain GaN nanocrystals (GaN-nc) embedded into silica-based matrix and to investigate their optical properties by photoluminescence (PL) spectroscopy. GaN-nc have been obtained both by the sol–gel chemistry and by the combustion method (CM). The GaN-nc obtained by CM have been introduced into the silica-based matrix during the formation of the film in the spin-on technique. Strong emission at 3.4 eV has been observed for the films doped by GaN-nc whereas no emission in UV has been observed for GaN-nc obtained by sol–gel chemistry.     

Microwave dielectric properties of (1 − x)(Mg0.95Co0.05)TiO3–x(Na0.5La0.5)TiO3 ceramic system

The microstructures and the microwave dielectric properties of the (1 − x)(Mg_0.95Co_0.05)TiO₃–x(Na_0.5La_0.5)TiO₃ ceramic system were investigated. Two-phase system was confirmed by the XRD patterns and the EDX analysis. A co-existed second phase (Mg_0.95Co_0.05)Ti₂O₅ was also detected. The microwave dielectric properties are strongly related to the density and the matrix of the specimen. A new microwave dielectric material 0.88(Mg_0.95Co_0.05)TiO₃–0.12(Na_0.5La_0.5)TiO₃, possessing an excellent combination of dielectric properties: ε_r  22.36, Q × f  110,000 GHz (at 9 GHz), τ_f  2.9 ppm/°C), is proposed as a candidate dielectric for GPS patch antennas.     

The effect of stoichiometry on the combustion behavior of a nanoscale Al/MoO3 thermite

The effect of stoichiometry on the combustion behavior of the nanoscale aluminum molybdenum trioxide (nAl/MoO₃) thermite was studied in a burn tube experiment by characterizing the propagation velocity and pressure output of the reaction. Changing the stoichiometry affects the combustion through changes in the product temperature, phase, and composition. The mixture ratios of the composites were varied over an extremely wide range (5% nAl (95% MoO₃)–90% nAl (10% MoO₃)). Results revealed three separate combustion regimes: a steady high speed propagation (100 to 1000 m/s) from approximately 10% to 65% nAl, an oscillating and accelerating wave near 70% nAl, and a steady-slow speed propagation (0.1–1 m/s) from approximately 75% to 85% nAl. Propagation was observed to fail both <10% nAl and >85% nAl. This is the first known observation of such limits for a nanoscale thermite in a tube geometry. The instrumented tube tests revealed peak pressures over 8 MPa near stoichiometric conditions in the steady high speed propagation region, no measurable pressure rise at low speed propagation, and building pressures for accelerating waves. The results suggest the propagation mode to be a supersonic convective wave for near stoichiometric mixtures and a conductive deflagration for extremely fuel-rich mixtures. The implications of these results for microscale combustion applications are discussed.     

Optical studies on a coherent InGaN/GaN layer

Photoluminescence (PL), photoluminescence excitation (PLE) and selective excitation (SE-PL) studies were performed in an attempt to identify the origin of the emission bands in a pseudomorphic In_0.05Ga_0.95N/GaN film. Besides the InGaN near-band-edge PL emission centred at 3.25 eV an additional blue band centred at 2.74 eV was observed. The lower energy PL peak is characterized by an energy separation between absorption and emission–the Stokes’ shift–(500 meV) much larger than expected. A systematic PLE and selective excitation analysis has shown that the PL peak at 2.74 eV is related to an absorption band observed below the InGaN band gap. We propose the blue emission and its related absorption band are associated to defect levels, which can be formed inside either the InGaN or GaN band gap.     

Quantum confinement and interface structure of Si nanocrystals of sizes 3–5 nm embedded in a-SiO2

Spectroscopic ellipsometry and Monte Carlo simulations are employed to answer the fundamental question whether the energy gaps of Si nanocrystals with sizes in the range of 3–5 nm, which are embedded in amorphous silica, follow or deviate from the quantum confinement model, and to examine their interfacial structure. It is shown that the optical properties of these nanocrystals are well described by the Forouhi–Bloomer interband model. Analysis of the optical measurements over a photon-energy range of 1.5–5 eV shows that the gap of embedded nanocrystals with a mean size of 3.9 nm follows closely quantum confinement theory. A large band gap expansion (0.65 eV) compared to bulk Si is observed. The Monte Carlo simulations reveal a non-abrupt interface and a large fraction of interface oxygen bonds. This, in conjunction with the experimental observations, indicates that oxygen states and the chemical disorder at the interface have a negligible influence on the optical properties of the material in this size regime.     

