We report on susceptibility measurements in the strongly correlated layered cobalt oxide [BiBa0.66K0.36O2]CoO2, which demonstrate the existence of a magnetic quantum critical point (QCP) governing the electronic properties. The investigated low frequency susceptibility displays a scaling behavior with both the temperature T and the magnetic field B ranging from the high-T non-Fermi liquid down to the low-T Fermi liquid. Whereas the inferred scaling form can be discussed within the standard framework of the quantum critical phenomena, the determined critical exponents suggest an unconventional magnetic QCP of a potentially generic type. Accordingly, these quantum critical fluctuations account for the anomalous logarithmic temperature dependence of the thermopower. This result allows us to conjecture that quantum criticality can be an efficient source of enhanced thermopower.
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…
Two different kinds of metal transition oxides have been studied for their large thermopower values. The first one corresponds to the Tl-based misfit cobaltite which is a hole-doped metal. We demonstrate that the partial Bi-substitution for Tl in this phase induces an increase of the room temperature (RT) thermopower (TEP) value. Same result is obtained with the new Pb_{1/3}SrCoO_{3+delta} misfit corresponding to the Tl complete replacement by lead. Simultaneously, the T dependence of their resistivity exhibits a re-entrance below 70-90K where a large negative magnetoresistance is observed. Ma…
We report the measurements of thermopower, electrical resistivity and thermal conductivity in a complex cobalt oxide Li$_{0.48}$Na$_{0.35}$CoO$_{2}$, whose crystal structure can be viewed as an intergrowth of the O3 phase of Li$_{x}$CoO$_{2}$ and the P2 phase of Na$_{y}$CoO$_{2}$ along the c axis. The compound shows large room-temperature thermopower of $\sim$180 $μ$V/K, which is substantially higher than those of Li$_{x}$CoO$_{2}$ and Na$_{y}$CoO$_{2}$. The figure of merit for the polycrystalline sample increases rapidly with increasing temperature, and it achieves nearly 10$^{-4}$ K$^{-1}$ a…
We investigate the low temperature magnetic field dependence of the resistivity in the thermoelectric misfit cobalt oxide [Bi1.7Ca2O4]0.59CoO2 from 60 K down to 3 K. The scaling of the negative magnetoresistance demonstrates a spin dependent transport mechanism due to a strong Hund's coupling. The inferred microscopic description implies dual electronic states which explain the coexistence between localized and itinerant electrons both contributing to the thermopower. By shedding a new light on the electronic states which lead to a high thermopower, this result likely provides a new potential …
We investigate both thermoelectric and thermodynamic properties of the misfit cobalt oxide [Bi$_{1.7}$Co$_{0.3}$Ca$_{2}$O$_{4}$]$^{RS}_{0.6}$CoO$_{2}$. A large negative magnetothermopower is found to scale with both magnetic field and temperature revealing a significant spin entropy contribution to thermoelectric properties giving rise to a constant S$_0\approx$ 60 $μ$V K$^{-1}$ equal to the high temperature asymptotic value of the spin 1/2 entropy. Low temperature specific heat measurements allow us to determine an enhanced electronic part with $γ\approx$ 50 mJ (mol K$^{2}$)$^{-1}$ attesting …
We present a series of arguments showing that the Seebeck coefficient can be used as a decisive experiment to characterize the nature of the quantum critical point (QCP) in heavy fermion compounds. Being reactive almost exclusively to the presence of delocalized entropic carriers, the Seebeck coefficient shows a drastic collapse at the Kondo breakdown QCP, as the reconstruction of the Fermi surface takes place. In contrast, around a Spin Density Wave (SDW) QCP, the Seebeck coefficient is broadly symmetric. We discuss the possibility of a change of sign at the QCP, the characteristic variation …
In high Tc superconductors a wide ranging connection between the doping dependence of the transition temperature Tc and the room temperature thermopower Q has been observed. A "universal correlation" between these two quantities exists with the thermopower vanishing at optimum doping as noted by OCTHH (Obertelli, Cooper, Tallon, Honma and Hor). In this work we provide an interpretation of this OCTHH universality in terms of a possible underlying quantum critical point (QCP) at Tc. Central to our viewpoint is the recently noted Kelvin formula relating the thermopower to the density derivative o…
