The metallicity of thin films and overlayers

Thin-film materials, normally considered metals, can exhibit behavior that is very nonmetallic. There is an increasing body of experimental information that this phenomenon is quite general at submonolayer coverages. With increasing coverage and/or temperature there is a nonmetal to metal transition. This unusual behavior can occur even for films deposited on metal surfaces. Insight and identification of this electronic phase transition originates from several experimental probes of metallicity. Among the several techniques that have now been applied to this problem are angle-resolved photoemission, core level photoemission, resonant photoemission, inverse photoemission, high resolution electron energy loss, scanning tunneling microscopy, electron and atom beam scattering and optical techniques such as second harmonic generation and optical conductivity. These techniques are often consistent and suggestive of a many body transition that can, in some respects, be discussed in the context of the Mott–Hubbard transition. The results lead to the interesting speculation that many metal overlayers may be nonmetallic. A number of aspects of the nonmetal to metal transition in thin films and overlayers can be compared with measurements probing the metallicity of free clusters.     

Vacancy-induced changes in the electronic structure of transition metal carbides and nitrides: Calculation of X-ray photoemission intensities

Starting from KKR-CPA and KKR-GF densities of states and cross-sections within the single-scatterer final-state approximation, X-ray photoemission intensities were calculated for a series of stoichiometric and substoichiometric transition metal carbides and nitrides. For all compounds nonmetal vacancies give rise to an additional peak in the XPS spectra. The theoretical results are compared to several experimental XPS measurements. In most cases very good agreement is found. The discrepancies between theory and experiment are discussed in detail.Dedicated to Prof. A. Neckel on the occasion of his 60th birthday     

Anomalous pressure dependence of the metal-nonmetal transition of NiS

The pressure dependence of the metal—nonmetal transition in the hexagonal form of NiS has been measured to 13.7 kbar. An anomalous pressure dependence in the transition temperature was observed near 4.5 kbar. We associate this with the unusual lattice parameter behaviour previously reported for this region.     

Mechanism of formation of the columnar structure in films of transition metal diborides

The formation of film coatings based on transition metal diborides was investigated using x-ray diffractometry and electron microscopy. A scheme of the transformation of the crystal lattice was proposed, and the corresponding interplanar distances were calculated. An analysis of the results obtained made it possible to describe qualitatively the mechanism of formation of a columnar structure of the films prepared from transition metal diborides by using tantalum diboride TaB₂ as an example. It was demonstrated that, upon the synthesis of the films of the superstoichiometric composition, metal and nonmetal atoms have the octahedral coordination and form strong covalent bonds along the 〈00.1〉 direction, which favors texturing and the formation of a columnar structure. The results obtained were confirmed by the investigation of the physicomechanical characteristics of the films synthesized.     

Theoretical study of the effects of alloying elements on Cu nanotwins

Nanotwins form in many metallic materials to improve their strength and toughness. In this study, we thoroughly studied the alloying effects of 10 common metal and nonmetal elements on Cu nanotwins by density functional theory(DFT). We calculated the segregation energies to determine if Cu nanotwins attract both the metal and nonmetal alloying elements; these segregation energies were then decomposed to mechanical and chemical components. The Cu-Sn bonds are different from other metal alloying elements, and the strong bond between Cu and the nonmetal element results in the negative values of the chemical contribution. Furthermore, the temperature and concentration have different effects on the nanotwin formation energy of the metal and nonmetal alloying elements. As determined by the Generalized Stacking Fault Energy, Al and nonmetals can inhibit the migration of Cu nanotwin boundary, and the effects of Li, Mg, and Sn are opposite. Our theoretical study serves as the foundation for the engineering nanotwin structures through alloying elements, the elements that may lead to new alloy compositions and thermomechanical processes, and are important complements to the experimental research.     

液态金属和玻璃的若干研究进展

概述了液态金属和玻璃的的结构和性质研究的一些近期发展，如液态金属的原子间相互作用势和结构的普适性描述，二元液态合金的物理性质的计算和金属－－非金属转变的解释，以及玻璃的结构、熔化和弛豫的微观描述。     

Quasi-two-dimensional mott transition system Ca2-xSrxRuO4

We have revealed the phase diagram of Ca2-xSrxRuO4: the quasi-two-dimensional Mott transition system that connects the Mott insulator Ca2RuO4 with the spin-triplet superconductor Sr2RuO4. Adjacent to the metal/nonmetal transition at x approximately 0.2, we found an antiferromagnetically correlated metallic region where non-Fermi-liquid behavior in resistivity is observed. Besides this, the critical enhancement of susceptibility toward the region boundary at x(c) approximately 0.5 suggests the crossover of magnetic correlation to a nearly ferromagnetic state, which evolves into the spin-triplet superconductor Sr2RuO4.     

