Theoretical study of structures of Ga5N5 cluster

The structures and energies of a Ga₅N₅ cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics technique. Twenty-four structures for a Ga₅N₅ cluster have been obtained. The most stable structure is a C₁ planar structure with a N₃ subunit. The Ga₅N₅ clusters show a preference for a N₃ subunit, revealing the same behavior as in the Ga₃N₃ and Ga₄N₄ clusters. The existence of strong N–N bonds dominates the structure of a Ga₅N₅ cluster. Through the calculation of the density of states we found that the most stable structure of Ga₅N₅ clusters presented semiconductor-like properties.     

Magneto-transport properties of La0.7Ca0.3MnO3/SrTiO3/La0.7Ce0.3MnO3 tunnel junction

Hole-doped rare-earth manganite La_0.7Ca_0.3MnO₃ and the electron-doped manganite La_0.7Ce_0.3MnO₃ both show a metal-insulator transition around 250 K associated with a ferromagnetic transition and colossal magnetoresistance. In an earlier publication we have reported the rectifying characteristic of La_0.7Ca_0.3MnO₃/SrTiO₃/La_0.7Ce_0.3MnO₃ tunnel junction at room temperature, showing that it is possible to fabricate a diode out of the polaronic insulator regime of doped manganites. Here we report the magneto-transport properties of such a tunnel junction above and below the metal-insulator transition. We show, from the large positive magnetoresistance of the tunnel junction at low temperature, that La_0.7Ce_0.3MnO₃ could be a minority spin carrier ferromagnet. The implication of this observation is discussed.     

Rfe10.5V1.5Nx化合物的结构和内禀磁性研究

系统地研究了Rfe_10.5V_1.5N_x（Ｒ＝Ｙ，Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｄｙ，Ｈｏ，Ｅｒ）化合物的结构和内禀磁性，并与相应的Rfe_10.5V_1.5N_x化合物进行了比较。同Rfe_10.5V_1.5N_x化会物相比，由于ｖ含量低，Rfe_10.5V_1.5N_{x关键词：}     

J-aggregates of pseudoisocyanine with long alkyl substituents in thin films: Synthesis, spectral properties, and thermal stability

The formation and properties of J-aggregates in thin solid films of pseudoisocyanines with long N-alkyl groups, obtained by centrifuging from solutions in organic solvents, were studied. It is shown for the first time that nonsymmetric cyanine dyes, containing a C₂H₅ group at one nitrogen atom and a C₁₀H₂₁, C₁₅H₃₁, or C₁₈H₃₇ group at another nitrogen atom, spontaneously form J-aggregates stable at room temperature and pressing a narrow absorption band with a half-width at half maximum of 200 cm^?1. The thermal stability of J-aggregates in thin films of pseudoisocyanines with alkyl substituents decreases in the following order: C₂H₅-C₂H₅> C₂H₅-C₆H₁₃>C₂H₅-C₁₈H₃₇>C₂H₅-C₁₀H₂₁>C₂H₅-C₁₅H₃₁. By introducing 1-octadecyl-2-methylquinolinium iodide in the film, it was found that the J-aggregates studied consist of a small number (2–4) of dye molecules.     

High pressure X-ray diffraction study of CdAl2Se4 and Raman study of AAl2Se4 (A=Hg, Zn) and CdAl2X4 (X=Se, S)

We report the results of an X-ray diffraction study of CdAl₂Se₄ and of Raman studies of HgAl₂Se₄ and ZnAl₂Se₄ at room temperature, and of CdAl₂S₄ and CdAl₂Se₄ at 80 K at high pressure. The ambient pressure phase of CdAl₂Se₄ is stable up to a pressure of 9.1 GPa above which a phase transition to a disordered rock salt phase is observed. A fit of the volume pressure data to a Birch-Murnaghan type equation of state yields a bulk modulus of 52.1 GPa. The relative volume change at the phase transition at ∼9 GPa is about 10%. The analysis of the Raman data of HgAl₂Se₄ and ZnAl₂Se₄ reveals a general trend observed for different defect chalcopyrite materials. The line widths of the Raman peaks change at intermediate pressures between 4 and 6 GPa as an indication of the pressure induced two stage order-disorder transition observed in these materials. In addition, we include results of a low temperature Raman study of CdAl₂S₄ and CdAl₂Se₄, which shows a very weak temperature dependence of the Raman-active phonon modes.     

