Prediction of the phase transition from ferromagnetic perovskite to non-magnetic post-perovskite in SrRuO3 : A first-principles study

The phase transition in the perovskite (Pv) SrRuO₃ under pressure has been studied by using first-principles calculations based on density functional theory. The post-perovskite (Ppv) phase transition of SrRuO₃ will take place under hydrostatic pressure of about 40 GPa. The stability of Ppv- SrRuO₃ is justified by the enthalpy calculations, and this phase transition accompanies volume disconnection and magnetic moment collapses. The crystallographic data and the electronic structure of Ppv- SrRuO₃ are also predicted. The crystal structure of Ppv- SrRuO₃ is similar to that of Ppv- CaRuO₃. A non-magnetic ground state is found in Ppv- SrRuO₃. The strong hybridization of Ru and O is evident in the electronic structures of both phases. We expect that these results will help further understanding of SrRuO₃ under high pressure.     

Synchrotron X-ray diffraction study of SrRuO<Subscript>3</Subscript>/SrTiO<Subscript>3</Subscript>/SrRuO<Subscript>3</Subscript> nano-sized heterostructures grown by laser MBE

Structural investigation using X-ray synchrotron radiation has been performed on SrRuO₃/SrTiO₃/SrRuO₃ epitaxial heterostructures, with each constituent layer a few unit cell thick grown on (001) SrTiO₃ substrate. Detailed information on the evolution of the in-plane lattice structure has been obtained, in these heterostructures, by grazing incidence diffraction measurements. The samples have been grown by low-pressure pulsed laser deposition. Under our deposition conditions, SrRuO₃ layers grow with an elongated cell perpendicular to the substrate surface. The in-plane pseudocubic lattice parameters do not match the in-plane square SrTiO₃ structure even in the case of very thin SrRuO₃ layers. Such a distortion was found to decrease with increasing the thickness of the SrTiO₃ barrier layer.     

SrRuO3的电子结构与磁性研究

用自洽的全势能线性丸盒轨道能带方法计算了氧化物体系SrRuO₃(SRO)的电子结构和磁性.对于理想的立方钙钛矿结构的计算得出的电子结构明显改善了已有的计算结果:每个元胞的磁矩为129μ_B,按原子球划分为084μ_B/Ru原子和011μ_B/O原子;Sr原子上的自旋磁矩几乎为零;费米能级处的态密度N(E_F)为435(states/Ryd/f.u.).关于实际的正交结构SRO,计算得出磁矩为108μ关键词： 过渡金属氧化物 电子结构 磁性     

Strain effect on transport properties of <Emphasis Type="Bold">SrRuO</Emphasis><Subscript><Emphasis Type="Bold">3</Emphasis></Subscript> films grown by laser MBE

Transport properties of SrRuO₃ thin films were studied as a function of the epitaxial strain. SrRuO₃ films were grown on (100) SrTiO₃ substrates by the Pulsed Laser Deposition technique equipped with Reflection High Energy Electrons Diffraction (RHEED). Samples thickness has been varied from a few unit cells to above 1000 ? while monitoring RHEED intensity oscillations. In thicker films epitaxial strain was found to be progressively relaxed. SrRuO₃ relaxed films (thickness 1000 ?) show metallic behavior for the whole temperature range with a ferromagnetic ordering at about 150 K. For thinner films, ferromagnetic ordering occurs at progressively lower temperatures, until in films thinner than 400 ? it disappears. Films thinner than 80 ? show a semiconducting behavior at low temperatures. Our results provide direct evidence of the crucial role of the strain effect for conducting and magnetic properties of SrRuO₃. Received 16 July 2001 and Received in final form 22 October 2001     

Effects of Ca2+ ion substitution on the structure and magnetism of SrRuO3: Elusive magnetism

SrRuO₃ is an orthogonally distorted perovskite (Pbnm) structure whose ferromagnetism is often viewed as an itinerant ferromagnet. Although SrRuO₃ has been studied for more than half a century, its structure, magnetism and transport properties are still poorly understood. In this paper, the structure and magnetic evolution of SrRuO₃ are discussed in depth through the substitution of Ca²⁺ for Sr²⁺ at A sites. The results show that as the Ca substitution increases, the lattice constant decreases, the orthogonal distortion becomes larger, and the saturation magnetization M_S, Curie temperature T_C and Weiss temperature θ_p decrease accordingly. Eventually, the ferromagnetic SrRuO₃ changes to paramagnetic CaRuO₃. The critical exponent β of samples with different substitution contents was obtained by fitting the experimental results, and the value for SrRuO₃ (β = 0.55) was similar to that obtained by mean field theory. However, the value increases with the substitution x of Ca, which can't be explained by any scaling theory. The results show that the increase in the value of β is related to the magnetic disorder caused by different magnetic interactions. Analysis using the Rhodes-Wohlfarth criterion indicates that Sr_1-xCa_xRuO₃ has both itinerant-electron and localized-electron magnetism, which is consistent with the theoretical predictions.     

