Structure of nanocrystalline ZnO up to 85 GPa

The structure of nanocrystalline and bulk polycrystalline ZnO were examined up to 85 GPa and 50 GPa, respectively using synchrotron X-rays and diamond anvil cells at ambient conditions. The transition from the wurtzite to the rock salt phase in the nano-ZnO takes place at 10.5 GPa; this transition pressure is 1.5 GPa higher than in bulk ZnO. A large volume collapse of about 17.5% is observed during the transition in both systems. The rocksalt phase is stable and no structural transitions are observed for both compounds at higher pressures up to the experimental limit. On decompression the rocksalt phase is found to co-exist with the wurtzite phase at ambient conditions for the nano-ZnO.     

Anisotropic vortex pinning in the β-pyrochlore oxide superconductor KOs2O6

Vortex pinning in the β-pyrochlore oxide superconductor KOs₂O₆ with T_c = 9.6 K is investigated by measuring magnetic torque. A large anisotropy of magnetic torque is observed in the superconducting state below T_p = 7.6 K, where a first-order structural transition takes place, in spite of the inherent isotropic nature of the structural and electronic properties. Magnetic torque is enhanced at external magnetic fields parallel to the [1 1 1] and [0 0 1] directions. Moreover, a pronounced peak effect is also observed in the magnetic field dependence of the torque in these two directions. We consider that the observed anisotropy is related to a microstructure associated with the structural transition.     

Quantum dots of Cd0.5Mn0.5Te semimagnetic semiconductor formed by the cold isostatic pressure method

Cd_0.5Mn_0.5Te is a semimagnetic semiconductor, which crystallizes in the zinc-blende structure (ZB) and exhibits a magnetic spin glass like transition at 21 K. Under pressure it shows a first-order phase transition around 2.6 GPa to the NaCl like structure. In this work, the pressure cycled method using a Paris–Edinburgh cell up to 8 GPa has been applied to Cd_0.5Mn_0.5Te samples in order to obtain recovered nanocrystals. The nanoparticles have been characterized by EDX and electron microscopy. The X-ray and electron diffraction results confirmed the existence of nanocrystals in the ZB phase with an average size of 7 nm. Magnetization measurements made in the range of 2–300 K at low field show that the temperature of the magnetic transition decreases when the crystallites’ size is reduced.     

Structural,magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

At ambient pressure CaFe₂As₂ has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ～ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ～0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ～1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe₂As₂ transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.     

Phase transition and structure of (C3N2H5)2SbF5 single crystal

New crystal of the formula (C₃N₂H₅)₂SbF₅ was obtained and characterized with DSC, DTA, TGA, structural and dielectric studies. DSC and dielectric studies revealed a structural phase transition of the first order at 216 K on cooling and 220 K on heating. The entropy of the transition ΔS equal to 11.5 J/mol·K gives evidence that the phase transition is order-disorder type. X-ray studies showed that transition undergoes from orthorhombic phase I with a space group of Pmmn to monoclinic phase II with a space group P2₁/m. The phase transition is proposed to be ferroelastic type. The molecular mechanism of the phase transition is related to ordering of imidazolium cations in phase II that are disordered in phase I.     

Synthesis and characterization of excess magnesium MgB2 superconductor under inert carbon environment

The structural, transport and magnetic properties of MgB₂ superconductor heavily blended with Mg is studied. The samples are synthesized with a new approach in both, pressed carbon environment and in flowing argon. The excess magnesium used is observed to play dual role: one being the prevention of Mg losses during the synthesis process and hence maintaining the stoichiometry of MgB₂ phase, and second being the formation of Mg milieu probably all around the MgB₂ grains to give a dense structure. Excess Mg also improves the grain connectivity by going into the pores and there by minimizing the insulating junctions. The residual resistivity of the sample is observed to decrease from 57.02 μΩ cm to 10.042 μΩ cm as it is progressively filled with superconductor–normal–superconductor (SNS) type junctions amongst the grains by the virtue of increased magnesium content. The synthesized samples devoid of porosity show the superconducting transition, T_c in the range of 39–34 K as of clean MgB₂ samples, though overloaded with Mg. The excess Mg resulted in enhanced critical current density, J_c from 6.8 × 10³ A cm^?2 to 5.9 × 10⁴ A cm^?2 at 20 K and 10 kOe, with reasonable decrease in the superconducting transition. Thus our samples being overloaded with Mg impart mechanical strength and competitive superconducting properties, which forms a part of interest.     

Soft phonons and structural phase transition in superconducting Ba0.59K0.41BiO3

We have observed a softening of phonons and a structural phase transition in a superconducting Ba_0.59K_0.41BiO₃ (T_c = 31 K) single crystal using elastic and inelastic neutron scattering measurements. The soft phonon occurs for the [1 1 1] transverse acoustic mode at the zone boundary. The phonon energies in this vicinity are found to continuously decrease with decreasing temperature from above room temperature. This softening stops at a temperature close to T_s, where a structural phase transition from cubic to tetragonal symmetry occurs. The overall results are consistent with previous data that reported phonon softening and a (0.5, 0.5, 0.5) type superstructure in several Ba_1?xK_xBiO₃ systems. However, we also find weaker (0.5, 0.5, 0) type superstructure peaks that reveal an additional component to the modulation. No significant change related to the superconductivity was observed for these soft phonon energies or linewidths.     

