An anomaly in the magnetic susceptibility of the Mg1−x CuxO solid solutions with 0.01≤x≤0.20

The problem of localized superconductivity has motivated the preparation of Mg_1−x Cu_xO solid solutions with NaCl structure and 0.01≤x≤0.20, as well as a study of the magnetization and magnetic susceptibility χ in the 2–400 K temperature range and in magnetic fields of up to 5 T. The temperature dependence of χ is described for all compositions by the Curie-Weiss law, χ = C/(T − θ), where the constant C is close to the value calculated for each composition for μ_eff = 1.7–1.9μ_B, and θ is close to zero. For T < 30 K, χ(T) deviates for all compositions toward lower χ, which can be attributed to magnetic ordering of exchange-coupled clusters in the solid solution. At T∼320–330 K, an anomaly of a diamagnetic type, i.e., a decrease of χ by 6–30% of its paramagnetic value, has been observed for all compositions against the background of the generally paramagnetic χ(T). A discussion is presented of alternative reasons for this anomaly and of its possible connection with localized superconductivity. __________ Translated from Fizika Tverdogo Tela, Vol. 42, No. 4, 2000, pp. 701–703. Original Russian Text Copyright ? 2000 by Samokhvalov, Arbuzova, Viglin, Naumov, Smolyak, Korolev, Lobachevskaya.     

Phase stratification in the Nd1 − x BaxCoO3 − δ (0.3 ≤ x ≤ 0.54) system

Slowly cooled Nd_{1 ? x} Ba_xCoO_{3 ? δ} samples were two-phase in the concentration interval 0.3 ≤ x ≤ 0.46. One of the phases had O-orthorhombic lattice distortions (Pbnm) characteristic of ferromagnetic samples with x ≤ 0.3, and the other phase had tetragonal distortions (P4/mmm) characteristic of samples with x ≥ 0.46. Tetragonal distortions were caused by ordering of Nd³⁺ and Ba²⁺ ions. Samples with ordered neodymium and barium ions (Nd_{1 ? y} Ba_{1 + y} Co₂O_{6 ? γ} at ?0.08 ≤ y ≤ 0.08) experienced metal-dielectric and orientation magnetic phase transitions.     

The influence of praseodymium concentration on the luminescence properties of Ca1 ? x Pr x F2 + x (0.002 ≤ x ≤0.35)

The possibility of implementing photon cascade emission in CaF₂-PrF₃ crystals by increasing the PrF₃ concentration in the CaF₂ matrix is studied. It is shown that an increase in the Pr³⁺ content leads to redistribution of radiative transitions in favor of the ¹ S ₀-luminescence. The decrease in the efficiency of the second step of photon cascade emission at high PrF₃ concentrations is caused by quenching of the ³ P ₀ ?? 4f ² transitions as a result of cross relaxation.     

Superconductivity,crystallization, and structural relaxation of the new metallic glass system La1−x Si x (0.15≤x≤0.27)

New metallic glass alloys have been prepared by melt spinning of La–Si samples in a pumped system. The superconducting transition temperature,T _c , increases linearly with the La concentration, from 3.00 K at 73 at. % La to 3.80 K at 85 at. %. Three new metastable phases: -, -, and -La₃Si, were formed by annealing and crystallizing amorphous La₃Si. Their crystal structures are orthorhombic (a=6.32 Å,b=8.06 Å,c=9.96 Å), hcp (a=10.55 Å,c=5.05 Å), and tetragonal (a=6.92 Å,c=5.05 Å) resp.T _c increased to 3.75 K, 6.00 K and 6.80 K, resp. During low temperature anneals of an amorphous La₃Si alloy,T _c changed logarithmically with time.On leave from Institute of Physics, Academica Sinica, Beijing, China     

Transport properties of the single-crystal La2−xBaxCuO4 (0≤x≤0.11)

We report on the temperature dependence of the in-plane electrical resistivity ρ_ab and the in-plane Hall coefficient R_H in various magnetic fields of the single-crystal La_2−xBa_xCuO₄ with x=0.083 and 0.11. In x=0.11, which is close to x=1/8, where the superconductivity is strongly suppressed, a clear jump in ρ_ab and a drop in R_H have been observed at T_d2∼53 K, where the structural phase transition between the orthorhombic mid-temperature and tetragonal low-temperature phases occurs. Moreover, a sign reversal of R_H has been observed below ∼25 K and the magnitude of the sign reversal increases with increasing magnetic field. In x=0.083, on the other hand, there is neither jump in ρ_ab nor drop in R_H at T_d2, and also no sign reversal in R_H at low temperatures even in magnetic fields up to 9 T. In conclusion, there is no doubt that a static stripe order of holes and spins, observed in La_1.6−xNd_0.4Sr_xCuO₄ with x∼1/8, is formed below T_d2 also in La_2−xBa_xCuO₄ with x∼1/8. The R_H in the stripe-ordered state has a negative value, which is consistent with the recent theory by Prelovšek et al.     

