Slater Insulator in Iridate Perovskites with Strong Spin-Orbit Coupling.

The perovskite SrIrO_{3} is an exotic narrow-band metal owing to a confluence of the strengths of the spin-orbit coupling (SOC) and the electron-electron correlations. It has been proposed that topological and magnetic insulating phases can be achieved by tuning the SOC, Hubbard interactions, and/or lattice symmetry. Here, we report that the substitution of nonmagnetic, isovalent Sn^{4+} for Ir^{4+} in the SrIr_{1-x}Sn_{x}O_{3} perovskites synthesized under high pressure leads to a metal-insulator transition to an antiferromagnetic (AF) phase at T_{N}≥225 K. The continuous change of the cell volume as detected by x-ray diffraction and the λ-shape transition of the specific heat on cooling through T_{N} demonstrate that the metal-insulator transition is of second order. Neutron powder diffraction results indicate that the Sn substitution enlarges an octahedral-site distortion that reduces the SOC relative to the spin-spin exchange interaction and results in the type-G AF spin ordering below T_{N}. Measurement of high-temperature magnetic susceptibility shows the evolution of magnetic coupling in the paramagnetic phase typical of weak itinerant-electron magnetism in the Sn-substituted samples. A reduced structural symmetry in the magnetically ordered phase leads to an electron gap opening at the Brillouin zone boundary below T_{N} in the same way as proposed by Slater.

Competition between heavy fermion and Kondo interaction in isoelectronic A-site-ordered perovskites.

With current research efforts shifting towards the 4d and 5d transition metal oxides, understanding the evolution of the electronic and magnetic structure as one moves away from 3d materials is of critical importance. Here we perform X-ray spectroscopy and electronic structure calculations on A-site-ordered perovskites with Cu in the A-site and the B-sites descending along the ninth group of the periodic table to elucidate the emerging properties as d-orbitals change from partially filled 3d to 4d to 5d. The results show that when descending from Co to Ir, the charge transfers from the cuprate-like Zhang-Rice state on Cu to the t(2g) orbital of the B site. As the Cu d-orbital occupation approaches the Cu(2+) limit, a mixed valence state in CaCu(3)Rh(4)O(12) and heavy fermion state in CaCu(3)Ir(4)O(12) are obtained. The investigated d-electron compounds are mapped onto the Doniach phase diagram of the competing RKKY and Kondo interactions developed for the f-electron systems.

Possible Kondo physics near a metal-insulator crossover in the a-site ordered perovskite CaCu3Ir4O12.

The A-site ordered perovskite (AA(3)')B(4)O(12) can accommodate transition metals on both A' and B sites in the crystal structure. Because of this structural feature, it is possible to have narrow-band electrons interacting with broadband electrons from different sublattices. Here we report a new A-site ordered perovskite (CaCu(3))Ir(4)O(12) synthesized under high pressure. The coupling between localized spins on Cu(2+) and itinerant electrons from the Ir-O sublattice makes Kondo-like physics take place at a temperature as high as 80 K. Results from the local density approximation calculation have confirmed the relevant band structure. The magnetization anomaly found at 80 K can be well rationalized by the two-fluid model.

Observation of electronic inhomogeneity and charge density waves in a bilayer La(2-2x)Sr(1+2x)Mn2O7 single crystal.

We employed a scanning tunneling microscope to image the (001) surface topography and local density of states (LDOS) in La(2-2x)Sr(1+2x)Mn(2)O(7) (x=0.32, LSMO) single crystals below the Curie temperature (T(C)≈120 K). The LDOS maps revealed a stripelike modulation propagating along the tetragonal a axis with a wavelength of about 16 Å, which is indicative of a charge density wave (CDW). The observed CDW in the x=0.32 sample is far from the Fermi surface nesting instability as compared with the data of angle resolved photoemission spectroscopy in an x=0.40 sample. The stripe model developed previously for cuprates can explain the observed CDW in our LSMO sample, indicating that competing interactions between localized and itinerant phases are the origin of the spatial modulations present intrinsically in cuprates and manganites.

Zhang-Rice physics and anomalous copper states in A-site ordered perovskites.

