Structural chemistry and the local charge picture of copper oxide superconductors

The crystal structures of the known copper oxide superconductors are described, with particular emphasis on the manner in which they fall into structural families. The local charge picture, a framework for understanding the influence of chemical composition, stoichiometry, and doping on the electrical properties of complex structures, is also described.     

Bulk Superconductivity at 122 K in T1(Ba,Ca)2Ca3Cu4O10.5+8 with Four Consecutive Copper Layers

The observed increase of superconducting transition temperature (T(c)) with the number of copper oxide planes continues in the four-[CuO(2)](-2) layer (single TI layer) oxide superconductor, which has been prepared with > 80% purity and was magnetically aligned for crystallographic identification. A master scaling curve is proposed, which ties together the T(c)'s of virtually all known Bi and Tl oxide superconductors, and shows that the Tl(Bi) layers play an essential role in the superconductivity. publication 350 of the Barnett Institute.     

Surface pinning as a determinant of the bulk flux-line lattice structure in copper oxide superconductors

Direct knowledge of crystal defects and their perturbation of magnetic flux lines is essential to understanding pinning and to devising approaches that enhance critical currents in superconductors with high critical temperatures (T(c)). Atomic force microscopy was used to simultaneously characterize crystal defects and the magnetic flux-line lattice in single crystals of Bi(2)Sr(2)CaCu(2)O(8). Images show that surface defects, which are present on all real samples, pin the flux-line lattice. Above a critical height, the pinning interaction is sufficiently strong to form grain boundaries in the bulk flux-line lattice. These results elucidate the structure of the defects that pin flux lines and demonstrate that surface pinning, through the formation of grain boundaries, can determine the bulk flux-line lattice structure in high-T(c) materials. The implications of these results to the bulk flux-line lattice structure observed in previous experiments and to enhancing critical currents are discussed.     

Magnetic flux-line lattices and vortices in the copper oxide superconductors

A variety of recent experiments on both the static and the dynamic properties of vortices and flux-line lattices in the mixed state of the copper oxide superconductors are discussed. The experiments are of two basic types: (i) experiments that image the magnetic flux patterns either with magnetic decoration or neutrons and give information about static structures, and (ii) experiments that explore the dynamics of vortices either through the resistivity or other electrodynamic responses of the material. Results of these experiments argue in favor of the existence of a true phase transition in the high-field vortex state from a low-temperature superconducting vortex glass phase into a disordered high-temperature vortex fluid phase. The vortex glass phase transition model does a good job of explaining high-precision measurements of the dynamics at the transition. At low fields and temperatures, very long range hexatic order in the flux-line lattice is observed.     

Photoemission studies of high-tc superconductors: the superconducting gap

Over the last several years there have been great improvements in the energy resolution and detection efficiency of angle-resolved photoemission spectroscopy. These improvements have made it possible to discover a number of fascinating features in the electronic structure of the high transition temperature (T(c)) superconductors: apparently bandlike Fermi surfaces, flat-band saddle points, and nested Fermi surface sections. Recent work suggests that these features, previously thought explainable only by one-electron band theory, may be better understood with a many-body approach. Furthermore, other properties of the high-T(c) superconductors, which are difficult to understand with band theory, are well described using a many-body picture. Angle-resolved photoemission spectroscopy has also been used to investigate the nature of the superconducting pairing state, revealing an anisotropic gap consistent with a d-wave order parameter and fueling the current debate over s-wave versus d-wave superconductivity.     

The physics of organic superconductors

The upper temperature for superconductivity in organic conductors has increased from 1 kelvin in 1980, when the phenomenon was discovered in the quasi-one-dimensional cation radical salt tetramethyltetraselenafulvalene phosphorus heptafluoride to 12 kelvin in a new series of organic salts that show nearly two-dimensional electronic properties. These superconductors are attracting interest because of the wide range of new phenomena that they exhibit, including the competition between various ground states, the influence of a magnetic field on a quasi-one-dimensional conductor, the quantization of the Hall effect in a three-dimensional material, the giant magnetoresistance effects related to the two-dimensional nature of the Fermi surface of some materials, and the coherent voltage oscillation of a spin-modulated ground state. Furthermore, there is reason to believe that organic conductors with high superconducting transition temperatures could be produced in the near future. The recent finding of superconductivity in "fullerene" doped with alkali metals supports this optimism.     

