Zero thermal expansion in YbGaGe due to an electronic valence transition

Most materials expand upon heating. Although rare, some materials expand on cooling, and are said to exhibit negative thermal expansion (NTE); but the property is exhibited in only one crystallographic direction. Such materials include silicon and germanium at very low temperature (<100 K) and, at room temperature, glasses in the titania-silica family, Kevlar, carbon fibres, anisotropic Invar Fe-Ni alloys, ZrW2O3 (ref. 4) and certain molecular networks. NTE materials can be combined with materials demonstrating a positive thermal expansion coefficient to fabricate composites exhibiting an overall zero thermal expansion (ZTE). ZTE materials are useful because they do not undergo thermal shock on rapid heating or cooling. The need for such composites could be avoided if ZTE materials were available in a pure form. Here we show that an electrically conductive intermetallic compound, YbGaGe, can exhibit nearly ZTE--that is, negligible volume change between 100 and 400 K. We suggest that this response is due to a temperature-induced valence transition in the Yb atoms. ZTE materials are desirable to prevent or reduce resulting strain or internal stresses in systems subject to large temperature fluctuations, such as in space applications and thermomechanical actuators.     

早期金属巴基球结构推断

通过计算推断六十年代中期，美国田纳西州树林国家实验室在同位素分离过程中形成的亮黑色物质可能京是迄今发现的最早的一种填隙式金属巴基球。     

Design of a novel optically stimulated luminescent dosimeter using alkaline earth sulfides doped with SrS:Eu,Sm materials

Optically stimulated luminescence （OSL） is the luminescence emitted from an irradiated insulator or semiconductor during exposure to light. The OSL intensity is a function of the dose of radiation absorbed by the sample and thus can be used as the basis of a radiation dosimetry method. Alkaline earth sulfides doped with rare-earth elements such as Ce, Sm and Eu are OSL dosimeters having very high sensitivity, and the OSL with a short time constant is separated from the stimulated light. In this paper, a novel OSL dosimeter designed with SrS：Eu,Sm materials is described. The dosimeter takes advantage of the characteristics of charge trapping materials SrS：Eu,Sm that exhibit OSL. The measuring range of the dosimeter is from 0.01 to 100Gy. The equipment, which is relatively simple and small in size, is promising for applications in space exploration and high dose radiation dosimetry.     

Closing the spin gap in the Kondo insulator Ce3Bi4Pt3 at high magnetic fields

Kondo insulator materials--such as CeRhAs, CeRhSb, YbB12, Ce3Bi4Pt3 and SmB6--are 3d, 4f and 5f intermetallic compounds that have attracted considerable interest in recent years. At high temperatures, they behave like metals. But as temperature is reduced, an energy gap opens in the conduction band at the Fermi energy and the materials become insulating. This contrasts with other f-electron compounds, which are metallic at all temperatures. The formation of the gap in Kondo insulators has been proposed to be a consequence of hybridization between the conduction band and the f-electron levels, giving a 'spin' gap. If this is indeed the case, metallic behaviour should be recovered when the gap is closed by changing external parameters, such as magnetic field or pressure. Some experimental evidence suggests that the gap can be closed in SmB6 (refs 5, 8) and YbB12 (ref. 9). Here we present specific-heat measurements of Ce3Bi4Pt3 in d.c. and pulsed magnetic fields up to 60 tesla. Numerical results and the analysis of our data using the Coqblin-Schrieffer model demonstrate unambiguously a field-induced insulator-to-metal transition.     

Quantum phase transition in a single-molecule quantum dot

Quantum criticality is the intriguing possibility offered by the laws of quantum mechanics when the wave function of a many-particle physical system is forced to evolve continuously between two distinct, competing ground states. This phenomenon, often related to a zero-temperature magnetic phase transition, is believed to govern many of the fascinating properties of strongly correlated systems such as heavy-fermion compounds or high-temperature superconductors. In contrast to bulk materials with very complex electronic structures, artificial nanoscale devices could offer a new and simpler means of understanding quantum phase transitions. Here we demonstrate this possibility in a single-molecule quantum dot, where a gate voltage induces a crossing of two different types of electron spin state (singlet and triplet) at zero magnetic field. The quantum dot is operated in the Kondo regime, where the electron spin on the quantum dot is partially screened by metallic electrodes. This strong electronic coupling between the quantum dot and the metallic contacts provides the strong electron correlations necessary to observe quantum critical behaviour. The quantum magnetic phase transition between two different Kondo regimes is achieved by tuning gate voltages and is fundamentally different from previously observed Kondo transitions in semiconductor and nanotube quantum dots. Our work may offer new directions in terms of control and tunability for molecular spintronics.     

