A scanning tunneling microscopy and potentiometry study of epitaxial thin films of La0.7Ca0.3MnO3

To investigate the role of grain boundaries and other growth related microstructure in manganite films, a scanning tunneling microscope is used to simultaneously probe surface topography and local potential distribution under current flow at nanometer level in films of epitaxial thin films of La0.7Ca0.3MnO3 deposited on single crystal SrTiO3 and NdGaO3 substrate by laser ablation. We have studied two types of films strained and strain relaxed. Thin (50nm) films (strained due to lattice mismatch between substrate and the film) show step growth (unit cell steps) and have very smooth surfaces. Relatively thicker films (strain relaxed, thickness 200nm) do not have these step growths and show rather smooth well connected grains. Charge transport in these films is not uniform on the nanometer level and is accompanied by potential jumps at the internal surfaces. In particular scattering from grain boundaries results in large variations in the local potential resulting in fields as high as 104-105V/cm located near the grain boundaries. We discuss the role of local strain and strain inhomogeneties in determining the current transport in these films and their resistance and magnetoresistivity. In this paper we attempt to correlate between bulk electronic properties with microscopic electronic conduction using scanning tunneling microscopy and scanning tunneling potentiometry.

Nanocrystallisation and Nanoquasicrystallisation in (Ti/Hf)-Zr-(Ni/Cu) Ternary Alloys

The applicability of the confusion principle and size factor in glass formation has been explored by following different combinations of isoelectronic Ti, Zr and Hf metals. Four alloys of nominal composition Zr41.5Ti41.5Ni17, Zr41.5Hf41.5Ni17, Zr25Ti25Cu50 and Zr34Ti16Cu50 have been rapidly solidified to obtain an amorphous phase and their crystallisation behaviour has been studied. The Ti-Zr-Ni alloy crystallises in three steps. Initially this alloy precipitates icosahedral quasicrystalline phase, which on further heat treatment precipitates cF96 Zr2Ni phase. The Zr-Hf-Ni alloy can not be amorphised under the same experimental conditions. The amorphous Zr-Ti-Cu alloys at the initial stages of crystallisation phase-separateinto two amorphous phases and then on further heat treatment cF24 Cu5Zr and oC68 Cu10Zr7 phase are precipitated. The lower glass-forming abilityof Zr-Hf-Ni alloy and the crystallisation behaviour of the above alloys has been studied. The rationale behind nanoquasicrystallisation and the formation of other intermetallic phases has been explained.

Growth and study of BaZrO3 thin films by pulsed excimer laser ablation

Thin films of BaZrO3 (BZ) were grown using a pulsed laser deposition technique on platinum coated silicon substrates. Films showed a polycrystalline perovskite structure upon different annealing procedures of in-situ and ex-situ crystallization. The composition analyses were done using Energy dispersive X-ray analysis (EDAX) and Secondary ion mass spectrometry (SIMS). The SIMS analysis revealed that the ZrO2 formation at the right interface of substrate and the film leads the degradation of the device on the electrical properties in the case of ex-situ crystallized films. But the in-situ films exhibited no interfacial formation. The dielectric properties have been studied for the different temperatures in the frequency regime of 40 Hz to 100kHz. The response of the film to external ac stimuli was studied at different temperatures, and it showed that ac conductivity values in the limiting case are correspond to oxygen vacancy motion. The electrical modulus is fitted to a stretched exponential function and the results clearly indicate the presence of the non-Debye type of dielectric relaxation in these materials.

Dielectric Properties of Pulsed Excimer Laser Ablated BaBi2Nb2O9 Thin Films

The dielectric response of BaBi2Nb2O9 (BBN) thin films has been studied as a function of frequency over a wide range of temperatures. Both dielectric constant and loss tangent of BBN thin films showed a ‘power law’ dependence with frequency, which was analyzed using the Jonscher's universal dielectric response model. Theoretical fits were utilized to compare the experimental results and also to estimate the value of temperature dependence parameters such as n(T) and a(T) used in the Jonscher's model. The room temperature dielectric constant (ε') of the BBN thin films was 214 with a loss tangent (tanδ) of 0.04 at a frequency of 100 kHz. The films exhibited the second order dielectric phase transition from ferroelectric to paraelectric state at a temperature of 220 °C. The nature of phase transition was confirmed from the temperature dependence of dielectric constant and sponteneous polarization,respectively. The calculated Currie constant for BBN thin films was 4 × 105°C.

