Glassy dielectric response in Tb2NiMnO6 double perovskite with similarities to a Griffiths phase

Results of frequency-dependent and temperature-dependent dielectric measurements performed on the double-perovskite Tb2NiMnO6 are presented. The real (epsilon(1)(f,T)) and imaginary (epsilon(2)(f,T)) parts of dielectric permittivity show three plateaus suggesting dielectric relaxation originating from the bulk, grain boundaries and the sample-electrode interfaces, respectively. The epsilon(1)(f,T) and epsilon(2)(f,T) are successfully simulated by a RC circuit model. The complex plane of impedance, Z'-Z `', is simulated using a series network with a resistor R and a constant phase element. Through the analysis of epsilon(f,T) using the modified Debye model, two different relaxation time regimes separated by a characteristic temperature, T*, are identified. The temperature variation of R and C corresponding to the bulk and the parameter alpha from modified Debye fit lend support to this hypothesis. Interestingly, the T* compares with the Griffiths temperature for this compound observed in magnetic measurements. Though these results cannot be interpreted as magnetoelectric coupling, the relationship between lattice and magnetism is markedly clear. We assume that the observed features have their origin in the polar nanoregions which originate from the inherent cationic defect structure of double perovskites. Copyright (C) EPLA, 2013

Thermoelectric Properties of Two-Phase PbTe with Indium Inclusions

The thermoelectric figure of merit (zT) can be increased by introduction of additional interfaces in the bulk to reduce the thermal conductivity. In this work, PbTe with a dispersed indium (In) phase was synthesized by a matrix encapsulation technique for different In concentrations. x-Ray diffraction analysis showed single-phase PbTe with In secondary phase. Rietveld analysis did not show In substitution at either the Pb or Te site, and this was further confirmed by room-temperature Raman data. Low-magnification (similar to 1500x) scanning electron microscopy images showed micrometer-sized In dispersed throughout the PbTe matrix, while at high magnification (150,000x) an agglomeration of PbTe particles in the hot-pressed samples could be seen. The electrical resistivity (rho) and Seebeck coefficient (S) were measured from 300 K to 723 K. Negative Seebeck values showed all the samples to be n-type. A systematic increase in resistivity and higher Seebeck coefficient values with increasing In content indicated the role of PbTe-In interfaces in the scattering of electrons. This was further confirmed by the thermal conductivity (kappa), measured from 423 K to 723 K, where a greater reduction in the electronic as compared with the lattice contribution was found for In-added samples. It was found that, despite the high lattice mismatch at the PbTe-In interface, phonons were not scattered as effectively as electrons. The highest zT obtained was 0.78 at 723 K for the sample with the lowest In content.

Phase formation and stability of alloy phases in free nanoparticles: some insights

This paper explores phase formation and phase stability in free nanoparticles of binary alloys. A procedure for estimating the size and composition dependent free energies incorporating the contributions from the interfaces has been presented. Both single phase solid solution and two phase morphology containing interphase interfaces have been considered. A free energy scenario has been evaluated for two binary alloy systems Ag-Ni and Ag-Cu to predict the microstructure of the alloy nanoparticles at different size ranges as a function of composition. Both Ag-Cu and Ag-Ni systems exhibit wide bulk immiscibility. Ag-Ni nanoparticles were synthesized using the wet chemical synthesis technique whereas Ag-Cu nanoparticles were synthesized using laser ablation of a Ag-Cu target immersed in distilled water. Microstructural and compositional characterization of Ag-Ni and Ag-Cu nanoparticles on a single nanoparticle level was conducted using transmission electron microscopy. Nanoparticle microstructures observed from the microscopic investigation have been correlated with thermodynamic calculation results. It is shown that the observed two phase microstructure consisting of Ag-Ni solid solution in partial decomposed state coexisting with pure Ag phases in the case of Ag-Ni nanoparticles can be only be rationalized by invoking the tendency for phase separation of an initial solid solution with increase in nanoparticle size. Smaller sized Ag-Ni nanoparticles prefer a single phase solid solution microstructure. Due to an increase in particle size during the synthesis process the initial solid solution decomposes into an ultrafine scale phase separated microstructure. We have shown that it is necessary to invoke critical point phenomenon and wetting transition in systems showing a critical point that leads to phase separated Ag-Ni nanoparticles providing a catalytic substrate for the nucleation of equilibrium Ag over it. In the case of the Ag-Cu system, we report the experimental observation of a core shell structure at small sizes. This can be rationalized in terms of a metastable solid solution. It is argued that the nucleation barrier can prevent the formation of biphasic morphology with an internal interface. In such a situation, demixing of the solid solution can bring the system to a lower energy configuration. This has lead to the observed core-shell morphology in the Ag-Cu system during room temperature synthesis.

