We report here a discovery of electrically driven insulator to metal transition (IMT) and concomitant isostructural volume expansion in the layered cobaltates which otherwise do not exhibit temperature dependent IMT. These findings are demonstrated at macroscopic, microscopic and atomic scales. With application of voltage growth of metallic regions have been observed in the 2D layered La2-xSrxCoO4. Growth of metallic regions is associated with volume increase (strain as high as 0.3%). Non thermal IMT and electro-strain are proposed to be caused by electro-proliferation of the Co3+ high spin states.
The structure of the low-energy electronic states in layered cobaltates is considered starting from the Mott insulating limit. We argue that the coherent part of the wave-functions and the Fermi-surface topology at low doping are strongly influenced by spin-orbit coupling of the correlated electrons on the $t_{2g}$ level. An effective t-J model based on mixed spin-orbital states is radically different from that for the cuprates, and supports unconventional, pseudospin-triplet pairing.
A natural explanation for the carrier concentration-dependent electronic behavior in the layered cobaltates emerges within correlated-electron Hamiltonians with finite on-site and significant nearest neighbor hole-hole Coulomb repulsions. The nearest neighbor repulsion decreases hole double-occupancy below hole density 1/3, but increases the same at higher hole densities. Our conclusion is valid for both single-band and three-band extended Hubbard Hamiltonians, and sheds light on concentration-dependent $e_g^\prime$ hole occupancy within the latter.
The apparently counterintuitive carrier concentration-dependent electronic properties of layered cobaltates have attracted wide interest. Here we point out that very similar carrier-concentration dependence has previously been noted in strongly correlated quasi-one dimensional (quasi-1D) organic charge-transfer solids. The normal states of both families can be understood, over the entire range of carrier concentration of interest, within the extended Hubbard Hamiltonian with significant intersite Coulomb interaction. As with the charge-transfer solids, superconductivity in the cobaltates appea…
Within the t-J model, the heat transport of electron-doped cobaltates is studied based on the fermion-spin theory. It is shown that the temperature dependent thermal conductivity is characterized by the low temperature peak located at a finite temperature. The thermal conductivity increases monotonously with increasing temperature at low temperatures T $<$ 0.1$J$, and then decreases with increasing temperature for higher temperatures T $>$ 0.1$J$, in qualitative agreement with experimental result observed from Na$_{x}$CoO$_{2}$ .
Engineered $Na_{0.75}CoO_2$ is considered a prime candidate to achieve high-efficiency thermoelectric systems to regenerate electricity from waste heat. In this work, three elements with outmost electronic configurations, (1) an open d shell (Ni), (2) a closed d shell (Zn), and (3) a half filled f shell (Eu) with maximum unpaired electrons, were selected to outline the dopants' effects on electronic and crystallographic structures of $Na_{0.75}CoO_2$. Systematic $ab$ $initio$ density functional calculations with $DMOL^3$ package showed that the Ni and Zn were more stable when substituting Co w…
Recently the unusual metallic state with a substantially non-uniform distribution of a charge and mag\-ne\-tic density in CoO$_2$ planes was found experimentally in the Na$_x$CoO$_2$ compound with $x>0.6$. We have investigated an origin of such electron disproportionation in the lamellar sodium cobaltates by calculating the ion states as a function of a strength of the electron correlations in the $d$(Co)-shells within the GGA+U approximation for the system with a realistic crystal structure. It was found that the nonuniformity of spin and charge densities are induced by an ordering of the sod…
We present the first angle-resolved photoemission (ARPES) measurement of Fermi Surface in the "misfit" cobaltate [Bi2Ba2O4].[CoO2]~2. This compound contains the same triangular Co planes as Na cobaltates, but in a different 3D environment. Our data establish the similarity of their electronic structure. We propose that the peculiar lineshape of all cobaltates is of the "peak-dip-hump" type, due to strong many-body effects. We detect a progressive transfer of spectral weight from the quasiparticle feature near Ef to a broad hump in misfit phases where Ba is replaced by Sr or Ca. This indicates …
Within the charge-spin separation fermion-spin theory, we have shown that the mechanism of superconductivity in the electron doped cobaltate Na$_{x}$CoO$_{2}\cdot y$H$_{2}$O is ascribed to its kinetic energy. The dressed fermions interact occurring directly through the kinetic energy by exchanging magnetic excitations. This interaction leads to a net attractive force between dressed fermions, then the electron Cooper pairs originating from the dressed fermion pairing state are due to the charge-spin recombination, and their condensation reveals the superconducting ground state. The superconduc…