Magnetic properties of UT2Si2 and UT2Ge2 (T = Co,Ni, Cu) intermetallic systems

Neutron diffraction and magnetization measurements indicate that, at low temperatures, long-range magnetic order is present in UCO₂Si₂, UNi₂Si₂, UCu₂Si₂, UNi₂Ge₂, and UCo₂Ge₂. UCo₂Si₂ and UNi₂Ge₂ are simple collinear antiferromagnets of +-+- type, UCu₂Si₂ a simple collinear ferromagnet. In UNi₂Si₂, a magnetic phase transition from a LSW type structure to collinear antiferromagnetism of +-+- type was found, while in UCu₂Ge₂, the antiferromagnetic structure of ++-- transforms into collinear ferromagnetism. Crystal structure and magnetic parameters are given. No magnetic moment on transition metal ions was found within the accuracy of a powder neutron diffraction experiment. The stability of particular magnetic ordering schemes is discussed in terms of an isotropic RKKY mechanism.     

Frustration driven magnetic states of A-site spinels probed by <Emphasis Type="Italic">μ</Emphasis>SR

The normal A-site spinels MnAl₂O₄, FeAl₂O₄, CoAl₂O₄, as well as related mixed (Mn_0.5Fe_0.5Al₂O₄) and partially inverted (Fe_1.4Al_1.6O₄) spinels have been studied by μSR. The magnetic ions are subject to magnetic frustration by competing interactions. In all materials and at all temperatures the μSR spectra consist of two signals suggesting a bimodal distribution of the fluctuation rates of magnetic moments. A characteristic temperature T _M is found in each compound, representing either a magnetic phase transition into a long-range ordered state (MnAl₂O₄, Fe_1.4Al_1.6O₄) or the formation of a spin liquid phase (FeAl₂O₄, CoAl₂O₄, Mn_0.5Fe_0.5Al₂O₄). The magnetic ground state of MnAl₂O₄ shows coexistence of antiferromagnetic and spin liquid phases. In FeAl₂O₄ and CoAl₂O₄ long-range order is suppressed altogether, the ground state can be characterized as a fast relaxing spin liquid coexisting with a small fraction of paramagnetic spins. The partial replacement of Mn by Fe in Mn_0.5Fe_0.5Al₂O₄ prevents long-range order and leads to a spin liquid state in the low temperature limit. The partial occupancy of B-sites by magnetic ions in Fe_1.4Al_1.6O₄ strengthens the exchange coupling, allowing the formation of long-range magnetic order at a rather high temperature (~100 K). Magnetic phase diagrams are presented demonstrating that for the studied compounds the magnetic properties are determined by the degree of frustration.     

纳米结构SmCo/FeCo多层薄膜的磁性

研究了用磁控溅射方法制备的纳米结构Sm₂₂Co₇₈单层膜、Sm₂₂Co₇₈/Fe₆₅Co₃₅双层膜及Sm₂₂Co₇₈/Fe₆₅Co₃₅/Sm₂₂Co₇₈三层膜的磁性,特别是双层膜及三层膜系统中的Fe₆₅Co₃₅软磁层厚度d对薄膜剩磁比(M_r/M_s)和矫顽力(H_c)的影响.所有样品的磁滞回线测量表明,该系列薄膜的易磁化轴在膜面内.磁滞回线的单一硬磁相特征,说明SmCo硬磁层与FeCo软磁层之间的交换相互作用使两相很好地复合在一起.在双层膜和三层膜中,M_r/M_s随软磁层厚度d的增加单调上升,而矫顽力随d的变化出现一峰值.通过研究ΔM随磁场H的变化,发现随着软、硬磁相界面数的增加,ΔM曲线的正峰数量逐渐减少;负峰数量逐渐增强,负峰的半高宽逐渐减少. 关键词：     

