Experimental investigation and thermodynamic calculation of the Bi-Ga-Sn phase equilibria

Binary thermodynamic data, successfully used for phase diagram calculations of binary systems Bi-Ga, Bi-Sn, and Ga-Sn, were used for prediction of phase equilibria in ternary Bi-Ga-Sn system. The thermodynamic functions, such as enthalpy of formation and activity, were calculated using the Redlich-Kister-Muggianu model and compared with experimental data reported in the literature. The liquidus surface, invariant equilibria and three vertical sections with molar ratio Ga:Sn=1, Bi:Sn=1 and Bi:Ga=1 of the Bi-Ga-Sn ternary system were calculated by the CALPHAD method. Alloys, situated along three calculated vertical sections, were investigated by Differential Scanning Calorimetry (DSC). The experimentally determined phase transition temperatures were compared with calculation results and good mutual agreement was noticed.     

Thermodynamic modeling of Fe–Ni pentlandite

Gibbs energy modeling of iron–nickel pentlandite has been performed using experimental data of ternary phase equilibria. A three-sublattice approach in the framework of the Compound Energy Formalism is developed to refine a two-sublattice model of pentlandite recently applied within a complete assessment of the Fe–Ni–S system. Experimental data about the iron site fraction on the octahedral sublattice at 523.15 K for the composition Fe₅Ni₄S₈ as well as the enthalpy of formation at 298.15 K for the composition Fe_4.5Ni_4.5S₈ are predicted satisfactorily by the novel model. New possibilities to interpret experimental phase equilibrium data on complex phase relations with pentlandite are discussed together on the basis of the recent extension of a second high-temperature heazlewoodite phase to a ternary solution phase.     

A survey of surface tension,molar volume and density for Sn–Ag–Cu–Bi–Sb quinary alloys as lead-free solders

ABSTRACT

By applying the geometric models and the theoretical equation, the surface tension, the molar volume and the density were studied. The empirical calculations were carried out in temperature range 623?K?≤?T?≤?1123?K. Only few thermophysical properties were estimated for eight quinary alloys: Sn3.55Ag0.5Cu3Bi3Sb, Sn3.48Ag0.5Cu3Bi5Sb, Sn3.48 Ag0.5Cu5Bi3Sb, Sn3.40 Ag0.5Cu5Bi5Sb, Sn3.53Ag1Cu3Bi3Sb, Sn3.46Ag1Cu3Bi5Sb, Sn3.46Ag1Cu5Bi3Sb, Sn3.38Ag1Cu5Bi5Sb. The results show that surface tension and density have a linear appearance for all temperatures. We have also studied the influence of the composition and temperature in the studied alloys. The obtained theoretical results are compared with the experimental ones and with the conventional Pb–Sn welds.     

Reconstructed (1 1 0) surfaces of FCC transition metals

The energies of the ideal, missing row (MR) and missing column (MC) (1 1 0) surfaces have been calculated by using modified embedded atom method (MEAM) for seven face centered cubic (FCC) transition metals Au, Pt, Ag, Pd, Rh, Cu and Ni. The results, that the MC reconstruction can not be formed for all metals, while the MR reconstruction can be formed naturally for Au and Pt, inductively for Ag, Pd, Rh and Cu and difficultly for Ni, are better than EAM calculated results in comparing with experimental results. In addition to the surface energy explanation, the results are also related to the surface topography and valence electron structure.     

Non-stoichiometry and properties of ternary semiconductor phases of variable composition based on IV-VI compounds

An overview and analysis of our experimental data on the crystal structure, mechanical, thermal, galvanomagnetic and thermoelectric properties vs composition of the ternary semiconductor phases based on IV-Te compounds in the IV-X-Te systems (IV-Ge, Sn, Pb; X-Cu, Ag, Cd, In, Ga, Bi, Sb, Mn, V) are given. The separate and joint effect of deviation from stoichiometry and cation substitution on the IV-X-Te phase properties is established using the method of ‘controlled atomic defects’. Some general regularities and new physical phenomena connected with simultaneous presence of intrinsic and impurity point defects are detected. The influence of the cation substitution on the intrinsic defect equilibrium is established. It is shown that critical phenomena of percolation nature are observed in the range of small impurity contents as well as small intrinsic defect concentrations. Principally new models of the energy band structure of IV-X-Te ternary phases, which take into consideration a high concentration of non-stoichiometric defects, are proposed. The role of long- and short-range ordering is discussed. The formation of complexes as a result of chemical interaction between impurity and host atoms is detected. The above-mentioned phenomena are common for ternary phases and should be taken into account when developing materials for different applications.     