Electronic structure and oxidation states in high-pressure synthesized isostructural CeCN$_5$ and TbCN$_5$
Linköping University（林雪平大学）；École polytechnique, Institut Polytechnique de Paris（巴黎综合理工学院，巴黎理工学院）；CNRS（法国国家科学研究中心）；Collège de France, Université PSL（法兰西学院，巴黎文理研究大学）
In the quest for materials hosting Kitaev spin liquids, much of the efforts have been focused on the fourth- and fifth-row transition metal compounds, which are spin-orbit coupling assisted Mott insulators. Here, we study the structural and magnetic properties of 3$d$ transition metal oxides, Na$_2$Co$_2$TeO$_6$ and Na$_3$Co$_2$SbO$_6$. The partial occupancy of sodium in former compound is addressed using a cluster expansion, and a honeycomb lattice of sodiums is found to be energetically favored. Starting from the \textit{ab initio} band structures, a many-body second order perturbation theor…
Transition metal oxides are promising candidates for thermoelectric applications, because they are stable at high temperature and because strong electronic correlations can generate large Seebeck coefficients, but their thermoelectric power factors are limited by the low electrical conductivity. We report transport measurements on Ca3Co4O9 films on various perovskite substrates and show that reversible incorporation of oxygen into SrTiO3 and LaAlO3 substrates activates a parallel conduction channel for p-type carriers, greatly enhancing the thermoelectric performance of the film-substrate syst…
We have performed non-resonant x-ray diffraction, resonant soft and hard x-ray magnetic diffraction, soft x-ray absorption and x-ray magnetic circular dichroism measurements to clarify the electronic and magnetic states of the Co3+ ions in GdBaCo2O5.5. Our data are consistent with a 3+ Py Co HS state at the pyramidal sites and a 3+ Oc Co LS state at the octahedral sites. The structural distortion, with a doubling of the a axis (2ap x 2ap x 2ap cell), shows alternating elongations and contractions of the pyramids and indicates that the metal-insulator transition is associated with orbital order…
ARPES is a priori a technique of choice to measure the Fermi velocities vF in metals. In correlated systems, it is interesting to compare this experimental value to that obtained in band structure calculations, as deviations are usually taken as a good indicator of the presence of strong electronic correlations. Nevertheless, it is not always straightforward to extract vF from ARPES spectra. We study here the case of layered cobaltates, an interesting family of correlated metals. We compare the results obtained by standard methods, namely the fit of spectra at constant momentum k (energy distr…
Layered misfit cobaltate [Ca$_2$CoO$_3$]$_{0.62}$[CoO$_2$], which emerged as an important thermoelectric material~[A. C. Masset et al. Phys. Rev. B, 62, 166 (2000)], has been explored extensively in the last decade for the exact mechanism behind its high Seebeck coefficient. Its complex crystal and electronic structures have inhibited consensus among such investigations. This situation has arisen mainly due to difficulties in accurate identification of the chemical state, spin state, and site symmetries in its two subsystems (rocksalt [Ca$_2$CoO$_3$] and triangular [CoO$_2$]). By employing res…
Cobaltates have rich spin-states and diverse properties. Using spin-state pictures and firstprinciples calculations, here we study the electronic structure and magnetism of the mixed-valent double perovskite YBaCo2O6. We find that YBaCo2O6 is in the formal intermediate-spin (IS) Co3+/low-spin (LS) Co4+ ground state. The hopping of eg electron from IS-Co3+ to LS-Co4+ via double exchange gives rise to a ferromagnetic half-metallicity, which well accounts for the recent experiments. The reduction of both magnetization and Curie temperature by oxygen vacancies is discussed, aided with Monte Carlo …
We present a combined experimental and theoretical x-ray absorption spectroscopy (XAS) study of the new class of cobaltates YBaCo4O7 and YBaCo3MO7 (M= Al, Fe). The focus is on the local electronic and magnetic properties of the transition metal ions in these geometrically frustrated kagome compounds. For the mixed valence cobaltate YBaCo4O7, both the Co2+ and Co3+ are found to be in the high spin state. The stability of these high spin states in tetrahedral coordination is compared with those in the more studied case of octahedral coordination. For the new compound YBaCo3FeO7, we find exclusiv…
