液体-液体相变与反常特性

绝大多数物质的液态密度随温度降低而增大,即常见的热胀冷缩现象.但存在一类物质,如水及第四主族的硅、锗等,其液态密度在一定温度范围内随温度的升高而增大,即密度反常现象.此外,该类物质还存在动力学反常(密度越大粒子运动越快)、热力学反常(热力学量的涨落随温度降低而升高)等其他反常特性.这类材料的化学性质千差万别,但却具有相似的物理反常特性.进一步的理论研究发现部分材料具有两种液态,即高密度液态和低密度液态,两者之间存在一级相变.因此,反常特性与液体-液体相变是否有直接关联是一个值得深入研究的课题.本文主要介绍了具有液体-液体相变的一类材料及其反常特性,包括高温高压下氢的液体-液体相变及其超临界现象,镓的反常特性及其与液体-液体相变的关联等.     

Structure of phase change materials for data storage

Phase change materials based on chalcogenide alloys play an important role in optical and electrical memory devices. Both applications rely on the reversible phase transition of these alloys between amorphous and metastable cubic states. However, their atomic arrangements are not yet clear, which results in the unknown phase change mechanism of the utilization. Here using ab initio calculations we have determined the atomic arrangements. The results show that the metastable structure consists of special repeated units possessing rocksalt symmetry, whereas the so-called vacancy positions are highly ordered and layered and just result from the cubic symmetry. Finally, the fast and reversible phase change comes from the intrinsic similarity in the structures of the amorphous and metastable states.     

Melting from one to two to three dimensions

The transformation of a crystalline solid into a liquid, seeming to have no precursor and no intermediate states, has challenged scientists for over a century. The search for the fundamental mechanism stimulated the development of quantum mechanics, concepts of the roles of dimensionality and topological order in condensed matter, and experimental techniques to test the theories. We now understand that the transition begins at lower temperatures than the melting point of the bulk. It starts at the edges of crystal planes, progresses across the surface, evolves into the successive melting of atomic layers, and ends in bulk phase coexistence. The memory of the process remains within a few molecular distances at the crystal-melt interface.     

Unraveling the solid-liquid-vapor phase transition dynamics at the atomic level with ultrafast x-ray absorption near-edge spectroscopy

X-ray absorption near-edge spectroscopy (XANES) is a powerful probe of electronic and atomic structures in various media, ranging from molecules to condensed matter. We show how ultrafast time resolution opens new possibilities to investigate highly nonequilibrium states of matter including phase transitions. Based on a tabletop laser-plasma ultrafast x-ray source, we have performed a time-resolved (～3 ps) XANES experiment that reveals the evolution of an aluminum foil at the atomic level, when undergoing ultrafast laser heating and ablation. X-ray absorption spectra highlight an ultrafast transition from the crystalline solid to the disordered liquid followed by a progressive transition of the delocalized valence electronic structure (metal) down to localized atomic orbitals (nonmetal-vapor), as the average distance between atoms increases.     

Tunable charge density wave in TiS_3 nanoribbons

Recently, modifications of charge density wave(CDW) in two-dimensional(2D) show intriguing properties in quasi-2D materials such as layered transition metal dichalcogenides(TMDCs). Optical, electrical transport measurements and scanning tunneling microscopy uncover the enormous difference on the many-body states when the thickness is reduced down to monolayer. However, the CDW in quasi-one-dimensional(1D) materials like transition metal trichalcogenides(TMTCs) is yet to be explored in low dimension whose mechanism is likely distinct from their quasi-2D counterparts.Here, we report a systematic study on the CDW properties of titanium trisulfide(TiS_3). Two phase transition temperatures were observed to decrease from 53 K(103 K) to 46 K(85 K) for the bulk and 15-nm thick nanoribbon, respectively,which arises from the increased fluctuation effect across the chain in the nanoribbon structure, thereby destroying the CDW coherence. It also suggests a strong anisotropy of CDW states in quasi-1D TMTCs which is different from that in TMDCs.Remarkably, by using back gate of-30 V ～ 70 V in 15-nm device, we can tune the second transition temperature from110 K(at-30 V) to 93 K(at 70 V) owing to the altered electron concentration. Finally, the optical approach through the impinging of laser beams on the sample surface is exploited to manipulate the CDW transition, where the melting of the CDW states shows a strong dependence on the excitation energy. Our results demonstrate TiS_3 as a promising quasi-1D CDW material and open up a new window for the study of collective phases in TMTCs.     