Prediction of nanoparticles’ size-dependent melting temperature using mean coordination number concept

Many models have been developed to predict size-dependent melting temperature of nanoparticles. A new model based on the cluster mean coordination number (MCN) calculations is developed in this work. Results of the model for Al, Au, Pb, Ag, Cu, In, Sn, and Bi were compared with other models and experiments. The comparison indicated that the MCN model is in good agreement with available experimental values. It is also found that the melting temperature is more dependent on particle size as the atomic radius increased.     

Half-metallic ferromagnetism in I2-VI compounds with non-magnetic dopants

First-principles calculations based on the tight-binding linear muffin-tin orbital (TB-LMTO) method were performed to investigate the occurrence of spin polarization in the alkali metal oxides (M₂O) [M: Li, Na, K, Rb] in antifluorite (anti- CaF₂-type) structure with non-magnetic (N, P, As, Sb and Bi) dopants. The calculations reveal that non-magnetic substitutional doping at anion site can induce stable half-metallic ferromagnetic ground state in I₂-VI compounds. Total energy calculations show that the antifluorite ferromagnetic state is energetically more stable than the antifluorite non-magnetic state at equilibrium volume. Ground state properties such as equilibrium lattice constant and bulk modulus were calculated. The calculated magnetic moment is found to be 1.00 μ_B per dopant atom. The magnetic moment is mainly contributed by p orbitals of dopant atom.     

Structural and electrical analysis of In–Sb–Te‐based PCM cells

Two In–Sb–Te compounds with low Te content (12 at.% and 17 at.%), deposited by metalorganic chemical vapour deposition, were implemented into prototype phase‐change memory devices of size 50 × 50 nm² and 93 × 93 nm². These chalcogenides yielded devices with higher threshold voltage than those based on Ge–Sb–Te alloys. The endurance and programming window were markedly improved (from 10³ to 10⁶ cycles and from 1 to 2 orders of magnitude, respectively) when employing the Te‐richer alloy. Moreover, in situ structural and electrical analysis on TiN/In–Sb–Te/dielectric stacks provided additional insight on the thermal stability of the two ternary phases In₃SbTe₂ and InSb_0.8Te_0.2, which were found to coexist in these compounds. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Bi induced step-flow growth in the homoepitaxial growth of Au(1 1 1)

Homoepitaxial growth of Au on Bi-covered Au(1 1 1) was studied at room temperature using reflection high-energy electron diffraction (RHEED) and Auger electron spectroscopy (AES). From observations of RHEED it is found that the Au(1 1 1) (23 × 1) reconstruction structure changes to a (1 × 1) by about 0.16-0.5 ML deposition of Bi and to a (2√3 × 2√3)R30° by about 1.0 ML deposition of Bi, respectively. The surface morphology evolution by Bi deposition leads to a change of Au homoepitaxial growth behavior from layer-by-layer to step flow. This indicates that the surface diffusion distance of Au atoms on the Bi-precovered (1 × 1) and (2√3 × 2√3)R30° surfaces is longer than that on the Au(1 1 1) (23 × 1) clean surfaces. A strong surface segregation of Bi was found at top of surface. It is concluded that Bi atoms acted as an effective surfactant in the Au homoepitaxial growth by promoting Au intralayer mass transport.     

Estimation of surface tension for high temperature melts of the binary Ag-X alloys

ABSTRACT

Surface tension is a key property to materials. In this work, the surface tension of the binary alloys Ag-X (Au, Cu, Ce, Bi, Sn, Sb, In, Ni, Y, Pd) is carried out by using Butler Model over enter composition ratio at a certain temperature. According to calculation results, the increasing surface tension of the Ag-X (Cu, Au, Ni, Y, Pd) alloy is accompanied by the composition increases. For Ag-Sn alloy, the surface tension calculated by Butler model is consistent with the experimental result at temperature 1273?K. However, other Ag-X alloys can’t be compared due to the lack of the related experimental data. Although the experimental data about surface tension of the Ag-X alloy are limited, we are possible to make a comparison between the calculated results for the surface tension in this study and the available experimental data. Taken together, the surface tension calculated by Butler model that especially the Ag-Sn alloy are consistent with the experimental results at temperature 1273?K.     

