Pressure-induced coordination crossover in magnetite; the breakdown of the Verwey–Mott localization hypothesis

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC), whereby charge density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse-spinel phase. The CC transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure the CC-transition temperature increases with pressure, reaching 300 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

La0.7Sr0.3MnO3 film prepared by dc sputtering on silicon substrate: Effect of working pressure

La_0.7Sr_0.3MnO₃ films were prepared by dc sputtering on Si (100) substrate at different working pressure. The possibility of controlling the magnetic and transport properties of colossal magnetoresistance film is investigated, which has attracted great research interest for practical application. The as-grown film shows different magnetic, transport and magnetoresistance change at different working pressure at room temperature, which is quite attractive from technological point of view. Maximum magnetoresistance (MR) of ?5.56%, Curie temperature (T_c) of 325 K and metal insulator transition temperature (T_MI) of 278 K was achieved at room temperature.     

Dielectric,ferroelectric and piezoelectric properties of (1−x)[K0.5Na0.5NbO3]−x[LiSbO3] ceramics

Lead-free (1?x)[K_0.5Na_0.5NbO₃]?x[LiSbO₃] (x=0, 0.04, 0.05 and 0.06)/(KNN-LS) ceramics were prepared by conventional solid-state reaction route (CSSR). For dense morphology pure KNN ceramic was sintered at 1120 °C and LS modified KNN ceramics were sintered at 1080 °C for 4 h, respectively. The structural study at room temperature (RT) revealed the transformation of pure orthorhombic to tetragonal structure with the increase in LS content in KNN-LS ceramics. Temperature dependent dielectric study confirmed the increase of diffuse phase transition nature with the increase in LS content in KNN-LS ceramics. The presence of orthorhombic to tetragonal (T_O?T) polymorphic phase transition temperature (PPT) ～43 °C confirmed the presence of two ferroelectric (orthorhombic and tetragonal) phases in 0.95KNN-0.05LS ceramics at RT. 0.95KNN-0.05LS ceramics showed better ferroelectric and piezoelectric properties i.e., remnant polarization (P_r)～18.7 μC/cm², coercive field (E_c)～11.8 kV/cm, piezoelectric coefficient (d₃₃)～215 pC/N, coupling coefficient (k_p)～0.415 and remnant strain ～0.07% were obtained.     

Pressure-induced coordination crossover in magnetite,a high pressure Mössbauer study

Temperature-dependent ⁵⁷Fe Mössbauer spectroscopy to 40 GPa shows that Fe₃O₄ magnetite undergoes a coordination crossover (CC) whereby charge-density is shifted from octahedral to tetrahedral sites and the spinel structure thus changes from inverse to normal with increasing pressure and decreasing temperature. A precursor to the CC is a d-charge decoupling within the octahedral sites at the inverse spinel phase. The CC-transition takes place almost exactly at the Verwey transition temperature (T_V=122 K) at ambient pressure. While T_V decreases with pressure, the CC-transition temperature increases with pressure, reaching 350 K at 10 GPa. The d electron localization mechanism proposed by Verwey and later by Mott for T<T_V is shown to be unrelated to the actual mechanism of the metal–insulator transition attributed to the Verwey transition. It is proposed that a first-order phase transition taking place at ∼T_V at ambient pressure opens a small gap within the oxygen p-band, resulting in the observed insulating state at T>T_V.     

AlH3 between 65 and 110 GPa: Implications of electronic band and phonon structures

A first-principles density-functional-theory method has been used to reinvestigate the mechanical and dynamical stability of the metallic phase of AlH₃ between 65 and 110 GPa. The electronic properties and phonon dynamics as a function of pressure are also explored. We find electron–phonon superconductivity in the cubic Pm-3n structure with critical temperature T_c = 37 K at 70 GPa which decreases rapidly with the increase of pressure. Further unlike a previously calculated T_c-value of 24 K at 110 GPa, we do not find any superconductivity of significance at this pressure which is consistent with experimental observation.     

Effects of Ni and Co doping on the physical properties of tetragonal FeSe0.5Te0.5 superconductor

Isoelectronic Tellurium (Te) substitution for Selenium (Se) in the tetragonal phase of FeSe (β-FeSe) increases the superconducting transition temperature (T_c) by applying a negative pressure on the lattice. However, the normal state resistivity increases and shows semi-metallic behavior for samples with higher Te concentration. With increasing Te concentration, the T_c increases and reaches a maximum for FeSe_0.5Te_0.5 and then decreases with further increase of Te. We have investigated the effect of Cobalt (Co) and Nickel (Ni) doping in FeSe_0.5Te_0.5 in the nominal composition range Fe_1?xTM_xSe_0.5Te_0.5 (TM = Co (x = 0.05, 0.1, 0.15, 0.2) and Ni (x = 0.05, 0.1)). Both Co and Ni doping suppress T_c and drives the system to metal–insulator transition. The in-plane (‘a’) and out-of-plane (‘c’) lattice constants decrease with increasing dopant concentration.     

