Molecular rulers for scaling down nanostructures

A method of constructing <30-nanometer structures in close proximity with precise spacings is presented that uses the step-by-step application of organic molecules and metal ions as size-controlled resists on predetermined patterns, such as those formed by electron-beam lithography. The organic molecules serve as a ruler for scaling down a larger "parent" structure. After metal deposition and lift-off of the organic multilayer resist, an isolated smaller structure remains on the surface. This approach is used to form thin parallel wires (15 to 70 nanometers in width and 1 micrometer long) of controlled thickness and spacing. The structures obtained were imaged with field emission scanning electron microscopy. A variety of nanostructures could be scaled down, including structures with hollow patterns.     

20CrMnMo钢稀土渗碳研究

采用稀土渗碳工艺对20CrMnMo钢进行渗碳处理,研究了渗层增厚的动力学、渗碳层组织和性能。结果表明:稀土渗碳层中沉淀析出了大量弥散分布的粒状碳化物,淬火后表层组织为针状马氏体、大量细小颗粒碳化物、少量残余奥氏体。渗碳层的硬度与传统工艺相比提高了10%,耐磨性提高了32%,接触疲劳寿命也有大幅提高。     

Complexity in strongly correlated electronic systems

A wide variety of experimental results and theoretical investigations in recent years have convincingly demonstrated that several transition metal oxides and other materials have dominant states that are not spatially homogeneous. This occurs in cases in which several physical interactions-spin, charge, lattice, and/or orbital-are simultaneously active. This phenomenon causes interesting effects, such as colossal magnetoresistance, and it also appears crucial to understand the high-temperature superconductors. The spontaneous emergence of electronic nanometer-scale structures in transition metal oxides, and the existence of many competing states, are properties often associated with complex matter where nonlinearities dominate, such as soft materials and biological systems. This electronic complexity could have potential consequences for applications of correlated electronic materials, because not only charge (semiconducting electronic), or charge and spin (spintronics) are of relevance, but in addition the lattice and orbital degrees of freedom are active, leading to giant responses to small perturbations. Moreover, several metallic and insulating phases compete, increasing the potential for novel behavior.     

Catalysis by transition metals: metal-carbon double and triple bonds

Several well-characterized transition metal catalysts contain a metal-carbon double bond or a metal-carbon triple bond. In other homogeneous (or heterogeneous) catalyst systems in which the metal is likely to be in a relatively high oxidation state, such as molybdenum(VI) or tungsten(VI), metal-carbon multiple bonds may play an important role. Some recent results suggest that even supposedly well understood reactions such as ethylene polymerization may actually involve catalysts that behave as if they contained a metal-carbon double bond instead of a metal-carbon single bond. The chemistry of metal-carbon double and triple bonds should eventually complement and perhaps. overlap the known chemistry of complexes containing metal-oxygen double bonds or metal-nitrogen triple bonds, respectively; unique catalytic reactions involving carbon, nitrogen, and oxygen ligands multiply bonded to transition metals are therefore possible.     

Theoretical organometallic chemistry

Organometallic chemists have synthesized a remarkable variety of new structural types. In these structures ligands, which are organic or inorganic molecules of variable independent stability, bind to one or more transition metal atoms. An approach to an understanding of the electronic structure, geometrical preferences, and reactivity of these complexes may be made if the molecule is "decomposed" conceptually into a metal fragment, ML(n), and a ligand. A library of the molecular orbitals of these fragments is becoming available. One then "reconstructs" the molecule by examining the interaction of the orbitals of the ligand, typically an organic molecule, with the orbitals of the ML(n), fragment.     

Activation volumes for solid-solid transformations in nanocrystals

The transition between four- and six-coordinate structures in CdSe nanocrystals displays simple transition kinetics as compared with the extended solid, and we determined activation volumes from the pressure dependence of the relaxation times. Our measurements indicate that the transformation takes place by a nucleation mechanism and place strong constraints on the type of microscopic motions that lead to the transformation. The type of analysis presented here is difficult for extended solids, which transform by complicated kinetics and involve ill-defined domain volumes. Solids patterned on the nanoscale may prove to be powerful models for the general study of structural transitions in small systems, as well as in extended solids.     

Rapid vapor deposition of highly conformal silica nanolaminates

Highly uniform and conformal coatings can be made by the alternating exposures of a surface to vapors of two reactants, in a process commonly called atomic layer deposition (ALD). The application of ALD has, however, been limited because of slow deposition rates, with a theoretical maximum of one monolayer per cycle. We show that alternating exposure of a surface to vapors of trimethylaluminum and tris(tert-butoxy)silanol deposits highly conformal layers of amorphous silicon dioxide and aluminum oxide nanolaminates at rates of 12 nanometers (more than 32 monolayers) per cycle. This process allows for the uniform lining or filling of long, narrow holes. We propose that these ALD layers grow by a previously unknown catalytic mechanism that also operates during the rapid ALD of many other metal silicates. This process should allow improved production of many devices, such as trench insulation between transistors in microelectronics, planar waveguides, microelectromechanical structures, multilayer optical filters, and protective layers against diffusion, oxidation, or corrosion.     

