Ionic and electronic transport in perovskite-type La(Ga,M)O3−δ (M=Mg, Cr, Fe, Co, Ni, Nb)

Oxygen ion conduction in La_0.9Sr_0.1Ga_1−xM_xO_3−δ (M=Cr, Fe; x=0 – 0.20), LaGa_1−xM_xO_3−δ (M=Co, Ni; x=0.20 – 0.60), LaGa_1−x−yCo_xMg_yO_3−δ (x=0.35 – 0.60; y=0.10 – 0.25) and LaGa_0.85−xMg_0.15(Nb_0.33Mg_0.66)_xO_3−δ (x=0 – 0.20) is reported. At temperatures below 1200 K the ionic conductivity of La(Ga,M)O_3−δ (M=Co, Ni) increases with increasing oxygen nonstoichiometry, but is lower than for La(Ga,Mg)O_3−δ and (La,Sr)GaO_3−δ. Co-doping with Nb and Mg was found to result in decreasing ionic transport in La(Ga,Nb,Mg)O_3−δ due to blocking of oxygen sites by Nb⁵⁺. Small additions of Fe to the B-site of La_0.9Sr_0.1GaO_3−δ increase the ionic conductivity, whereas substitution of Cr for Ga has the opposite effect. Incorporation of transition metal cations into the Ga site leads to a higher p-type electronic conductivity in all studied perovskites. Paper presented at the 6th Euroconference on Solid Sate Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

Electron paramagnetic resonance,electrical resistivity,and magnetization studies in the high Tc superconductors EuBa2Cu3O9−xandEuBa2 (Cu1−yMy)3O9−x (M = Cr,Mn, Fe,Co, Ni,ORZn)

We have measured electron paramagnetic resonance (EPR), electrical resistivity, and dc magnetic susceptibility from 2 K – 300 K for the high T_c oxide superconductor EuBa₂Cu₃O_9−x, either undoped or doped with 3d ions (Cr, Mn, Fe, Ni, Co, or Zn), which presumably substitute at the Cu sites. We have observed an EPR line at low temperatures (T ≤ 40 K), which exhibits an increase in intensity and decrease in field for resonance as the temperature is lowered. The EPR linewidth is also temperature dependent and exhibits a minimum at about 15 K. In some of the samples another EPR signal is observed over the entire temperature range studied, with properties that depend on sample preparation conditions. This signal is likely to be due to small amounts of an additional phase. The behavior and origin of these EPR signals are discussed. The variation of T_c with 3d ion concentration over the range (1 – 8%) is also presented.     

Mössbauer study of hydrided amorhous Fe−M−Zr (M=Co,Cr) alloys

Mössbauer spectra of hydrided amorphous Fe₉₀?_xCo_xZr₁₀ (A_x) and Fe₉₀?_yCr_yZr₁₀ (B_y) (x=4, 10, 20; y=0, 4, 7, 13, 16, 20) are studied. For low hydriding time values (t), the average hyperfine field \(\left( {\bar B_{hf} } \right)\) and isomer shift δ_is show a drastic increase which can mainly be associated with the volume effect. For higher (t) values, an electron transfer effect can be responsible for the hyperfine parameter variation. The influence of hydrogenation on magnetic anisotropy is also discussed.     

Single crystal growth and superconductivity of Ca(Fe1−x Co x )2As2

We report the single crystal growth of Ca(Fe_1?x Co _x )₂As₂ (0?≤?x?≤?0.082) from Sn flux. The temperature–composition phase diagram is mapped out based on the magnetic susceptibility and electrical transport measurements. The phase diagram of Ca(Fe_1?x Co _x )₂As₂ is qualitatively different from those of Sr and Ba; this could be due to both the charge doping and structural tuning effects associated with Co substitution.     

Structural and Thermodynamic Properties of M3W3N （M=Fe,Co, Ni）

Ternary transition metal nitrides, Fe3 W3N, Coa W3N, and Nia WaN~ are studied by the use of interatomic potentials acquired from lattice inversion. The study indicates that Fe3 WaN would be more stable than the other compounds in the family of intermetallic tungsten nitrides. The investigation of phonon density of states indi- cates that the lower frequency modes are mostly excited by the metal atoms, and the higher frequency modes are mostly excited by the nitrogen atoms. A qualitative analysis is carried out with the relevant potentials for the phase stability and vibrational modes.     

Local atomic arrangement in mechanosynthesized Co x Fe1−x−y Ni y alloys studied by Mössbauer spectroscopy

Mechanosynthesized Co _x Fe_1?x?y Ni _y alloys were examined using X-ray diffraction (XRD) and Mössbauer spectroscopy. In order to explain the shape of hyperfine magnetic field (HMF) distributions for the alloys, a local environment model based on a multinomial distribution was proposed. The model was in agreement with the XRD data and confirmed that the studied alloys were disordered solid solutions. It was successfully applied to describe the samples with bcc and fcc crystalline lattice type within the relatively broad range of components concentration. The results showed that the change of the crystalline lattice type does not cause an abrupt change of the HMF value. Moreover, a mean number of unpaired spins for the first coordination sphere may be used as a parameter to describe the HMF value experienced by ⁵⁷Fe nucleus. Finally, a set of the most probable atomic configurations and their corresponding contributions to the HMF distribution were obtained.     