Pinning,thermally activated depinning and their importance for tuning the nanoprecipitate size and density in high Jc YBa2Cu3O7−x films

YBa₂Cu₃O_7?x (Y123) films with quantitatively controlled artificial nanoprecipitate pinning centers were grown by pulsed laser deposition (PLD) and characterized by transport over wide temperature (T) and magnetic field (H) ranges and by transmission electron microscopy (TEM). The critical current density J_c was found to be determined by the interplay of strong vortex pinning and thermally activated depinning (TAD), which together produced a non-monotonic dependence of J_c on c-axis pin spacing d_c. At low T and H, J_c increased with decreasing d_c, reaching the very high J_c ～ 48 MA/cm² ～20% of the depairing current density J_d at 10 K, self-field and d_c ～ 10 nm, but at higher T and H when TAD effects become significant, J_c was optimized at larger d_c because longer vortex segments confined between nanoprecipitates are less prone to thermal fluctuations. We conclude that precipitates should extend at least several coherence lengths along vortices in order to produce irreversibility fields H_irr(77 K) greater than 7 T and maximum bulk pinning forces F_p,max(77 K) greater than 7–8 GN/m³ (values appropriate for H parallel to the c-axis). Our results show that there is no universal pin array that optimizes J_c at all T and H.     

Sputtered magnesium diboride thin films: Growth conditions and surface morphology

Magnesium diboride (MgB₂) thin films were deposited on C-plane sapphire substrates by sputtering pure B and Mg targets at different substrate temperatures, and were followed by in situ annealing. A systematic study about the effects of the various growth and annealing parameters on the physical properties of MgB₂ thin films showed that the substrate temperature is the most critical factor that determines the superconducting transition temperature (T_c), while annealing plays a minor role. There was no superconducting transition in the thin films grown at room temperature without post-annealing. The highest T_c of the samples grown at room temperature after the optimized annealing was 22 K. As the temperature of the substrate (T_s) increased, T_c rose. However, the maximum T_s was limited due to the low magnesium sticking coefficient and thus the T_c value was limited as well. The highest T_c, 29 K, was obtained for the sample deposited at 180 °C, annealed at 620 °C, and was subsequently annealed a second time at 800 °C. Three-dimensional (3D) AFM images clearly demonstrated that the thin films with no transition, or very low T_c, did not have the well-developed MgB₂ grains while the films with higher T_c displayed the well-developed grains and smooth surface. Although the T_c of sputtered MgB₂ films in the current work is lower than that for the bulk and ex situ annealed thin films, this work presents an important step towards the fabrication of MgB₂ heterostructures using rather simple physical vapor deposition method such as sputtering.     

Addendum to “Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)” by K.-S. Lee et al. [J. Phys. Chem. Solids 73 (2012) 890]

While a paper mentioned above being published on line, we have become aware of the high-pressure neutron diffraction study of squaric acid (H₂C₄O₄) by C.L. Bull et al. They developed that neutron diffraction experiments could be performed under quasi-hydrostatic conditions to pressures of up to 18 GPa and showed that the tetragonal phase of H₂C₄O₄ was still observed at 14.5 GPa (above the critical pressure of P_c=0.75 GPa at room temperature) beyond the previous pressure limits of 7 GPa. Taking the high-pressure neutron diffraction results into consideration, modified temperature-pressure phase diagram in the paper stated above is reported.     

Superconductivity and thermal properties of sulphur doped FeTe with effect of oxygen post annealing

Here, we report the synthesis and characterization of sulphur-substituted iron telluride i.e. FeTe_1?xS_x; (x = 0–30 %) system and study the impact of low temperature oxygen (O₂) annealing as well. Rietveld analysis of room temperature X-ray diffraction (XRD) patterns shows that all the compounds are crystallized in a tetragonal structure (space group P4/nmm) and no secondary phases are observed. Lattice constants are decreased with increasing S concentration. The parent compound of the system i.e. FeTe does not exhibit superconductivity but shows an anomaly in the resistivity measurement at around 78 K, which corresponds to a structural phase transition. Heat capacity C_p(T) measurement also confirms the structural phase transition of FeTe compound. Superconductivity appears by S substitution; the onset of superconducting transition temperature is about 8 K for FeTe_0.75S_0.25 sample. Thermoelectric power measurements S(T) also shows the superconducting transition at around 7 K for FeTe_0.75S_0.25 sample. The upper critical fields H_c2(10%), H_c2(50%) and H_c2(90%) are estimated to be 400, 650 and 900 kOe respectively at 0 K by applying Ginzburg Landau (GL) equation. Interestingly, superconducting volume fraction is increased with low temperature (200 °C) O₂ annealing at normal pressure. Detailed investigations related to structural (XRD), transport [S(T), R(T)H], magnetization (AC and DC susceptibility) and thermal [C_p(T)] measurements for FeTe_1?xS:O₂ system are presented and discussed.     