Optimizing Photovoltaic Response by Tuning Light-Harvesting Nanocrystal Shape Synthesized Using a Quick Liquid-Gas Phase Reaction

The electron recombination lifetime in a sensitized semiconductor assembly is greatly influenced by the crystal structure and geometric form of the light-harvesting semiconductor nanocrystal. When such light harvesters with varying structural characteristics are configured in a photoanode, its interface with the electrolyte becomes equally important and directly influences the photovoltaic efficiency. We have systematically probed here the influence of nanocrystal crystallographic structure and shape on the electron recombination lifetime and its eventual influence on the light to electricity conversion efficiency of a liquid junction semiconductor sensitized solar cell. The light-harvesting cadmium sulfide (CdS) nanocrystals of distinctly different and controlled shapes are obtained using a novel and simple liquid gas phase synthesis method performed at different temperatures involving very short reaction times. High resolution synchrotron X-ray diffraction and spectroscopic studies respectively exhibit different crystallographic phase content and optical properties. When assembled on a mesoscopic TiO2 film by a linker molecule, they exhibit remarkable variation in electron recombination lifetime by 1 order of magnitude, as determined by ac-impedance spectroscopy. This also drastically affects the photovoltaic efficiency of the differently shaped nanocrystal sensitized solar cells.

Optimizing Photovoltaic Response by Tuning Light-Harvesting Nanocrystal Shape Synthesized Using a Quick Liquid-Gas Phase Reaction

The electron recombination lifetime in a sensitized semiconductor assembly is greatly influenced by the crystal structure and geometric form of the light-harvesting semiconductor nanocrystal. When such light harvesters with varying structural characteristics are configured in a photoanode, its interface with the electrolyte becomes equally important and directly influences the photovoltaic efficiency. We have systematically probed here the influence of nanocrystal crystallographic structure and shape on the electron recombination lifetime and its eventual influence on the light to electricity conversion efficiency of a liquid junction semiconductor sensitized solar cell. The light-harvesting cadmium sulfide (CdS) nanocrystals of distinctly different and controlled shapes are obtained using a novel and simple liquid gas phase synthesis method performed at different temperatures involving very short reaction times. High resolution synchrotron X-ray diffraction and spectroscopic studies respectively exhibit different crystallographic phase content and optical properties. When assembled on a mesoscopic TiO2 film by a linker molecule, they exhibit remarkable variation in electron recombination lifetime by 1 order of magnitude, as determined by ac-impedance spectroscopy. This also drastically affects the photovoltaic efficiency of the differently shaped nanocrystal sensitized solar cells.

Stress-strain fields and the effectiveness shear properties for three-phase composites with imperfect interface

Based on the 'average stress in the matrix' concept of Mori and Tanaka (:Mori, T., Tanaka, K., 1973. Average stress in matrix and average elastic energy of materials with misfitting inclusion. Acta Metall. 21, 571-580) a micromechanical model is presented for the prediction of the elastic fields in coated inclusion composites with imperfect interfaces. The solutions of the effective elastic moduli for this kind of composite are also obtained. In two kinds of composites with coated particulates and fibers, respectively, the interface imperfections are takes to the assumption that the interface displacement discontinues are linearly related to interface tractions like a spring layer of vanishing thickness. The resulting effective shear modulus for each material and the stress fields in the composite are presented under a transverse shear loading situation.