Synthesis and native defectivity of Zn1−x V x O (0 ≤ x ≤ 0.03) photocatalysts

Nanodisperse solid solutions Zn_1?x V _x O (0 ≤ x ≤ 0.03) with high numbers of defects in an oxygen sublattice are synthesized via the precursor technique. ESR analysis reveals that V _O ⁺ oxygen vacancies are the main defects of the oxygen sublattice in the Zn_1?x V _x O structure. The Zn_1?x V _x O (0 < x ≤ 0.15) solid solutions exhibit high photocatalytic activity during hydroquinone oxidation in water upon irradiation with UV and visible light.     

Lithium/vacancy ordering in the monoclinic LixNiO2 (0.50≤x≤0.75) solid solution

Lithium de-intercalation from the nearly stoichiometric LiNiO₂ phase (z=0.02 in Li_1−zNi_1+zO₂) entails a structural transition from the rhombohedral to the monoclinic symmetry. As this macroscopic lattice distortion appears in a wide composition range (0.50<x<0.75, x in `Li_xNiO₂'), a detailed electron diffraction study has been performed on the intermediate Li_0.63Ni_1.02O₂ composition in order to find the driving force of this transition. A superstructure cell, four times bigger than the one deduced from the X-ray Rietveld refinement, has been derived from the electron diffraction data. The existence of such a superstructure is suggestive of a possible ordering of vacancies among the lithium layers. Indeed, the existence of three lithium crystallographic positions in this supercell allows us to understand, on the one hand, why a monoclinic distortion occurs, and, on the other hand, its composition limits (Li_0.50□_0.25□_0.25′NiO₂ and Li_0.50Li_0.25□_0.25′NiO₂). Moreover, the presence of twinned crystals has also been shown in this monoclinic phase and has been related to the structural change which occurs on lithium de-intercalation from the pristine rhombohedral Li_0.98Ni_1.02O₂ phase.     

K-doping effect of the superconductivity in K2xFeTe1-xSx (0.07≤x≤0.3)

Bulk samples of K doping K_2xFeTe_1-xS_x with x = 0.07, 0.1, 0.2, 0.3 are successfully prepared by using easy-to-use stable compound K₂S as the reactant. The lattice constant calculated from X-ray diffraction patterns indicate that K ions enter the Fe-Te-S layers. K doping is beneficial enhance the superconductivity transition temperature from the R-T curves. The apparent diamagnetic signal is observed in M-T curves when the content of K is smaller than 0.1. However, differential curves (dM/dT) in K-rich samples appear sharp slope mutations, which means that the Meissner effect signal is covered by the increased excess ferromagnetic ions. The number of excess Fe magnetic ions is proportional to K content, which may play an important role in determining the superconductivity.     

Effect of Nd on the Superconductivity of Nd1+x Ba2-x Cu3O y with 0.1 ≤ x ≤ 0.35

The effect of Nd substitution at the Ba sites has been studied in Nd_1+x Ba_2-x Cu₃O _y system for 0.1 x 0.35. Orthorhombic to tetragonal structural phase transition occurs at about x = 0.17. With the increase of Nd, the T _c value decreases and T increases, where T is the difference between the onset and critical temperatures and indicates the sharpness of the transition. These changes are explained by ac-susceptibility measurements on Nd_1.1Ba_1.9Cu₃O_7.12 at 0.10 Oe. The susceptibility curves show the presence of about four phases, which are not detectable by X-ray diffraction technique.     