First principles prediction of the elastic,electronic and optical properties of Sn3X4 (X = P,As, Sb,Bi) compounds: Potential photovoltaic absorbers

We report a first-principles study of structural, mechanical and optoelectronic properties of the Sn₃X₄ (X = P, As, Sb, Bi) compounds. The calculations were performed using the full-potential linearized augmented plane wave approach (FP-LAPW). The structural and mechanical properties of Sn₃X₄ (X = P, As, Sb, Bi) compounds were obtained using GGA-PBE. In addition, The Tran-Blaha modified Becke-Johnson exchange potential (TB-mBJGGA) technique was used to calculated the optoelectronic properties. The calculated electronic band structures and density of states reveal a direct band gap at Γ points varied from 0.11 eV to 1.23 eV for X = P, As, Sb, Bi. The optical absorption calculations show that all compounds have high absorption coefficients about twenty times greater than that of CuInSe₂ and CdTe in the visible region. The high absorption of these materials could be attributed to the localized p-states of cation (X = P, As, Sb, Bi) in the lower region of the conduction band.     

氢化物发生-原子荧光法直接测定锑及其化合物中的硒和铋

通过研究在不同酸度下Sb5+对Se,Bi的干扰情况,发现在高酸度下,Sb对Se,Bi的干扰明显减弱,并结合锑在不同价态发生氢化反应的差异性,建立了不需通过任何化学分离而直接测定锑及其相关产品中的微量硒和铋的方法,并用于实际样品的分析.方法对实际样品加标回收率在95%～105%之间,检测下限(含量)硒和铋分别为0.00004×10-2mg@L-1和0.0001×10-1mg@L-1,对实际样品分析精度分别为RSD(Se)=2.4%(含量为0.00169×10-2mg@L-1时),5.4%(含量为0.00056×10-mg@L-1时)和RSD(Bi)=5.0%(含量为0.00024×10-2mg@L-1时),1.3%(含量为0.00229×10-2mg@L-1时),完全满足实际样品分析的要求.     

Thermoelectric properties of Ge-doped Bi85Sb15 alloys at low temperatures

Bulk polycrystalline Bi₈₅Sb_15−xGe_x (x=0, 0.5, 1, 1.5, 2) composites were prepared by mechanical alloying followed by pressureless sintering. The thermoelectric properties were studied in the temperature range of 77–300 K. The results indicate that increasing the Ge concentration causes the Seebeck coefficient to change sign from negative to positive. Moreover, it is found that the maximum value of the Seebeck coefficient can be precisely controlled with the Ge concentration. The maximum dimensionless figure of merit reaches 0.07 at 140 K. These results suggest that the preparation of p-type Bi–Sb alloys is possible by using the Ge-doping approach.     

Topological surface states in lead-based ternary telluride Pb(Bi(1-x)Sb(x))2Te4

We have performed angle-resolved photoemission spectroscopy on Pb(Bi(1-x)Sb(x))2Te4, which is a member of lead-based ternary tellurides and has been theoretically proposed as a candidate for a new class of three-dimensional topological insulators. In PbBi2Te4, we found a topological surface state with a hexagonally deformed Dirac-cone band dispersion, indicating that this material is a strong topological insulator with a single topological surface state at the Brillouin-zone center. Partial replacement of Bi with Sb causes a marked change in the Dirac carrier concentration, leading to the sign change of Dirac carriers from n type to p type. The Pb(Bi(1-x)Sb(x))2Te4 system with tunable Dirac carriers thus provides a new platform for investigating exotic topological phenomena.     

Asymmetric double-barrier S–I1–N–I2–S Josephson heterojunctions: experiment and theory

Double-barrier highly asymmetric Nb–Al oxide–Al–Nb oxide–Nb structures with reproducible characteristics were fabricated. The heterocontacts with the middle Al layer thickness ranging from 4 to 6 nm exhibited a well-defined d.c. Josephson supercurrent I_c at 4.2 K and characteristic voltages V_c=I_cR_N (R_N is the normal resistance, V_c defines the response time of the junction) from 0.3 to 0.4 mV. Two prominent features in the quasiparticle current–voltage curves have been observed: a so-called ‘knee' in the energy-gap region and an additional (to the linear voltage dependence) current at higher biases. They are discussed within a simple Landauer–Büttiker scattering approach to the phase-coherent quasiparticle transport in a quasiballistic S–I₁–N–I₂–S heterostructure with an extremely great difference between the barrier transparencies.     