Magnetic properties of RPdIn (R=Gd–Er) compounds

AC susceptibility and DC magnetization measurements were performed for the RPdIn (R=Gd–Er) compounds both in the paramagnetic and in the ordered state. In opposite to GdPdIn, which is a ferromagnet (T_c=102 K), the other samples show a complex ferrimagnetic behavior with the additional transition at T_t<T_c. In the high-temperature phase (for T_t<T<T_c), a ferromagnetic interaction dominates, while in the low-temperature phase (for T⩽T_t) antiferromagnetic interactions with the magnetocrystalline anisotropy, especially strong for TbPdIn, come into play. The ordering temperatures are T_c=70, 34, 25 and 12.3 K for Tb-, Dy-, Ho- and ErPdIn respectively, while transition temperatures are T_t=6, 14 and 6 K for Tb-, Dy- and HoPdIn respectively. TbPdIn reveals an additional transition at 27 K connected with the intermediate ferrimagnetic phase. The critical fields for the magnetization process of the low-temperature phase are high (52 and 150 kOe for TbPdIn and 32 kOe for DyPdIn at T=4.2 K) yet these values decrease remarkably with increasing temperature. Results of the study are compared with magnetic and neutron diffraction data hitherto available. We state that irreversibility of the zero-field cooled–field cooled magnetization is not connected with the spin-glass phase claimed elsewhere.     

Theoretical investigation of the electronic structure and structural phase stability of CeGa2 under pressure

Recently, Chandra Shekar et al. (Phys. Stat. Sol. B 241(2004)2893), studied the structural stability of CeGa₂ under high pressure up to ∼32 GPa and reported a structural transition from hexagonal AlB₂-type to omega trigonal-type starting at ∼16 GPa with a volume collapse of ∼6%. The high-pressure omega triginal phase is found to coexist with the parent phase up to 32 GPa. In this paper, we report the results of our band structure calculations on this system as a function of reduced volume by the tight-binding linear muffin–tin orbital (TB-LMTO) method, in order to look into this structural transition and to understand it in terms of changes in its electronic structure. Our calculations indicate a structural transition at ∼30.6 GPa with a volume collapse of 3.5%, in good agreement with the experimental results. The possible mechanism of the phase transition may be due to f→d electron transfer under pressure. The theoretically calculated ground-state properties, namely the lattice parameters and the bulk modulus are also in good agreement with the experimental values.     

Effects of Immersion Temperature on Self-Assembled Monolayers of Octanethiol on Au(111)

Self-assembled monolayers (SAMs) of 1-octanethiol (OT) on Au(111) surfaces, prepared at immersion temperatures between 300 K and 363 K in a sealed stainless steel chamber, were studied by scanning tunneling microscopy (STM). An oblique (√3 × √3)R30° OT-SAM structure was observed below 348 K, whereas a superstructure (3×√7)R11° covered the gold surfaces at 363 K. The highly resolved STM images permitted assignment of four symmetry-inequivalent OT molecules per 8.7 × 7.6 Å² unit cell at 363 K. Differences in the topographical heights of the molecules were attributed to the binding of OT sulfur head groups at different adsorption sites on Au(111). This structure was not observed in stirring reflux at a high temperature, which indicates a higher pressure (> 1 atm) in the chamber may be one of crucial factors for structural transition. As the immersion temperature increased, a lower density of vacancy islands and a higher fraction of island area were observed.     

Superconductivity in CeO1−xFxFeAs with upper critical field of 94 T

We have successfully synthesized Ce based oxypnictide superconductors with fluorine doping (CeO_1?xF_xFeAs) by a two step solid state reaction method. Detailed XRD and EDX confirm the crystal structure and chemical compositions. We observe that an extremely high H_c2(0) of 94 T can be achieved in the x = 0.1 composition. This increase in H_c2(0) is accompanied by a decrease in transition temperature (38.4 K in x = 0.1 composition) from 42.5 K for the x = 0.2 phase. The in-plane Ginzburg–Landau coherence length is estimated to be ～27 Å at x = 0.2 suggesting a moderate anisotropy in this class of superconductors. The Seebeck coefficient confirms the majority carrier to be electrons and strong dominance of electron–electron correlations in this multiband superconductor.     

Large magnetoresistance in Ni1–xVxS

Large magnetoresistance (MR) was observed in Ni_1−x V_xS(x=0, 0.02, 0.04, 0.06 and 0.08), MR=1530% at 268 K for x=0, MR=1180% at 255 K for x=0.02, MR=980% at 248 K for x=0.04, MR=810% at 224 K for x=0.06 and MR=490% at 198 K for x=0.08 in magnetic field 4 T. The large MR is due to magnetic field-induced magnetic and electrical transition from antiferromagnetic (AFM) nonmetal phase to paramagnetic (PM) metal phase.     