Variable energy gap of SiCN nanopowders

SiCN and SiC nanopowders were prepared by infrared laser pyrolysis of gaseous precursors starting from a SiH₄C₂H₂NH₃ gas mixture. The SiCN powders were composed of an amorphous phase ascribed to the ternary compound with a β-SiC crystalline phase, while the SiC powders consisted of β phase only. The chemical bonding and the local atomic order in the SiCN powders are much more complicated than those of pure SiCSi₃N₄ mixtures and are strongly dependent on the variation in the initial gas composition. The average grain size was estimated from X-raydiffraction (XRD) patterns and atomic force microscopy (AFM). The UV-VIS transmittance data were used for the bandgap determination in these new materials. Absorption studies suggested that the direct energy gap is more favourable in SiCN and SiC nanoparticles and is blueshifted with regard to the crystalline bulk (SiC). The change of type of band-to-band transition in SiC nanopowders, due to the size effects, and increasing of the energy gap value in SiCN powders with different local atomic arrangement, makes them attractive for blue-UV optoelectronic applications. PACS 61.46.+w; 78.70.Ck; 68.3.Ps; 78.40.-q     

利用胶体系统研究玻璃态

玻璃态是一种无序结构的固体,组成单元可以是原子、分子、高分子、胶体粒子等等。尽管玻璃态材料在生活中很常见,有广泛的工业应用,但相关理论,尤其是液体到玻璃态转变的理论是物理学中争议最多的领域之一。溶液中的胶体粒子可以形成晶体、液体、玻璃等各种态。在光学显微镜下可以直接看到三维内部单个微米胶体粒子,通过图像处理还可以得到粒子的布朗运动轨迹,从而得到玻璃化转变过程中的微观动力学信息,这是原子分子玻璃系统中难以测量的。文章介绍了胶体作为模型系统对玻璃态的研究,主要包括传统的过冷液体到玻璃态的转变,另外还涉及气相、凝胶、多晶等其他无序或半无序态与玻璃态之间的过渡或转变。     

Crystalline amorphous semiconductor superlattice

A new class of superlattice, crystalline amorphous superlattice (CASL), by alternatively depositing two semiconductor materials, is proposed. CASL displays three states depending on the component materials' phase: both polycrystalline phases, both amorphous phases, and one polycrystalline phase while another amorphous phase. Using materials capable of reversible phase transition, CASL can demonstrate reversibility among three states. GeTe/Sb(2)Te(3) CASL has been synthesized and proved by x-ray reflectometry and TEM results. The reversible transition among three states induced by electrical and laser pulse was observed. The changes in the optical absorption edge, electrical resistivity, thermal conductivity, and crystallization temperature as a function of layer thickness are interpreted as quantum or nanoeffects. The unique properties of CASL enable the design of materials with specific properties.     

Unique melting behavior in phase-change materials for rewritable data storage

Ge2Sb2Te5 (GST) is a technologically very important phase-change material for rewritable optical and electrical storage because it can be switched rapidly back and forth between amorphous and crystalline states for millions of cycles by appropriate pulsed heating. However, an understanding of this complicated phenomenon has not yet been achieved. Here, by ab initio molecular dynamics, we unravel the reversible phase transition process of GST. The melting of rocksalt-structured GST is unique in that it forms two-dimensional linear or tangled clusters while keeping order in the perpendicular direction. It is this specific character that results in the fast and reversible phase transition between amorphous and crystalline and hence rewritable data storage.     

Recent results on some columnar paramagnetic metallomesogens

The liquid crystalline and selected physical properties of some vanadyl and manganese(III)-porphyrin-TCNE complexes are discussed. These materials form linear chains from a magnetic point of view and columnar discotic LC phases. Some of the manganese complexes exhibit a bulk magnetic phase below ∼20 K. The discussed materials are studied by means of DSC, X-ray powder diffraction, dielectric spectroscopy, reversal current characterization and magnetic susceptibility measurements. A broader view on some physical properties of columnar paramagnetic metallomesogens is given.     

PdAu25Fe21和PdAu24Fe21Al4合金反常电磁特性的研究

PdAu₂₅Fe₂₁和PdAu₂₄Fe₂₁Al₄合金(以下简称PdAuFe,PdAuFeAl)分别在临界温度500℃和550℃产生无序—有序转变。有序相是典型的Cu₃Au型结构。有序化时合金由铁磁体转变为反铁磁体,电导率和磁化率大大减小,热电势改变符号。研究结果表明,合金反常的电磁特性起因于原子的有序排列和d带电子能态的变化。 关键词：     

The influence of short-range order on electronic properties of transition metals: I. Crystalline systems

Densities of states and electronic parameters related to superconductivity have been calculated for the transition metals Nb and Tc, representing the bulk materials by a finite cluster of atoms. The Schrödinger equation is solved for atomic potentials which have been obtained in a self-consistent band structure calculation. The results show that, in these systems, the electronic structure is determind predominantly by short-range order.     

过渡金属化合物OsB2与OsO2低压缩性的第一性原理计算研究

利用基于密度泛函理论平面波赝势法的第一性原理计算,研究了过渡金属化合物OsB2和OsO2的金红石相、黄铁矿相与萤石相三种结构在高压下的状态方程和结构特性以及OsO2可能的高压相变.理论计算结果支持OsB2与OsO2的萤石相是潜在超低可压缩性的硬性材料.同时,也分析了它们的电子结构,力求理解大体变模量和高硬度的微观机制.结果表明,可以利用过渡金属高的价电子浓度,掺入硼、氧、碳、氮等轻的元素形成强的方向键,这可能提供了一种合成超硬材料的新途径.     