金属和非金属共掺杂锐钛矿相TiO2的第一性原理计算

本文运用第一性原理的计算方法, 以C/TM和N/TM共掺杂(碳与过渡金属共掺杂和氮与过渡金属共掺杂)TiO₂为例, 分别计算了它们共掺杂TiO₂的束缚能、能带结构和态密度等, 通过对双掺杂结构的束缚能计算, 发现非金属和金属杂质有团聚成键的趋势, 其正的束缚能说明了掺杂原子与周围的原子成键, 因成键作用减少的体系能量高于因几何畸变带来的应力能. 在对N/V和C/Cr共掺杂能带结构和分子成键的详细分析中, 发现非金属和金属共掺杂TiO₂, 要使掺杂后TiO₂的光吸收边红移较大, 光催化性能较好, 就要符合金属和非金属共掺杂协同机制, 即 掺杂后在导带底下方和价带顶上方分别出现由金属3d和非金属2p态提供的杂质能级.     

Departures from Amonton's law of friction

The method of transition from light friction (rolling) to heavy friction (sliding) is used for analyzing the principal departure from Amonton's law (force of sliding friction T proportional to the normal pressure force N) for several metal — nonmetal pairs when the sliding time t approaches zero. It appears that the departure mode is, under these conditions, the same for all pairs which have been tested here. Experimental and theoretical evidence is given to prove that all other modes of departure from Amonton's law represent consequences of changes in the rubbing surfaces which occur during sliding and that, therefore, such departures will appear only after a long enough period of sliding.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 94–98, November, 1974.     

Computationally predicting spin semiconductors and half metals from doped phosphorene monolayers

First-principles computations are performed to investigate phosphorene monolayers doped with 30 metal and nonmetal atoms. The binding energies indicate the stability of all doped configurations. Interestingly, the magnetic atom Co doping induces the absence of the magnetism while the magnetism is realized in phosphorene with substitutional doping of nonmagnetic atoms (O, S, Se, Si, Br, and Cl). The magnetic moment of transition metal (TM)-doped systems is suppressed in the range of 1.0-3.97 μ_B. The electronic properties of the doped systems are modulated differently; O, S, Se, Ni, and Ti doped systems become spin semiconductors, while V doping makes the system a half metal. These results demonstrate potential applications of functionalized phosphorene with external atoms, in particular to spintronics and dilute magnetic semiconductors.     

电极表面特性对甘油介质击穿特性的影响

基于几种常见的电极表面处理工艺,制作了外形一致、表面不同的砂纸打磨、羊毛抛光、金属电镀和非金属电镀四种同轴电极,对比了电极在微观下的形貌特点,通过实验研究了不同电极表面特性与甘油介质耐压的关系。搭建了基于晶闸管控制的空心脉冲变压器升压实验平台,最大输出电压500 kV,上升时间26 s。实验结果表明:四种电极的微观形貌存在较大差异,并引起了甘油击穿特性的不同,在相同充电电压条件下,甘油的平均击穿场强为210~260 kV/cm;与使用常规的砂纸打磨电极相比,使用羊毛抛光、金属电镀、非金属电镀电极可分别使击穿场强提高14.51%,11.60%,19.67%,其中非金属电镀电极表面均匀程度远高于其他电极,最高击穿场强可达288 kV/cm,比对照组平均击穿场强提高33.09%。     

Pressure induced transitions in calcium: a tight-binding approach

A tight-binding (TB) hamiltonian for calcium is built with a high precision parametrization technique based on density functional calculations of the energy bands and the total energy at various lattice volumes. The new set of TB parameters is appropriate to study phenomena under pressures as high as 20 GPa. Specifically, both the metal to nonmetal transition at 4 GPa and the structural transition fcc to bcc at 19 GPa are well reproduced. These transitions and several static properties are in excellent agreement with experiments. Phonon frequencies, plasmon energy, melting temperature and the coefficient of thermal expansion were calculated with a molecular dynamics scheme of this TB hamiltonian.     

Molecular Dynamics Simulations of Liquid Phosphorus at High Temperature and Pressure

By performing ab initio molecular dynamics simulations, we have investigated the microstructure, dynamical and electronic properties of liquid phosphorus （P） under high temperature and pressure. In our simulations, the calculated coordination number （CN） changes discontinuously with density, and seems to increase rapidly after liquid P is compressed to 2.5 g/cm3. Under compression, liquid P shows the first-order liquid-liquid phase transition from the molecular liquid composed of the tetrahedral P4 molecules to complex polymeric form with three-dimensional network structure, accompanied by the nonmetal to metal transition of the electronic structure. The order parameters Q6 and Q4 are sensitive to the microstructural change of liquid P. By calculating diffusion coefficients, we show the dynamical anomaly of liquid P by compression. At lower temperatures, a maximum exists at the diffusion coefficients as a function of density; at higher temperatures, the anomalous behavior is weakened. The excess entropy shows the same phenomena as the diffusion coefficients. By analysis of the angle distribution functions and angular limited triplet correlation functions, we can clearly find that the Peierls distortion in polymeric form of liquid P is reduced by further compression.     

