Physics of the pseudogap phase of high Tc cuprates, or, RVB meets umklapp

It is argued that the dominant feature of the phase diagram of the high T_c cuprates is the crossover to the pseudogap phase in the energy (temperature) region E(T^∗). We argue that this scale is determined by the effective anti-ferromagnetic interaction which we calculate to be J_eff=J_{superexchange}−xt where x is the hole percentage and t the hopping integral.     

Constraints on the mechanism of superconductivity for MgB2 from Tc and the total isotope effect

We examine the possible electron-phonon spectra that produce both T_c=39 K and an isotope coefficient β=0.32±0.01, with Eliashberg theory. We assess the viability of the conventional electron-phonon mechanism in light of these results, compared with ab initio calculations of the electron-phonon spectrum. Comparisons are made with similar considerations for low T_c materials.     

Suppression of Tc by Zn impurity in the electron-type LaFe0.925−y Co0.075ZnyAsO system

The effect of non-magnetic Zn impurity on superconductivity in electron-type pnictide superconductor LaFe_0.925−yCo_0.075Zn_yAsO is studied systematically. The optimally doped LaFe_0.925Co_0.075AsO without Zn impurity exhibits superconductivity at T_c^mid of 13.2 K, where T_c^mid is defiend as the mid-point in the resistive transition. In the presence of Zn impurity, the superconducting transition temperature, T_c^mid, is severely suppressed. The result is consistent with the theoretic prediction on the effect of non-magnetic impurity in the scenario of s_± pairing, but it is in sharp contrast to the previous report on the effect of Zn impurity in the F-doped systems. The possible interpretation of the different effects of Zn impurity on superconductivity in different systems is discussed.     

The impact of Y substitution on the 110 K high Tc phase in a Bi (Pb):2223 superconductor

The structural and superconducting properties of Bi_1.7Pb_0.3Sr₂Ca_2−xY_xCu₃O_y superconducting samples are investigated by X-ray diffraction (XRD), resistivity and thermoelectric power (TEP) measurements. XRD results reveal that the volume percentage of the 2223 high T_c phase decreases with an increase in Y content. The replacement of the Ca²⁺ ion by the Y³⁺ ion does not influence the tetragonal structure of the pure Bi (Pb): 2223 system and the lattice parameters vary with Y content. The results of resistivity indicate that the critical temperatures T_c of the samples decrease monotonically with an increase in Y content. Further, the critical concentration of Y to completely suppress superconductivity in the Y-doped Bi (Pb):2223 system is higher (0.60) than that reported (0.20) for the other rare-earth elements. On the other hand, the values of TEP at room temperature are found to be negative for Y=0.00 and 0.10 samples, and it changed to positive with further increase in Y content. The hole-carrier concentration per Cu ion (P) is deduced by using two different ways: the first in terms of T_c values in the superconducting state and the other in terms of TEP values in the normal state. Interestingly, it is found that the values of P deduced from the formal way are not consistent with the reported parabolic behavior for superconducting systems in the under-doped region, and consequently disagree with the general roles of substitution. However, the vice versa is recorded for the values of P deduced from the latter way. The results are discussed in terms of the possible reasons for the suppression of superconductivity in the considered system.     

Increase of Tc in the 1:2:3 superconductors YBCO and (CaxLa1−x)(LauBa1−u)2Cu3Oy after slow cooling or low temperature annealing

The well known phenomenon of the increase of T_c of YBCO after slow cooling or low temperature annealing without change of the oxygen content, was found also for the YBCO like tetragonal superconductors of (Ca_xLa_1−x)(La_uBa_1−u)₂Cu₃O_y (this compound has been previously denoted as CLBLCO, CLBCO or CaLaBaCuO). It has been observed at 150 and 100 °C for oxygen underdoped, optimally- and overdoped ceramics. The products retain their tetragonal unit cells. The possible reasons of this phenomenon are discussed.     