Density functional study of structural and electronic properties of Al<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>P (2 ≤ <Emphasis Type="Italic">n</Emphasis> ≤ 12) clusters

Low-lying equilibrium geometric structures of Phosphorus-doped aluminum cluster Al _n P (n = 2–12) clusters obtained by an all-electron linear combination of atomic orbital approach, within spin-polarized density functional theory, are reported. The binding energy, dissociation energy, and stability of these clusters are studied within the local spin density approximation (LSDA) and the three-parameter hybrid generalized gradient approximation (GGA) due to Becke-Lee-Yang-Parr (B3LYP). Ionization potentials, electron affinities, hardness, and static polarizabilities are calculated for the ground-state structures within the GGA. It is observed that symmetric structures with the P atom occupying a peripheral position are lowest-energy geometries of Al _n P (n = 2, 4–11), while the P impurities of Al₃P and Al₁₂P prefer to occupy internal sites in the aluminum clusters. Generalized gradient approximation extends bond lengths as compared to the LSDA lengths. The odd-even oscillations in the dissociation energy, the second differences in energy, the HOMO–LUMO gaps, the ionization potential, the electron affinity, and the hardness are more pronounced within both GGA and LSDA. The stability analysis based on the energies clearly shows the clusters with an even number of valence electrons are more stable than clusters with odd number of valence electrons.     

First-principle study of the electronic structure and magnetism in RuSr<Subscript>2</Subscript>GdCu<Subscript>2</Subscript>O<Subscript>8</Subscript> under pressure

We have performed a first-principle calculation of the structural, electronic and high pressure properties of RuSr₂GdCu₂O₈, a ferromagnetic superconductor, by employing a full-potential linearized augmented plane-wave method within the density-functional theory. The effect of pressure was achieved by varying the volume of the unit cell with constant a:b:c ratio. The experimentally observed anti-phase rotation of RuO₆ octahedra has been attributed to the residual forces on O_Ru which results in shear strain in the RuO₂ layer. Partial charge analysis shows that applying pressure up to 6 GPa leads to hole creation in the CuO₂ sheets which causes increase in the superconducting transition temperature. We have estimated the Curie temperature T _M of this compound in the mean-field approximation using Heisenberg model with first-nearest neighbor exchange interactions determined from DFT calculations for parallel and anti-parallel spin configurations of Ru moment in RuO₂ planes. The effect of pressure causes the magnetic moment of Ru atoms to decrease due to the increase of hybridization between the adjacent Ru atoms. The calculated exchange splitting in Cu d _{x 2 - y 2} states increases slightly with pressure but it is still very small that it does not affect superconductivity, and the hole doping mechanism is dominant.     

Electronic structure of the TbMn<Subscript>0.33</Subscript>Ge<Subscript>2</Subscript> compound: Band calculation and optical experiment

The results of the investigation of the electronic structure and optical properties of the TbMn_0.33Ge₂ compound have been presented. The spin-polarized calculations of the band spectrum have been performed within the framework of the local spin density approximation (LSDA) with a correction for strong correlations in the 4f shell of the rare-earth ion (the LSDA + U method). The optical constants have been measured using the ellipsometric method and a number of spectral and electronic characteristics of the compound under investigation have been determined over a wide range of wavelengths. The interband part of the experimental dependence of the optical conductivity has been interpreted using the results of the calculation of the electron density of states.     

Electronic and magnetic structure of a possible iron based superconductor BaFe<Subscript>2</Subscript>Se<Subscript>3</Subscript>

We present results of LDA calculations (band structure, densities of states, Fermi surfaces) for possible iron based superconductor BaFe₂Se₃ (Ba123) in normal (paramagnetic) phase. Results are briefly compared with similar data on prototype BaFe₂As₂ and (K,Cs)Fe₂Se₂ superconductors. Without doping this system is anti-ferromagnetic with T _N^exp ∼ 250 K and rather complicated magnetic structure. Neutron diffraction experiments indicated the possibility of two possible spin structures (antiferromagnetically ordered “plaquettes” or “zigzags”), indistinguishable by neutron scattering. Using LSDA calculated exchange parameters we estimate Neel temperatures for both spin structures within the molecular field approximation and show τ₁ (plaquettes) spin configuration to be more favorable than τ₂ (zigzags).     