Gas-phase vibrational spectroscopy and ab initio calculations of Rb(H2O)n and Rb(H2O)nAr cluster ions

The competition between ion–water electrostatic interactions and water–water hydrogen bonding in cluster ions depends on several factors, including charge density of the ion and temperature of the system. Infrared photodissociation spectra of Rb⁺(H₂O)_n=2–5 and Rb⁺(H₂O)_n=1–5Ar are presented here and compared to previous experiments involving potassium and cesium. The temperature, or internal energy, of hydrated rubidium cluster ions is controlled by varying the evaporative path available for cluster formation. Warmer clusters (with effective temperatures of 250–500 K) are formed by the evaporation of water, while colder clusters (40–120 K) can be formed by argon evaporation. Colder cluster ions tend to favor conformers with more hydrogen bonds compared to those cluster ions at warmer temperatures. Previous work from this laboratory has shown significant and dramatic differences between the spectra of hydrated potassium and cesium ions. With a charge density intermediate between that of K⁺ and Cs⁺, Rb⁺ plays an important role in bridging the gap in our previous studies.     

Arsenic-related recombination in MOVPE-grown ZnO/GaAs films

In this paper, ZnO films grown by metalorganic vapour phase epitaxy on various substrates (GaAs, silicon, sapphire) and using different VI /II ratios, are investigated by photoluminescence (PL) spectroscopy. The PL spectra of layers grown on GaAs show significant recombination at 3.320 eV, 3.305 eV and 3.270 eV. These energies are remarkably similar to what have been reported for hybrid beam deposited ZnO:As [Y.R. Ryu, T.S. Lee, H.W. White, Appl. Phys. Lett. 83 (2003) 87] and arsenic-implanted ZnO crystals [T.S. Jeong, M.S. Han, C.J. Youn, Y.S. Park, J. Appl. Phys. 96 (2004) 175], and the lines are ascribed to the incorporation of arsenic, which diffuses from the substrate into the films. Two acceptor levels are deduced at 120 meV and at 140–150 meV.     

The size distributions of nanoparticles of the oxides of Mg, Ba and Al in flames: Their measurement and dependence on the concentrations of free radicals in the flame

Flat, pre mixed, laminar, and very O₂-rich flames of C₂H₂ + O₂ + N₂ with [O₂]/[O₂]_stoich  2.8 and a temperature 2000 K have been burned at atmospheric pressure. Trace amounts (13 ppm) of the metals Mg, Ba or A1 were added to the unburnt gases by nebulising an aqueous solution of a halide of the metal, so that e.g., Mg formed molecules of Mg(OH)₂, MgOH and MgO, as well as free atoms of Mg. The relative abundances of these species were governed by well-characterised equilibria and consequently depended on the temperature and also the concentrations of the flame’s free radicals H, OH and O. Transmission electron microscopy showed that nanoparticles of the oxides of these metals formed from their pool of molecular species in these flames. Particle size distributions were also measured (much less tediously) with a mobility analyser (DMS 500, Cambustion) operating at 0.25 bara. The optimal way of continuously sampling the gases at a point along the flame’s axis was investigated and shown to require expanding the sample (to a pressure of 1/3 bara) supersonically through an orifice with a diameter greater than 0.4 mm. In addition, the sample had to be diluted with N₂, with a volumetric flow rate of 10–20 times that of the sample, all at 1/3 bara. The sizes of oxide nanoparticles, as measured by transmission electron microscopy, agreed with the values of 6–10 nm from the mobility analyser. With Mg all the metal appeared very rapidly as nearly spherical nanoparticles of MgO early in a flame’s reaction zone. This was also true for Ba, which, according to thermodynamic considerations at the final temperature of the flame, should not form any particles of BaO. That particles do actually form is due to the reaction zone having a relatively low temperature and super-equilibrium concentrations of the free radicals H, OH and O. Aluminium was expected to form particles of A1₂O₃. However, only a small fraction of the Al formed particles; this is attributed to the production of gas-phase molecules of Al₂O₃ (i.e., the nuclei) from AlO and AlO₂ being by a relatively slow three-body reaction, as well as Al₂O₃ being a very minor member of the gas-phase pool of molecular species containing Al.     