Re-emerging superconductivity at 48 kelvin in iron chalcogenides

Pressure has an essential role in the production and control of superconductivity in iron-based superconductors. Substitution of a large cation by a smaller rare-earth ion to simulate the pressure effect has raised the superconducting transition temperature T(c) to a record high of 55?K in these materials. In the same way as T(c) exhibits a bell-shaped curve of dependence on chemical doping, pressure-tuned T(c) typically drops monotonically after passing the optimal pressure. Here we report that in the superconducting iron chalcogenides, a second superconducting phase suddenly re-emerges above 11.5?GPa, after the T(c) drops from the first maximum of 32?K at 1?GPa. The T(c) of the re-emerging superconducting phase is considerably higher than the first maximum, reaching 48.0-48.7?K for Tl(0.6)Rb(0.4)Fe(1.67)Se(2), K(0.8)Fe(1.7)Se(2) and K(0.8)Fe(1.78)Se(2).     

钐、铕-3-噻吩乙酸二元、三元配合物的合成及表征

以3-噻吩乙酸为第一配体合成钐、铕的二元配合物,以3-噻吩乙酸为第一配体,phen为第二配体合成钐、铕的三元配合物,通过元素分析和EDTA滴定分析确定其通式为REY32H2O、REY3phen（RE=Eu,Sm;Th=3-噻吩乙酸根,phen=邻菲啰啉）后,测定4种配合物的红外光谱、紫外光谱和荧光光谱及TG-DTG曲线。结果表明,由于第二配体的加入,对稀土离子的发光起到了敏化作用,增强了稀土离子的发光强度,并且三元配合物热稳定性比二元配合物的热稳定性好。     

Superconductivity at 39 K in magnesium diboride

In the light of the tremendous progress that has been made in raising the transition temperature of the copper oxide superconductors (for a review, see ref. 1), it is natural to wonder how high the transition temperature, Tc, can be pushed in other classes of materials. At present, the highest reported values of Tc for non-copper-oxide bulk superconductivity are 33 K in electron-doped Cs(x)Rb(y)C60 (ref. 2), and 30 K in Ba(1-x)K(x)BiO3 (ref. 3). (Hole-doped C60 was recently found to be superconducting with a Tc as high as 52 K, although the nature of the experiment meant that the supercurrents were confined to the surface of the C60 crystal, rather than probing the bulk.) Here we report the discovery of bulk superconductivity in magnesium diboride, MgB2. Magnetization and resistivity measurements establish a transition temperature of 39 K, which we believe to be the highest yet determined for a non-copper-oxide bulk superconductor.     

CaMnO_3和LaMnO_3的电子结构研究

密度泛函理论(DFT)方法通常难以处理强关联体系,而DFT+U方法的计算结果强烈地依赖于U的取值.利用一种混合了部分DFT交换关联势和非局域Hartree-Fock精确交换势的杂化泛函HSE方法,研究了钙钛矿锰氧化物的两个典型反铁磁绝缘体CaMnO3和LaMnO3的电子结构,分析了二者的能隙特征与Mn离子价态和磁有序态的关联.根据ZSA方案CaMnO3可划分为电荷转移型绝缘体.LaMnO3的能隙表现出各向异性特征,其中沿c轴方向及ab面内的自旋多数通道中能隙的Mott-Hubbard特征更为显著,而自旋少数通道显示出完全的电荷转移型特征.     