Electronic conduction properties of Au/C60/p-Si and C60/Au/p-Si sandwich structures: I–V and transducer characteristics

Gold-fullerite [C₆₀]-silicon (p-type) sandwich structures have been fabricated in order to investigate intrinsic cross-sectional and planar electronic conductive properties, in particular the C₆₀/p-Si p–n heterojunction. The turn-on voltage of this p–n heterojunction lies in the range 0.25–0.27 V. The I–V characteristics of the Au/C₆₀/p-Si structure are mostly defined by the bulk specific resistance of the fullerite crystal film itself (6×10⁷ Ω cm). I–V curves in the C₆₀/Au/p-Si structure are shown to be ohmic. Au/C₆₀/p-Si sandwiches irradiated with swift (300 MeV) heavy ions, (⁸⁴Kr¹⁴⁺) to a total fluence 10¹⁰ ion/cm² yield structures which are sensitive to ambient air pressure, specifically in the case of a transverse contact configuration, and if one of the contacts is located on the irradiated part of the fullerite film. The sandwich-structure sensitivity to pressure is 5×10⁻⁶ Pa⁻¹. This exceeds the sensitivity of conventional silicon pressure transducers by almost three orders of magnitude.     

An investigation of influencing of Sb and Bi contents on surface tensions associated with Pb-free Sn-Zn-Sb-Bi quaternary and sub-quaternary solder alloys

The surface tensions of ternary and quaternary systems of Sn-based Pb-free solder alloys have been calculated using geometric models, such as Muggianu, Kohler, Chou’s general solution model (GSM), Toop, Guggenheim, ideal Butler and Butler models. It is observed from the calculation carried out in the present work that Sb and Bi contents decrease the surface tension of the solder alloys Sn-Zn-Sb-Bi. It is inferred from the statistical analysis that the best agreement between the experimental results and the corresponding calculated values of the surface tensions is generally observed in GSM and Muggianu models among the geometric models. Whereas Muggianu model is the most appropriate. Relatively good agreements have been observed between models considered in this study and experimental data.     

Large enhancement of Faraday rotation by localized surface plasmon resonance in Au nanoparticles embedded in Bi:YIG film

A large enhancement of the Faraday rotation, which is associated with localized surface plasmon resonance (LSPR), was obtained in a sample with Au nanoparticles embedded in a Bi-substituted yttrium iron garnet (Bi:YIG) film. On a quartz substrate, Au nanoparticles were formed by heating an Au thin film, and a Bi:YIG film was then deposited on them. A sample containing the Au nanoparticles produced by 1000 °C heating showed a resonant attenuation with narrower bandwidth in the transmission spectrum than nanoparticles of other samples formed by low-temperature heating. The sharp resonant Faraday rotation angle was 4.4 times larger than the estimated intrinsic Bi:YIG film at the LSPR wavelength; the angular difference was 0.14°. A discrepancy in the bandwidth between the transmission attenuation and the resonant Faraday rotation is discussed.     

Ultrasonic characterization of heavy metal TeO2–WO3–PbO glasses below room temperature

The longitudinal ultrasonic attenuation measurements have been made using pulse echo method at fundamental frequencies of 2, 4, 6 and 8 MHz in 20WO₃–(80−x) TeO₂–xPbO ternary tellurite glasses (x=10, 12.5, 15, 17.5 and 20 mol%) in the temperature range 160–280 K. The results showed the presence of a broad peak which shifts to higher temperature with increasing frequency. The ultrasonic attenuation peaks suggest that the experimental behavior is controlled by thermally activated structural relaxations. The internal friction, acoustic activation energy, deformation potential, relaxation strength, number of loss centers and density of state have been calculated both as a function of temperature and PbO content. The acoustic activation energy was found to decrease from 0.156 to 0.135 eV with the increase of PbO content. The results showed that both the number of loss centers and their activation energy decrease with the atomic ring size. An increase in the density of state is observed with addition of PbO content at the same frequency in the whole range of temperature which is associated with structural units formed when PbO is added.