Superconductivity, Seebeck coefficient, and band structure transformation in Y1−x CaxBa2Cu3−x CoxOy (x=0–0.3)

The temperature dependences of the resistivity and of the Seebeck coefficient S is studied in three series of Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples (x=0–0.3) differing in oxygen content. It was found that the critical temperature decreases for y≈7.0, and S(T=300 K) increases with doping, whereas oxygen deficiency results in a nonmonotonic variation of these quantities with increasing x. The band structure parameters have been determined from an analysis of the S(T) relations using a phenomenological theory of electron transport. It was found that an increase in x results in a gradual increase in band asymmetry, which is caused by calcium-induced creation of additional states in the band responsible for conduction in the normal phase. An analysis has shown that high impurity concentrations in oxygen-deficient Y_1−x Ca_xBa₂Cu_3−x Co_xO_y samples bring about an additional ordering of the structure, which may be caused by formation of a cobalt superlattice. It has also been shown that, in the case of Ca and Co codoping, the dependence of critical temperature on effective conduction-band width coincides with the universal correlation relation observed in the YBa₂Cu₃O_y system with single substitutions in various lattice sites. Fiz. Tverd. Tela (St. Petersburg) 41, 1363–1371 (August 1999)     

Mn(SiO2)3(M=Fe,Co,Ni;n=1-3)团簇的几何结构、光电性质及磁性

基于密度泛函理论中的广义梯度近似系统研究M_n(SiO₂)₃(M=Fe,Co,Ni;n=1-3)团簇的几何结构、光电性质和磁学性质.结果表明:Fe,Co原子相对于Ni原子更易于在(SiO₂)₃团簇上聚集;通过分析团簇的分裂途径及其产物,发现稳定性较好的氧化硅是一种很好的用于负载过渡金属"岛膜"的载体材料;M_n(SiO₂)₃团簇的能隙恰好位于近红外光谱范围内.通过磁性分析发现,该复合团簇的磁矩主要局域在过渡金属原子周围,而且,Fe₂(SiO₂)₃和Co₃(SiO₂)₃具有相对较大的磁矩,这主要源于过渡金属原子的d轨道间相互耦合.能隙和磁性两方面性质进一步肯定了二氧化硅磁性复合材料在医学界被用作光动力靶向治疗的可观前景.     

Magnetically two-phase state in Eu1−x AxMnO3 (A=Ca, Sr)

It is observed that low-temperature magnetic properties (dependence of the magnetization on the cooling conditions and the presence of a maximum in the initial magnetic susceptibility) of Eu_{1− x} A_xMnO₃ (A=Ca, Sr; x=0,0.3) samples are similar to those of spin glasses. However, there are also substantial differences: The magnetization depends on the cooling conditions right up to the maximum measurement fields H=45 kOe, and the temperature of T _N of the maximum of the initial magnetic susceptibility is independent of the frequency of the ac magnetic field in which the susceptibility is measured. The magnetization isotherms for T<T _N are a superposition of a linear part, characteristic for an antiferromagnet, and a small spontaneous part. For compositions containing Sr a maximum of the resistivity ρ (ρ_max∼10⁸ Ω ·cm) is observed near T _N; in a 120 kOe magnetic field this maximum is lowered by four orders of magnitude and the temperature of the maximum is two times higher. In compositions with x=0.3 the paramagnetic Curie point is much higher than for the composition with x=0: θ=110 K (A=Ca), 175 K (A=Sr), and −100 K (x=0). These characteristic features of the magnetic and electric properties are explained by the existence of a magnetically two-phase state in this system, consisting of ferromagnetic clusters, in which the charge carriers are concentrated, embedded in an insulating antiferromagnetic matrix. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 5, 375–380 (10 March 1999)     

Zr-M(M=Fe,Co,Ni,Cu)型金属玻璃的电子-电子相互作用和超导涨落效应

本文系统地研究了顺磁性金属玻璃 Zr_xCo_(100-x)(x=78,72,66.8)和 Zr_(66.7)M_(33.3)(M=Fe,Ni,Cu)的低温电导率与温度的关系σ(T)发现,在很宽的温区内,σ(T)与弱局域化理论相符.随着温度的降低,σ(T)∝T~(1/2),此规律来源于电子-电子相互作用效应,在超导临界温度Tc 附近,σ(T)∝ε~(-1/2);这是 Aslamusou-Larkin 项(AL 项)对超导涨落效应的贡献.     