Temperature dependent photoluminescence from ZnO/MgZnO multiple quantum wells grown by pulsed laser deposition

We have studied temperature dependent photoluminescence (PL) from ZnO Multiple Quantum Wells (MQWs) of different well layer thicknesses in the range 1–4 nm grown on (0001) sapphire by a novel in-house developed buffer assisted pulsed laser deposition. At 10 K the PL peak shifted toward blue with decreasing well layer thickness and at constant well layer thickness the PL peak shifted towards red with increasing temperature. To the best of our knowledge we have observed for the first time an efficient room temperature (RT) PL emanating from such MQWs. The red shift of the PL peak with increasing temperature has been found to be due to the band gap shrinkage in accordance with the Varshni’s empirical relation. The spectral linewidth was found to increase with increasing temperature due to the scattering of excitons with acoustic and optical phonons in different temperature regimes. Both at RT and at 10 K the PL peak shifted with respect to the well layer thickness in the range of 3.35–3.68 eV with decreasing thickness in agreement with the calculated values.     

Low-threshold operation of a 355-nm pumped nanosecond β-BaB2O4 optical parametric oscillator

We report the low-threshold operation of a nanosecond β-BaB₂O₄ optical parametric oscillator (OPO) pumped by the third harmonic of a Q-switched Nd:YAG laser. Using cylindrical focusing of the pump beam, a threshold pulse energy of 0.5 mJ is obtained at the signal wavelength of 560 nm, which is about sixteen times lower than that of a spherical focusing configuration. The importance of diffraction loss in the design of tightly focused OPOs is discussed in terms of a simple extension of the conventional OPO model.     

Effect of the synthesis route on the structural properties and shape of the indium oxide (In2O3) nano-particles

Nano-crystalline indium oxide (In₂O₃) particles have been synthesized by sol–gel and hydro-thermal techniques. A simple hydro-alcoholic solution consisting indium nitrate hydrate and citric acid (in sol–gel method) and 1, 4-butandiol (in hydro-thermal method) have been utilized. The structural properties of indium oxide nano-powders annealed at 450 °C (for both methods) have been characterized by the X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and specific surface area (SSA) analysis. Structural analysis of the samples shows cubic phase in sol–gel and cubic-hexagonal phase mixture in hydro-thermally prepared particles. The nano-particles prepared by sol–gel method have nearly spherical shape, whereas hydro-thermally-made ones display wire- and needle-like shape in addition to the spherical shape. The obtained In₂O₃ nano-particles surface areas were 23.2 and 55.3 in sol–gel and hydro-thermal methods, respectively. The optical direct band gap of In₂O₃ nano-particles were determined to be ∼4.32 and ∼4.24 eV for sol–gel and hydro-thermal methods, respectively. These values exhibit ∼0.5 eV blue shift from that the bulk In₂O₃ (3.75 eV), which is related to the particle size reduction and approaching the quantum confinement limit of nano-particles.     

High-performance pyroelectric single crystals for uncooled infrared detection applications

Uncooled pyroelectric infrared detectors based on ferroelectric single crystals 0.74Pb(Mg_1/3Nb_2/3)O₃–0.26PbTiO₃ (PMN–0.26PT) were fabricated. The performances of pyroelectric detectors dependence on detector fabrication temperature, absorption layer, and element thickness were compared. The room-temperature voltage responsivity (R_v) of 200 V/W and specific detectivity (D^*) of 10⁸ cm Hz^1/2/W at 12.5 Hz have been achieved. The results reveal that the better pyroelectric response can be expected by controlling temperature below 70 °C during the fabrication of the pyroelectric detectors, selecting absorption layer with high absorption coefficient, and decreasing the thickness of the elements.     

Structure and reaction pathways of methyl lactate on Pd(1 1 1)

The adsorption and reaction of methyl lactate (CH₃CH(OH)COOCH₃) is studied in ultrahigh vacuum on a Pd(1 1 1) surface using temperature-programmed desorption (TPD) and reflection–absorption infrared spectroscopy (RAIRS). Methyl lactate reacts at relatively low temperatures (220 K) by O–H bond scission. This intermediate can either react with hydrogen to reform methyl lactate at 280–300 K or undergo β-hydride elimination to form flat-lying methyl pyruvate. This decomposes to form acetyl and methoxy carbonyl species as found previously following methyl pyruvate adsorption on Pd(1 1 1). These species predominantly react to form carbon monoxide, methane and hydrogen.     