Dependence of transport coefficients of the Yb(Rh$_{1-x}$Co$_x$)$_2$Si$_2$ series of alloys on temperature and cobalt concentration is explained by an asymmetric Anderson model which takes into account the exchange scattering of conduction electrons on ytterbium ions and the splitting of 4$f$-states by the crystalline electric field (CEF). The substitution of rhodium by cobalt is described as an increase of chemical pressure which reduces the exchange coupling and the CEF splitting. The scaling analysis and numerical NCA solution of the model show that the effective degeneracy of the 4$f$-stat…
We investigated the effect of pressure on the magnetic and thermoelectric properties of Sr$_{3.1}$Y$_{0.9}$Co$_{4}$O$_{10+δ}$. The magnetization is reduced with the application of pressure, reflecting the spin-state modification of the Co$^{3+}$ ions into the nonmagnetic low-spin state. Accordingly, with increasing pressure, the Seebeck coefficient is enhanced, especially at low temperatures, at which the effect of pressure on the spin state becomes significant. These results indicate that the spin-orbital entropy is a key valuable for the thermoelectric properties of the strongly correlated c…
We reveal and explain a scaling behavior of the thermopower $S/T$ exhibiting by the archetypical heavy-fermion (HF) metal $\rm{YbRh_2Si_2}$ under the application of magnetic field $B$ at temperatures $T$. We show that the same scaling is demonstrated by such different HF compounds as $β$-${\rm YbAlB_4}$ and the strongly correlated layered cobalt oxide $\rm [BiBa_{0.66}K_{0.36}O_{2}]CoO_{2}$. Using $\rm{YbRh_2Si_2}$ as an example, we demonstrate that the scaling behavior of $S/T$ is violated at the antiferromagnetic phase transition, while both the residual resistivity $ρ_0$ and the density of …
We present a comparative study of CoO2 layers in the Bi-misfit and NaxCoO2 cobaltates. Co NMR measures the intrinsic susceptibility of the Co layers and is not affected by spurious contributions. At low dopings where room-temperature thermopower (TEP) is large, Curie-Weiss susceptibilities are observed in both materials. But NMR and muSR experiments find neither charge nor spin order down to low temperatures in Bi-misfit, in contrast to the case of NaxCoO2. This demonstrates that metallicity, charge and magnetic orders are specific of the Na layers in NaxCoO2 whereas strong correlations are ge…
The sodium cobaltate system Na$_{x}$CoO$_2$ is a prominent representant of strongly correlated materials with promising thermoelectric response. In a combined theoretical and experimental study we show that by doping the Co site of the compound at $x$=0.7 with iron, a further increase of the Seebeck coefficient is achieved. The Fe defects give rise to effective hole doping in the high-thermopower region of larger sodium content $x$. Originally filled hole pockets in the angular-resolved spectral function of the Fe-free material shift to low energy when introducing Fe, leading to a multi-sheet …
We report infrared spectroscopic properties of the strongly correlated layered cobalt oxide [BiBa$_{0.66}$K$_{0.36}$O$_2$]CoO$_2$. These measurements performed on single crystals allow us to determine the optical conductivity as a function of temperature. In addition to a large temperature dependent transfer of spectral weight, an unconventional low energy mode is found. We show that both its frequency and damping scale as the temperature itself. In fact, a basic analysis demonstrates that this mode fully scales onto a function of $ω$/T up to room temperature. This behavior suggests low energy…
Using muon spin spectroscopy we have found that, for both Na$_x$CoO$_2$ (0.6 $\leq x \leq$ 0.9) and 3- and 4-layer cobaltites, a common low temperature magnetic state (which in some cases is manifest as an incommensurate spin density wave) forms in the CoO$_2$ planes. Here we summarize those results and report a dome-shaped relation between the transition temperature into the low-$T$ magnetic state and the composition $x$ for Na$_x$CoO$_2$ and/or the high-temperature asymptotic limit of thermopower in the more complex 3- and 4-layer cobaltites. This behavior is explained using the Hubbard mode…
We report the Nernst effect (v) and thermoelectric power (S) data for the Ce2PdIn8 heavy-fermion compound. Both S and v behave anomalously at low temperatures: the thermopower shows a Kondo-like maximum at T = 37 K, while the Nernst coefficient becomes greatly enhanced and field dependent below T ~ 30 K. In the zero-T limit S/T and v/T diverge logarithmically, what is related to occurrence of the quantum critical point (QCP). Presented results suggest that the antiferromagnetic spin-density-wave scenario may be applicable to QCP in Ce2PdIn8.