Magnetic properties of the intermetallic compounds Y15Fe77−xTxB8 (T = Mn,Co, Ni,x = 7, 17)

Magnetic properties of the compounds Y₁₅Fe_77−xT_xB₈, where T stands for Mn, Co or Ni and x equals 7 or 17 were investigated within the temperature range 80 to 650 K. X-ray diffraction yielded a tetragonal structure of Nd₂Fe₁₄B type for all samples. The compounds appeared ferromagnetic: substitution of Mn or Ni for Fe leads to decrease of the Curie temperature and magnetization, while an increase of both quantities was observed for T = Co.     

Magnetism and Superconductivity inCeCu2(Si1−xGex)2 Probed by Cu NQR

We report Cu-NQR results on Ge-doped heavy-fermion superconductor CeCu₂(Si_1–x Ge _x )₂ (0<x0.2) and undoped Ce_0.99Cu_2.02Si₂. The main effect of the Ge doping is considered to be a negative pressure, since the strength of hybridization decreases by the Ge doping. With increasing x, the dynamical characteristics of the magnetic order at x=0 change to more static ones which suggests a localized regime above x0.25. From the derived T–x phase diagram, it is suggested that the magnetic and the superconducting phases are almost degenerate in undoped CeCu₂Si₂. An exotic interplay between the magnetism characterized by the slow fluctuations and the superconductivity is implied in the region of small x.     

Effect of doping with iron on the charge ordering in La0.33Ca0.67Mn1−y Fe y O3 (y = 0, 0.05) manganites

The formation and specific features of the superstructure in La_0.33Ca_0.67Mn_1?y Fe _y O₃ (y = 0, 0.05) manganites doped with iron are investigated using transmission electron microscopy. The electron diffraction patterns of the manganites are studied in the temperature range 90–300 K, and the high-resolution electron microscope images recorded at temperatures of 91–92 K are analyzed. In both manganites, the structural transition that is accompanied by the formation of the superstructure and which is directly observed from the appearance of additional peaks in the electron diffraction patterns occurs at a temperature that is in close agreement with the charge ordering temperature T _CO determined from the temperature dependences of the magnetization M(T). In the temperature range 90 < T < 200 K, the undoped compound has a commensurate superstructure characterized by the vector q = 1/3a* and triple the unit cell «3a × b × c» (where a ≈ b ≈ √2a _c , c ≈ 2a _c , and a _c ～ 3.9 Å is the lattice parameter of a simple perovskite). The doping with iron (5 at. %) brings about a decrease in the charge ordering temperature T _CO by 50 K and the formation of an incommensurate structure for which the magnitude of the vector q is smaller by approximately 15%. The unit cell of the superstructure in the iron-doped compound is not triple the unit cell but involves defects of ordering, such as quadrupling of the unit cell, numerous translations by a _c √2 along the a direction, and dislocation-type defects in the stripe structure of the charge ordering. These pseudoperiodic defects lead to a decrease in the magnitude of the vector q and are responsible for the incommensurability of the structure. A decrease in the charge ordering temperature T _CO due to the doping with iron and the incommensurability of the superstructure correlate with the change in the concentration of Mn³⁺ Jahn-Teller ions as a result of their replacement by Fe³⁺ non-Jahn-Teller ions.     

Low-temperature magnetic ordering in the perovskites Pr1−xAxCoO3 (A=Ca,Sr)

The magnetic and electrical properties of polycrystalline Pr_1?xA_xCoO₃ cobaltites with A=Ca, Sr and 0≤x≤0.5 were studied in the temperature range 4 K≤T≤1000 K and field up to 7 T. The X-ray analyses show the presence of only one phase having monoclinic or orthorhombic symmetry. The magnetic measurements indicate that the Ca-doped samples have at low temperatures, similar properties to the frustrated magnetic materials. PrCoO₃ is a paramagnetic insulator in the range from 4 to 1000 K. The Sr-doped cobaltites exhibit two phase transitions: a paramagnetic–ferromagnetic (or magnetic phase separated state) phase transition at about 240 K and a second one at about 100 K. The magnetic measurements suggest the presence of magnetic clusters and a change in the nature of magnetic coupling between Co ions at low temperatures. A semiconducting type behavior and high negative magnetoresistance was found for the Ca-doped samples, while the Sr-doped ones were metallic and with negligible magnetoresistance. The results are analyzed in the frame of a phase separation scenario in the presence of the spin-state transitions of Co ions.     

Optical properties of layered III–VI semiconductor γ-InSe:M (M=Mn,Fe, Co,Ni)

Indium selenide belongs to layered III–VI semiconductors with highly anisotropic optical and electronic properties. Energy gap of 1.32 eV makes this material very attractive for solar energy conversion. We investigated the influence of 1% 3-d transition metals M=Mn, Fe, Co, Ni, used as dopants, on energy levels of InSe:M in the range 1.4–6.5 eV and especially in the range of energy gap <1.4 eV by means of ellipsometric measurements. It was concluded that at ambient temperature foregoing dopants, all divalent, with 4s² valent electrons, in the similar way influenced on blue-shift of energy levels in valent zone, but did not influence on the fundamental energy gap. Photoluminescence measurements confirmed blue-shift of the valent zone energy levels and an existence of deep impurity levels.