Electrical and magnetic properties of the complete solid solution series between SrRuO3 and LaRhO3: Filling t2g versus tilting

A complete solid solution series between the t2g^4 perovskite ferromagnet SrRuO3 and the diamagnetic t2g^6 perovskite LaRhO3 has been prepared. The evolution with composition x in (SrRuO3)(1-x)(LaRhO3)(x) of the crystal structure and electrical and magnetic properties has been studied and is reported here. As x increases, the octahedral tilt angle gradually increases, along with the pseudocubic lattice parameter and unit cell volume. Electrical resistivity measurements reveal a compositionally driven metal to insulator transition between x = 0.1 and 0.2. Ferromagnetic ordering gives over to glassy magnetism for x > 0.3 and no magnetic ordering is found above 2 K for x > 0.5. M_sat and Theta_CW decrease with increasing x and remain constant after x = 0.5. The magnetism appears poised between localized and itinerant behavior, and becomes more localized with increasing x as evidenced by the evolution of the Rhodes-Wohlfarth ratio. mu_eff per Ru is equal to the quenched spin-only S value across the entire solid solution. Comparisons with Sr(1-x)Ca(x)RuO3 reinforce the important role of structural distortions in determining magnetic ground state. It is suggested that electrical transport and magnetic properties are not strongly coupled in this system

The effect of Mg location on Co-Mg-Ru/γ-Al2O3 Fischer–Tropsch catalysts

© 2016 The Author(s) Published by the Royal Society. All rights reserved.The effectiveness of Mg as a promoter of Co-Ru/γ-Al2O3 Fischer-Tropsch catalysts depends on how and when the Mg is added. When the Mg is impregnated into the support before the Co and Ru addition, some Mg is incorporated into the support in the form of MgxAl2O3+x if the material is calcined at 550°C or 800°C after the impregnation, while the remainder is present as amorphous MgO/MgCO3 phases. After subsequent Co-Ru impregnation MgxCo3-xO4 is formed which decomposes on reduction, leading to Co(0) particles intimately mixed with Mg, as shown by high-resolution transmission electron microscopy. The process of impregnating Co into an Mg-modified support results in dissolution of the amorphous Mg, and it is this Mg which is then incorporated into MgxCo3-xO4. Acid washing or higher temperature calcination after Mg impregnation can remove most of this amorphous Mg, resulting in lower values of x in MgxCo3-xO4. Catalytic testing of these materials reveals that Mg incorporation into the Co oxide phase is severely detrimental to the site-Time yield, while Mg incorporation into the support may provide some enhancement of activity at high temperature

Raman response of Stage-1 graphite intercalation compounds revisited

We present a detailed in-situ Raman analysis of stage-1 KC8, CaC6, and LiC6 graphite intercalation compounds (GIC) to unravel their intrinsic finger print. Four main components were found between 1200 cm-1 and 1700 cm-1, and each of them were assigned to a corresponding vibrational mode. From a detailed line shape analysis of the intrinsic Fano-lines of the G- and D-line response we precisely determine the position ({\omega}ph), line width ({\Gamma}ph) and asymmetry (q) from each component. The comparison to the theoretical calculated line width and position of each component allow us to extract the electron-phonon coupling constant of these compounds. A coupling constant {\lambda}ph < 0.06 was obtained. This highlights that Raman active modes alone are not sufficient to explain the superconductivity within the electron-phonon coupling mechanism in CaC6 and KC8.Comment: 6 pages, 3 figures, 2 table

Substitution of Re7+ into CaMnO3: an efficient free electron generation dopant for tuning of thermoelectric properties.

Highly dense CaMn1-xRexO3 (0 ≤ x ≤ 0.04) samples were prepared by solid-state synthesis. The effect of Re doping was assessed by the characterisation of crystal structure, oxygen content, and electrical and thermal transport properties. The oxidation state of the substituted Re was determined by X-ray absorption near edge spectra to be Re7+, and led to expansion of the lattice and an increase in electron carrier concentration due to the formation of Mn3+. The thermal behaviour of the electrical conductivity and the thermopower over a wide temperature range allowed identification of different conduction mechanisms: (1) below 110 K, 3D variable range hopping, (2) between 110 and 650 K, small polaron transport, and (3) above 650 K, activation of carriers over a mobility edge. Evaluation of the power factor expected for different dopant oxidation states as a function of dopant concentration shows that the doping strategy using a heavy heptavalent ion allows accessibility of the peak power factor at lower dopant concentrations, lowering the amount of non-ionised impurities, and therefore improves the electronic substitution efficiency, the ratio of activated carriers over the nominal doping concentration, compared to previously studied dopants. An increased power factor and a reduced lattice thermal conductivity are obtained with a peak figure of merit ZT = 0.16(3) at 947 K for CaMn0.98Re0.02O3. This is an approximately two-fold increase compared to undoped CaMnO3, and is comparable to the highest values reported for highly dense B-site doped CaMnO3