A further discussion on basic equations for two-phase flow: On collision stress of solid phase

The following points are argued: (i) there are two independent kinds of interaction on interfaces, i.e. the interaction between phases and the collision interaction, and the jump relations on interfaces can accordingly be resolved; (ii) the stress in a particle can also be divided into background stress and collision stress corresponding to the two kinds of interaction on interfaces respectively; (iii) the collision stress, in fact, has no jump on interface, so the averaged value of its derivative is equal to the derivative of its averaged value; (iv) the stress of solid phase in the basic equations for two\|phase flow should include the collision stress, while the stress in the expression of the inter\|phase force contains the background one only. Based on the arguments, the strict method for deriving the equations for two\|phase flow developed by Drew, Ishii et al. is generalized to the dense two\|phase flow, which involves the effect of collision stress.

Crystal-growth in floating zone with phase-change and thermosolutal convections

Floating zone crystal growth in microgravity environment is investigated numerically by a finite element method for semiconductor growth processing, which involves thermocapillary convection, phase change convection, thermal diffusion and solutal diffusion. The configurations of phase change interfaces and distributions of velocity, temperature and concentration fields are analyzed for typical conditions of pulling rates and segregation coefficients. The influence of phase change convection on the distribution of concentration is studied in detail. The results show that the thermocapillary convection plays an important role in mixing up the melt with dopant. The deformations of phase change interfaces by thermal convection-diffusion and pulling rods make larger variation of concentration field in comparison with the case of plane interfaces.

Investigations of charge-carrier dynamics at semiconductor/liquid interfaces

Theoretical and experimental investigations of charge-carrier dynamics at semiconductor/liquid interfaces, specifically with respect to interfacial electron transfer and surface recombination, are presented.

Fermi's golden rule has been used to formulate rate expressions for charge transfer of delocalized carriers in a nondegenerately doped semiconducting electrode to localized, outer-sphere redox acceptors in an electrolyte phase. The treatment allows comparison between charge-transfer kinetic data at metallic, semimetallic, and semiconducting electrodes in terms of parameters such as the electronic coupling to the electrode, the attenuation of coupling with distance into the electrolyte, and the reorganization energy of the charge-transfer event. Within this framework, rate constant values expected at representative semiconducting electrodes have been determined from experimental data for charge transfer at metallic electrodes. The maximum rate constant (i.e., at optimal exoergicity) for outer-sphere processes at semiconducting electrodes is computed to be in the range 10^-17-10^-16 cm⁴ s^-1, which is in excellent agreement with prior theoretical models and experimental results for charge-transfer kinetics at semiconductor/liquid interfaces.

Double-layer corrections have been evaluated for semiconductor electrodes in both depletion and accumulation conditions. In conjuction with the Gouy-Chapman-Stern model, a finite difference approach has been used to calculate potential drops at a representative solid/liquid interface. Under all conditions that were simulated, the correction to the driving force used to evaluate the interfacial rate constant was determined to be less than 2% of the uncorrected interfacial rate constant.

Photoconductivity decay lifetimes have been obtained for Si(111) in contact with solutions of CH₃OH or tetrahydrofuran containing one-electron oxidants. Silicon surfaces in contact with electrolyte solutions having Nernstian redox potentials > 0 V vs. SCE exhibited low effective surface recombination velocities regardless of the different surface chemistries. The formation of an inversion layer, and not a reduced density of electrical trap sites on the surface, is shown to be responsible for the long charge-carrier lifetimes observed for these systems. In addition, a method for preparing an air-stable, low surface recombination velocity Si surface through a two-step, chlorination/alkylation reaction is described.

An Arbitrary Lagrangian Eulerian Method for Three-Phase Flows with Triple Junction Points

We present a moving mesh method suitable for solving two-dimensional and axisymmetric three-liquid flows with triple junction points. This method employs a body-fitted unstructured mesh where the interfaces between liquids are lines of the mesh system, and the triple junction points (if exist) are mesh nodes. To enhance the accuracy and the efficiency of the method, the mesh is constantly adapted to the evolution of the interfaces by refining and coarsening the mesh locally; dynamic boundary conditions on interfaces, in particular the triple points, are therefore incorporated naturally and accurately in a Finite- Element formulation. In order to allow pressure discontinuity across interfaces, double-values of pressure are necessary for interface nodes and triple-values of pressure on triple junction points. The resulting non-linear system of mass and momentum conservation is then solved by an Uzawa method, with the zero resultant condition on triple points reinforced at each time step. The method is used to investigate the rising of a liquid drop with an attached bubble in a lighter liquid.