This paper reviews the current progress on searching the Kitaev spin liquid state in 3d electron systems. Honeycomb cobaltates were recently proposed as promising candidates to realize the Kitaev spin liquid state, due to the more localized wave functions of 3d ions compared with that of 4d and 5d ions, and also the easy tunability of the exchange Hamiltonian in favor of Kitaev interaction. Several key parameters that have large impacts on the exchange constants, such as the charge-transfer gap and the trigonal crystal field, are identified and discussed. Specifically, tuning crystal field eff…
Dimensionality reduction induced metal-insulator transitions in oxide heterostructures are usually coupled with structural and magnetic phase transitions, which complicate the interpretation of the underlying physics. Therefore, achieving isostructural MIT is of great importance for fundamental physics and even more for applications. Here, we report an isostructural metal-insulator transition driven by dimensional-crossover in spin-orbital coupled SrIrO3 films. By using in-situ pulsed laser deposition and angle-resolved photoemission spectroscopy, we synthesized and investigated the electronic…
For describing the first-order isostructural valence phase transition in mixed valence compounds we develop a new approach based on the lattice Anderson model. We take into account the Coulomb interaction between localized f and conduction band electrons and two mechanisms of electron-lattice coupling. One is related to the volume dependence of the hybridization. The other is related to local deformations produced by f- shell size fluctuations accompanying valence fluctuations. The large f -state degeneracy allows us to use the 1/N expansion method. Within the model we develop a mean-field the…
Using a small amount of radioactive 111Cd atoms implanted in cerium lattice to probe the hyperfine electric quadrupole interaction, we have detected a quadrupole electron charge density component in alpha-Ce, which is absent in gamma-Ce. The appearance of the quadrupole density in alpha-Ce predicted by the quadrupole scenario of the phase transition demonstrates that the spacial symmetry is lowered at the gamma->alpha phase transition. This finding makes cerium the first element where the symmetry change is driven exclusively by the valence electron degrees of freedom while the atomic centers …
We study the exchange interactions and resulting magnetic phases in the honeycomb cobaltates. For a broad range of trigonal crystal fields acting on Co2+ ions, the low-energy pseudospin-1/2 Hamiltonian is dominated by bond-dependent Ising couplings that constitute the Kitaev model. The non-Kitaev terms nearly vanish at small values of trigonal field Δ, resulting in spin liquid ground state. Considering Na3Co2SbO6 as an example, we find that this compound is proximate to a Kitaev spin liquid phase, and can be driven into it by slightly reducing Δby \sim 20 meV, e.g., via strain or pressure cont…
We present X-ray spectroscopic evidence for the evolution of valence-specific spin states and tetragonal distortions in single-layer cobaltates. Measurements of Co $L_3$-edge resonant inelastic X-ray scattering reveal the $t_{2g}$ electronic structure of Co for hole-doped La$_{2-x}$Sr$_x$CoO$_4$ ($x$ = 0.5, 0.7 and 0.8). As the Sr-doping $x$ increases, the tetragonal splitting of the $t_{2g}$ states of high-spin Co$^{2+}$ decreases, whereas that of low-spin Co$^{3+}$ increases and the fraction of high-spin Co$^{3+}$ increases. The results enable us to clarify the origin of the change of magnet…
Layered van~der~Waals materials of the family TaTMTe$_4$ (TM=Ir, Rh, Ru) are showing very interesting electronic properties. Here we report the synthesis, crystal growth and structural characterization of TaIrTe$_4$, TaRhTe$_4$, TaIr$_{1-x}$Rh$_{x}$Te$_4$ ($x = 0.06$; 0.14; 0.78; 0.92) and Ta$_{1+x}$Ru$_{1-x}$Te$_4$ single crystals. For Ta$_{1+x}$Ru$_{1-x}$Te$_4$ off-stoichiometry is shown. X-ray powder diffraction confirms that TaRhTe4 is isostructural to TaIrTe4. We show that all these compounds are metallic with diamagnetic behavior. Ta$_{1.26(2)}$Ru$_{0.75(2)}$Te$_{4.000(8)}$ exhibits an u…
Pressure induced isostructural insulator to metal transition for SmS is characterised by the presence of an intermediate valence state at higher pressure which cannot be captured by the density functional theory. As a direct outcome of including the charge and spin fluctuations incorporated in dynamical mean field theory, we see the emergence of insulating and metallic phases with increasing pressure as a function of changing valence. This is accompanied by significantly improved predictions of the equilibrium lattice constants and bulk moduli for all Sm-monochalcogenides verifying experiments…
A polycrystalline sample of YNiGe3, being a non-magnetic isostructural counterpart to the unconventional pressure-induced superconductor CeNiGe3, was studied by means of specific heat and electrical resistivity measurements at temperatures down to 360 mK and in magnetic fields up to 500 Oe. The compound was found to exhibit an ambient-pressure superconductivity below Tc = 0.46 K. The superconducting state in YNiGe3 is destroyed by magnetic field of the order of 500 Oe.