Fluctuating valence in a correlated solid and the anomalous properties of delta-plutonium

Although the nuclear properties of the late actinides (plutonium, americium and curium) are fully understood and widely applied to energy generation, their solid-state properties do not fit within standard models and are the subject of active research. Plutonium displays phases with enormous volume differences, and both its Pauli-like magnetic susceptibility and resistivity are an order of magnitude larger than those of simple metals. Curium is also highly resistive, but its susceptibility is Curie-like at high temperatures and orders antiferromagnetically at low temperatures. The anomalous properties of the late actinides stem from the competition between itinerancy and localization of their f-shell electrons, which makes these elements strongly correlated materials. A central problem in this field is to understand the mechanism by which these conflicting tendencies are resolved in such materials. Here we identify the electronic mechanisms responsible for the anomalous behaviour of late actinides, revisiting the concept of valence using a theoretical approach that treats magnetism, Kondo screening, atomic multiplet effects and crystal field splitting on the same footing. We find that the ground state in plutonium is a quantum superposition of two distinct atomic valences, whereas curium settles into a magnetically ordered single valence state at low temperatures. The f(7) configuration of curium is contrasted with the multiple valences of the plutonium ground state, which we characterize by a valence histogram. The balance between the Kondo screening and magnetism is controlled by the competition between spin-orbit coupling, the strength of atomic multiplets and the degree of itinerancy. Our approach highlights the electronic origin of the bonding anomalies in plutonium, and can be applied to predict generalized valences and the presence or absence of magnetism in other compounds starting from first principles.     

Superconductivity at 43 K in SmFeAsO1-xFx

Since the discovery of high-transition-temperature (high-T(c)) superconductivity in layered copper oxides, extensive effort has been devoted to exploring the origins of this phenomenon. A T(c) higher than 40 K (about the theoretical maximum predicted from Bardeen-Cooper-Schrieffer theory), however, has been obtained only in the copper oxide superconductors. The highest reported value for non-copper-oxide bulk superconductivity is T(c) = 39 K in MgB(2) (ref. 2). The layered rare-earth metal oxypnictides LnOFeAs (where Ln is La-Nd, Sm and Gd) are now attracting attention following the discovery of superconductivity at 26 K in the iron-based LaO(1-x)F(x)FeAs (ref. 3). Here we report the discovery of bulk superconductivity in the related compound SmFeAsO(1-x)F(x), which has a ZrCuSiAs-type structure. Resistivity and magnetization measurements reveal a transition temperature as high as 43 K. This provides a new material base for studying the origin of high-temperature superconductivity.     

Origin of ferromagnetic exchange interactions in a fullerene-organic compound

Organic ferromagnets, which exhibit exchange interactions between unpaired electrons in pi-orbitals, are rare, and the origin of ferromagnetism in these compounds has so far remained unexplained. Tetrakis(dimethylamino)ethylene-fullerene[60] (TDAE-C60) shows a transition to a ferromagnetic state with fully saturated s = 1/2 molecular spins at the relatively high Curie temperature (for organic materials) of 16 K (ref. 4). It has been suggested that the orientations of the C60 molecules may be important for ferromagnetism in this material, but in the absence of structural data at low temperatures there has been little progress towards understanding these microscopic interactions. Here we report the results of a comparative structural study of two different magnetic forms of TDAE-C60 crystals at low temperatures, correlating the structural properties--in particular, the intermolecular orientations--with the magnetic properties. We find that both ferromagnetism and spin-glass-like ordering are possible in this material, and depend on the orientational state of C60 molecules. This resolves the apparent contradictions posed by different macroscopic measurements, and opens the way to a microscopic understanding of pi-electron ferromagnetic exchange interactions in organic materials.     