Effects of BaTiO<Subscript>3</Subscript> and SrTiO<Subscript>3</Subscript> as the buffer layers of epitaxial BiFeO<Subscript>3</Subscript> thin films

BiFeO₃ (BFO) thin films with BaTiO₃ (BTO) or SrTiO₃ (STO) as buffer layer were epitaxially grown on SrRuO₃-covered SrTiO₃ substrates. X-ray diffraction measurements show that the BTO buffer causes tensile strain in the BFO films, whereas the STO buffer causes compressive strain. Different ferroelectric domain structures caused by these two strain statuses are revealed by piezoelectric force microscopy. Electrical and magnetical measurements show that the tensile-strained BFO/BTO samples have reduced leakage current and large ferroelectric polarization and magnetization, compared with compressively strained BFO/STO. These results demonstrate that the electrical and magnetical properties of BFO thin films can be artificially modified by using a buffer layer.     

Role of electrodes materials in determining the interfacial and magnetoelectric properties in BaTiO<Subscript>3</Subscript>-based multiferroic tunnel junctions

Using the first-principles calculations based on density functional theory, the important role of electrode materials in determining the interfacial, ferroelectric stability and magnetoelectric properties in BaTiO₃-based multiferroic tunnel junctions (MFTJs) have been investigated comparatively. It is found that the SrO–TiO₂ interface of MFTJs with oxide electrode SrRuO₃ is the most favorable interfacial structure. The average ferroelectric polarizations of MFTJs with electrode Co, FeCo and SrRuO₃ are 25, 36 and 0 μC/cm², respectively. The using of alloy electrode FeCo is more contributed to ferroelectric stability and the enhancement of magnetoelectric coupling of BaTiO₃-based MFTJs. We expect our findings can provide an essential evaluation for the selection of electrode materials in spintronic storage devices.     

Suppression of ferroelectricity and quantum fluctuations in Ru-doped TbMnO<Subscript>3</Subscript>

We investigate the effects of Ru-doping in polycrystalline TbMn_1−x Ru _x O₃ (x≤0.10) on the multiferroicity. It is observed that the Ru substitution gradually melts away the dielectric anomaly at the ferroelectric transition point and the ferroelectricity by suppressing the polarization, accompanied with a surprising low-temperature dielectric plateau. While it is reasonable to observe the significant suppression of ferroelectricity, owing to the fact that the Ru-doping disrupts the Mn spiral spin ordering and reduces the Mn–Mn spin angle, quantum fluctuations associated with the Ru substitution, responsible for the low-temperature dielectric plateau, seems to be significant.     

Mott Transition in GdMnO<Subscript>3</Subscript>: an Ab Initio Study

Orthorhombic GdMnO₃ is studied using density functional theory considering the pseudo-potential plane-wave method within local-spin-density approximation, LSDA. The electronic band structure and density of states, for several hydrostatic pressures, are studied. The Mott transition was observed at 60 GPa. Calculated lattice parameters are close to the experimental measurements, and some indirect band gaps (S→Γ) were obtained within the LSDA level of calculation, between the occupied O-2p and unoccupied Gd-4f states. The variation of the gap reduces with increasing pressure, being well fitted to a quadratic function.     

Surface morphology of PrBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> single crystals after the long-lasting high-temperature reduction

The results of the detailed scanning electron microscopy study of PrBa₂Cu₃O_7-δ single crystals after the long-lasting high-temperature post-growth treatment are reported. The presence of the unstable decomposition products on the crystal surface indicates that the onset of superconductivity must be related to the structural transformations in the bulk (approximately 20% of the total volume of the examined crystals). The time-dependent character of the superconductivity in the Pr-123 crystals could be attributed to the migration of defects in the Pr−Ba sublattice from the bulk toward the surface.     

Effect of B-site dopants on magnetic and transport properties of LaSrCoRuO<Subscript>6</Subscript>

Effect of Co, Ru and Cu substitution at B and B’ sites on the magnetic and transport properties of LaSrCoRuO₆ have been investigated. All the doped compositions crystallize in the monoclinic structure in the space group P2₁/n indicating a double perovskite structure. While the magnetization and conductivity increase in Co and Ru doped compounds, antiferromagnetism is seen to strengthen in the Cu doped samples. These results are explained on the basis of a competition between linear Co-O-Ru-O-Co and perpendicular Co-O-O-Co antiferromagnetic interactions and due to formation of Ru-O-Ru ferromagnetic networks.     

