Spectroscopic studies of the ferroelectric and magnetic phase transitions in multiferroic Sr1-xBaxMnO3.

Dielectric response of perovskite Sr1-xBaxMnO3 (x = 0.43 and 0.45) ceramics was investigated using microwave, THz and infrared spectroscopic techniques in order to study the ferroelectric and antiferromagnetic phase transitions with critical temperatures TC ≈ 350 K and TN ≈ 200 K, respectively. The two lowest-frequency polar phonons are overdamped above TN and they exhibit pronounced softening on heating towards TC. Nevertheless, permittivity ε' in the THz range shows only a small anomaly at TC because the phonon contribution to ε' is rather small. The phonons are coupled with a central mode which provides the main contribution to the dielectric anomaly at TC. Thus, the ferroelectric phase transition has characteristics of a crossover from displacive to order-disorder type. At the same time, the intrinsic THz central peak is partially screened by conductivity and related Maxwell-Wagner relaxation, which dominates the microwave and lower-frequency spectra. Below TN, the ferroelectric distortion markedly decreases, which has an influence on the frequencies of both the central and soft modes. Therefore, ε' in the THz range increases at TN on cooling. In spite of the strong spin-phonon coupling near TN, surprisingly no magnetodielectric effect was observed in the THz spectra upon applying magnetic field of up to 7 T, which is in contradiction with the theoretically expected huge magnetoelectric coupling. We explain this fact as due to the insensitivity of TN to magnetic field.

Fragile charge order in the nonsuperconducting ground state of the underdoped high-temperature superconductors.

The normal state in the hole underdoped copper oxide superconductors has proven to be a source of mystery for decades. The measurement of a small Fermi surface by quantum oscillations on suppression of superconductivity by high applied magnetic fields, together with complementary spectroscopic measurements in the hole underdoped copper oxide superconductors, point to a nodal electron pocket from charge order in YBa2Cu3(6+δ). Here, we report quantum oscillation measurements in the closely related stoichiometric material YBa2Cu4O8, which reveals similar Fermi surface properties to YBa2Cu3(6+δ), despite the nonobservation of charge order signatures in the same spectroscopic techniques, such as X-ray diffraction, that revealed signatures of charge order in YBa2Cu3(6+δ). Fermi surface reconstruction in YBa2Cu4O8 is suggested to occur from magnetic field enhancement of charge order that is rendered fragile in zero magnetic fields because of its potential unconventional nature and/or its occurrence as a subsidiary to more robust underlying electronic correlations.

High temperature neutron diffraction studies of PrInO3 and the measures of perovskite structure distortion.

The crystal structure of PrInO(3) was investigated in the temperature range 303-1123 K by high-resolution neutron-powder diffraction. The PrInO(3) adopts a highly distorted variant of the perovskite structure with the orthorhombic Pnma space group in the whole temperature range investigated. The bond length and bond-angle analysis revealed a very slow tendency to decrease structural distortion with increasing temperature. Comparison of different parameters quantifying perovskite structure distortion calculated for PrInO(3) and the similar PrAlO(3) and PrGaO(3) shows the advantage of using the tolerance factor t12 calculated for the 12-fold coordinated Pr by geometrical averaging of the individual interatomic distances. An additional advantage of the tolerance factor method results from the possibility of extending it to predict the average structural distortion and the geometrical stability of the perovskites at various temperatures once the accurate dependence of t(x,T,d) on the composition, temperature and oxygen content is found. By comparing PrInO(3) with several AMO(3) perovskites containing ions in the fixed oxidation state on the A and M crystal sites it was found that structural distortion and the tolerance factor t12 for PrInO(3) are consistent with the empirical thermal expansion coefficient based on the bond strength calculation [R. M. Hazen, and C. T. Prewitt, Am. Mineral., 1977, 62(3-4), 309]. In contrast to perovskites AMO(3-d) containing mixed-valent M ions, which allow for a wide range of changes of the tolerance factor t(12)(T,d) as a function of oxygen content, perovskites AMO(3) with M ions in the fixed oxidation state show much less flexibility. This flexibility is further reduced for the A(3+)M(3+)O(3) perovskites like PrInO(3) for which even a large change of the synthesis temperature has a minor effect on controlling the resulting t(12)(T) and the structural phase in comparison with A(2+)M(4+)O3 perovskites. The only parameter left for A(3+)M(3+)O(3) materials allowing formation of various perovskites and hexagonal phases is the total pressure, which may significantly change t(12)(T,P).