In low dimensional cuprates several interesting phenomena, including high Tc superconductivity, are deeply connected to electron correlations on Cu and the presence of the Zhang-Rice (ZR) singlet state. Here, we report on direct spectroscopic observation of the ZR state responsible for the low-energy physical properties in two isostructural A-site ordered cuprate perovskites, CaCu(3)Co(4)O(12) and CaCu(3)Cr(4)O(12) as revealed by resonant soft x-ray absorption spectroscopy on the Cu L(3,2)- and O K-edges. These measurements reveal the signature of Cu in the high-energy 3+ (3d(8)), the typical 2+ (3d(9)), as well as features of the ZR singlet state (i.e., 3d(9)L, L denotes an oxygen hole). First principles GGA + U calculations affirm that the B-site cation controls the degree of Cu-O hybridization and, thus, the Cu valency. These findings introduce another avenue for the study and manipulation of cuprates, bypassing the complexities inherent to conventional chemical doping (i.e. disorder) that hinder the relevant physics.

Study of atomic structure and electronic structure of an AA'3B4O12 double-perovskite CaCu3Ir4O12 using STEM imaging and EELS techniques.

A newly discovered 1:3 A-site-ordered AA'3B4O12 perovskite oxide CaCu3Ir4O12 which has unusual electrical and magnetic properties was investigated using STEM imaging and EELS techniques in a probe corrected microscope. The target sample was compared with the other two iso-structural oxides of CaCu3Ru4O12 and CaCu3Ti4O12 with dissimilar physical properties. It has been found by STEM HAADF imaging that Ca and Cu on A and A' sites are ordered as expected. Oxygen atoms are imaged with STEM ABF imaging. The fine structures of the Cu L2,3 core loss and O-K edges show that the electronic structure of CaCu3Ir4O12 is very close to that of CaCu3Ru4O12, but different from CaCu3Ti4O12. The O-K near edge fine structures show extensive hybridization of Ir 5d and O 2p band. Cu L2,3 peaks indicate Cu in CaCu3Ir4O12 has 2+ valence, though Cu(2+) electrons mainly localized, they might have strong interactions with Ir(4+) 5d electrons through Ir-O-Cu, similar to the strong coupling of Ru with Cu in CaCu3Ru4O12.

Chemical pressure effects on pyrochlore spin ice.

A comparison among the two sets of studied pyrochlore spin ices, Ho2Sn2O7, Ho2Ti2O7, and Ho2Ge2O7 with Ho3+ spins and Dy2Sn2O7, Dy2Ti2O7, and Dy2Ge2O7 with Dy3+ spins, shows that the application of chemical pressure through each set drives the system toward the antiferromagnetic phase boundary from the spin ice region, which agrees with the prediction of the "dipolar spin ice" model of den Hertog and Gingras. Among all the studied pyrochlore spin ices, Dy2Ge2O7 has the smallest ratio of Jnn/Dnn=-0.73.

Pressure effect on the structural transition and suppression of the high-spin state in the triple-layer T'-La4Ni3O8.

We report a comprehensive high-pressure study on the triple-layer T'-La4Ni3O8 with a suite of experimental probes, including structure determination, magnetic, and transport properties up to 50 GPa. Consistent with a recent ab inito calculation, application of hydrostatic pressure suppresses an insulator-metal spin-state transition at P(c)≈6 GPa. However, a low-spin metallic phase does not emerge after the high-spin state is suppressed to the lowest temperature. For P>20 GPa, the ambient T' structure transforms gradually to a T(†)-type structure, which involves a structural reconstruction from fluorite La-O2-La blocks under low pressures to rock-salt LaO-LaO blocks under high pressures. Absence of the metallic phase under pressure has been discussed in terms of local displacements of O2- ions in the fluorite block under pressure before a global T(†) phase is established.

High-pressure sequence of Ba3NiSb2O9 structural phases: new S = 1 quantum spin liquids based on Ni2+.