Solid state electrodes for high energy batteries

A new class of electrode materials for high energy density, rechargeable batteries based on topochemical reactions of lithium and transition metal compounds is evolving. The physical and structural properties relevant to the ability of transition metal oxides with framework structures to topochemically incorporate lithium are discussed. Perovskite-related structures are particularly attractive hosts for lithium.     

Quantum criticality without tuning in the mixed valence compound beta-YbAlB4

Fermi liquid theory, the standard theory of metals, has been challenged by a number of observations of anomalous metallic behavior found in the vicinity of a quantum phase transition. The breakdown of the Fermi liquid is accomplished by fine-tuning the material to a quantum critical point by using a control parameter such as the magnetic field, pressure, or chemical composition. Our high-precision magnetization measurements of the ultrapure f-electron-based superconductor β-YbAlB(4) demonstrate a scaling of its free energy that is indicative of zero-field quantum criticality without tuning in a metal. The breakdown of Fermi liquid behavior takes place in a mixed-valence state, which is in sharp contrast with other known examples of quantum critical f-electron systems that are magnetic Kondo lattice systems with integral valence.     

Solar Energy Conversion by Water Photodissociation: Transition metal complexes can provide low-energy cyclic systems for catalytic photodissociation of water

The basic concepts for direct and catalyzed photodissociation of water have been summarized. Water dissociation in closed-cycle processes based on endothermic photochemical reactions offers a potential solution to the solar energy conversion problem. Transition metal complexes, whose excited state chemistry is extremely rich (23, 24) although mostly unexplored, are, in principle, suitable "catalysts" for cycles of this type. The most interesting cycles are those involving metal hydrido complexes or binuclear complexes in which the two metal atoms are bound into a macrocyclic ligand. Systematic investigations of the photochemistry of transition metal complexes with the aim of designing suitable systems for solar energy conversion have long-range promise and merit further consideration.     

材料理论硬度与键合性质的关系研究

以往的研究表明材料硬度与键合性质之间有密切的联系,但材料硬度和晶体体弹模量（B）、剪切模量（G）之间的联系不存在一一对应关系.基于密度泛函理论,在广义梯度近似的计算条件下得到了多种典型晶体材料的结构参数和弹性模量参数,将参数代入Simunek A.理论小组的理论硬度计算模型可获得晶体的理论硬度值.通过分析晶体的硬度值与体弹模量（B）、剪切模量（G）之间的关系,认为“难压缩”并不等同于“高硬度”;通过对晶体键密度和键布居等成键电子结构信息的分析,改进了Simunek理论小组硬度计算模型中一个参数的获取方法,使计算结果更具合理性;通过定性分析认为拥有强的共价键和三维立体空间结构是晶体具有高硬度的典型特征,为今后新型超硬材料的理论研究和实验合成提供重要参考.     

Agriculture in the transition from a command to a market economy: the case of Latvia

The study presented is the result of a field survey conducted in Latvia in 1991. The brief of this research was to trace the role of the ‘private’ farm sector that has begun to emerge in the wake of the transition from a central-command to a market-oriented economy. Thus a look at the legislative acts embodying the agrarian reform is ccompanied by an analysis of the recent developments in local production systems. The study of ‘production systems’, or that part of economic analysis that comes under the rubric of ‘farm systems’, was employed here for the first time to analyze a Soviet-type economic system in transition. The first and second sections, which focus on the historical evolution of Latvia's agriculture and the economics underpinning it, range in compass from the ‘first’ agrarian reform to collectivization and on to the present situation. This is followed by a look at the current, or ‘third’, land reform initiative (section 3), particular emphasis being accorded the emergence of new production structures and the problems posed by the transformation of the old ones (sections 4 and 5). The next section includes a discussion of the links between the farms of the socialized sector and of the nascent private one (section 6). The concluding remarks provide a recapitulation of the study's main findings.     

Polymer replicas of photonic porous silicon for sensing and drug delivery applications

Elaborate one-dimensional photonic crystals are constructed from a variety of organic and biopolymers, which can be dissolved or melted, by templating the solution-cast or injection-molded materials in porous silicon or porous silicon dioxide multilayer (rugate dielectric mirror) structures. After the removal of the template by chemical dissolution, the polymer castings replicate the photonic features and the nanostructure of the master. We demonstrate that these castings can be used as vapor sensors, as deformable and tunable optical filters, and as self-reporting, bioresorbable materials.     