The influence of short-range order on electronic properties of transition metals: I. Crystalline systems

Densities of states and electronic parameters related to superconductivity have been calculated for the transition metals Nb and Tc, representing the bulk materials by a finite cluster of atoms. The Schrödinger equation is solved for atomic potentials which have been obtained in a self-consistent band structure calculation. The results show that, in these systems, the electronic structure is determind predominantly by short-range order.     

Superconductivity of topological matters induced via pressure

By applying pressure on the topological insulator Bi₂Te₃ single crystal, superconducting phase was found without a crystal structure phase transition. The new superconducting phase is under the pressure range of 3 GPa to 6 GPa. The high pressure Hall effect measurements indicated that the superconductivity caused by bulk hole pockets. The high pressure structure investigations with synchrotron X-ray diffraction indicated that the superconducting phase is of similar structure to that of ambient phase structure with only slight change with lattice parameter and internal atomic position. The topological band structures indicate the superconducting phase under high pressure remained topologically nontrivial. The results suggested that topological superconductivity can be realized in Bi₂Te₃ due to the proximity effect between superconducting bulk states and Diractype surface states. We also discussed the possibility that the bulk state could be a topological superconductor.     

Electronic properties of SnTe-class topological crystalline insulator materials

The rise of topological insulators in recent years has broken new ground both in the conceptual cognition of condensed matter physics and the promising revolution of the electronic devices.It also stimulates the explorations of more topological states of matter.Topological crystalline insulator is a new topological phase,which combines the electronic topology and crystal symmetry together.In this article,we review the recent progress in the studies of SnTe-class topological crystalline insulator materials.Starting from the topological identifications in the aspects of the bulk topology,surface states calculations,and experimental observations,we present the electronic properties of topological crystalline insulators under various perturbations,including native defect,chemical doping,strain,and thickness-dependent confinement effects,and then discuss their unique quantum transport properties,such as valley-selective filtering and helicity-resolved functionalities for Dirac fermions.The rich properties and high tunability make SnTe-class materials promising candidates for novel quantum devices.     

Supersolid versus phase separation in atomic bose-fermi mixtures

We show that a two-dimensional atomic mixture of bosons and fermions cooled into their quantum degenerate states and subject to an optical lattice develops a supersolid phase characterized by the simultaneous presence of a nontrivial crystalline order and phase order. This transition is in competition with phase separation. We determine the phase diagram of the system and propose an experiment allowing for the observation of the supersolid phase.     

Pressure-induced phase transition of crystalline and amorphous silicon and germanium at low temperatures

Abstract

X-ray diffraction has been measured for crystalline silicon, crystalline germanium, amorphous silicon and amorphous germanium at temperatures down to 100 K and pressures up to 20 GPa using a diamond anvil cell and synchrotron radiation. The structural phase transitions, including amorphization, take place in the pressure-temperature range. It has been found that the structures after the phase transitions strongly depend on the path in the pressure-temperature diagram through which the system undergoes the phase transitions. For any of the aforementioned four materials, the high-pressure phase with the p-Sn structure is quenched during a release of pressure at 100 K, and transforms into an amorphous state when heated up to around 2 GPa. The path dependence of the states is discussed in relation to the pressure dependence of the heights of the energy barriers which have to be overcome when phase transitions occur. The effect of a structural disorder on the phase transition is also discussed by comparing the experimental results for the crystalline and amorphous materials.     

Atomic motion in Se nanoparticles embedded into a porous glass matrix

By neutron diffraction it was shown that nanostructured Se confined within a porous glass matrix exists in a crystalline as well as in an amorphous state. The spontaneous crystallization of crystalline Se from confined amorphous phase was observed. The root-mean-square amplitudes of the atomic motions in the bulk as well as in confinement are found to be essentially different in a basal plane and in the perpendicular direction along the hexagonal axis. The atomic motions in the confined Se differ from the atomic motions in the bulk at low temperatures. The results shows an unusual “freezing" of the atomic motion along the chains, while the atomic motions in the perpendicular plane still keep. This “freezing" is accompanied by the deformation of nanoparticles and the appearance of inner stresses. This effect is attributed to the interaction of confined nanoparticle with the cavity walls.     

Two-dimensional quasicrystals of decagonal order in one-component monolayer films

By using Monte Carlo simulations we demonstrate that atomic monolayers formed on a crystalline surface may exhibit quasicrystalline decagonal order. It is shown that the stability of two-dimensional quasicrystals (QCs) is determined by the misfit between the adsorbate and the surface lattice and by the corrugation of the surface potential. QCs may be stable at the ground state or develop from the compressed commensurate c(2 x 2) structure, via the first-order phase transition at finite temperatures. The decagonally ordered phase melts into a partially ordered liquidlike phase, which then disorders via a continuous Ising-like transition.