Sm3+掺杂LnNbO4(Ln=La,Y)红色荧光粉的性能分析

通过高温固相法合成系列Sm3+掺杂LnNbO4(Ln=La,Y)红色荧光粉,并对样品的物相结构、荧光特性、衰减寿命和荧光热猝灭等性能进行实验分析。分析结果表明:合成的样品不含杂质相,可以被近紫外光LED和蓝光LED芯片有效激发,发出色坐标为(0615 5,0380 2)的红光对于LnNbO4(Ln=La,Y)基质来说,Sm3+掺杂LaNbO4基质的荧光强度比较强,最佳的Sm3+掺杂浓度为2%;随着Sm3+掺杂浓度的提高衰减寿命曲线由单指数线形变双指数线形,且衰减寿命不断变短;Sm3+之间的电偶极 电偶极作用是导致荧光浓度猝灭发生的原因;样品在293~450 K这一温度范围内具有良好的热稳定性。说明Sm3+掺杂的LaNbO4红色荧光粉具备成为白光LED用红色荧光粉的潜力。     

Observation of the two-channel Kondo effect

Some of the most intriguing problems in solid-state physics arise when the motion of one electron dramatically affects the motion of surrounding electrons. Traditionally, such highly correlated electron systems have been studied mainly in materials with complex transition metal chemistry. Over the past decade, researchers have learned to confine one or a few electrons within a nanometre-scale semiconductor 'artificial atom', and to understand and control this simple system in detail(3). Here we combine artificial atoms to create a highly correlated electron system within a nano-engineered semiconductor structure. We tune the system in situ through a quantum phase transition between two distinct states, each a version of the Kondo state, in which a bound electron interacts with surrounding mobile electrons. The boundary between these competing Kondo states is a quantum critical point-namely, the exotic and previously elusive two-channel Kondo state, in which electrons in two reservoirs are entangled through their interaction with a single localized spin.     

Superconductivity at 43 K in an iron-based layered compound LaO(1-x)F(x)FeAs

The iron- and nickel-based layered compounds LaOFeP (refs 1, 2) and LaONiP (ref. 3) have recently been reported to exhibit low-temperature superconducting phases with transition temperatures T(c) of 3 and 5 K, respectively. Furthermore, a large increase in the midpoint T(c) of up to approximately 26 K has been realized in the isocrystalline compound LaOFeAs on doping of fluoride ions at the O2- sites (LaO(1-x)F(x)FeAs). Experimental observations and theoretical studies suggest that these transitions are related to a magnetic instability, as is the case for most superconductors based on transition metals. In the copper-based high-temperature superconductors, as well as in LaOFeAs, an increase in T(c) is often observed as a result of carrier doping in the two-dimensional electronic structure through ion substitution in the surrounding insulating layers, suggesting that the application of external pressure should further increase T(c) by enhancing charge transfer between the insulating and conducting layers. The effects of pressure on these iron oxypnictide superconductors may be more prominent than those in the copper-based systems, because the As ion has a greater electronic polarizability, owing to the covalency of the Fe-As chemical bond, and, thus, is more compressible than the divalent O2- ion. Here we report that increasing the pressure causes a steep increase in the onset T(c) of F-doped LaOFeAs, to a maximum of approximately 43 K at approximately 4 GPa. With the exception of the copper-based high-T(c) superconductors, this is the highest T(c) reported to date. The present result, together with the great freedom available in selecting the constituents of isocrystalline materials with the general formula LnOTMPn (Ln, Y or rare-earth metal; TM, transition metal; Pn, group-V, 'pnicogen', element), indicates that the layered iron oxypnictides are promising as a new material platform for further exploration of high-temperature superconductivity.     

Superconductivity in single crystals of the fullerene C70.

The observation of superconductivity in doped C60 has attracted much attention, as these materials represent an entirely new class of superconductors. A maximum transition temperature (Tc) of 40 K has been reported for electron-doped C60 crystals, while a Tc of 52 K has been seen in hole-doped crystals; only the copper oxide superconductors have higher transition temperatures. The results for C60 raise the intriguing questions of whether conventional electron-phonon coupling alone can produce such high transition temperatures, and whether even higher transition temperatures might be observed in other fullerenes. There have, however, been no confirmed reports of superconductivity in other fullerenes, though it has recently been observed in carbon nanotubes. Here we report the observation of superconductivity in single crystals of electric-field-doped C70. The maximum transition temperature of about 7 K is achieved when the sample is doped to approximately four electrons per C70 molecule, which corresponds to a half-filled conduction band. We anticipate superconductivity in smaller fullerenes at temperatures even higher than in C60 if the right charge density can be induced.     

