Electrical properties and defect model of tin-doped indium oxide layers

Tin-doped In₂O₃ layers were prepared by the spray technique with doping concentrationsc _Sn between 1 and 20 at. % and annealed at 500 °C in gas atmospheres of varying oxygen partial pressures. The room-temperature electrical properties were measured. Maximum carrier concentrationsN=1.5×10²¹cm^–3 and minimum resistivities =1.3×10^–4 cm are obtained if the layers are doped withc _Sn9 at. % and annealed in an atmosphere of oxygen partial pressurep _O2 10^–20 bar. At fixed doping concentration, the carrier mobility increases with decreasing oxygen pressure. The maximum obtainable mobility can be described in terms of electron scattering by ionized impurities. From an analysis of the carrier concentration and additional precision measurements of the lattice constants and film thicknesses, a defect model for In₂O₃:Sn is developed. This comprises two kinds of interstitial oxygen, one of which is loosely bound to tin, the other forming a strongly bound Sn₂O₄ complex. At low doping concentrationc _Sn4 at. % the carrier concentration is governed by the loosely bound tin-oxygen defects which decompose if the oxygen partial pressure is low. The carrier concentration follows from a relationN=K ₁ ·p _O2 ^–1/8 ·(3 ×10¹⁰ × c_Sn –N)^1/4 with an equilibrium constantK ₁=1.4×10¹⁵ cm^–9/4bar^1/8, determined from our measurements.     

Hydrodynamics of reactive systems: Chemical reactions near the critical points

The rate of a chemical reaction is expressed in terms of the correlation functions which are found from the full system of hydrodynamic equations in reactive systems. In the limiting cases one obtains all three types of behavior of reaction rates near the critical points found in experiments (slowing-down, speeding-up, insensitivity to criticality). This behavior depends on the number of reactive and inert components in a system, proximity and path of approach to the critical point.     

CO2 laser CVD of a-Si:H: in situ gas analysis and model calculations

4 and disilane Si₂H₆ induced by continuous wave CO₂ laser irradiation has been investigated under the conditions of chemical vapor deposition (CVD) of amorphous hydrogenated silicon a-Si:H. At the very position of depositing the thin film the stationary chemical composition of the processing gas is probed in situ by an effusive molecular beam which passes through a differential pumping stage into a quadrupole mass spectrometer (QMS). With SiH₄ as educt and SF₆ as a sensitizer, SiH₄ and Si₂H₆ are found in the processing gas while Si₃H₈ or higher silanes are lacking. Si₂H₆ and SF₆ lead to SiH₄, Si₂H₆, and Si₃H₈, but higher silanes are missing. The experimentally determined composition of the processing gas is semi-quantitatively reproduced by model calculations based on the assumption of stationary local equilibrium conditions and applying thermodynamic and spectroscopic data (molecular statistics). The mass balance of the processing gas entering and leaving the CVD chamber states an atomic ratio Si:H of 1:2 for the gas phase species forming the solid deposit on the reactor walls. This finding together with theoretical considerations indicates the intermediate Si₂H₄ to be the dominating gas phase species forming the a-Si:H thin films. Received: 17 July 1998/Accepted: 20 July 1998     

High pressure X-ray diffraction study of copper hydride at room temperature

Abstract

High pressure X-ray studies on CuH up to 23 GPa have been performed at room temperature using a gasketed diamond anvil cell. The experimental data on the molar volume of CuH as a function of pressure have been fitted to Murnaghan's equation of state giving a bulk modulus: B₀ = 72.5±2 GPa and B₀ = 2.7 ± 0.3. By comparison with the equation of state for pure copper the effective additive volume of hydrogen has been evaluated as a function of pressure. It decreases from 3.2 cm³/mol H, at ambient pressure reaching a flattening value of 1.7cm³hol H at about 60 GPa. This suggests a continuous transition of CuH from ionic or covalent character at normal pressure to metallic hydride behavior at high pressure     

Decomposition of binary sulphate KHSO4 at high pressure

Abstract

Pressure induced decomposition (PID) is known to occur only at elevated temperatures. Here we report its first occurrence at ambient temperature in a binary sulphate, KHSO₄ at 4kbar. Raman spectroscopy is used for identifying the decomposition products as K₃H(SO_{2 4}) and H₂SO₄ from their characteristic spectra. One of the decomposition products being a liquid is argued to be the reason for the occurrence of the phenomenon at ambient temperature. Other possible decomposition routes are also examined.     