A recently synthesised series of isostructural compounds Ba$_4$NbTM$_3$O$_{12}$ (TM = Mn, Rh and Ir) with transition-metal trimers in a face-sharing geometry makes it possible to examine a tendency to the molecular orbitals (MO) formation going from $3d$ to $5d$ transition metal ions. Our $ab$ $initio$ calculations of electronic and magnetic properties describe the experimental findings and demonstrate gradual transition from the picture of localized electrons for Mn to the MO picture for Rh and especially for Ir. We also show that the often used criterion, according to which the metal-metal d…
Widespread adoption of superconducting technologies requires the discovery of new materials with enhanced properties, especially higher superconducting transition temperatures T$_{c}$. The unexpected discovery of high T$_{c}$ superconductivity in cuprates and in materials as diverse as heavy fermions, organic conductors, and endohedrally-doped fullerenes suggests that the highest T$_{c}$s occur when pressure or doping transform the localized and moment-bearing electrons in antiferromagnetic insulators into itinerant and weakly magnetic metals. The absence of this delocalization transition in F…
We investigate the temperature evolution of the electronic states in the vicinity of the Fermi level of a non-Fermi liquid (NFL) system, CaRuO3 using ultra high-resolution photoemission spectroscopy; isostructural SrRuO3 exhibiting Fermi liquid behavior despite similar electron interaction parameters as that of CaRuO3, is used as a reference. High-energy resolution in this study helps to reveal particle-hole asymmetry in the excitation spectra of CaRuO3 in contrast to that in SrRuO3. In addition, we observe signature of phonon excitations in the photoemission spectra of CaRuO3 at finite temper…
Metal-insulator transition underlies many remarkable and technologically important phenomena in VO2. Even though its monoclinic structure had before been the reserve of the insulating state, recent experiments have observed an unexpected monoclinic metallic state. Here we use a modified approach combining first-principles calculations with orbital-biased potentials to reproduce the correct stability ordering and electronic structure of different phases of VO2. We identify a ferromagnetic monoclinic metal that is likely to be the experimentally observed mysterious metastable state. Furthermore,…
Semimetallic osmium pyrochlore oxide Cd2Os2O7 undergoes a magnetic transition to an all-in-all-out (AIAO)-type order at 227 K, followed by a crossover to an AIAO insulator at around 210 K. Here, we studied the isostructural and isoelectronic compound Hg2Os2O7 through thermodynamic measurements, muSR spectroscopy and neutron diffraction experiments. A similar magnetic transition, probably to an AIAO-type order, was observed at 88 K, while the resistivity showed a decrease at the transition and remained metallic down to 2 K. Thus, the ground state of Hg2Os2O7 is most likely an AIAO semimetal, wh…
We report the structural, vibrational and electrical transport properties up to 16 GPa of the 1T-TiTe2, a prominent layered 2D system, which is predicted to show a series of topologically trivial - nontrivial transitions under hydrostatic compression. We clearly show signatures of two iso-structural transition at 2 GPa and 4 GPa obtained from the minima in c/a ratio concomitant with the phonon linewidth anomalies of Eg and A1g modes at around the same pressures, providing strong indication of unusual electron-phonon coupling associated to these transitions. Resistivity presents nonlinear behav…
Electron Spin Resonance and optical reflectivity measurements demonstrate a metal-insulator transition in Na_2CsC_60 as the system passes from the low temperature simple cubic to the high temperature {\it fcc} structure above 300 K. The non-conducting electronic state is especially unexpected in view of the metallic character of other, apparently isostructural fullerides, like K_3C_60. The occurence of this phase in Na_2CsC_60 suggests that alkali specific effects can not be neglected in the description of the electronic properties of alkali doped fullerides. We discuss the origin of the insul…