Specific heat of TbMn2(H,D)2

Specific heat (SH) measurements on TbMn₂(H,D)₂ powders have been performed in the temperature range from 2 to 350 K, in zero magnetic field and in 9 T. Due to the low heat conductivity of the samples, the measurements were carried out on a mixed Cu- and sample-powder pellet. For TbMn₂, the anti-ferromagnetic phase transition was manifest by a single SH peak at T_N=47 K, whereas a double SH peak at 281 and 288 K and an upturn below 5 K were observed for the hydride sample. Upon applying the magnetic field of 9 T, the SH upturn was suppressed, whereas no visible influence was found on the specific heat in the whole temperature range above 10 K as well as on the double peak.     

Charge transport in polycrystalline titanium dioxide☆

This work reports semiconducting properties of undoped polycrystalline TiO₂ studied using the measurements of the electrical conductivity (EC) and thermopower as a function of oxygen partial pressure and temperature in the ranges of p(O₂) between 10 Pa and 70 kPa and temperature 1173–1273 K. The width of the band gap, determined from the minimum of EC, is equal to 3.055±0.012 eV. It was found that the apparent concentration of negatively charged defects, involving both acceptor-type aliovalent ions and Ti vacancies, increases with temperature from 0.6 at% at 1173 K to the level of 0.9–1.4 at% at 1273 K. This effect is considered in terms of Schottky-type defects. It was observed that the minimum of EC at the n–p transition is lower than that for TiO₂ single crystal thus suggesting that grain boundaries are responsible for the formation of conductivity weak links.     

BaT2As2 single crystals (T = Fe,Co, Ni) and superconductivity upon Co-doping

The crystal structure and physical properties of BaFe₂As₂, BaCo₂As₂, and BaNi₂As₂ single crystals are surveyed. BaFe₂As₂ gives a magnetic and structural transition at T_N = 132(1) K, BaCo₂As₂ is a paramagnetic metal, while BaNi₂As₂ has a structural phase transition at T₀ = 131 K, followed by superconductivity below T_c = 0.69 K. The bulk superconductivity in Co-doped BaFe₂As₂ below T_c = 22 K is demonstrated by resistivity, magnetic susceptibility, and specific heat data. In contrast to the cuprates, the Fe-based system appears to tolerate considerable disorder in the transition metal layers. First principles calculations for BaFe_1.84Co_0.16As₂ indicate the inter-band scattering due to Co is weak.     

Magnetic transitions in Cu2−xSe below room temperature

We have measured the magnetic susceptibility, resistivity, magnetoresistivity and Hall effect of nonstoichiometric cuprous selenide between 5 and 350 K. Our results show that below 170 K Cu_2−xSe is a mixture of diamagnetic Cu_1.995Se and paramagnetic Cu₃Se₂. The phase diagram of the Cu–Se system, in which 170 K represents the eutectic isotherm, governs the relative content of the two phases. For the Cu₃Se₂ phase a transition to an antiferromagnetic state is observed at about 50 K, with the corresponding Weiss temperature Θ=120 K. On heating above 170 K Cu_2−xSe becomes completely diamagnetic, but the transformation is slow and strongly time dependent. The complicated magnetic behaviour is ascribed to a broad temperature hysteresis of the process.     

Structural and magnetic ordering in La0.6Ca0.4MnO3

The structural and magnetic ordering in La_0.6Ca_0.4MnO₃ has been studied by neutron powder diffraction as a function of temperature between 15 and 300 K. The para-ferromagnetic transition at T∼250 K is accompanied by significant structural distortions in the form of octahedral Mn–O₆ rotations. At 15 K, the total refined ferromagnetic moment on the Mn site was obtained as 3.1 μ_B, in reasonable agreement with the total expected average moment of mixed Mn³⁺/Mn⁴⁺ matrix.     

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.     

Effect of fluorine doping on phase formation and properties of Bi(Pb)-2223 ceramics

Superconducting ceramics of Bi_1.6Pb_0.4Sr₂Ca₂Cu₃O_yF_x (x = 0–0.6) are prepared in air by conventional solid state reaction and characterized. The study shows that the melting point of the samples decreases as fluorine content increases. As a consequence, the grain size increases with the doping level and for x = 0.6, the sample is completely deformed and presents a concave shape making impossible the measurements on it. The Vickers microhardness reaches its maximum for x = 0.2. The analysis of the X-ray diffraction results reveals that all the samples are composed of only Bi(Pb)-2212 and Bi(Pb)-2223 phases. The highest proportion of the high T_c phase (Bi(Pb)-2223) is also observed for x = 0.2 and is about 67.32%. The refinement of cell parameters is done by considering the structural modulation. The results show that the doping leads to a reduction of cell volume as well as the a axis component of modulation. From resistivity versus temperature measurements, it is shown that the doped phases exhibit higher onset critical transition temperatures than the undoped one. The residual resistivity increases with fluorine content suggesting that the doping introduces structural defects and disorder into the samples. The obtained critical current density at 77 K under zero magnetic field also increases with fluorine doping.     

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.