Phase stability in the LnCa2Mn2O7 (Ln=Pr, Nd, Sm and Gd) Ruddlesden-Popper series

The synthesis of the Ruddlesden-Popper series, LnCa₂Mn₂O₇, (Ln=Pr, Nd, Sm and Gd) is described and their structure and electronic properties investigated. The reduction in size of the A-site cation causes an increase in the distortion of their orthorhombic structures (space group Cmcm). All of these compounds form with a perovskite impurity, the amount of which increases on reduction of the cation size. The synthesis temperature also alters the amount of perovskite impurity in the phase, but only to a lower limit, implying the perovskite phase is intrinsic to the material and that a phase equilibrium exists between the layered Ruddlesden-Popper and perovskite phases, which is controlled by the cation size. The magnetic susceptibility show transitions characteristic of the perovskite phase, therefore little direct information can be obtained about the Ruddlesden-Popper phases, except that ferromagnetism is not observed in any of these materials.     

Low field AC susceptibility study of intergranular critical current density in Mg-substituted CuBa2Ca3Cu4O12−y high temperature superconductors

Measurements of the a.c.susceptibility (χ=χ′+iχ″) have been made on the Mg substituted high T_C superconducting system, CuBa₂(Mg_xCa_1−x)₃Cu₄O_12−y (Cu-1234) with x=0, 0.10 & 0.20, at different values of the a.c.field amplitude. Estimates of the intergranular critical current density(J_C) made from the field dependent χ″-T curves show an improvement in the Mg-substituted Cu-1234 system. Results have been analysed in the light of the crystal structure and the superconducting anisotropy factor (γ=ξ_ab/ξ_c) of the Cu-1234 system. Lower superconducting anisotropy emanating from Mg substitution has been found to be significant, resulting in better superconducting properties.     

Ground state electronic and magnetic properties of RCrSb3 (R=La, Ce, Nd, Gd and Dy): A first principles study

The electronic density of states (DOS) and magnetic moments of rare-earth antimonides (RCrSb₃) have been studied by the first principles full-potential linearized augmented plane wave (FP-LAPW) method based on density functional theory (DFT). For the exchange-correlation potential, the LSDA+U method is used. The effective moments of LaCrSb₃, CeCrSb₃, NdCrSb₃, GdCrSb₃, and DyCrSb₃ were found to be , , , and respectively. The exchange-splittings of Cr-3d state electrons and 4f-states of rare earth elements were analyzed to explain the magnetic nature of these systems. The Cr atom plays a significant role on the magnetic properties due to the hybridization between Cr-3d and Sb-5p state orbitals. The results obtained are compared and found to be in close agreement with the available data.     

Thermal diffusivity of double perovskite Sr2MMoO6 (M=Fe, Mn and Co) and La doping effects studied by mirage effect

The thermal diffusivity has been investigated in double perovskite Sr₂MMoO₆ (M=Fe, Mn and Co) by means of the mirage effect. We have found that the thermal diffusivity of metallic Sr₂FeMoO₆ is 0.39 cm²/s, which is larger than that (0.33 cm²/s) of insulating Sr₂MnMoO₆ and Sr₂CoMoO₆. We further investigate the substitution effects of the La³⁺ ions for the Sr²⁺ ions in Sr₂FeMoO₆ and Sr₂MnMoO₆, and have found that the thermal diffusivities of both samples significantly increase with the La concentration. Such an enhancement of the thermal diffusivities has been ascribed to occupation of the extra itinerant electrons on the conduction Mo4d band.     

Structural and magnetic ordering in the two-dimensional coordination polymer Co(ox)(bpy-d8), (ox=C2O4, bpy-d8=4,4′-bipyridine-d8)