Laser gain by electron collisional pumping of Ar VII–V XII

Gain coefficients have been calculated for transitions of singlet levels ns–np of orbital n=4 and n=5 in magnesium-like ions with atomic numbers Z=18, 19, 20, 21, 22 and 23. Population inversions for 4p and 5p levels in these ions were also calculated, via electron collisional excitation, for electron temperature range of 93–231 eV and electron density range of 10¹⁶–10¹⁷ cm⁻³. Under these plasma conditions, the maximum gain that occurred for 4s–4p transition was at electron temperature of 231 eV and electron density of 4×10¹⁷ cm⁻³. Scaling of the maximum gain coefficients with atomic number Z and the plasma parameters is also presented.     

Dimensional evolution of silicon nanowires synthesized by Au–Si island-catalyzed chemical vapor deposition

This study explores the nucleation and morphological evolution of silicon nanowires (Si-NWs) on Si (0 0 1) and (1 1 1) substrates synthesized using nanoscale Au–Si island-catalyzed rapid thermal chemical vapor deposition. The Au–Si islands are formed by Au thin film (1.2–3.0 nm) deposition at room temperature followed by annealing at 700 °C, which are employed as a liquid-droplet catalysis during the growth of the Si-NWs. The Si-NWs are grown by exposing the substrates with Au–Si islands to a mixture of gasses SiH₄ and H₂. The growth temperatures and the pressures are 500–600 °C and 0.1–1.0 Torr, respectively. We found a critical thickness of the Au film for Si-NWs nucleation at a given growth condition. Also, we observed that the dimensional evolution of the NWs significantly depends on the growth pressure and temperature. The resulting NWs are 30–100 nm in diameter and 0.4–12.0 μm in length. For Si (0 0 1) substrates 80% of the NWs are aligned along the 1 1 1 direction which are 30° and 60° with respect to the substrate surface while for Si (1 1 1) most of the NWs are aligned vertically along the 1 1 1 direction. In particular, we observed that there appears to be two types of NWs; one with a straight and another with a tapered shape. The morphological and dimensional evolution of the Si-NWs is significantly related to atomic diffusion kinetics and energetics in the vapor–liquid–solid processes.     

Infrared spectra of two isomers of OCS–C2H2 and OCS–C2D2 in the region of OCS ν1 fundamental

Infrared spectra of OCS–C₂H₂ and OCS–C₂D₂ complexes in the region of the C–O stretching fundamental of OCS (2060 cm⁻¹) are studied in a pulsed supersonic slit-jet expansion using a tunable diode laser. For each complex, two bands are observed and assigned to distinct near-parallel and the T-shaped isomers. Ground state parameters were previously determined from microwave studies, so analysis of the infrared spectra gives information on the vibrational shifts upon complex formation as well as rotational and centrifugal distortion parameters for the excited states. All four bands show a red shift with respect to the monomer band origin, with the T-shaped isomer having a much larger shift than the near-parallel isomer. Disappearance of the T-shaped isomer when argon is used as a carrier gas supports the notion that the near-parallel isomer is the lowest energy form of the complex.     

The order with respect to oxygen and the activation energy for the burning of an anthracitic char in O2 in a fluidised bed, as measured using a rapid analyser for CO and CO2

Measurements of the oxidation of a coal char in a fluidised bed have the advantages that the rates of heat and mass transfer to and from a reacting particle are large and characterised well. However, problems have arisen from a combination of the slow, but typical, response–time (4 s) of the analysers for CO and CO₂ and the slow mixing of gases when filling a fairly large fluidised bed. The resulting time constant for the sampling system was 8 s and comparable to the time for combustion at 900 °C or above. The purpose of this work was to measure the kinetics of oxidation of a char in a smaller fluidised bed (with a shorter mixing time) using an analyser for CO and CO₂ with a response time as low as 0.1 s. The result is that the oxidation of an anthracitic char is now found to be first order in O₂ between 700 and 900 °C; at 900 °C the order previously measured was almost zero. The activation energy is now measured here to be 145 ± 25 kJ/mol, in agreement with some early work.