农机用65Mn钢激光表面处理后的组织与性能

研究了农机用６５Ｍｎ钢激光相变和激光熔凝处理后的显微组织和显微硬度，结果表明：显微组织由表面相变硬化区，过渡区和基体组成，硬化区是超细针状马氏体，显微硬度达ＨＶ９００￣１０００，激光相变多道搭接扫描后在搭接区有明显的回火软化现象。     

Crystal Structures Adopted by Black Phosphorus at High Pressures

Black phosphorus undergoes two reversible structural transitions at high pressures. The first is to a structure of the type arsenic A7. This structure is transformed to a simple cubic structure at higher pressures. The reversibility between the A7 and simple cubic structures at 111 kilobars indicates that the transition obtainable at this pressure provides a good calibration point by which high-pressure x-ray data may be united with volumetric or resistance measurements, or both.     

Mott transition in VO2 revealed by infrared spectroscopy and nano-imaging

Electrons in correlated insulators are prevented from conducting by Coulomb repulsion between them. When an insulator-to-metal transition is induced in a correlated insulator by doping or heating, the resulting conducting state can be radically different from that characterized by free electrons in conventional metals. We report on the electronic properties of a prototypical correlated insulator vanadium dioxide in which the metallic state can be induced by increasing temperature. Scanning near-field infrared microscopy allows us to directly image nanoscale metallic puddles that appear at the onset of the insulator-to-metal transition. In combination with far-field infrared spectroscopy, the data reveal the Mott transition with divergent quasi-particle mass in the metallic puddles. The experimental approach used sets the stage for investigations of charge dynamics on the nanoscale in other inhomogeneous correlated electron systems.     

川西林盘群落类型及其多样性

川西林盘是成都平原与都江堰灌溉水系所形成的集生产、生活、景观于一体的独特复合型居住模式和农耕环境形态,以林为核心组分,以水、宅、田为自然和人工构成要素.在分析川西林盘分布现状的基础上,选取代表性林盘24个,研究其群落类型、群落水平与垂直结构、出现频率等.结果表明,①川西林盘植被可划分为5个植被型组,11个植被型,107...     

Strong interactions in supported-metal catalysts

Many commercially important catalysts consist of small metal particles dispersed on inorganic oxide surfaces. Although in most cases there is no significant interaction between the metal and the support, strong bonding can be demonstrated in a recently discovered class of supported-metal catalysts. These cases typically involve group VIII metals dispersed on transition metal oxides whose surfaces can be reduced to form cations with lower valences. Spectroscopic measurements indicate that an electron is transferred from the cation (such as Ti(3+) or Nb(4+)) to the metal particle. This, in turn, leads to profound changes in the catalytic and chemisorption properties and the morphology of the metal particles.     

Hydrogen Embrittlement of Metals: Atomic hydrogen from a variety of sources reduces the ductility of many metals

Hydrogen interacts with many metals to reduce their ductility (2) and frequently their strength also. It enters metals in the atomic form, diffusing very rapidly even at normal temperatures. During melting and fabrication, as well as during use, there are various ways in which metals come in contact with hydrogen and absorb it. The absorbed hydrogen may react irreversibly with oxides or carbides in some metals to produce a permanently degraded structure. It may also recombine at internal surfaces of defects of various types to form gaseous molecular hydrogen under pressures sufficiently high to form metal blisters when the recombination occurs near the outer surface. In other metals, brittle hydrides that lower the mechanical properties of the metal are formed. Another type of embrittlement is reversible, depending on the presence of hydrogen in the metal lattice during deformation for its occurrence. Under some conditions the failure may be delayed for long periods. A number of different mechanisms have been postulated to explain reversible embrittlement. According to some theories hydrogen interferes with the processes of plastic deformation in metals, while according to others it enhances the tendency for cracking.     

Ion binding by synthetic macrocyclic compounds

The existence of synthetic macrocyclic molecules with hydrophilic cavities containing multiple binding atoms and with hydrophobic exteriors gives rise to extraordinary possibilities with respect to the design and synthesis of molecules with specific cation and anion binding properties. The preparation of many new macrocyclic compounds has recently been reported, but few practical applications for them have been suggested. From the information available, it is becoming clear that it should be possible to synthesize macrocycles that will have specified, or selected, ion binding properties. Cavity size can be varied to accommodate only those cations or anions within a specified narrow band of sizes. Numbers and types of coordinating atoms can be chosen to give essentially electrostatic or covalent bonding or a combination of the two in a metalmacrocycle complex. The metal ligand bond appears to be predominantly ionic in the case of the cyclic polyethers but the covalent character increases on substitution of sulfur or nitrogen for oxygen donor atoms. The essential hydrophobic exteriors of the macrocycles can be modified by the addition of side chains and groups to facilitate the solution of anions and cations in organic solvents. The structures of many macrocycles can be made to approximate naturally occurring molecules, that is, cyclic polyethers similar to macrocyclic antibiotics of the valinomycin and nonactin types and cyclic polyamines similar to porphyrins. Macrocycles are also useful as model compounds for the study of metal interactions with biological systems. The synthetic macrocycles thus represent an intriguing new area of coordination chemistry, the systematic study of which should lead to many interesting and useful chemical applications in the field of metal complexation in solution.