Neutron diffraction and magnetic susceptibility studies of the two-dimensional coordination polymer Co(ox)(bpy-d8) are presented, where ox=C₂O₄²⁻ and bpy-d8=4,4′-bipyridine-d8 (fully deuterated). The neutron powder diffraction data reveal a second-order crystallographic phase transition at 290 K. Above 290 K, a disordered structure, space group Immm, is observed that is closely related to the ordered structure previously proposed on the basis of single crystal X-ray diffraction. At low temperatures, the structure is an ordered variant of the high-temperature phase with space group I222. In both phases, the Co ions are linked by the oxalate forming infinite chains that are crosslinked by the bpy ligands.The magnetic susceptibility follows qualitatively a quasi one-dimensional chain behavior. It exhibits a broad maximum around 35 K, corresponding to a strong antiferromagnetic coupling through the oxalate bridges. A kink at 9 K marks the onset of long-range antiferromagnetic ordering due to much weaker interchain magnetic interactions.The magnetically ordered structure determined from the low-temperature neutron diffraction data can be described with the propagation vector (1/2, 1/2, 1/2), i.e. a doubling of the unit cell in each principal direction. It is concluded that a significant antiferromagnetic interaction is mediated through the bpy ligands, although the Co-Co distance along these bridges is 11.4 Å.     

Calorimetric investigation of the magnetic transition in quasi-one-dimensional molecule-based ferrimagnets: [Mn(OC14H29)4TPP][TCNE]·MeOH and [MnF4TPP][TCNE]·0.5MeOH

Heat capacity study was performed, for the first time, for [MnF₄TPP][TCNE]·0.5MeOH and [Mn(OC₁₄H₂₉)₄TPP][TCNE]·MeOH complexes in the 1.8-100 K temperature range under the 0-9 T magnetic field and disclosed new aspects inherent in such strongly coupled charge-transfer Mn-porphyrin-TCNE linear chain systems, where TPP=5,10,15,20-tetraphenylporphyrinato, TCNE=tetracyanoethylene and MeOH=methanol. Any heat capacity anomaly due to the onset of the magnetic long-range-order was not detected, whereas the magnetic phase transition has clearly been observed around 20 K by previous magnetic studies. As these materials are well approximated by quasi-one-dimensional ferrimagnetic Heisenberg chains with very large intrachain spin-spin interactions, the most part of the magnetic entropy is retained above the phase transition temperature as the dominant short-range order. This is the reason why no magnetic phase transition was detected by calorimetry. On the other hand, the big effect observed in the magnetic susceptibility is well accounted for if the formation of magnetic domains is assumed in the crystal.     

A magnetic study of the ThCr2Si2-type RPd2Ge2 (R=Pr, Nd) compounds. Magnetic structure of PrPd2Ge2 from powder neutron diffraction

The magnetic properties of the PrPd₂Ge₂ and NdPd₂Ge₂ compounds have been investigated by magnetic measurements, specific heat measurements and neutron diffraction experiments. The PrPd₂Ge₂ compound orders antiferromagnetically below T_N=5.0(2) with an original modulated magnetic structure characterized by a magnetic cell three times larger than the chemical one by tripling of the c parameter. The palladium atom is non magnetic and the Pr moments are parallel to the c-axis with a value of ≈2.0 μ_B at 2 K. The specific heat measurements clearly detect a low temperature transition for the NdPd₂Ge₂ compound, interpreted as a Nd sublattice antiferromagnetic ordering below 1.3(2) K.     

Superparamagnetic-like behavior and spin-orbit coupling in (Co,Zn)RE4W3O16 tungstates (RE=Nd, Sm, Eu, Gd, Dy and Ho)

Magnetic susceptibility measurements carried out on (Co,Zn)RE₄W₃O₁₆ compounds revealed a disordered state of magnetic moments above 4.2 K for all compounds under study, and a weak response to magnetic field and temperature for ZnSm₄W₃O₁₆ and ZnEu₄W₃O₁₆ samples. The temperature independent component of magnetic susceptibility has a negative value for ZnGd₄W₃O₁₆ and a positive one for the rest of the tungstates, indicating a domination of van Vleck contribution. The magnetization isotherms of majority of the tungstates under study revealed both spontaneous magnetic moments and hysteresis characteristic for the superparamagnetic-like behavior with blocking temperature T_B∼30 K, except for ZnEu₄W₃O₁₆. Fitting procedure of the Landé factor revealed that the stronger the orbital contribution, the weaker the superparamagnetic effect, namely for ZnRE₄W₃O₁₆. In case of CoRE₄W₃O₁₆ a significant participation of the Co²⁺ moment in the spontaneous magnetization was observed.     