Electronic and magnetic properties of Fe<Subscript>2</Subscript>SiC

The electronic structure and magnetic properties of Fe₂SiC compound have been studiedusing the framework of an all-electron full-potential linearized augmented-plane wave(FP-LAPW) method within the local density (LSDA) and + U corrected(LSDA + U)approximations. An antiferromagnetic spin ordering of Fe atoms is shown to be the groundstate for this compound. From the electronic band structures and density of states (DOS),Fe₂SiC has ametallic character and from the analysis of the site and momentum projected densities, itis deduced that the bonding is achieved through hybridization of Fe-3d with C-2p states andFe-3d withSi-3pstates. It is also pointed out that the Fe-C bonding is more covalent than Fe-Si. In theFM phase, the spin polarized calculations indicate that the total magnetic moment ofFe₂SiC increasesfrom 0.41 to 4.33μ _B when the Hubbard U parameter for iron isconsidered.     

A Fiber-Optic Evanescent Wave O<Subscript>2</Subscript> Sensor Based on Ru(II)-Doped Fluorinated ORMOSILs

A novel fiber-optic evanescent wave sensor (FOEWS) for O₂ detection based on [Ru(bpy)₃]²⁺-doped hybrid fluorinated ORMOSILs (organically modified silicates) has been developed. The sensing element was fabricated by dip-coating the optical fiber with [Ru(bpy)₃]²⁺-doped hybrid fluorinated ORMOSILs composed of n-propyltrimethoxysilane (n-propyl-TriMOS) and 3, 3, 3-trifluoropropyltrimethoxysilane (TFP–TriMOS). Fluorophores of [Ru(bpy)₃]²⁺ were excited by the evanescent wave field produced on the fiber core surface and the emission fluorescence was quenched by O₂. Spectroscopic properties have been characterized by FTIR and UV–VIS absorption measurements. By using the presented hybrid fluorinated ORMOSILs, which enhances the coating surface hydrophobicity, the quenching response is increased. The sensitivity of the sensor is 7.5, which is quantified in terms of the ratio I _N2/I _O2 (I _N2 and I _O2 represent the fluorescence intensities in pure N₂ and pure O₂ environments, respectively). The limit of detection (L.O.D.) is 0.01% (3σ) and the response time is about 1 s. Meanwhile, the proposed FOEWS has the advantages of easy fabrication, low cost, fast response and suitable sensitivity for oxygen monitoring using a cheap blue LED as light source and coupling a miniature PMT detector directly to the optical fiber probe.     

Formation,thermal stability and mechanical properties of Ti<Subscript>42.5</Subscript>Zr<Subscript>7.5</Subscript>Cu<Subscript>40</Subscript>Ni<Subscript>5</Subscript>Sn<Subscript>5</Subscript> bulk metallic glass

Ti_42.5Zr_7.5Cu₄₀Ni₅Sn₅ bulk metallic glass with a critical diameter of 4 mm was fabricated by the conventional copper mould casting method. The supercooled liquid region ΔT _x, reduced glass transition temperature T _rg, γ parameter, and δ parameter of the alloy were measured to be 63.9 K, 0.561, 0.393, and 1.400, respectively, implying that the alloy has an excellent glass-forming ability. The bulk metallic glass exhibits high compressive fracture strength of 2162 MPa with distinct plastic strain of 0.9%. The fracture surface consists mainly of vein-like patterns, typical of bulk glassy alloys. Supported by the Program for New Century Excellent Talents in University of China and the National Natural Science Foundation of China (NSFC)(Grant No. 50771040)     

Photoluminescence of nanoparticles of (Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>)<Subscript>0.95</Subscript>(Eu<Subscript>2</Subscript>O<Subscript>3</Subscript>)<Subscript>0.05</Subscript> solid solution

We have ground bulk samples to obtain nanoparticles of (Ga₂S₃)_1–x (Eu₂O₃) _x solid solutions, the sizes of which were determined using an atomic force microscope. The photoluminescence spectra of the nanoparticles were studied in the temperature interval 77–300 K. We have established the mechanisms for emission and transfer of energy from the matrix to the rare-earth ion, and we determined the Stokes shift (ΔS = 0.7 eV), the Huang–Rhys parameter (S = 16), and the optical phonon energy (ħ−ω = 23 meV).