Thermodynamic model for the size-dependent melting of prism-shaped nanoparticles

We report on the size-dependent melting of prism-shaped nanoparticles based on thermodynamic model and applied to understand the melting of prism-shaped indium nanoparticles. It is shown here that the bulk melting temperature cannot be extrapolated from the nanoscale and the extrapolated value will always be lower than the bulk melting temperature as has been observed experimentally.     

Calculation of geometrical changes in cylindrical copper hollow cathodes due to sputtering

To fine the reasons for the distortion of a cylindrical hollow cathode into a row of hollow spheres, the system of diffusion equations for the three most important types of particles in the hollow cathode discharge is solved, taking into consideration the essential source terms. In qualitative agreement with the experiments, the results show inhomogeneities of the cathode erosion at the cathode edges and at the boundary between hollow cathode discharge and normal glow discharge areas.     

Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage material

The dehydriding of sodium aluminum hydride, NaAlH₄, is kinetically enhanced and rendered reversible in the solid state upon doping with selected titanium compounds. Following the initial reports of this catalytic effect, further kinetic improvement and stabilization of the cyclable hydrogen capacity have been achieved upon variation in the method of the introduction of titanium and particle-size reduction. Rapid evolution of 4.0-wt % hydrogen at 100 °C has been consistently achieved for several dehydriding/rehydriding cycles. An improved, 4.8-wt % cyclable capacity has been observed in the material doped with a combination of Ti and Zr alkoxide complexes. Doping the hydride with Ti(OBuⁿ)₄ and Fe(OEt)₂ also produces a synergistic effect, resulting in materials that can be rehydrided to 4 wt % at 104 °C and 87 atm of hydrogen within 17 h. The improved kinetics allowed us to carry out constant-temperature, equilibrium-pressure studies of NaAlH₄ that extended to temperatures well below the melting point of the hydride. The 37-kJ/mol value determined for enthalpy of the dehydriding of NaAlH₄(s) to Na₃AlH₆ and Al and the hydrogen plateau pressure of 7 atm at 80 °C are in line with the predictions of earlier studies. The nature of the active catalyst and the mechanism of catalytic action are unknown. The catalytically enhanced hydrides appear to be strong candidates for development as hydrogen carriers for onboard proton exchange membran (PEM) fuel cells. However, further research and development in the areas of rehydriding catalysts, large-scale, long-term cycling, safety and adjustment of the plateau hydrogen pressure associated with dehydriding of AlH₆ ^- are required before these materials can be utilized in commercial onboard hydrogen-storage systems. Received: 7 September 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Electronic band gap of SrSe at high pressure

The electronic band gap of SrSe, in the CsCl-stuctured phase, was measured to 42 GPa via optical absorption studies. The indirect electronic band gap was found to close monotonically with pressure for the range of pressures studied. The change in band gap with respect to pressure, dE_gap/dP, was determined to be −6.1(5)×10⁻³ eV/GPa. By extrapolation of our line fit, we estimate band gap closure to occur at 180(20) GPa.     

高导无氧铜的高压与高应变率本构模型研究

基于Y/G及G/B为常数的假设,构建了高导无氧铜的七种高压与高应变率本构模型.对于高导无氧铜进行了平面冲击波试验,采用纵向与横向锰铜应力计记录了试件中的纵向与横向应力,从而得到了屈服应力历史.用所构建的七种本构模型进行了数值模拟,并与高导无氧铜的平面冲击波试验结果进行比较.结果表明,平面冲击波载荷下高导无氧铜的屈服强度对于压力、密度、温度以及塑性应变的依赖性是本构描述的关键.而由Hopkinson试验取得的高导无氧铜高应变率本构模型,并不适合描述平面冲击波载荷下的本构特性. 关键词： 本构模型 高导无氧铜 平面冲击波试验 锰铜应力计     

Two-stage amorphization of scandium molybdate at high pressure

Using Raman spectroscopy and X-ray diffraction we find that at high pressure amorphization of scandium molybdate occurs in two stages. Excessive broadening of molybdate internal modes arising from distortion and disordering of MoO₄ tetrahedra, together with rapid weakening of diffraction from large d-spacings and disappearance of diffraction from small d-spacings suggest gross molybdate ion disorder above 4 GPa. On the other hand, complete amorphization occurs at the significantly higher pressure of 12 GPa, where diffraction disappears completely. The amorphization is also found to be irreversible.     