Microscopic magnetic properties of (V1−xTix)2O3 near the phase boundary of the metal–insulator transition

Magnetic susceptibility (χ) and ⁵¹V NMR have been measured in (V_1−xTi_x)₂O₃ near the phase boundary of the metal–insulator transition. It is established that the transition from antiferromagnetic insulating (AFI) to antiferromagnetic metallic phases near x_c≈0.05 is not quantum critical, but is discontinuous with a jump of the transition temperature. In the AFI phase at 4.2 K, we observed the satellite in the zero-field ⁵¹V NMR spectrum around 181 MHz in addition to the ‘host’ resonance around 203 MHz. The satellite is also observable in the paramagnetic metallic phase of the x=0.055 sample. We associated the satellite with the V sites near Ti, which are in the V³⁺-like oxidation state, but has different temperature dependence of the NMR shift from that of the host V site. The host d-spin susceptibility for x=0.055 decreases below ∼60 K, but remains finite in the low-temperature limit.     

Structural changes in ab-plane of Zn doped Bi-2212 HTSC single crystals

Single crystals of undoped and 1% Zn-doped Bi-2212 are grown by self-flux slow cooling method under similar growth conditions. T_c(ΔT_c) are found to be 84 K (2 K) and 82 K (8 K) for undoped and doped samples respectively. Effect of Zn doping on structure and modulation is studied. Different change in the value of a- and b-axes are observed resulting in a transformation of structure from tetragonal to orthorhombic one. However, no effective change in modulation is there. Distortions are compared in c- and b-axes for undoped and doped samples. The asymmetry in position and intensity of satellite peaks has been discussed. The value of a in excess of b has been reported for the first time. These results are discussed in terms of valancy, coordinates and position of occupancy of Zn ions vis-à-vis those of Cu⁻ ions in Cu–O plane of the structure.     

Pressure-induced magnetic transition in MnRhAs

The magnetic properties of a Fe₂P-type intermetallic compound MnRhAs have been investigated under high pressure up to 8.0 GPa by AC susceptibility measurement. Initially, both the antiferromagnetic (AF(I)) to the canted state magnetic transition temperature T_t and the canted state to another antiferromagnetic one (AF(II)) transition temperature T_C increase with compression. At 4.0 GPa, however, T_t decreases abruptly, while the increasing rate of T_C becomes larger above this pressure. A pressure-induced magnetic phase transition was seen at around this pressure when T_t and T_C are plotted in the pressure–temperature phase diagram. The transition from the antiferromagnetic to the ferromagnetic state observed below 160 K with increasing pressure is not frequently observed.     

Intrinsic pinning properties of FeSe0.5Te0.5

The intrinsic pinning properties of FeSe_0.5Te_0.5, which is a superconductor with a critical temperature T_c of approximately 14 K, were studied through the analysis of magnetization curves obtained using an extended critical state model. For the magnetization measurements carried out with a superconducting quantum interference device (SQUID), external magnetic fields were applied parallel and perpendicular to the c-axis of the sample. The critical current density J_c under the perpendicular magnetic field of 1 T was estimated using the Kimishima model to be equal to approximately 1.6 × 10⁴, 8.8 × 10³, 4.1 × 10³, and 1.5 × 10³ A/cm² at 5, 7, 9, and 11 K, respectively. Furthermore, the temperature dependence of J_c was fitted to the exponential law of J_c(0) × exp(?αT/T_c) up to 9 K and the power law of J_c(0) × (1 ? T/T_c)ⁿ near T_c.     