Quantitative analysis of mixed self-assembled monolayers using ToF-SIMS

The spacing of chemical functional groups on self-assembled monolayers (SAMs) plays an important role in controlling the density of biomolecules in biochips and biosensors. In this sense, a mixed SAM made of two different terminal groups is a useful organic surface since spacing can be easily controlled by changing a relative mole fraction in a mixture solution. In this study, an acetylene-OCH₂O(EG)₃(CH₂)₁₁S-S(CH₂)₁₁(EG)₃OCH₂O-propene (Eneyne) SAM and mixed SAMs made by a mixture of (S(CH₂)₁₁(EG)₃OCH₂O-acetylene)₂ (Diyne) and (S(CH₂)₁₁(EG)₃OCH₂O-propene)₂ (Diene) were produced on gold substrates and measured by using ToF-SIMS. The secondary ion yield ratio of [Au·S(CH₂)₁₁(EG)₃OCH₂O-acetylene]⁻ to [Au·S(CH₂)₁₁(EG)₃OCH₂O-propene]⁻ was measured for each mixed SAM and plotted as a function of the mole fraction of Diyne to Diene in a SAM solution. The ion yield ratio of a mixed SAM produced from a solution with a mole fraction of 0.5 (i.e., 1:1 mixture) was 0.3, which corresponded well to the ion yield ratio measured from an Eneyne SAM. A time-dependent experiment of Eneyne SAM formation and immersion experiment of Eneyne SAM into Diyne solution or into Diene solution were performed. The relative ion yield ratio of 0.3 was due to a different secondary ion formation and not due to the difference in the amount of adsorbates on the surface, nor to the different binding strengths onto the gold surface. Our study shows that a mixed SAM with well-controlled spacing can be produced and quantified by using the ToF-SIMS technique.     

Structural studies of phase transitions in crystalline and liquid halides (ZnCl<Subscript>2</Subscript>, AlCl<Subscript>3</Subscript>) under pressure

The results of investigating the phase diagrams of ZnCl₂ and AlCl₃ halides, as well as the structure of the shortrange order of the corresponding melts under pressures up to 6.5 GPa, by the method of energy-dispersive x-ray diffraction are reported. When a ZnCl₂ crystal is compressed, a phase transition occurs from the γ phase (HgI₂ structure type) to the δ phase (distorted CdI₂ structure, WTe₂ type). The structural studies of the liquid state of ZnCl₂ and AlCl₃ indicate that the intermediate-range order decreases rapidly in the tetrahedral network of both melts as the pressure increases to 1.8 and 2.3 GPa for ZnCl₂ and AlCl₃, respectively. With further compression, the transitions in both melts occur with a change in the structure of the short-range order and with an increase in the coordination number. In this case, the transition in AlCl₃ occurs at ≈4 GPa and is a sharp first order transition, whereas the transition in ZnCl₂ occurs more smoothly in a pressure range of 2–4 GPa with a maximum intensity near 3 GPa. Thus, the AlCl₃ and ZnCl₂ compounds exemplify the existence of two phenomena—gradual decay of intermediate-range structural correlations and a sharper liquid-liquid coordination transition.     

Photoemission valence band spectra and electronic density of states in copper oxides and copper based ceramic super-conductors

Photoemission valence band spectra with three different photon energies (21.2 eV, 40.8 eV, 1253.6 eV) for Cu₂O and CuO and a number of copper oxide based superconducting ceramics are investigated, namely La₂CuO₄ (LCO), Y₁Ba₂Cu₃O₇ (YBCO), Bi₂Sr₂CaCu₂O₈ (BSCCO) and Tl₂Ba₂Ca₂Cu₃O₁₀ (TBCCO). From the Cu₂O data it can be infered, that the He-II (40.8 eV) spectra give a fair representation of the density of states (DOS). In addition the agreement between the calculated density of states (DOS) and the He-II photoemission spectrum is almost perfect for Cu₂O. This agreement is worse for CuO and the other materials which all have a Cu groundstate close to a 3d ⁹ configuration indicating a large contribution of thed-d correlation energy to the excitation spectra which is absent in Cu₂O because of the filled 3d-shell. In all cases the experimental DOS atE _F is very small and only the spectra of BSCCO show a well defined Fermi edge. The relevance of these findings with respect to the theoretical local functional density DOS calculations is discussed.     