Observations of Co4+ in a higher spin state and the increase in the Seebeck coefficient of thermoelectric Ca3Co4O9.

Ca3Co4O9 has a unique structure that leads to exceptionally high thermoelectric transport. Here we report the achievement of a 27% increase in the room-temperature in-plane Seebeck coefficient of Ca3Co4O9 thin films. We combine aberration-corrected Z-contrast imaging, atomic-column resolved electron energy-loss spectroscopy, and density-functional calculations to show that the increase is caused by stacking faults with Co4+-ions in a higher spin state compared to that of bulk Ca3Co4O9. The higher Seebeck coefficient makes the Ca3Co4O9 system suitable for many high temperature waste-heat-recovery applications.

Asymmetric orbital-lattice interactions in ultrathin correlated oxide films.

Using resonant x-ray spectroscopies combined with density functional calculations, we find an asymmetric biaxial strain-induced d-orbital response in ultrathin films of the correlated metal LaNiO3 which are not accessible in the bulk. The sign of the misfit strain governs the stability of an octahedral "breathing" distortion, which, in turn, produces an emergent charge-ordered ground state with an altered ligand-hole density and bond covalency. Control of this new mechanism opens a pathway to rational orbital engineering, providing a platform for artificially designed Mott materials.

Effect of substrate on the atomic structure and physical properties of thermoelectric Ca3Co4O9 thin films.

The incommensurately layered cobalt oxide Ca(3)Co(4)O(9) exhibits an unusually high Seebeck coefficient as a polycrystalline bulk material, making it ideally suited for many high temperature thermoelectric applications. In this paper, we investigate properties of Ca(3)Co(4)O(9) thin films grown on cubic perovskite SrTiO(3), LaAlO(3), and (La(0.3)Sr(0.7))(Al(0.65)Ta(0.35))O(3) substrates and on hexagonal Al(2)O(3) (sapphire) substrates using the pulsed laser deposition technique. X-ray diffraction and transmission electron microscopy analysis indicate strain-free growth of films, irrespective of the substrate. However, depending on the lattice and symmetry mismatch, defect-free growth of the hexagonal CoO(2) layer is stabilized only after a critical thickness and, in general, we observe the formation of a stable Ca(2)CoO(3) buffer layer near the substrate-film interface. Beyond this critical thickness, a large concentration of CoO(2) stacking faults is observed, possibly due to weak interlayer interaction in this layered material. We propose that these stacking faults have a significant impact on the Seebeck coefficient and we report higher values in thinner Ca(3)Co(4)O(9) films due to additional phonon scattering sites, necessary for improved thermoelectric properties.

Bonding of microfluidic devices fabricated in polycarbonate.

A simple method for bonding polycarbonate, based on controlled exposure of the pieces to vapours of solvents, yields a tight seal and unmodified geometry of the channels.

Quantum oscillations in the underdoped cuprate YBa2Cu4O8.

We report the observation of quantum oscillations in the underdoped cuprate superconductor YBa2Cu4O8 using a tunnel-diode oscillator technique in pulsed magnetic fields up to 85 T. There is a clear signal, periodic in inverse field, with frequency 660+/-15 T and possible evidence for the presence of two components of slightly different frequency. The quasiparticle mass is m(*)=3.0+/-0.3m(e). In conjunction with the results of Doiron-Leyraud et al. for YBa2Cu3O6.5, the present measurements suggest that Fermi surface pockets are a general feature of underdoped copper oxide planes and provide information about the doping dependence of the Fermi surface.

Negative refraction in ferromagnet-superconductor superlattices.

Negative refraction, which reverses many fundamental aspects of classical optics, can be obtained in systems with negative magnetic permeability and negative dielectric permittivity. This Letter documents an experimental realization of negative refraction at millimeter waves, finite magnetic fields, and cryogenic temperatures utilizing a multilayer stack of ferromagnetic and superconducting thin films. In the present case the superconducting YBa2Cu3O7 layers provide negative permittivity while negative permeability is achieved via ferromagnetic (La:Sr)MnO3 layers for frequencies and magnetic fields close to the ferromagnetic resonance. In these superlattices the refractive index can be switched between positive and negative regions using external magnetic field as tuning parameter.

Exchange interaction in the insulating phase of RNiO3.