We investigated size effects on thermoelectricity in thin films of a strongly correlated layered cobaltate. At room temperature, the thermopower is independent of thickness down to 6 nm. This unusual behavior is inconsistent with the Fuchs-Sondheimer theory, which is used to describe conventional metals and semiconductors, and is attributed to the strong electron correlations in this material. Although the resistivity increases, as expected, below a critical thickness of $\sim$ 30 nm. The temperature dependent thermopower is similar for different thicknesses but resistivity shows systematic ch…
The search for semiconductors with high thermoelectric figure of merit has been greatly aided by theoretical modeling of electron and phonon transport, both in bulk materials and in nanocomposites. Recent experiments have studied thermoelectric transport in ``strongly correlated'' materials derived by doping Mott insulators, whose insulating behavior without doping results from electron-electron repulsion, rather than from band structure as in semiconductors. Here a unified theory of electrical and thermal transport in the atomic and ``Heikes'' limit is applied to understand recent transport e…
Dilation and thermopower measurements on YbAgGe, a heavy-fermion antiferromagnet, clarify and refine the magnetic field-temperature (H-T) phase diagram and reveal a field-induced phase with T-linear resistivity. On the low-H side of this phase we find evidence for a first-order transition and suggest that YbAgGe at 4.5 T may be close to a quantum critical end point. On the high-H side our results are consistent with a second-order transition suppressed to a quantum critical point near 7.2 T. We discuss these results in light of global phase diagrams proposed for Kondo lattice systems.
Research on the oxide perovskites has uncovered electronic properties that are strikingly enhanced compared with those in conventional metals. Examples are the high critical temperatures of the cuprate superconductors and the colossal magnetoresistance in the manganites. The conducting layered cobaltate $\rm Na_xCoO_2$ displays several interesting electronic phases as $x$ is varied including water-induced superconductivity and an insulating state that is destroyed by field. Initial measurements showed that, in the as-grown composition, $\rm Na_xCoO_2$ displays moderately large thermopower $S$ …
Resistivity under magnetic field, thermopower and Hall coefficient are systematically studied for [Bi$_2$Ba$_{1.3}$K$_{0.6}$Co$_{0.1}$]$^{RS}$[CoO$_2$]$_{1.97}$ single crystal. In-plane resistivity ($ρ_{ab}$(T)) shows metallic behavior down to 2 K with a $T^2$ dependence below 30 K; while out-of-plane resistivity ($ρ_{c}(T)$) shows metallic behavior at high temperature and a thermal activation semiconducting behavior below about 12 K. Striking feature is that magnetic field induces a ln(1/$T$) diverging behavior in both $ρ_{ab}$ and $ρ_{c}(T)$ at low temperature. The positive magnetoresistance…
Quasi-two dimensional itinerant fermions in the Anti-Ferro-Magnetic (AFM) quantum-critical region of their phase diagram, such as in the Fe-based superconductors or in some of the heavy-fermion compounds, exhibit a resistivity varying linearly with temperature and a contribution to specific heat or thermopower proportional to $T \ln T$. It is shown here that a generic model of itinerant AFM can be canonically transformed such that its critical fluctuations around the AFM-vector $Q$ can be obtained from the fluctuations in the long wave-length limit of a dissipative quantum XY model. The fluctu…
We have performed both in-plane resistivity, Hall effect and specific heat measurements on the thermoelectric cobalt oxide Ca$_{3}$Co$_{4}$O$_{9}$. Four distinct transport regimes are found as a function of temperature, corresponding to a low temperature insulating one up to $T_{min}\approx $63 K, a strongly correlated Fermi liquid up to $T^*\approx $140 K, with $ρ=ρ_0+AT^2$ and $A\approx 3.63$ $10^{-2} μΩcm/K^{2}$, followed by an incoherent metal with $k_Fl\leq 1$ and a high temperature insulator above T$^{**}\approx $510 K . Specific heat Sommerfeld coefficient $γ= 93$ mJ/(mol.K$^{2}$) confi…