Effect of Nd doping on the magnetic properties of charge-ordered Bi0.6−x Nd x Ca0.4MnO3 (0.0≤x≤0.6) perovskite manganites

We have studied structure, magnetic and transport properties of polycrystalline Bi_0.6?x Nd _x Ca_0.4MnO₃ (x=0.0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6). Substitution of Nd at Bi sites induces a strong interplay between the magnetic and charge ordering. The charge-ordering temperature (T _CO) decreases with increasing x. Further, the antiferromagnetic ordering temperature (T _N) increases sharply at both extremes and remains nearly constant for x=0.2–0.4. At T<T _N a transition to a metamagnetic glass-like state is also seen. Nd doping also leads to enhancement in the magnetic moment and a concomitant decrease in resistivity up to x=0.3 and then an increase in resistivity up to x=0.5. Furthermore, Nd doping promotes an antiferromagnetic to ferromagnetic type fluctuation in the materials at room temperature, as evidenced by the change in the value of the paramagnetic Curie temperature. We find that the local lattice distortion induced by the size mismatch between the A-site cations and the 6s² character of Bi³⁺ lone pair electrons explains the observed peculiarity in magnetic and transport properties of Nd-doped Bi_0.6Ca_0.4MnO₃.     

Structural deformations in metastable cubic compounds Ni(1 − x)Zn x O (0.60 ≤ x ≤ 0.99)

X-ray diffraction has been used for studying the fine crystal structure of metastable cubic oxide compounds Ni_{(1 ? x)}Zn _x O (0.60 ≤ x ≤ 0.99) obtained from the initial hexagonal phase by quenching of the samples at a high temperature and under external hydrostatic pressure. It has been found that the diffraction patterns of these compounds include a system of diffuse superstructure maxima, whose number and intensity essentially depend on the composition. The origin of this superstructure has been discussed.     

Separation of magnetic phases in La1 − x CaxMnO3 manganites with 0.6 ≤ x ≤ 0.9

The magnetic properties of La_{1 ? x} Ca_xMnO₃ solid solutions were studied in wide temperature and magnetic field ranges, T = 2–600 K and H ≤ 50 kOe. Semiconducting compositions with 0.6 < × < 0.9 exhibited an unusual temperature behavior of magnetization and susceptibility with well-defined Curie and Néel temperatures. The simultaneous manifestation of both ferromagnetic and antiferromagnetic properties is evidence of the coexistence of two collinear magnetic phases. The content of impurity ions was shown to have a strong influence on the T _C and T _N values, whereas the ratio between the ferro-and antiferromagnetic phase volumes heavily depended on thermal treatment conditions. The magnetic properties of the whole series of La_{1 ? x} Ca_xMnO₃ solid solutions can be explained in terms of the phase separation model.     

Features of magnetic properties of La x MnO3 + δ (0.815 ≤ x ≤ 1.0)

Magnetic and resonance studies of the system of polycrystalline samples of self-doped manganites La _x MnO_{3 + δ} (x = 0.815, 0.90, 0.94, 0.97, and 1.0) have been performed in a temperature range of 77–300 K. According to ⁵⁵Mn NMR data, all samples contain a ferromagnetic phase at 77 K. As the defect density increases (x changes from 1.0 to 0.815), samples become more magnetically ordered. In this case, the ferromagnetic state of the system gradually changes from a mixed state in which both ferromagnetic insulating (basic) and ferromagnetic metal (for x = 0.97 and 1.0) phases coexist to only the ferromagnetic metal state (for x = 0.815 and 0.90). It has been shown that both ferromagnetic metal and ferromagnetic insulating phases are inhomogeneous, and either phase consists of two phases with different dynamics of nuclear spins and different Curie temperatures. The diagram of the magnetic phase state of the La _x MnO_{3 + δ} system (x = 0.815, 0.90, 0.94, 0.97, 1.0) has been constructed for a temperature range of 120–240 K and Mn⁴⁺ contents of 12–30%.     

Magnetotransmission of unpolarized infrared radiation in Hg1 − x Cd x Cr2Se4 (0 ≤ x ≤ 1) single crystals studied using the voigt geometry

The features characterizing the behavior of magnetotransmission in Hg_{1 ? x} Cd _x Cr₂Se₄ single crystals are studied using natural light in the infrared spectral range. The relation between the changes in the magneto-optical properties and in the electron band structure is found. It is shown that the most significant changes in the magnetotransmission spectrum and the band structure occur within the 0.1 < x < 0.25 range.     