Conducting organic materials

Some of the current directions of scientific research on electrically conducting organic solids are reviewed. Both molecular charge transfer salts and polymers are included, with emphasis on the present level of understanding of the novel solid-state properties of these materials in terms of their chemistry and structure. For the charge transfer salts the various types of metal-to-insulator phase transitions which dominate the properties of most of these materials are discussed. Also described are the superconducting and magnetic states which have been found recently. In the case of the polymers the chemistry and physics of the conduction mechanism is examined and contrasted with that of their classical inorganic counterparts.     

A Molecular Ferromagnet with a Curie Temperature of 6.2 Kelvin: [Mn(C5(CH3)5)2]+[TCNQ]-

The study of magnetic phase transitions in insulating molecular solids provides new insights into mechanisms of magnetic coupling in the solid state and into critical phenomena associated with these transitions. Only a few such materials are known to display cooperative magnetic properties. The use of high-spin molecular components would enhance intermolecular spin-spin interactions and thus a series of chargetransfer (CT) salts have been synthesized that utilize the spin S = 1 molecular cation, [Mn(C(5)(CH(3))(5))(2)](+) (decamethylmanganocenium). The structure and cooperative magnetic behavior of [Mn(C(5)(CH(3))(5))(2)](+)[TCNQ(-) (decamethylmanganocenium 7,7,8,8-tetracyano-p-quinodimethanide) are reported. This salt is a bulk molecular ferromagnet with the highest critical (Curie) temperature (T(c) = 6.2 K) and coercive field (3.6 x 10(3) gauss), yet reported for such a material.     

Oxygen isotope effect in high-temperature oxide superconductors

The effect of oxygen isotope substitution on the superconducting transition temperature, T(c), has been measured for BaBi(0.25)Pb(0.75)O(3) (T(c), approximately 11 K) and Lal(1.85) Ca(0.15)CuO(4) (T(c) approximately 20 K), and is compared to the shifts observed for La(1.85)Sr(0.15)CuO(4) (T(c) approximately 37 K) and YBa(2)Cu(3)O(7) (T(c) approximately 92 K). For all four materials, the transition temperature is shifted to lower temperature upon substitution of oxygen-18 for oxygen-16. The observed shifts demonstrate that phonons are involved in the electron-pairing mechanism in these oxide superconductors.     

The Resonating Valence Bond State in La2CuO4 and Superconductivity

The oxide superconductors, particularly those recently discovered that are based on La(2)CuO(4), have a set of peculiarities that suggest a common, unique mechanism: they tend in every case to occur near a metal-insulator transition into an odd-electron insulator with peculiar magnetic properties. This insulating phase is proposed to be the long-sought "resonating-valence-bond" state or "quantum spin liquid" hypothesized in 1973. This insulating magnetic phase is favored by low spin, low dimensionality, and magnetic frustration. The preexisting magnetic singlet pairs of the insulating state become charged superconducting pairs when the insulator is doped sufficiently strongly. The mechanism for superconductivity is hence predominantly electronic and magnetic, although weak phonon interactions may favor the state. Many unusual properties are predicted, especially of the insulating state.     

Electrodeposited defect chemistry superlattices

Nanometer-scale layered structures based on thallium(III) oxide were electrodeposited in a beaker at room temperature by pulsing the applied potential during deposition. The conducting metal oxide samples were superlattices, with layers as thin as 6.7 nanometers. The defect chemistry was a function of the applied overpotential: High overpotentials favored oxygen vacancies, whereas low overpotentials favored cation interstitials. The transition from one defect chemistry to another in this nonequilibrium process occurred in the same potential range (100 to 120 millivolts) in which the rate of the back electron transfer reaction became significant. The epitaxial structures have the high carrier density and low electronic dimensionality of high transition temperature superconductors.     