Microstructural characterization of bulk Ti3AlC2 ceramics

The microstructural characteristics of the bulk Ti₃AlC₂ ceramic, synthesized by a solid–liquid reaction and simultaneous in-situ hot pressing, have been studied by electron diffraction and high-resolution transmission electron microscopy. It was found that the as-synthesized ceramic is fully dense and free from amorphous phase at the grain boundaries. The ceramic is predominantly a single phase of hexagonal Ti₃AlC₂ with a minor volume of tetragonal Al₃Ti and cubic TiC. The Al₃Ti grains are crystallographically independent of the Ti₃AlC₂, whereas TiC is intergrown with Ti₃AlC₂, forming thin platelets and maintaining a close orientational relationship with the Ti₃AlC₂ matrix.     

The modification effect in magnetization behaviors for CoFe2O4–p-NiFe2O4 binary ferrofluids

The magnetization curves of CoFe₂O₄ ferrofluids, p-NiFe₂O₄ paramagnetic fluids and CoFe₂O₄–p-NiFe₂O₄ binary ferrofluids, in which the volume fraction of CoFe₂O₄ particles φ _Co is 0.6% and one of p-NiFe₂O₄ particles φ _Ni is 0.2%, 0.4%, 0.6% and 0.8% respectively, prepared by the Massart method, have been measured at room temperature. Comparison of the experimental data from the CoFe₂O₄ ferrofluids with the Langevin theory curves demonstrates a considerable difference between them, but a curve fitted using a model of a gas-like compression (MGC) agrees with the experimental data very well. The experimental results show that the magnetization of the CoFe₂O₄–p-NiFe₂O₄ binary ferrofluid is not a simple summation of the ferrimagnetic CoFe₂O₄ part and the paramagnetic p-NiFe₂O₄ part. From the fitted results, it was found that the saturation magnetization of the CoFe₂O₄ part of the binary ferrofluid depends non-monotonically on the p-NiFe₂O₄ particle volume fraction, and the CoFe₂O₄ part is a stronger “hard” magnet than CoFe₂O₄ in simple ferrofluids. The magnetization behavior of the binary ferrofluids is explained by the modification of the microstructure of CoFe₂O₄ nanoparticle system by the p-NiFe₂O₄ nanoparticle system.     

Ferromagnetic transition in ordered double perovskites and related alloys

We study the electronic and magnetic properties of ordered perovskites Sr ₂FeMO₆ (where M is a transition metal), among which some compounds, like Sr₂FeMoO₆ are half-metallic with high Curie temperature while Sr₂FeWO₆ is an antiferromagnetic insulator. Using a double exchange type model with an interaction between localized spins and conduction electrons together with a tight-binding Hamiltonian and the renormalized perturbation expansion method, we study the behavior of T_c as a function of the number of conduction electrons and also as a function of the Fe-M energy difference. We also consider the Sr₂FeMo_xW_1-xO₆ compounds which present a magnetic and metal-insulator transition as a function of doping.     

Design, formation and characterization of a novel multifunctional window with VO2 and TiO2 coatings

A novel multifunctional window was demonstrated using VO₂-based thermochromic films with a TiO₂ antireflection coating. A strong enhancement in luminous transmittance of VO₂ was calculated using either a single layer or a double layer of TiO₂ for antireflection, with the double layer giving the better performance. A TiO₂ (25 nm)/VO₂ (50 nm)/TiO₂ (25 nm) structure, of which the film thickness has been optimized to a maximum integrated luminous transmittance (T_lum) by calculation, was formed on SiO₂ glass by sputtering in turn a V target in Ar+O₂ for VO₂ and a TiO₂ target in Ar for TiO₂. Optical properties were measured with a spectrophotometer, and the integrated solar and luminous properties were calculated based on the measured spectra. A maximum increase in T_lum by 86% (from 30.9% to 57.6%) was obtained for VO₂ after double-layer TiO₂ antireflection coating. The deposited VO₂ film on SiO₂ exhibits good thermochromism with a sharp optical transition at 58.5 °C, which decreased slightly to 57.5 °C after TiO₂ coating. The proposed window is the most advanced among those similarly reported in being multifunctional with automatic solar/heat control, ultraviolet stopping and possibly a wide range of photocatalytic functions in addition to a high value of the luminous transmittance. PACS 42.79.Wc; 78.20.-e; 71.30.+h     