Two new gapless quantum spin-liquid candidates with S = 1 (Ni(2+)) moments: the 6H-B phase of Ba(3)NiSb(2)O(9) with a Ni(2+)-triangular lattice and the 3C phase with a Ni(2/3)Sb(1/3)-three-dimensional edge-shared tetrahedral lattice were obtained under high pressure. Both compounds show no magnetic order down to 0.35 K despite Curie-Weiss temperatures θ(CW) of -75.5 (6H-B) and -182.5 K (3C), respectively. Below ~25 K, the magnetic susceptibility of the 6H-B phase saturates to a constant value χ(0) = 0.013 emu/mol, which is followed below 7 K by a linear-temperature-dependent magnetic specific heat (C(M)) displaying a giant coefficient γ = 168 mJ/mol K(2). Both observations suggest the development of a Fermi-liquid-like ground state. For the 3C phase, the C(M) perpendicular T(2) behavior indicates a unique S = 1, 3D quantum spin-liquid ground state.

High pressure route to generate magnetic monopole dimers in spin ice.

The gas of magnetic monopoles in spin ice is governed by one key parameter: the monopole chemical potential. A significant variation of this parameter could access hitherto undiscovered magnetic phenomena arising from monopole correlations, as observed in the analogous electrical Coulomb gas, like monopole dimerization, critical phase separation, or charge ordering. However, all known spin ices have values of chemical potential imposed by their structure and chemistry that place them deeply within the weakly correlated regime, where none of these interesting phenomena occur. Here we use high-pressure synthesis to create a new monopole host, Dy(2)Ge(2)O(7), with a radically altered chemical potential that stabilizes a large fraction of monopole dimers. The system is found to be ideally described by the classic Debye-Huckel-Bjerrum theory of charge correlations. We thus show how to tune the monopole chemical potential in spin ice and how to access the diverse collective properties of magnetic monopoles.

Magnetic structure of LaCrO3 perovskite under high pressure from in situ neutron diffraction.

The temperature-pressure phase diagram for both the crystal and magnetic structures of LaCrO(3) perovskite has been mapped out by in situ neutron-diffraction experiments under pressure. The system offers the opportunity to study the evolution of magnetic order, spin direction, and magnetic moment on crossing the orthorhombic-rhombohedral phase boundary. Moreover, a microscopic model of the superexchange interaction has been developed on the basis of the crystal structure obtained in this work to account for the behavior of T(N) under high pressure.

Enhancement of the Nernst effect by stripe order in a high-T(c) superconductor.

The Nernst effect in metals is highly sensitive to two kinds of phase transition: superconductivity and density-wave order. The large, positive Nernst signal observed in hole-doped high-T(c) superconductors above their transition temperature (T(c)) has so far been attributed to fluctuating superconductivity. Here we report that in some of these materials the large Nernst signal is in fact the result of stripe order, a form of spin/charge modulation that causes a reconstruction of the Fermi surface. In La(2-x)Sr(x)CuO(4) (LSCO) doped with Nd or Eu, the onset of stripe order causes the Nernst signal to change from being small and negative to being large and positive, as revealed either by lowering the hole concentration across the quantum critical point in Nd-doped LSCO (refs 6-8) or by lowering the temperature across the ordering temperature in Eu-doped LSCO (refs 9, 10). In the second case, two separate peaks are resolved, respectively associated with the onset of stripe order at high temperature and superconductivity near T(c).

Critical behavior of the ferromagnetic perovskite BaRuO3.

A thorough study has been made of the physical properties under high pressure of the perovskite BaRuO3 synthesized under pressure; it includes the critical behavior in the vicinity of Tc to 1 GPa and the temperature dependences of resistivity and ac magnetic susceptibility up to 8 GPa. The ferromagnetism in BaRuO3 is suppressed at 8 GPa. Critical fluctuations in the vicinity of Tc have been found in BaRuO3 and they are enhanced under pressure. These observations are in sharp contrast to SrRuO3 where mean-field behavior is found at Tc.

Transition from orbital liquid to Jahn-Teller insulator in orthorhombic perovskites RTiO3.

Following the same strategy used for RVO3, thermal conductivity measurements have been made on a series of single-crystal perovskites RTiO3 (R=La,Nd,...,Yb). Results reveal explicitly a transition from an orbital liquid to an orbitally ordered phase at a magnetic transition temperature, which is common for both the antiferromagnetic and ferromagnetic phases in the phase diagram of RTiO3. This spin/orbital transition is consistent with the mode softening at T_{N} in antiferromagnetic LaTiO3 and is supported by an anomalous critical behavior at T_{c} in ferromagnetic YTiO3.

High-pressure synthesis of the cubic perovskite BaRuO3 and evolution of ferromagnetism in ARuO3 (A = Ca, Sr, Ba) ruthenates.