The Impact of High-Temperature Superconductivity on SQUID Magnetometers

DC and RF Superconducting QUantum Interference Devices (SQUIDs) fabricated from low transition temperature (T(c)) superconductors and operated at liquid (4)He temperatures are routinely used as ultrasensitive detectors in many applications, for example, as magnetometers, magnetic gradiometers, voltmeters, and motion detectors. SQUIDs fabricated from high T(c) superconductors such as YBa(2)Cu(3)O(7) and operated in liquid nitrogen at 77 K offer a greater convenience in operation at the expense of a poorer noise performance, particularly at low frequencies. The resolution of SQUID-based magnetometers is compared with that of other types of magnetometers operatng at ambient temperatures.     

铜陵铜尾矿废弃地中氧化铁研究

[目的]对铜尾矿废弃地中的氧化铁进行研究,探讨不同类型氧化铁对土壤形成过程的影响。[方法]以铜陵2处不同时间弃置的铜尾矿废弃地为对象,采用化学分析法研究了自然生态恢复过程中3类铁氧化物（无定形氧化铁、游离氧化铁和络合态氧化铁）的含量。[结果1尾矿废弃物无定形氧化铁含量为（1．73±0．77）～（9．68±2．94）g/kg,氧化铁活化度为（4．80±3．85）％-（91．94±4．34）％;游离氧化铁、晶质态氧化铁含量和游离度分别为（9．10±1．57）～（42．77±12．69）、（2．50±0．57）～（42．05±13．46）g／kg和（8．17±1．77）％～（20．02．±5．38）％;成土时间较短的杨山冲铜尾矿废弃地不同发育层尾矿中3种氧化铁含量差异较小,而弃置时间较长的铜官山尾矿废弃地随深度增加无定形氧化铁逐渐降低,游离氧化铁和络合态氧化铁逐渐增加。相关分析表明：2处尾矿废弃地pH值与无定形氧化铁含量及氧化铁活化度呈极显著正相关．而与游离氧化铁含量、铁游离度、晶质态氧化铁含量和络合态氧化铁含量呈极显著负相关;有机质含量与无定形氧化铁含量和氧化铁活化度呈极显著负相关,而与游离氧化铁含量、游离度及晶质态氧化铁含量呈极显著正相关.目前,铜陵铜尾矿废弃地尚处于成土过程的初期阶段,大量问题仍有待于进一步研究。[结论]探索了自然生态恢复过程中尾矿废弃地中铁氧化物的形态、含量变化特征及其影响因素,为进一步揭示铜尾矿及类似尾矿废弃物的成土过程、成土机制等理论研究提供参考。     

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.     

Ferroelectricity at the nanoscale: local polarization in oxide thin films and heterostructures

Ferroelectric oxide materials have offered a tantalizing potential for applications since the discovery of ferroelectric perovskites more than 50 years ago. Their switchable electric polarization is ideal for use in devices for memory storage and integrated microelectronics, but progress has long been hampered by difficulties in materials processing. Recent breakthroughs in the synthesis of complex oxides have brought the field to an entirely new level, in which complex artificial oxide structures can be realized with an atomic-level precision comparable to that well known for semiconductor heterostructures. Not only can the necessary high-quality ferroelectric films now be grown for new device capabilities, but ferroelectrics can be combined with other functional oxides, such as high-temperature superconductors and magnetic oxides, to create multifunctional materials and devices. Moreover, the shrinking of the relevant lengths to the nanoscale produces new physical phenomena. Real-space characterization and manipulation of the structure and properties at atomic scales involves new kinds of local probes and a key role for first-principles theory.     