Strong electron correlations in the normal state of FeSe0.42Te0.58

We investigate the normal state of the '11' iron-based superconductor FeSe0.42Te0.58 by angle resolved photoemission. Our data reveal a highly renormalized quasiparticle dispersion characteristic of a strongly correlated metal. We find sheet dependent effective carrier masses between ~ 3 - 16 m_e corresponding to a mass enhancement over band structure values of m*/m_band ~ 6 - 20. This is nearly an order of magnitude higher than the renormalization reported previously for iron-arsenide superconductors of the '1111' and '122' families but fully consistent with the bulk specific heat.Comment: 5 pages, 4 figures, to appear in Phys. Rev. Let

Two-electronic component behavior in the multiband FeSe0.42_{0.42}Te0.58_{0.58} superconductor

We report X-band EPR and $^{125}$Te and $^{77}$Se NMR measurements on single-crystalline superconducting FeSe$_{0.42}$Te$_{0.58}$ ($T_c$ = 11.5(1) K). The data provide evidence for the coexistence of intrinsic localized and itinerant electronic states. In the normal state, localized moments couple to itinerant electrons in the Fe(Se,Te) layers and affect the local spin susceptibility and spin fluctuations. Below $T_c$, spin fluctuations become rapidly suppressed and an unconventional superconducting state emerges in which $1/T_1$ is reduced at a much faster rate than expected for conventional $s$- or $s_\pm$-wave symmetry. We suggest that the localized states arise from the strong electronic correlations within one of the Fe-derived bands. The multiband electronic structure together with the electronic correlations thus determine the normal and superconducting states of the FeSe$_{1-x}$Te$_x$ family, which appears much closer to other high-$T_c$ superconductors than previously anticipated.Comment: 5 pages, 4 figure

Jahn-Teller orbital glass state in the expanded fcc Cs3C60 fulleride

The most expanded fcc-structured alkali fulleride, Cs3C60, is a Mott insulator at ambient pressure because of the weak overlap between the frontier t1u molecular orbitals of the C603− anions. It has a severely disordered antiferromagnetic ground state that becomes a superconductor with a high critical temperature, Tc of 35 K upon compression. The effect of the localised t1u3 electronic configuration on the properties of the material is not well-understood. Here we study the relationship between the intrinsic crystallographic C603− orientational disorder and the molecular Jahn–Teller (JT) effect dynamics in the Mott insulating state. The high-resolution 13C magic-angle-spinning (MAS) NMR spectrum at room temperature comprises three peaks in the intensity ratio 1:2:2 consistent with the presence of three crystallographically-inequivalent carbon sites in the fcc unit cell and revealing that the JT-effect dynamics are fast on the NMR time-scale of 10−5 s despite the presence of the frozen-in C603− merohedral disorder disclosed by the 133Cs MAS NMR fine splitting of the tetrahedral and octahedral 133Cs resonances. Cooling to sub-liquid-nitrogen temperatures leads to severe broadening of both the 13C and 133Cs MAS NMR multiplets, which provides the signature of an increased number of inequivalent 13C and 133Cs sites. This is attributed to the freezing out of the C603− JT dynamics and the development of a t1u electronic orbital glass state guided by the merohedral disorder of the fcc structure. The observation of the dynamic and static JT effect in the Mott insulating state of the metrically cubic but merohedrally disordered Cs3C60 fulleride in different temperature ranges reveals the intimate relation between charge localization, magnetic ground state, lifting of electronic degeneracy, and orientational disorder in these strongly-correlated systems

Three-dimensional electronic instabilities in polymerized solid A1C60

The low-temperature structure of A1C60 (A=K, Rb) is an ordered array of polymerized C60 chains, with magnetic properties that suggest a non-metallic ground state. We study the paramagnetic state of this phase using first-principles electronic-structure methods, and examine the magnetic fluctuations around this state using a model Hamiltonian. The electronic and magnetic properties of even this polymerized phase remain strongly three dimensional, and the magnetic fluctuations favor an unusual three-dimensional antiferromagnetically ordered structure with a semi-metallic electronic spectrum.Comment: REVTeX 3.0, 10 pages, 4 figures available on request from [email protected]