Local equilibrium of the Gibbs interface in two-phase systems

We analyze the local equilibrium assumption for interfaces from the perspective of gauge transformations, which are the small displacements of Gibbs' dividing surface. The gauge invariance of thermodynamic properties turns out to be equivalent to conditions for jumps of bulk densities across the interface. This insight strengthens the foundations of the local equilibrium assumption for interfaces and can be used to characterize nonequilibrium interfaces in a compact and consistent way, with a clear focus on gauge-invariant properties. Using the principle of gauge invariance, we show that the validity of Clapeyron equations can be extended to nonequilibrium interfaces, and an additional jump condition for the momentum density is recognized to be of the Clapeyron type. © 2012 Europhysics Letters Association.

Single sublattice endotaxial phase separation driven by charge frustration in a complex oxide.

Complex transition-metal oxides are important functional materials in areas such as energy and information storage. The cubic ABO3 perovskite is an archetypal example of this class, formed by the occupation of small octahedral B-sites within an AO3 network defined by larger A cations. We show that introduction of chemically mismatched octahedral cations into a cubic perovskite oxide parent phase modifies structure and composition beyond the unit cell length scale on the B sublattice alone. This affords an endotaxial nanocomposite of two cubic perovskite phases with distinct properties. These locally B-site cation-ordered and -disordered phases share a single AO3 network and have enhanced stability against the formation of a competing hexagonal structure over the single-phase parent. Synergic integration of the distinct properties of these phases by the coherent interfaces of the composite produces solid oxide fuel cell cathode performance superior to that expected from the component phases in isolation.

Ni(Pt)-silicide contacts on CMOS devices: Impact of substrate nature and Pt concentration on the phase formation

Ni silicides used as contacts in source/drain and gate of advanced CMOS devices were analyzed by atom probe tomography (APT) at atomic scale. These measurements were performed on 45 nm nMOS after standard self-aligned silicide (salicide) process using Ni(5 at.% Pt) alloy. After the first annealing (RTA1), δ-Ni2Si was the only phase formed on gate and source/drain while, after the second annealing (RTA2), two different Ni silicides have been formed: NiSi on the gate and δ-Ni2Si on the source and drain. This difference between source/drain and gate regions in nMOS devices has been related to the Si substrate nature (poly or mono-crystalline) and to the size of the contact. In fact, NiSi seems to have difficulties to nucleate in the narrow source/drain contact on mono-crystalline Si. The results have been compared to analysis performed on 28 nm nMOS where the Pt concentration is higher (10 at.% Pt). In this case, θ-Ni2Si is the first phase to form after RTA1 and NiSi is then formed at the same time on source (or drain) and gate after RTA2. The absence of the formation of NiSi from δ-Ni 2Si/Si(1 0 0) interface compared to θ-Ni2Si/Si(1 0 0) interface could be related to the difference of the interface energies. The redistributions of As and Pt in different silicides and interfaces were measured and discussed. In particular, it has been evidenced that Pt redistributions obtained on both 45 and 28 nm MOS transistors correspond to respective Pt distributions measured on blanket wafers. © 2013 Elsevier B.V. All rights reserved.

Optical characteristics of DBR with inhomogeneous graded interfaces

Optical properties of Al0.9Ga0.1As/Al gamma Ga1-gamma As/GaAs/Al chi Ga1-chi As DBR with inhomogeneous graded interfaces has been investigated by using characteristic matrix method. The refractive index model and the analytic characteristic matrix of graded interfaces are obtained. The reflectance spectrum and the reflective phase shift are calculated for GaAs/Al-0.9 Ga-0.1 As DBR and graded interfaces DBR by using characteristic matrix method. The effect of graded interfaces on the optical properties of DBR is discussed. The result shows an extra graded phase matching layer must he added in front of the graded interfaces DBR to fulfil the conditions of phase matching at central wavelength. The accurate thickness of phase matching layer is calculated by optical thickness approximation method.