Impact of Template Layers on Dielectric and Electrical Properties of Pulsed-Laser Ablated Pb(Mg1/3 Nb2/3)O3 - PbTiO3 Thin Films

A study was done on pulsed laser deposited relaxor ferroelectric thin films of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 (PMN-PT) deposited on platinized silicon substrates with template layers to observe the influence of the template layers on physical and electrical properties. Initial results, showed that perovskite phase (80% by volume) was obtained through proper selection of the processing conditions on Pt/Ti/SiO2/Si substrates. The films were grown at 300°C and then annealed in a rapid thermal annealing furnace in the temperature range of 750-850°C to induce crystallization. Comparison of the films annealed at different temperatures revealed a change in crystallinity, perovskite phase formation and grain size. These results were further used to improve the quality of the perovskite PMN-PT phase by inserting thin layers of TiO2 on the Pt substrate. These resulted in an increase in perovskite phase in the films even at lower annealing temperatures. Dielectric studies on the PMN-PT films show very high values of dielectric constant (1300) at room temperature, which further improved with the insertion of the template seed layer. The relaxor properties of the PMN-PT were correlated with Vogel-Fulcher theory to determine the actual nature of the relaxation process.

Lopsidedness and sloshing in centres of advanced mergers of galaxies

We measure the non-axisymmetry in the luminosity distribution in the central few kpc of a sample of advanced mergers of galaxies, by analyzing their 2MASS images. All mergers show a high central asymmetry: the centres of isophotes show a striking sloshing pattern with a spatial variation of upto 30% within the central 1 kpc; and the Fourier amplitude for lopsidedness (m = 1) shows high values upto 0.2 within the central 5 kpc. The central asymmetry is estimated to be long-lived, lasting for ~ a few Gyr or ~ 100 local dynamical timescales. This will significantly affect the dynamical evolution of this region, by helping fuel the central active galactic nucleus, and also by causing the secular growth of the bulge driven by lopsidedness.

Comparison of CVD and MOCVD-grown Al2O3 coatings in the performance of cemented carbide cutting tool inserts

Low-pressure MOCVD, with tris(2,4 pentanedionato)aluminum(III) as the precursor, was used in the present investigation to coat alumina on to cemented carbide cutting tools. To evaluate the MOCVD process, the efficiency in cutting operations of MOCVD-coated tools was compared with that of tools coated using the industry-standard CVD process.Three multilayer cemented carbide cutting tool inserts, viz., TiN/TiC/WC, CVD-coated Al2O3 on TiN/TiC/WC, and MOCVD-coated Al2O3 on TiN/TiC/WC, were compared in the dry turning of mild steel. Turning tests were conducted for cutting speeds ranging from 14 to 47 m/min, for a depth of cut from 0.25 to 1 mm, at the constant feed rate of 0.2 mm/min. The axial, tangential, and radial forces were measured using a lathe tool dynamometer for different cutting parameters, and the machined work pieces were tested for surface roughness. The results indicate that, in most of the cases examined, the MOCVD-coated inserts produced a smoother surface finish, while requiring lower cutting forces, indicating that MOCVD produces the best-performing insert, followed by the CVD-coated one. The superior performance of MOCVD-alumina is attributed to the co-deposition of carbon with the oxide, due to the very nature of the precursor used, leading to enhanced mechanical properties for cutting applications in harsh environment.

Standard Gibbs energy of formation of Pb2Ru2O6.5

Lead ruthenate is used as a bifunctional electrocatalyst for both oxygen evolution and reduction and as a conducting component in thick-film resistors. It also has potential applications in supercapacitors and solid oxide fuel cells. However, thermodynamic properties of the compound have not been reported in the literature. The standard Gibbs energy of formation has now been determined in the temperature range from 873 to 1123 K using a solid-state cell incorporating yttria-stabilized zirconia (YSZ) as the electrolyte, a mixture of PbO + Pb2Ru2O6.5 + Ru as the measuring electrode, and Ru + RuO2 as the reference. The design of the measuring electrode is based on a study of phase relations in the ternary system Pb–Ru–O at 1123 K. For the reaction,S0884291400095625_eqnU1 the standard enthalpy of formation and standard entropy at 298.15 K are estimated from the high-temperature measurements. An oxygen potential diagram for the system Pb–Ru–O is composed based on data obtained in this study and auxiliary information from the literature