The elastic behaviour of tetrahedral materials with vacant sites

As part of a study of defect tetrahedral structure compounds, the elastic constants of single crystal specimens of Hg₃Ga₂□Te₆ and HgIn₂□Te₄ have been measured between 77 K and room temperature using the pulse superposition technique. These compounds are included in the series HgTe, Hg₅In₂□Te₈, Hg₃In₂□Te₆ and HgIn₂□Te₄ and HgTe, Hg₅Ga₂□Te₈, Hg₃Ga₂□Te₆ where there is a progressive increase in the concentration of vacant sites. While the other compounds studied are cubic, HgIn₂□Te₄ has a tetragonal structure with a $\text{c}\text{a}$ ratio of 2.0. The components of the elastic stiffness tensor of this material at 77 K are (in units of 10¹¹ dyne cm^?2) C₁₁ = 4.31 C₁₂ = 2.54 C₄₄ = 2.14 C₃₃ = 4.47 C₁₃ = 2.18 C₆₆ = 2.41. In a cubic material C₁₁ = C₃₃, C₄₄ = C₆₆ and C₁₂ = C₁₃: the elastic behaviour of this tetragonal compound closely resembles that of a cubic material, as might be anticipated from its structure. This similarity is further illustrated by reference to the symmetry of phase velocity and Young's modulus surfaces. Examination of the elastic constants and reduced elastic constants of these compounds shows a regular trend, the elastic stiffness decreases as the number of vacant sites increases. There is an approximately linear relationship between the reduced bulk modulus and the number of sited vacancies.     

Mechanisms of inelastic scattering of low-energy protons by C6H6, C60, C6F12, and C60F48 molecules

The mechanisms of inelastic scattering of low-energy protons with a kinetic energy of 2–7 eV by C₆H₆, C₆F₁₂, C₆₀, and C₆₀F₄₈ molecules are studied using the methods of quantum chemistry and nonempirical molecular dynamics. It is shown that, for the C₆H₆ + proton and C₆₀ + proton systems, starting from a distance of 6 Å from the carbon skeleton, the electronic charge transfer from the aromatic molecule to H⁺ occurs with a probability close to unity and transforms the H⁺ ion into a hydrogen atom and the neutral C₆H₆ and C₆₀ molecules into cation radicals. The mechanism of interaction of low-energy protons with C₆F₁₂ and C₆₀F₄₈ molecules has a substantially different character and can be considered qualitatively as the interaction between a neutral molecule and a point charge. The Coulomb perturbation of the system arising from the interaction of the noncompensated proton charge with the Mulliken charges of fluorine atoms results in an inversion of the energies of the electronic states localized, on the one hand, on the positively charged hydrogen ion and, on the other hand, on the C₆F₁₂ and C₆₀F₄₈ molecules. As a result, the neutral molecule + proton state becomes the ground state. In turn, this inversion makes the electronic charge transfer energetically unfavorable. Quantum-chemical and molecular-dynamics calculations on different levels of theory showed that, for fluorine derivatives of some aromatic structures (C₆F₁₂, C₆₀F₄₈), the barriers to proton penetration through carbon hexagons are two to four times lower than for the corresponding parent systems (C₆H₆, C₆₀). This effect is explained by the absence of active π-electrons in the case of fluorinated molecules.     

Shape memory behaviour of annealed Ti48.5Ni(51.5− x )Cu x (x = 6.2–33.5) thin films