Spontaneous Magnetic Ordering in the Fullerene Charge-Transfer Salt (TDAE)C60

The zero-field muon spin relaxation technique has been used in the direct observation of spontaneous magnetic order below a Curie temperature (T(c)) of approximately 16.1 kelvin in the fullerene charge-transfer salt (tetrakisdimethylaminoethylene)C(60) [(TDAE)C(60)]. Coherent ordering of the electronic magnetic moments leads to a local field of 68(1) gauss at the muon site at 3.2 kelvin (parentheses indicate the error in the last digit). Substantial spatially inhomogeneous effects are manifested in the distribution of the local fields, whose width amounts to 48(2) gauss at the same temperature. The temperature evolution of the internal magnetic field below the freezing temperature mirrors that of the saturation magnetization, closely following the behavior expected for collective spin wave (magnon) excitations. The transition to a ferromagnetic state with a T(c) higher than that of any other organic material is now authenticated.     

有机无机肥料配施对土壤酶活性、微生物量及玉米产量影响

以玉米为供试作物,田间试验在黑龙江省海林农场玉米种植区完成,探讨有机肥与无机肥不同配比对玉米产量、土壤酶活性和微生物量影响。试验设5个处理,100%有机肥N+PK肥(T1)、20%有机肥N-80%无机肥N+PK肥(T2)、30%有机肥N-70%无机肥N+PK肥(T3)、100%无机肥N+PK肥(T4)和不施肥(T5)。结果表明,有机无机肥配施有利于玉米增产,T2产量为11 206.33 kg·hm-2,T3为10 862.25 kg·hm-2,分别较T1高62.1%和57.2%,较T4高10.5%和7.1%。T2和T3均有利于提高土壤酶活性及微生物碳、氮含量,其中T2处理土壤酶活性及微生物碳、氮含量均最高。可知,20%有机肥与无机肥配施是适宜的施肥方式,可通过调控土壤微生物区系提高作物产量。     

Crystallization at Inorganic-organic Interfaces: Biominerals and Biomimetic Synthesis

Crystallization is an important process in a wide range of scientific disciplines including chemistry, physics, biology, geology, and materials science. Recent investigations of biomineralization indicate that specific molecular interactions at inorganic-organic interfaces can result in the controlled nucleation and growth of inorganic crystals. Synthetic systems have highlighted the importance of electrostatic binding or association, geometric matching (epitaxis), and stereochemical correspondence in these recognition processes. Similarly, organic molecules in solution can influence the morphology of inorganic crystals if there is molecular complementarity at the crystal-additive interface. A biomimetic approach based on these principles could lead to the development of new strategies in the controlled synthesis of inorganic nanophases, the crystal engineering of bulk solids, and the assembly of organized composite and ceramic materials.     

Hole density dependence of the critical temperature and coupling constant in the cuprate superconductors

A bond valence sum (BVS) analysis was performed for the p-type cuprate superconductors. The superconducting critical temperature T(c) versus in-plane Cu-O BVS correlation for copper is grouped into classes and subclasses. Only within a class or subclass for which the nonelectronic effect is constant does the variation of the in-plane Cu-O BVS reflect the corresponding change in the hole density n(H) of the CuO(2) layers. This study strongly suggests that the T(c) for every class or subclass of the superconductors is an inverted parabolic function of n(H), and so is the coupling constant lambda for Cooper pair formation.     

Bulk Superconductivity up to 122 K in the Tl-Pb-Sr-Ca-Cu-O System

New high-temperature superconductors based on oxides of thallium and copper, but not containing barium, have been prepared. A transition temperature (T(c)) of about 85 K is found for (Tl(0.5)Pb(0.5)) Sr(2)CaCu(2)O(7) whereas (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9) has a T(c) of about 120 K. Both materials possess tetragonal symmetry with a = 3.80 A, c = 12.05 A for (Tl(0.5)Pb(0.5))Sr(2)CaCu(2)O(7), and a = 3.81 A, c = 15.23 A for (Tl(0.5)Pb(0.5))Sr(2)Ca(2)Cu(3)O(9). A structure refinement of the latter phase has been carried out with single-crystal x-ray diffraction data.