Anharmonicity in aluminum hydride at high pressures

Aluminum hydride has been predicted to be a superconductor with a transition temperature of 24 K at 110 GPa, in disagreement with the experimental observation. In this work, it is shown that the bulk of the electron–phonon coupling can be associated with modes that are highly anharmonic according to frozen phonon calculations. This large anharmonicity could partially explain the origin of the disagreement between previous predictions and experiments.     

Melting of copper and nickel at high pressure: the role of d electrons

Melting curves of Cu and Ni were measured in the laser-heated diamond cell to 97 GPa (3800 K) and 60 GPa (2970 K), respectively. The temperatures of Cu are in good agreement with recent theoretical calculations. The Cu melting slope (dT/dP) is about 2.5 times steeper than for Ni. The present results confirm the key role d-shell electrons play in determining the temperature dependence of high pressure melting curves in transition metals that have filled or partially filled d electron bands.     

Synthesis of new La nitrides at high pressure and temperature

We have succeeded in synthesizing two new lanthanum nitrides in a supercritical nitrogen fluid at high pressure (about 30 GPa) and high temperature (about 2000 K), using a diamond anvil cell and a YAG laser heating system. These nitrides were found to be stable down to 5 GPa and ∼300 K in a nitrogen atmosphere. One of the new lanthanum nitrides is a cubic P lattice-type phase, which is a main phase synthesized nitride. The calculated lattice parameter is at 5 GPa, 300 K. The other nitride is of a trigonal P lattice-type. The calculated lattice parameters are and at 5 GPa, 300 K. The most likely phase of the former new La nitride is , the structure of which may be similar to the   Mn₂O₃-type (Ia80). The phase of the latter nitride is , the structure of which is the same as the   La₂O₃-type (hP5).     

Magnetic properties of PrCu2 at high pressure

We report a study of the low-temperature high-pressure phase diagram of the intermetallic compound PrCu₂, by means of molecular-field calculations and ^63,65Cu nuclear-quadrupole-resonance (NQR) measurements under pressure. The pressure-induced magnetically-ordered phase can be accounted for by considering the influence of the crystal electric field on the 4f electron orbitals of the Pr³⁺ ions and by introducing a pressure-dependent exchange interaction between the corresponding local magnetic moments. Our experimental data suggest that the order in the induced antiferromagnetic phase is incommensurate. The role of magnetic fluctuations both at high and low pressures is also discussed.     

More on shear modulus collapse of lattices at high pressure

In his recent paper, Shear modulus collapse of lattices at high pressure, J. Phys. Cond. Matt. 16 (2004) L125, V.V. Kechin claims that the zero temperature shear modulus of a metallic solid vanishes at a high critical pressure, and the critical pressures for this shear modulus collapse lie in the range 0-250 Mbar for elemental metals. Here we demonstrate that Kechin's arguments contain an erroneous assumption, and therefore, do not prove that all metals become mechanically unstable at high pressures. Ab initio calculations and experimental results on a number of solids are analyzed to confirm our conclusion.     

Theoretical investigation on structural, magnetic and electronic properties of ferromagnetic GdN under pressure

The tight-binding linear muffin tin orbital (TB-LMTO) method within the local density approximation is used to calculate structural, electronic and magnetic properties of GdN under pressure. Both nonmagnetic (NM) and magnetic calculations are performed. The structural and magnetic stabilities are determined from the total energy calculations. The magnetic to ferromagnetic (FM) transition is not calculated. Magnetically, GdN is stable in the FM state, while its ambient structure is found to be stable in the NaCl-type (B₁) structure. We predict NaCl-type to CsCl-type structure phase transition in GdN at a pressure of 30.4 GPa. In a complete spin of FM GdN the electronic band picture of one spin shows metallic, while the other spin shows its semiconducting behavior, resulting in half-metallic behavior at both ambient and high pressures. We have, therefore, calculated electronic band structures, equilibrium lattice constants, cohesive energies, bulk moduli and magnetic moments for GdN in the B₁ and B₂ phases. The magnetic moment, equilibrium lattice parameter and bulk modulus is calculated to be 6.99 μ_B, 4.935 Å and 192.13 GPa, respectively, which are in good agreement with the experimental results.