Structural and physical properties of SrMn1−xRuxO3SrMn_{1-x}Ru_xO_3 perovskites

We combine the results of magnetic and transport measurements with neutron diffraction data to construct the structural and magnetic phase diagram of the entire family of SrMn$_{1-x}$Ru$_{x}$O$_3$ ($0 \leqslant x \leqslant 1$) perovskites. We have found antiferromagnetic ordering of the C type for lightly Ru-substituted materials ($0.06 \leqslant x \leqslant 0.5$) in a similar manner to $R_{y}$Sr$_{1-y}$MnO$_3$ ($R$=La, Pr), due to the generation of Mn$^{3+}$ in both families of manganite perovskites by either $B$-site substitution of Ru$^{5+}$ for Mn$^{4+}$ or $A$-site substitution of $R^{3+}$ for Sr$^{2+}$. This similarity is driven by the same ratio of $d^4$ / $d^3$ ions in both classes of materials for equivalent substitution level. In both cases, a tetragonal lattice distortion is observed, which for some compositions ($0.06 \leqslant x \leqslant 0.2$) is coupled to a C-type AF transition and results in a first order magnetic and resistive transition. Heavily substituted SrMn$_{1-x}$Ru$_{x}$O$_3$ materials are ferromagnetic due to dominating exchange interactions between the Ru$^{4+}$ ions. Intermediate substitution ($0.6 \leqslant x \leqslant 0.7$) leads to a spin-glass behavior instead of a quantum critical point reported previously in single crystals, due to enhanced disorder.Comment: 9 pages, 10 figures, accepted for publication in Physical Review

Overdoped Cuprates With High Temperature Superconducting Transitions

Evidence for High Tc cuprate superconductivity is found in a region of the phase diagram where non-superconducting Fermi liquid metals are expected. Cu valences estimated independently from both x-ray absorption near-edge structure (XANES) and bond valence sum (BVS) measurements are > 2.3 for structures in the homologous series (Cu0.75Mo0.25)Sr2(Y,Ce)sCu2O5+2s+{\delta} with s = 1, 2, 3, and 4. The s = 1 member, (Cu0.75Mo0.25)Sr2YCu2O7+{\delta}, 0 \leq {\delta} \leq 0.5, is structurally related to YBa2Cu3O7 in which 25% of the basal Cu cations [i.e. those in the chain layer] are replaced by Mo, and the Ba cations are replaced by Sr. After oxidation under high pressure the s = 1 member becomes superconducting with Tc = 88K. The Cu valence is estimated to be ~2.5, well beyond the ~2.3 value for which other High-Tc cuprates are considered to be overdoped Fermi liquids. The increase in valence is attributed to the additional 0.5 oxygen ions added per chain upon oxidation. The record short apical oxygen distance, at odds with current theory, suggests the possibility of a new pairing mechanism but further experiments are urgently needed to obtain more direct evidence. From the structural point of view the members with s \geq 2 are considered to be equivalent to single-layer cuprates. All have Tc ~ 56 K which is significantly higher than expected because they also have higher than expected Cu valences. The XANES-determined valences normalized to give values in the CuO2 layers are 2.24, 2.25, and 2.26 for s = 2, 3, and 4, while the BVS values determined for the valence in the CuO2 layer alone are 2.31-2.34 for the s = 2 and 3 members. No evidence for periodic ordering has been detected by electron diffraction and high resolution imaging studies. The possibility that the charge reservoir layers are able to screen long range coulomb interactions and thus enhance Tc is discussed

Tuning of magnetic and electronic states by control of oxygen content in lanthanum strontium cobaltites

We report on the magnetic, resistive, and structural studies of perovskite La$_{1/3}$Sr$_{2/3}$CoO$_{3-\delta}$. By using the relation of synthesis temperature and oxygen partial pressure to oxygen stoichiometry obtained from thermogravimetric analysis, we have synthesized a series of samples with precisely controlled $\delta=0.00-0.49$. These samples show three structural phases at $\delta=0.00-0.15$, $\approx0.25$, $\approx0.5$, and two-phase behavior for other oxygen contents. The stoichiometric material with $\delta=0.00$ is a cubic ferromagnetic metal with the Curie temperature $T_{\rm C}=274$ K. The increase of $\delta$ to 0.15 is followed by a linear decrease of $T_{\rm C}$ to $\approx$ 160 K and a metal-insulator transition near the boundary of the cubic structure range. Further increase of $\delta$ results in formation of a tetragonal $2a_p\times 2a_p \times 4a_p$ phase for $\delta\approx 0.25$ and a brownmillerite phase for $\delta\approx0.5$. At low temperatures, these are weak ferromagnetic insulators (canted antiferromagnets) with magnetic transitions at $T_{\rm m}\approx230$ and 120 K, respectively. At higher temperatures, the $2a_p\times 2a_p \times 4a_p$ phase is $G$-type antiferromagnetic between 230 K and $\approx$360 K. Low temperature magnetic properties of this system for $\delta<1/3$ can be described in terms of a mixture of Co$^{3+}$ ions in the low-spin state and Co$^{4+}$ ions in the intermediate-spin state and a possible spin transition of Co$^{3+}$ to the intermediate-spin state above $T_{\rm C}$. For $\delta>1/3$, there appears to be a combination of Co$^{2+}$ and Co$^{3+}$ ions, both in the high-spin state with dominating antiferromagnetic interactions.Comment: RevTeX, 9 pages, 7 figures, to be published in Physical Review