Electrical conductivity and equations of states of β-rhombohedral boron in the megabar dynamic pressure range

The pressure dependence of the conductivity of boron under conditions of a stepwise shock compression of megabaric range is studied. With this purpose, the following problems have been solved. The conductivity of boron has been measured in the range of dynamic pressures, where boron has different high-pressure phases. The equations of state of β-rhombohedral and amorphous boron have been constructed in a megabaric pressure range. The thermodynamic states of boron in the conditions of these experiments are calculated, which, in combination with the measurement data, made it possible to determine the change in the boron conductivity in the conditions of strong stepwise shock compression at dynamic pressures to 110 GPa. The increase in the conductivity of polycrystalline boron at megabar pressures is interpreted as a result of a nonmetal–metal transition.

     

Suppression of charge ordering and thermal hysteresis of electronic transport and magnetisation in La0.5Ca0.5Mn1−xNixO3

A series of polycrystalline La_0.5Ca_0.5Mn_1?xNi_xO₃ (x = 0.00, 0.025, 0.050, 0.075, 0.100 and 0.125) was synthesised using solid state reaction. Measurements in a cooling and warming cycle between 300 and 80 K were carried out to study the Ni-doping effects on the electrical resistivity, thermopower and magnetisation of single-phase La_0.5Ca_0.5Mn_1?xNi_xO₃. Partial substitution of Ni for Mn leads to the suppression of charge ordering state, the evidence of which is shown by the dramatic decrease in electrical resistivity and thermal hysteresis width in electrical resistivity, thermopower and magnetisation. However, the magnitude of both electrical resistivity and thermopower increases with increasing Ni content. This can be attributed to an increase in the Mn⁴⁺ concentration, which favours the antiferromagnetic state and leads to a gradual disappearance of ferromagnetic double exchange interaction. Besides, the metal–nonmetal transition temperature decreases with increasing Ni content until x = 0.075, which might arise from increased electron–phonon coupling due to less ordered spins at temperatures above ferromagnetic transition. For samples with x greater than 0.075, no metal–nonmetal transition is observed due to the suppression of double exchange mechanism.     

Neutron diffraction and electrical transport studies on the incommensurate magnetic phase transition in holmium at high pressures

Neutron diffraction and electrical transport measurements have been made on the heavy rare earth metal holmium at high pressures and low temperatures in order to elucidate its transition from a paramagnetic (PM) to a helical antiferromagnetic (AFM) ordered phase as a function of pressure. The electrical resistance measurements show a change in the resistance slope as the temperature is lowered through the antiferromagnetic Néel temperature. The temperature of this antiferromagnetic transition decreases from approximately 122 K at ambient pressure at a rate of -4.9 K GPa(-1) up to a pressure of 9 GPa, whereupon the PM-to-AFM transition vanishes for higher pressures. Neutron diffraction measurements as a function of pressure at 89 and 110 K confirm the incommensurate nature of the phase transition associated with the antiferromagnetic ordering of the magnetic moments in a helical arrangement and that the ordering occurs at similar pressures as determined from the resistance results for these temperatures.     

NIR-VIS reflectivity spectra of some transition metal thiophosphates

Summary Room temperature optical-reflectivity measurements on some transition metal thiophosphates were carried out in the near infrared and visible regions. The resulting spectra, interpreted on the basis of the ?transition metal weakly interacting? model, agree well with earlier optical transmission measurements. Below the fundamental absorption edge, the observed features have been assigned to 3d–3d transitions occurring on the transition metal ion, while those observed at photon energies greater than the absorption threshold have been attributed to transitions from the valence bands to discrete 3d orbital levels or to the conduction bands. A more detailed information on the metal ion 3d levels energy distribution with respect to the valence band states belonging to the (P₂S₆)^4- cluster and a more precise determination of the MPS₃ absorption edge energy position have been obtained.     

Differences in emission parameters and adsorption properties of single-crystal faces

Published data on the work function and adsorbtion properties of faces of metal and nonmetal single crystals are considered from the viewpoint of a model of solids based on configurational localization. An explanation is proposed for the different values of work function yielded by different faces of a crystal of the same metal.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, Vol. 12, No. 6, pp. 42–47, June, 1969.     

Transition probabilities of Mn(II) lines lying between 237 and 357 nm from arc emission measurements

The arc arc emission method has been used to determine transition probabilities for 326 lines of Mn(II) belonging to 134 multiplet. The spectra were emitted from a plasma produced in a wall-stabilized arc. A new method has been developed to introduce Mn vapour (created by evaporation of solid metal in a combined arc-spark discharge) into the Ar-H-plasma. Plasma have been performed by spectroscopic methods. The relative transition probabilities are placed on an absolute scale by using A-values deduced from lifetime measurements.     

A strategy of enhancing the photoactivity of TiO2 containing nonmetal and transition metal dopants

An effective structural codoping approach is proposed to modify the photoelectrochemical （PEC） properties of anatase TiO2 by being doped with nonmetal （N or/and C） and transition metal （Re） elements. The electronic structures and for- mation energies of different doped systems are investigated using spin-polarized density functional theory. We find that （C, Re） doped TiO2, with a low formation energy and a large binding energy, reduces the band gap to a large extent, thus it could contribute to the significant enhancement of the photocatalytic activity in the visible-light region. It should be pointed out that, to be successful, the proper proportion of the dopants C and Re should be controlled, so that reasonable PEC properties can be achieved.