Surfactant-mediated Synthesis of Functional Metal Oxide Nanostructures via Microwave Irradiation-assisted Chemical Synthesis

Nanostructured materials have attracted considerable interest in recent years due to their properties which differ strongly from their bulk phase and potential applications in nanoscale electronic and optoelectronic devices. Metal oxide nanostructures can be synthesized by variety of different synthesis techniques developed in recent years such as thermal decomposition, sol-gel technique, chemical coprecipitation, hydrothermal process, solvothermal process, spray pyrolysis, polyol process etc. All the above processes go through a tedious synthesis procedure followed by prolonged heat treatment at elevated temperature and are time consuming. In the present work we describe a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant, without the use of any templates The method is simple, inexpensive, and helps one to prepare nanostructures in a very simple way, and in a very short time, measured in minutes. The synthesis procedure employs high quality metalorganic complexes (typically -diketonates) featuring a direct metal-to-oxygen bond in its molecular structure. The complex is dissolved in a suitable solvent, often with a surfactant added, and the solution then subjected to microwave irradiation in a domestic microwave oven operating at 2.45 GHz frequency with power varying from 160-800 W, from a few seconds to a few minutes, leading to the formation of corresponding metal oxides. This method has been used successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with the change of different parameters such as microwave power, irradiation time, appropriate solvent, surfactant type and concentration. Cationic, anionic, nonionic and polymeric surfactants have been used to generate a variety of nanostructures. Even so, to remove the surfactant, there is either no need of heat treatment or a very brief exposure to heat suffices, to yield highly pure and crystalline oxide materials as prepared. By adducting the metal complexes, the shape of the nanostructures can be controlled further. In this manner, very well formed, single-crystalline, hexagonal nanorods and nanotubes of ZnO have been formed. Adducting the zinc complex leads to the formation of tapered ZnO nanorods with a very fine tip, suitable for electron emission applications. Particle size and their monodispersity can be controlled by a suitable choice of a precursor complex, the surfactant, and its concentration. The resulting metal oxide nanostructures have been characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, FTIR spectroscopy, photoluminescence, and electron emission measurements.

Microstructure and mechanical properties of electron beam weld joints of a Zr41Ti14Cu12Ni10Be23 bulk metallic glass with Zr

The electron beam welding technique was used to join Zr41Ti14Cu12Ni10Be23 bulk metallic glass (BMG) to crystalline pure Zr. Compositional, microstructural, and mechanical property variations across the welded interface were evaluated. It is shown that a crystalline layer develops close to the welding interface. Transmission electron microscopy of this layer indicates the crystalline phase to be tetragonal with lattice parameters close to that reported for Zr2Ni. However, the composition of this phase is different as it contains other alloying additions. The interface layer close to the bulk metallic glass side contains nanocrystalline Zr2Cu phase embedded in the glassy matrix. Nanoindentation experiments indicate that the hardness of the crystalline layer, although less than the bulk metallic glass, is more than the Zr itself. Commensurately, tensile tests indicate that the failure of the welded samples occurs at the Zr side rather than at the weld joint.

Microstructural Studies of Ferroelectric Bi2VO5.5 Thin Films With LaNiO3 Electrodes

Thin films of Bi2VO5.5 (BVO), a vanadium analog of the n = I member of the Aurivillius family, have been prepared by pulsed laser deposition. The BVO films grow along the [001] direction on LaNiO3(LNO) and YBa2Cu3O7 (YBCO) electrode buffer layers on LaA- IO3(LAO) substrates as obtained from X-ray diffraction studies. The microstructure of the films and of the interfaces within the film and between the film and the substrate were characterized using transmission electron microscopy. The in-plane epitaxial relationship of the rhombohedral LNO on perovskite LAO was [100] LNO // [100] LAO and [001] LNO // [001] LAO. High resolution lattice images showed a sharp interface between LNO and LAO. However, the LNO film is twinned with a preferred orientation along the growth direction. The BVO layer is single crystalline on both LNO/LAO and YBCO/LAO with the caxis parallel to the growth direction except for a thin layer of about 400 Å at the interface which is polycrystalline.