Emerging local Kondo screening and spatial coherence in the heavy-fermion metal YbRh2Si2

The entanglement of quantum states is both a central concept in fundamental physics and a potential tool for realizing advanced materials and applications. The quantum superpositions underlying entanglement are at the heart of the intricate interplay of localized spin states and itinerant electronic states that gives rise to the Kondo effect in certain dilute magnetic alloys. In systems where the density of localized spin states is sufficiently high, they can no longer be treated as non-interacting; if they form a dense periodic array, a Kondo lattice may be established. Such a Kondo lattice gives rise to the emergence of charge carriers with enhanced effective masses, but the precise nature of the coherent Kondo state responsible for the generation of these heavy fermions remains highly debated. Here we use atomic-resolution tunnelling spectroscopy to investigate the low-energy excitations of a generic Kondo lattice system, YbRh(2)Si(2). We find that the hybridization of the conduction electrons with the localized 4f electrons results in a decrease in the tunnelling conductance at the Fermi energy. In addition, we observe unambiguously the crystal-field excitations of the Yb(3+) ions. A strongly temperature-dependent peak in the tunnelling conductance is attributed to the Fano resonance resulting from tunnelling into the coherent heavy-fermion states that emerge at low temperature. Taken together, these features reveal how quantum coherence develops in heavy 4f-electron Kondo lattices. Our results demonstrate the efficiency of real-space electronic structure imaging for the investigation of strong electronic correlations, specifically with respect to coherence phenomena, phase coexistence and quantum criticality.     

Superconductivity at 52 K in hole-doped C60

Superconductivity in electron-doped C60 was first observed almost ten years ago. The metallic state and superconductivity result from the transfer of electrons from alkaline or alkaline-earth ions to the C60 molecule, which is known to be a strong electron acceptor. For this reason, it is very difficult to remove electrons from C60--yet one might expect to see superconductivity at higher temperatures in hole-doped than in electron-doped C60, because of the higher density of electronic states in the valence band than in the conduction band. We have used the technique of gate-induced doping in a field-effect transistor configuration to introduce significant densities of holes into C60. We observe superconductivity over an extended range of hole density, with a smoothly varying transition temperature Tc that peaks at 52 K. By comparison with the well established dependence of Tc on the lattice parameter in electron-doped C60, we anticipate that Tc values significantly in excess of 100 K should be achievable in a suitably expanded, hole-doped C60 lattice.     

锰表面和氧气及二氧化碳反应的电子能谱研究

用XPS和UUP法,通过Mn2p_2~3、O_(1s)和C_(1s)及X射线诱导的MnLMM Auger谱图的变化,研究了Mn的清洁表面与O_2及CO_2的反应.在室温下把Mn暴露于O_2中,530.1eV的Ols峰逐渐增强,同时Mn~0 2p逐渐峰代替了Mn~0 2p峰,X射线诱导的Auger峰明显减弱且L_3M_(23)M_(23)和L_3M_1M_(23)峰最终消失.由O_(1s)峰计算所得的表面氧浓度与~lj Mn2p及MnLMM的改变相对应,由此表征了Mn的氧化态.CO_2在清洁Mn表面分解为O~(2-)、C、CO_3~(2-)和CO 上述Mn与O_2及CO_2的反应也由UPS得以证实.     

高温固相法制备Sm2O3掺杂La2Ce2O7热障涂层材料

以La2 O3、CeO2和Sm2 O3为原料,采用高温固相反应法制备了Sm2 O3部分掺杂La2 Ce2 O7热障涂层陶瓷材料,其化学式为(SmxLa1-x)2Ce2O7.采用X射线衍射法研究了试样的物相结构,并通过对比各实验条件下制备的试样的X射线衍射图谱,对试样的掺杂比例、烧制温度及烧制时间进行了探究.结果表明,所制备试样为萤石结构,当掺杂摩尔比Sm：La为1：2或1：3时试样均能保持良好的相结构,以掺杂摩尔比Sm：La=1：2制备的( Sm0.33 La0.67)2 Ce2 O7材料在1600℃下具有良好的相稳定性,且其最佳制备条件为1550℃下烧制10 h,该材料是一种很有潜力的新型热障涂层陶瓷材料.