The cubic perovskite BaRuO(3) has been synthesized under 18 GPa at 1,000 degrees C. Rietveld refinement indicates that the new compound has a stretched Ru-O bond. The cubic perovskite BaRuO(3) remains metallic to 4 K and exhibits a ferromagnetic transition at T(c) = 60 K, which is significantly lower than the T(c) approximately = 160 K for SrRuO(3). The availability of cubic perovskite BaRuO(3) not only makes it possible to map out the evolution of magnetism in the whole series of ARuO(3) (A = Ca, Sr, Ba) as a function of the ionic size of the A-site r(A,) but also completes the polytypes of BaRuO(3). Extension of the plot of T(c) versus r(A) in perovskites ARuO(3) (A = Ca, Sr, Ba) shows that T(c) does not increase as the cubic structure is approached, but has a maximum for orthorhombic SrRuO(3). Suppressing T(c) by Ca and Ba doping in SrRuO(3) is distinguished by sharply different magnetic susceptibilities chi(T) of the paramagnetic phase. This distinction has been interpreted in the context of a Griffiths' phase on the (Ca Sr)RuO(3) side and bandwidth broadening on the (Sr,Ba)RuO(3) side.

Frustrated superexchange interaction versus orbital order in a LaVO3 crystal.

Measurements of magnetic, transport properties, thermal conductivity, and magnetization under pressure as well as neutron diffraction have been made on a single crystal and powder sample of LaVO3. The Néel temperature was found to mark a transition from the phase with both frustrated superexchange interaction and spin-orbit lambdaL.S coupling to the phase where the Jahn-Teller orbital-lattice coupling dominates. The dramatic reduction of absolute entropy in the paramagnetic phase is explained in terms of forming a long-range coherent state due to the interference between frustrated orbits and spins.

Superexchange interaction in orbitally fluctuating RVO3.

Changes in pressure and magnetic field in the orbital and magnetic ordering temperatures of RVO3 perovskites are reported; they reveal a competition between two magnetic orbitally ordered phases that have opposite preferences for the e-orbital component in the localized {3}T{1g} ground state of the V(3+) ion. This competition is shown to be biased by the VO{6/2} site distortion intrinsic to the orthorhombic structure. A remarkable enhancement of T{N} with pressure is found where the competition leads to enhanced orbital critical fluctuations.

Enhanced pressure dependence of magnetic exchange in A2+[V2]O4 spinels approaching the itinerant electron limit.

We report a systematic enhancement of the pressure dependence of T(N) in A(2+)[V(2)]O(4) spinels as the V-V separation approaches the critical separation for a transition to itinerant-electron behavior. An intermediate phase between localized and itinerant-electron behavior is identified in Zn[V(2)]O(4) and Mg[V(2)]O(4) exhibiting mobile holes as large polarons. Partial electronic delocalization, cooperative ordering of V-V pairs in Zn[V(2)]O(4) below T(s) approximately T(N) and dT(N)/dP<0, signals that lattice instabilities associated with the electronic crossover are a universal phenomenon.

Orbital fluctuations and orbital flipping in RVO3 perovskites.

The effect of the average R-site ionic radius IR and variance on the orbital and magnetic order in R3+-doped YVO3 was studied in Y1-xLaxVO3 and Y1-x(La0.2337Lu0.7663)xVO3 with fixed IR. The orbital flipping temperature T{CG} increases nonlinearly with increasing R-site variance, indicating that the V-O-V bond angle is not the primary driving force stabilizing the C-type orbitally ordered phase. The suppressed thermal conductivity in the G-type orbitally ordered phase signals some remaining orbital randomness that is enhanced by t{2} and et hybridization in {3}T{1g} site symmetry.

Unusual evolution of the magnetic interactions versus structural distortions in RMnO3 perovskites.

We report the refinement of x-ray powder diffraction together with magnetic and thermal conductivity measurements made on the entire family of RMnO3 perovskites prepared by melt growth or under high pressure. Analysis of the data has identified the origin of the transition from type-A to type-E magnetic order as a competition between t-orbital and e-orbital spin-spin interactions within each Mn-O-Mn bond in the (001) planes, the e-orbital interactions decreasing with decreasing R3+-ion size.