Specific heat of Ce x La1 − x B6 in the low cerium concentration limit (x ≤ 0.03)

The specific heat of high-quality Ce _x La_{1 ? x} B₆ (x = 0, 0.01, 0.03) single crystals is studied in the temperature range 0.4–300 K. LaB₆ samples with various boron isotope compositions (¹⁰B, ¹¹B, ^nat B) are analyzed to estimate the effect of boron vacancies. The experimental data are used to take into account the electron component correctly under the renormalization of the density of states at T < 8 K, the contribution of the quasi-local vibrational mode of a rare-earth ion with the Einstein temperature Θ_E ≈ 152 K, the Debye contribution from the rigid cage of boron atoms with the Debye temperature Θ_D ≈ 1160 K, and the low-temperature Schottky contribution related to the presence of 1.5?2.3% boron vacancies in the rare-earth hexaborides. The detected low-temperature anomalies in the specific heat are shown to be interpreted in terms of the formation of two-level systems with an energy ΔE = 92–98 K caused by the displacement of rare-earth ions from their centrosymmetric positions. A scenario of heavy fermion formation that is alternative to the Kondo mechanism is proposed for the systems with a magnetic impurity.     

Evidence for nano-scale inhomogeneities in bilayer manganites in the Mn4+ rich region: 0.54≤x≤0.80

The atomic pair distribution function (PDF) technique is employed to probe the atomic local structural responses in naturally double layered manganites La_2−2xSr_1+2xMn₂O₇ in the doping range 0.54≤x≤0.80. Our low temperature neutron powder diffraction measurements suggest the coexistence of two different Jahn-Teller (JT) distorted MnO₆ octahedra when its ordered magnetic structure crosses over from type A (0.54≤x≤0.66) to type C/C* (0.74≤x≤0.90) ordering. At all doping levels at low temperature the doped holes reside predominantly in the plane of the bilayer. In the type A magnetic ordering regime, the e_g electrons appear to be significantly delocalized in the plane resulting in undistorted octahedra, while in type C/C* regime, elongated JT distorted octahedra are apparent. This is consistent with the presence of inhomogeneous coexisting delocalized and localized electronic states. No evidence of macroscopic phase separation has been observed. Such nanoscale inhomogeneities may explain the magnetically frustrated behavior observed in the spin disordered ‘gap’ region (0.66≤x≤0.74).     

Cation disorder and structural studies on Bi4−x Nd x Ti3O12 (0.0≤x≤2.0)

Here we report the results of combined powder X-ray and neutron diffraction studies of Bi_4?x Nd _x Ti₃O₁₂ (0.0 ≤ x ≤ 2.0) compositions. The parent Bi₄Ti₃O₁₂ has an orthorhombic lattice (space group: B2cb) with unit cell parameters a = 5.4432(5) Å, b = 5.4099(5) Å and c = 32.821(2) Å, and V = 966.5(1) ų. This orthorhombic lattice is retained in all the studied compositions. The unit cell parameters gradually decrease with Nd³⁺ ion concentration with a discontinuity at x = 0.75. Orthorhombicity of the lattice decreases with increase in Nd³⁺ content in the lattice. The orthorhombic unit cell parameters for a representative Bi₂Nd₂Ti₃O₁₂ composition are: a = 5.3834(9), b = 5.3846(9) and c = 32.784(1) Å. The observed orthorhombic distortion at x = 2.0 is very small and thus the crystal structure apparently has a pseudo-tetragonal lattice. In addition, Nd³⁺ preferentially substitutes in the perovskite slab of the Aurivillius structure. The fraction of Nd³⁺ in the fluorite slab increases with increase in Nd³⁺ contents.     

Pre-exponential factor for non-isothermal crystallization of glassy Se85− x Te15Sb x (0 ≤ x ≤ 10) alloys

We report observations of the Meyer–Neldel rule for the non-isothermal crystallization of glassy Se_{85? x} Te₁₅Sb _x (x =?0, 2, 4, 6, 8, 10) alloys. We found a strong co-relation between the pre-exponential factor K ₀ of the rate constant K(T) for crystallization and the activation energy of crystallization E _c. This indicates the presence of a compensation effect for the non-isothermal crystallization process in this glassy system. The composition dependence of the crystallization temperature T _c and the activation energy for crystallization E _c is discussed.     

Fine structure and magnetism of bulk Zn1 − x Cr x Se single-crystal cubic compounds (0 ≤ x ≤ 0.045)

The character of structural and magnetic features of the cubic lattice of bulk Zn_{1 ? x} Cr _x Se crystals (0 ≤ x ≤ 0.045) has been investigated using thermal neutron diffraction and magnetic measurements. It has been found that the diffraction scans of doped crystals contain effects of nuclear diffuse scattering caused by local static atomic displacements in the face-centered cubic (fcc) lattice. Results of magnetic measurements of doped crystals indicate the presence of weak antiferromagnetic correlations, which are a consequence of structural features of these compounds.