In order to characterize the spin-spin exchange interactions responsible for the Type-E' antiferromagnetic order in inhomogeneous RNiO3 perovskites (R=Y or rare earth), the pressure dependence of the Néel temperature T(N) was systematically measured for samples with T(N)

Pressure-induced non-Fermi-liquid behavior of PrNiO3.

Comprehensive temperature scans of the resistivity of a high-quality sample of PrNiO3 were made under different pressures up to 30 kbar; they have revealed that the insulator phase is suppressed completely at P approximately equal to 13 kbar, transforming to a non-Fermi-liquid phase in which the resistivity varies as Deltarho=rho(T)-rho(0) approximately T(n) with n=1.33 and 1.60 over a broad pressure range.

Disorder-induced polaron formation in the magnetoresistive perovskite La0.54Ba0.46MnO3.

Neutron studies of the effect of A-site chemical disorder on the ferromagnetic transition and spin dynamics for the magnetoresistive perovskite La0.54Ba0.46MnO3 are reported. The low temperature spin waves reveal that disorder reduces exchange interactions by only 9%. The development of a quasielastic peak in the spectrum below TC and long-time relaxation of the order parameter indicate that the transition is discontinuous in the disordered sample, while it appears continuous for the ordered sample. These results strongly suggest that chemical disorder lowers the energy for polaron formation in manganese perovskites, and is the origin of the dramatic 50 K reduction in TC.

Enhanced susceptibility in LNiO3 perovskites ( L = La,Pr,Nd,Nd0.5Sm0. 5)

The temperature dependence of the resistivity rho(T) and of the dc magnetic susceptibility chi(T) were measured on high-quality LNiO3 (L = La,Pr,Nd,Nd0.5Sm0.5) samples synthesized under high oxygen pressure. Subtraction of the rare-earth contribution to chi(T) allows the presentation of the evolution of the susceptibility of the NiO3 array from Pauli to Curie-Weiss paramagnetism with decreasing bandwidth. A metal-insulator transition occurring at a temperature T(t) = T(N) is first order for L = Pr and Nd; it becomes second order and produces no anomaly in chi(-1)(T) at a T(t)>T(N) for L = Nd0.5Sm0.5. In the antiferromagnetic domain T

Charged-particle multiplicity near midrapidity in central Au+Au collisions at sqrt[SNN]=56 and 130 GeV.

We present the first measurement of pseudorapidity densities of primary charged particles near midrapidity in Au+Au collisions at sqrt[s(NN)] = 56 and 130 GeV. For the most central collisions, we find the charged-particle pseudorapidity density to be dN/deta|(|eta|<1) = 408+/-12(stat)+/-30(syst) at 56 GeV and 555+/-12(stat)+/-35(syst) at 130 GeV, values that are higher than any previously observed in nuclear collisions. Compared to proton-antiproton collisions, our data show an increase in the pseudorapidity density per participant by more than 40% at the higher energy.

Chloride ions formation during degradation of organochloride compounds using TiO2 deposited on glass microspheres.

Aqueous solutions containing 200 mg/dm3 of p,p'-DDT and methoxychlor were photodegraded for 60 min in UV/TiO2/O2 system and chloride ions concentration and pH were measured. From 60 to 80% of the investigated pesticides were eliminated after treatment. Over 27% of chlorine atoms were splitted off for methoxychlor and 10% for p,p'-DDT. The experimental data suggest, that chlorine atoms were removed from the -CCl3 moiety but the chlorine atoms bound to aromatic ring were left intact at this step of photodegradation.

Magnetic-field-induced low-energy spin excitations in YBa(2)Cu(4)O(8) measured by high field Gd(3+) electron spin resonance.

We have measured the spin susceptibility, chi(s), of the CuO(2) planes in the underdoped high T(c) superconductor, YBa(2)Cu(4)O(8) by Gd(3+) electron spin resonance (ESR) in single crystals and aligned powders in fields up to 15.4 T. At low temperatures and high fields, chi(s) is enhanced slightly in the B parallel c orientation with respect to the B perpendicular c orientation. The enhancement at 15.4 T (approximately equal to 0.15H(c2)) at 16 K (0.2 T(c)) is small: approximately 10% of chi(s)(T(c)), suggesting that the second critical field of superconductivity, H(c2) approximately equal to 100 T, would not suppress the pseudogap. This work demonstrates the potential of high field ESR in single crystals for studying high T(c) superconductors.