Dielectric and piezoelectric properties of (Bi1−x−yNdxNa1−y)0.5BayTiO3 lead-free ceramics

New lead-free (Bi_1−x−yNd_xNa_1−y)_0.5Ba_yTiO₃ ceramics were prepared by a conventional ceramic technique and their dielectric and piezoelectric properties were studied. X-ray diffraction studies reveal that Nd³⁺ and Ba²⁺ diffuse into the Bi_0.5Na_0.5TiO₃ lattices to form a new solid solution with a pure perovskite structure, and a morphotropic phase boundary (MPB) of rhombohedral and tetragonal phases is formed at 0.04 < y < 0.10. The partial substitutions of Nd³⁺ and Ba²⁺ decrease effectively the coercive field E_c and increase significantly the remanent polarization P_r. Because of lower E_c, larger P_r and the formation of the MPB, the piezoelectric properties of the ceramics are significantly enhanced at x/y = 0.02/0.06: d₃₃ = 150 pC/N and k_p = 30.5%. The ceramics exhibit relaxor characteristic, which is probably resulted from the cation disordering in the 12-fold coordination sites. The depolarization temperature T_d shows a strong compositional dependence and reaches a minimum value at the MPB. The temperature dependences of the ferroelectric and dielectric properties suggest that the ceramics may contain both the polar and non-polar regions near the depolarization temperature T_d, which cause the polarization hysteresis loop become deformed near/above T_d.     

Influence of Zr and Ce doping on electromagnetic properties of (Gd,Y)–Ba–Cu–O superconducting tapes fabricated by metal organic chemical vapor deposition

(Gd,Y)Ba₂Cu₃O_x tapes have been fabricated by metal organic chemical vapor deposition (MOCVD) with Zr-doping levels of 0–15 mol.% and Ce doping levels of 0–10 mol.% in 0.4 μm thick films. The critical current density (J_c) of Zr-doped samples at 77 K, 1 T applied in the orientation of H 6 c is found to increase with Zr content and shows a maximum at 7.5% Zr doping. The 7.5% Zr-doped sample exhibits a critical current density (J_c) of 0.95 MA/cm² at H 6 c which is more than 70% higher than the J_c of the undoped sample. The peak in J_c at H 6 c is 83% of that at H 6 a–b in the 7.5% Zr-doped sample which is more than twice as that in the undoped sample. Superconducting transition temperature (T_c) values as high as about 89 K have been achieved in samples even with 15% Zr and 10% Ce. Ce-doped samples with and without Ba compensation are found to exhibit substantially different J_c values as well as angular dependence characteristics.     

Logarithmic temperature variations of the elastic constant of barium titanate near the ferroelectric phase transition

The temperature variations of the elastic constant C₁₁ and the corresponding acoustic attenuation coefficient of barium titanate single crystals grown by two different methods in the paraelectric phase were obtained in a wide temperature by means of Brillouin light scattering. Two phenomenological approaches were adopted to attempt to explain the anomalous change in C₁₁ (denoted as ΔC₁₁) in the paraelectric phase. ΔC₁₁ exhibited a logarithmic variation as log[(T ? T₀)/T₀] in a certain temperature range from T_c to about T_c + 80 °C instead of the other variation of (T ? T₀)^ζ predicted by the mean-field approach. This temperature range was almost the same as the range where precursor dynamics were theoretically predicted to set in. The fact that the logarithmic variation was proposed for uniaxial systems might indicate that the correlated deformation of precursor polar clusters is tetragonal, as was suggested from nuclear magnetic resonance study [7].     

Defect interaction and solid electrolyte transition in AgI-based materials

The first-order phase transition that leads to the superionic phase in AgI-based materials is studied by dc-conductivity measurements and a free energy model. By properly adjusting the model parameters, an abrupt change of disordering concentration, Δη?, is predicted at a transition temperature, T_t. The temperature dependence of the dc-conductivity, σ(T), is well fitted to the η?(T) equilibrium configuration obtained from the trial free energy function. The reported comparative study was done using an AgI–KI modified sample. The model also predicts a transition temperature, T_c for a continuous phase transition (Δη? = 0).     

Yttrium doped La1−xYxO0.9F0.1FeAs superconductors: Hall and thermopower studies

The effect of yttrium substitution at the lanthanum site on the superconducting properties of La_1?xY_xO_0.9F_0.1FeAs (‘x’ = 0, 0.10, 0.20, 0.30, 0.50 and 0.60) oxypnictides has been studied. Powder X-ray diffraction studies confirm single phases till x = 0.1 beyond which minor amount of Y₂O₃ is observed. The temperature dependence of resistivity measurements confirm the superconducting transition temperature (T_c) of 34.8 (±0.05) K and corresponding Meissner transition at 34.3 K in the ‘x’ = 0.3 composition which is higher than that reported for the parent phase (LaO_0.9F_0.1FeAs (T_c = 28 K)). Further increase in the concentration of yttrium leads to broadening and suppression of the superconducting transition. The value of H_c2 at zero temperature is estimated to be about 60.5 T. The Seebeck coefficient (S) shows a negative sign indicating that the major contribution to the conductivity is by electrons. The Hall coefficient (R_H) also remains negative throughout the temperature range supporting the thermopower results. The lattice parameters (a and c) decreases and the charge-carrier density increases with yttrium doping.