We study the effect of hole-doping and chemical pressure (isovalent doping) in single crystals of K$_x$Eu$_{1-x}$Fe$_2$As$_2$ and EuFe$_2$(As$_{1-y}$P$_y$)$_2$, respectively, by measurements of the thermopower, $S(T)$, and electrical resistivity, $ρ(T)$. The evolution of $S(T)$ upon doping indicates drastic changes of the electronic configuration at critical values $x_{\mathrm{cr}}=0.3$ and $y_{\mathrm{cr}}=0.21$, respectively, as the spin-density-wave transition is completely suppressed and superconductivity (SC) emerges. For the case of chemical pressure, the comparison with published ARPES …
The layered cobaltite [Ca$_2$CoO$_3$]$_{0.62}$[CoO$_2$], often expressed as the approximate formula Ca$_3$Co$_4$O$_9$, is a promising candidate for efficient oxide thermoelectrics but an origin of its unusual thermoelectric transport is still in debate. Here we investigate \textit{in-plane} anisotropy of the transport properties in a broad temperature range to examine the detailed conduction mechanism. The in-plane anisotropy between $a$ and $b$ axes is clearly observed both in the resistivity and the thermopower, which is qualitatively understood with a simple band structure of the triangular…
We study the electrical resistivity in the quantum Griffiths phase associated with the antiferromagnetic quantum phase transition in a metal. The resistivity is calculated by means of the semi-classical Boltzmann equation. We show that the scattering of electrons by locally ordered rare regions leads to a singular temperature dependence. The rare-region contribution to the resistivity varies as $T^λ$ with temperature $T,$ where the $λ$ is the usual Griffiths exponent which takes the value zero at the critical point and increases with distance from criticality. We find similar singular contribu…
A quantum critical point (QCP), separating the non-Fermi liquid region from the Fermi liquid, exists in the phase diagram of the 2D Hubbard model [Vidhyadhiraja et. al, Phys. Rev. Lett. 102, 206407 (2009)]. Due to the vanishing of the critical temperature associated with a phase separation transition, the QCP is characterized by a vanishing quasiparticle weight. Near the QCP, the pairing is enhanced since the real part of the bare d-wave p-p susceptibility exhibits algebraic divergence with decreasing temperature, replacing the logarithmic divergence found in a Fermi liquid [Yang et. al, Phys.…
The Sachdev-Ye-Kitaev (SYK) model describes electrons with random and all-to-all interactions, and realizes a many-body state without quasiparticle excitations, and a non-vanishing extensive entropy $S_0$ in the zero temperature limit. Its low energy theory coincides the low energy theory of the near-extremal charged black holes with Bekenstein-Hawking entropy $S_0$. Several mesoscopic experimental configurations realizing SYK quantum dynamics over a significant intermediate temperature scale have been proposed. We investigate quantum thermoelectric transport in such configurations, and descri…
Ruthenates provide comprehensive platform to study a plethora of novel properties, such as quantum magnetism, superconductivity and magnetic fluctuation mediated metal-insulator transition. In this article, we provide an overview of quantum mechanical phenomenology in calcium ruthenium oxide with varying compositions. While the stochiometric composition of CaRuO$_{3}$ exhibits non-Fermi liquid behavior with quasi-criticality, chemically doped compounds depict prominent signatures of quantum magnetic fluctuations at low temperature that in some cases are argued to mediate in metal-insulator tra…
Searching for high-performance thermoelectric (TE) materials in the paradigm of narrow-bandgap semiconductors has lasted for nearly 70 years and is obviously hampered by a bottleneck of research now. Here we report on the discovery of a few metallic compounds, TiFexCu2x-1Sb and TiFe1.33Sb, showing the thermopower exceeding many TE semiconductors and the dimensionless figure of merits comparable with the state-of-the-art TE materials. A quasi-linear temperature (T) dependence of electrical resistivity in 2 K - 700 K and the logarithmic T-dependent electronic specific heat at low temperature are…