Symmetry of re-entrant tetragonal phase in Ba1-xNaxFe2As2: Magnetic versus orbital ordering mechanism

Magneto-structural phase transitions in Ba1-xAxFe2As2 (A = K, Na) materials are discussed for both magnetically and orbitally driven mechanisms, using a symmetry analysis formulated within the Landau theory of phase transitions. Both mechanisms predict identical orthorhombic space-group symmetries for the nematic and magnetic phases observed over much of the phase diagram, but they predict different tetragonal space-group symmetries for the newly discovered re-entrant tetragonal phase in Ba1-xNaxFe2As2 (x ~ 0.24-0.28). In a magnetic scenario, magnetic order with moments along the c-axis, as found experimentally, does not allow any type of orbital order, but in an orbital scenario, we have determined two possible orbital patterns, specified by P4/mnc1' and I4221' space groups, which do not require atomic displacements relative to the parent I4/mmm1' symmetry and, in consequence, are indistinguishable in conventional diffraction experiments. We demonstrate that the three possible space groups are however, distinct in resonant X-ray Bragg diffraction patterns created by Templeton & Templeton scattering. This provides an experimental method of distinguishing between magnetic and orbital models

High-Tc Superconducting Cuprates, (Ce,Y)sO2s-2Sr2(Cu2.75Mo0.25 )O6+[delta] : Tc-increase with apical Cu-O decrease at constant Cu-O planar distance

Evidence for high-Tc cuprate superconductivity is found in a region of the phase diagram where non-superconducting Fermi liquid metals are expected. Cu valences estimated independently from both XANES measurements and bond valence sum calculations are greater than 2.25 and are in close agreement with each other for structures of the homologous series given in the title with s = 1, 2, 3, 4 and 5. Two questions arise from the present perspective: 1) Is all the action in the CuO2 layers? 2) Is there superconductivity beyond the usual dome? The record short apical oxygen distance found in the homologous series especially in the s = 1 member, at odds with the current theory, suggests the possibility of a new pairing mechanism. The apical Cu-O distance in the s = 1 member decreases upon oxygenation from 2.29 to 2.15 dot A while the Cu valence increases to 2.45 dot A.Peer reviewe

Electronic structure of spinel-type LiV_2O_4

The band structure of the cubic spinel compound LiV_2O_4, which has been reported recently to show heavy Fermion behavior, has been calculated within the local-density approximation using a full-potential version of the linear augmented-plane-wave method. The results show that partially-filled V 3d bands are located about 1.9 eV above the O 2p bands and the V 3d bands are split into a lower partially-filled t_{2g} complex and an upper unoccupied e_{g} manifold. The fact that the conduction electrons originate solely from the t_{2g} bands suggests that the mechanism for the mass enhancement in this system is different from that in the 4f heavy Fermion systems, where these effects are attributed to the hybridization between the localized 4f levels and itinerant spd bands.Comment: 5 pages, revte

Magnetic phase diagram of cubic perovskites SrMn_1-xFe_xO_3

We combine the results of magnetic and transport measurements with Mossbauer spectroscopy and room-temperature diffraction data to construct the magnetic phase diagram of the new family of cubic perovskite manganites SrMn_1-xFe_xO_3. We have found antiferromagnetic ordering for lightly and heavily Fe-substituted material, while intermediate substitution leads to spin-glass behavior. Near the SrMn_0.5Fe_0.5O_3 composition these two types of ordering are found to coexist and affect one another. The spin glass behavior may be caused by competing ferro- and antiferromagnetic interactions among Mn^4+ and observed Fe^3+ and Fe^5+ ions.Comment: 8 pages, 10 figures, revtex, accepted to Phys. Rev.