Magnetic properties of compounds in the system CaBaCo4−x−yZnxAlyO7 (x=0,1,2, y=0,1)

The magnetic properties of four compounds in the series CaBaCo_4−x−yZn_xAl_yO₇ (x=0,1,2, y=0,1) were investigated. Using AC-susceptibility and DC-magnetometry, magnetic transitions (T_fs) were found for all four compositions in the range 50-3 K. The data from the AC measurements proved to be frequency dependent: T_f increases with higher frequencies. An energy-loss in the magnetic coupling, indicated as contributions in the imaginary part of the magnetic susceptibility (χ″), was seen for every compound and its maximum appeared just below the maximum χ′. Modelling the data with Arrhenius-, Vogel-Fulcher-, and the power-law made it possible to relate the four compounds to spin-glass materials. The Casimir-du Pré relation was used to extract average relaxation times at T_f. The DC magnetisations clearly show differences between field-cooled and zero-field-cooled measurements. None of the compounds exhibit any metamagnetic properties up to 8 T. A new method is presented to calculate the saturation fields using DC data. Relaxation measurements on three compounds indicate that the systems relax very fast, in contrast to spin-glasses. Aging does not affect the fast relaxations. The compounds are interpreted as disordered anti-ferromagnets with spin-glass features.     

Effect of Dy substitution on structural,magnetic and optical properties of BiFeO3 ceramics

Bi_1−xDy_xFeO₃ (x=0.0, 0.03, 0.05, 0.07, 0.10 and 0.12) ceramics were synthesized by solid state reaction method. Effects of Dy substitution on structural distortion, magnetic and optical properties of BiFeO₃ were examined by X-ray diffraction, Raman and UV–Visible spectroscopy. The samples were found to crystallize in rhombohedral structure of BiFeO₃ with R3c space group. The reduction in lattice parameters and unit cell volume indicate the distortion in FeO₆ octahedra of the rhombohedral structure without any signature of phase transformation up to x=0.12. The predictable weak ferromagnetic hysteresis loops can be observed in the Dy doped samples with maximum remnant magnetization of 0.2103 emu/g for x=0.12. The weak ferromagnetism is ascribed to the suppressed spiral spin structure and magnetically active characteristic of Dy³⁺ ions together with ferromagnetic coupling between Dy³⁺ and Fe³⁺ ions. With optical band gap in visible region, Dy doped BiFeO₃ ceramics are potential material for optoelectronic device and solar cell applications.     

Photocatalytic properties of lanthanide tungstates Ln2W2O9 (Ln=La,Pr, Nd,Sm, and Gd)

Lanthanide tungstates, Ln₂W₂O₉ (Ln=La, Pr, Nd, Sm, and Gd), were prepared via the polymerized complex method at 1273 K for 2 h, and their photocatalytic activities for hydrogen and oxygen evolution were investigated. Pt-loaded Gd₂W₂O₉ exhibited activity for H₂ evolution from an aqueous methanol solution under light irradiation (λ>300 nm). The remaining Ln₂W₂O₉ were inactive for H₂ evolution due to the influence of the Ln elements and their crystal structures. All Ln₂W₂O₉ were inactive for O₂ evolution from an aqueous AgNO₃ solution due to the lack of O₂ evolution sites on the surface.     

Mössbauer spectroscopic study of the thermal spin crossover in [Fe(II)(isoxazole)6](ClO4)2

The ⁵⁷Fe Mössbauer spectroscopy of mononuclear [Fe(II)(isoxazole)₆](ClO₄)₂ has been studied to reveal the thermal spin crossover of Fe(II) between low-spin (S=0) and high-spin (S=2) states. Temperature-dependent spin transition curves have been constructed with the least-square fitted data obtained from the Mössbauer spectra measured at various temperatures between 84 and 270 K during a cooling and heating cycle. This compound exhibits an unusual temperature-dependent spin transition behaviour with T_C(↓)=223 and T_C(↑)=213 K occurring in the reverse order in comparison to those observed in SQUID observation and many other spin transition compounds. The compound has three high-spin Fe(II) sites at the highest temperature of study of which two undergo spin transitions. The compound seems to undergo a structural phase transition around the spin transition temperature, which plays a significant role in the spin crossover behaviour as well as the magnetic properties of the compound at temperatures below T_C. The present study reveals an increase in high-spin fraction upon heating in the temperature range below T_C, and an explanation is provided.     