Constitutive Response of Passivated Copper Films: Experiments and Analyses

The constitutive behavior of passivated copper films is studied. Stresses in copper films of thickness ranging from 1000 nm to 40 nm, passivated with silicon oxide on a quartz or silicon substrate, were measured using the curvature method. The thermal cycling spans a temperature range from - 196 to 600°C. It is seen that the strong relaxation at high temperatures normally found in unpassivated films is nonexistent for passivated films. The copper film did not show any rate-dependent effect over a range of heating/cooling rate from 5 to 25°C/min. Further analyses showed that significant strain hardening exists during the course of thermal loading. In particular, the measured stress- temperature response can only be fitted with a kinematic hardening model, if a simple constitutive law within the continuum plasticity framework is to be used. The analytic procedures for extracting the film properties are presented. Implications to stress modeling of copper interconnects in actual devices are discussed.

Growth and Characterization Studies of ABi2ta2o9 (A = Ba, Sr and Ca) Ferroelectric Thin Films

Thin films of ferroelectric ABi2Ta2O9 bismuth-layered structure, where A = Ba, Sr and Ca, were prepared by pulsed laser deposition technique on Pt/TiO2/SiO2/Si(100) substrates. The influence of substrate temperature between 500 to 750°C, and oxygen partial pressure 100-300 mTorr, on the structural and electrical properties of the films was investigated. The films deposited above 650°C substrate temperature showed complete Aurivillius layered structure. Films annealed at 750°C for 1h in oxygen atmosphere have exhibited better electrical properties. Atomic force microscopy study of surface topography shows that the films grown at lower temperature has smaller grains and higher surface roughness. This paper discusses the pronounced influence of A-site cation substitution on the structural and ferroelectric properties with the aid of Raman spectroscopy, X-ray diffraction and electrical properties. The degradation of ferroelectric properties with Ba and Ca substitution at A-sites is attributed to the higher structural distortion caused by changing tolerance factor. A systematic proportionate variation of coercive field is attributed to electronegativity difference of A-site cations.

Crack formation due to annealing of Al2O3 films grown on Si(100) by MOCVD

We report crack formation in alumina films grown on Si(100), caused by annealing in a controlled oxidizing ambient. The films were grown in a low-pressure CVD reactor, using aluminium acetylacetonate as precursor. High purity argon and nitrous oxide were employed as carrier and oxidizing gas, respectively. The films were characterized by optical microscopy and SEM/EDAX. The proportion and chemical nature of the heteroatoms, namely C and H, incorporated into the films from the precursor, were characterized by XPS, and FTIR. As-deposited films do not exhibit any cracks, while post-deposition annealing results in cracks. Apart from the delamination of the films, annealing in nitrous oxide ambient leads to an unusual crack geometry, which we term the “railway-track”. These twin cracks are very straight and run parallel to each other for as much as several millimeters. Often, two such linear tracks meet at exactly 90°. Between some of these tracks lie bullet-like structures with very sharp tips, oriented in a specific direction. As cracks are generally activated by residual stress, both thermal and intrinsic, the origins of the stresses that generate these linear cracks are discussed. The redistribution of stress, arising from the removal of C and H during annealing, will also be discussed. An attempt has been made to correlate the formation of cracks with the crystal structure of the film.

Full Sphere Axisymmetric Simulations of the Solar Dynamo

We explore a full sphere (2D axisymmetric) kinematic solar dynamo model based on the Babcock-Leighton idea that the poloidal field is generated in the surface layers from the decay of tilted bipolar solar active regions. This model incorporates the helioseismically deduced solar rotation profile and an algorithm for buoyancy motivated from simulations of flux tube dynamics. A prescribed deep meridional circulation plays an important role in the advection of magnetic flux. We specifically address the parity issue and show that – contrary to some recent claims – the Babcock-Leighton dynamo can reproduce solar-like dipolar parity if certain reasonable conditions are satisfied in the solar interior, the most important requirement being that the poloidal field of the two hemispheres be efficiently coupled across the equator.