The shape memory behaviour of (Ni,Cu)-rich Ti–Ni–Cu thin films (Ti_48.9Ni_44.9Cu_6.2, Ti_48.5Ni₄₀Cu_11.5, Ti_48.6Ni_35.9Cu_15.5, Ti_48.3Ni_28.4Cu_23.3, Ti_48.3Ni_23.9Cu_27.8 and Ti_48.5Ni₁₈Cu_33.5) annealed at 773, 873 and 973 K for 1 h was investigated. The films with 6.2, 11.5–15.5 and 23.3–33.5 at% Cu showed a single-stage deformation due to a B2 ? B19′ transformation, a two-stage deformation due to the B2 ? B19 ? B19′ transformation and a single-stage deformation due to the B2 ? B19′ transformation, respectively. The martensitic transformation start temperature (M _s) increased with increasing Cu content and then levelled off for more than 15 at% Cu, indicating a high Ms temperature of 345 K. Temperature hystereses were almost 15 K for all films with more than 10 at% Cu. The critical stress for slip increased with increasing Cu content and increased significantly for the Ti_48.5Ni₁₈Cu_33.5 film, whereas the maximum recoverable strain significantly decreased for the Ti_48.5Ni₁₈Cu_33.5 film. With decreasing annealing temperature, the critical stress for slip increased, but the M _s temperature decreased. It was found that films with 11.5 at% Cu or more, annealed at 873 K, showed a high martensitic transformation temperature and a high critical stress for slip.     

Structural and electrical properties of γ-alumina - lithium sulphate films

Li₂SO₄ as a model ionic conductor has received very much attention over several decades. Especially, in recent years Li₂SO₄ and Li₂SO₄-Al₂O₃ have been mentioned as promising proton conducting electrolytes for applications such as intermediate temperature fuel cells and novel cogeneration systems regarding H₂S handling devices. This has encouraged us to strive towards further improvement of the properties of the materials to meet the demands of the applications. In order to improve the properties of this system, a new process, a suspension technique, has been recently developed to prepare nanostructured powder and thin film Li₂SO₄-Al₂O₃ membranes. The powders and thin films have a well crystallised structure composed of two phases, Li₂SO₄ and γ-Al₂O₃, and excellent mechanical strength. The thin film thickness is in the scale of a few to several mm with a smooth and shining surface and a homogeneous macroscopic structure. It is a very interesting phenomenon that all samples show no significant conductivity increase at the temperature of the phase transition (∼ 577 °C) from β to α phase of pure Li₂SO₄. This transition has important significance for applications. The conductivity of the two-phase film materials has been greatly enhanced, where the xLi₂SO₄-(1-x)Al₂O₃ (x=58) sample shows the highest conductivity, about 1 S/cm at 600 °C; the activation energy decreases with increasing Li₂SO₄ content. These results agree with the so called composite effect for the conductivity enhancement observed earlier for two-phase bulk materials. Based on the four-step proton conducting mechanism in sulphate-based materials, this work may propose a new mechanism. The protons might jump in a water network associated with the water molecular re-orientation, which is accompanied with the single proton jump of the four-step transportation among SO ₄ ²⁻ groups from one Li₂SO₄ molecule to another. The former mechanism occur in the interfacial region between the Li₂SO₄ and the Al₂O₃ grains, while the latter occur in the bulk of the Li₂SO₄ grains. These thin film materials are intended for use as proton conducting ceramic membranes in applications such as desulphurisation and fuel cell co-generation plants. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Investigation of exchange bias in 0.1MFe2O4/0.9BiFeO3 (M=Co, Cu, Ni) nanocomposite

The 0.1MFe₂O₄/0.9BiFeO₃ (M=Co, Cu, Ni) nanocomposite samples were synthesized by the sol-gel method. Phase composition analysis was carried out, which showed that these bulk samples were composed of a ferrimagnetic MFe₂O₄ (M=Co, Cu, Ni) and a ferroelectric antiferromagnet (FEAF) BiFeO₃ phases, respectively. The magnetic properties of all the samples were investigated by measuring their magnetization as a function of temperature and magnetic field. These results indicated that the magnetic hysteresis loops of 0.1CuFe₂O₄/0.9BiFeO₃ sample sintered in air atmosphere at 550 °C for 3 h exhibited a negative shift and an enhanced coercivity at low temperature ascribed to strong exchange coupling between the BiFeO₃ and CuFe₂O₄ grains. However, there were no magnetic hysteresis loops in both the 0.1CoFe₂O₄/0.9BiFeO₃ sample and the 0.1NiFe₂O₄/0.9BiFeO₃ sample. In view of these results, we tend to think the CuFe₂O₄/BiFeO₃ nanocomposite system may be a useful multifunctional material.