Effect of holmium substitution for the improvement of multiferroic properties of BiFeO3

This paper reports on multiferroic properties of Ho substituted BiFeO₃ (Bi_1−xHo_xFeO₃) ceramics. It is observed that for x=0.15, a prominent ferroelectric loop is seen at 300 K even if the system remains in rhombohedral (R3c) phase without appearance of any observable impurity phases. A well shaped M-H loop is observed at 10 K for x=0.15. However it showed ferromagnetism, confirming the contribution of Ho³⁺ towards enhancement of ferromagnetic properties of BiFeO₃ at 300 K. Suppression of impurity phases of pure BiFeO₃ bulk ceramic favors the reduction of mobile oxygen vacancies and reduces leakage current, due to which ferroelectric properties of BiFeO₃ is enhanced. We argue that Ho substitution at Bi site is likely to suppress the spiral spin modulation and at the same time increase the canting angle, which favors enhanced multiferroic properties. XRD, SEM, magnetization, polarization and chemical bonding analysis measurements were carried out to explain the multiferroic behavior.     

Relaxation and conductivity behaviour in the compounds: FeRGe2O7 (R=Pr,Tb)

AC measurements were performed on the thortveitite-like layered compounds, FeRGe₂O (R=Pr,Tb) in order to study their dielectric features, e.g. as a function of temperature. The main electrical response lies on impedance plots composed of two successive arcs with depressed centers. Bulk conductivity behavior is mostly Arrhenius for the measured temperatures. The associated bulk activation energies are close to 1 eV. Raw data were used to follow the temperature dependence of the dynamic parameters, ε′(ω) and σ′(ω). From logarithmic σ′(ω) vs. ω curves the dc component was obtained. ε′(ω) vs. log ω curves exhibit a dispersive behavior at low frequencies, reflecting blocking effects. E_dc and E_ac activation energies were also calculated, the last one obtained from σ′(ω) vs. 1000/T plots. Conductivity results suggest the occurrence of an extrinsic conducting mechanism. A structural instability was detected via the temperature dependence of permittivity, which has been ascribed to the presence of Ga-O-Ga bonds having associated angles different of 180°. Analyses of the results show that the interchange of Tb and Pr in the general formula FeRGe₂O₇ (R=Pr, Tb) involves only small differences in their global ac and dc behavior.     

Thermochemical studies on RE2O2CO3 (RE=Gd, Nd) decomposition

Thermochemistry in the decomposition of gadolinium di-oxycarbonate, Gd₂O₂CO₃(s) and neodymium di-oxycarbonate, Nd₂O₂CO₃(s) was studied over the temperature region of 774-952 K and 775-1105 K, respectively. The equilibrium properties of the decomposition reactions were obtained by tensimetric measurement of the CO₂(g) pressure over the biphasic mixture of RE₂O₂CO₃(s) and RE₂O₃(s) at different temperatures (RE=Gd, Nd) and also by thermogravimetric analysis of the decomposition temperature at different CO₂ pressures. The temperature dependence of the equilibrium pressure of CO₂ thus measured could be given by

ln p_CO2/Pa (±0.13)=−22599.1/T+35.21 (774≤T (K)≤952) for Gd₂O₂CO₃ decomposition and

ln p_CO2/Pa (±0.19)=−23824.7/T+33.14 (775≤T (K)≤1105) for Nd₂O₂CO₃ decomposition.

From the above vapor pressure expressions, the median enthalpy and entropy of the decomposition of the oxycarbonates were calculated by the second law analysis and their thermodynamic stabilities were derived. The results are discussed in the light of available thermochemical data of the compounds.