Search

Despite the fruitful achievements in the development of hydrogen production catalysts with record-breaking performances, there is still a lack of durable catalysts that could work under large current densities (> 1000 mA cm− 2). In the context of this need, we investigated the catalytic behaviors of Sr2RuO4 (SRO) bulk single crystals with well-defined surface crystal structures, which is a benchmark material to explore exotic metallic states and electronic structures. This single crystal has demonstrated remarkable activities under the current density of 1000 mA cm− 2, which require overpotentials of 182 and 278 mV in 0.5 M H2SO4 and 1 M KOH electrolytes, respectively, after ohmic correction. These values slightly increased to 272 and 354 mV even without iR correction, exhibiting high potential for industrial-scale hydrogen production. The high performance is also evidenced by the 56 days of continuous testing at a high current density of above 1000 mA cm− 2 and then under operating temperatures of 70 ℃ for alkaline electrolysis. The in-situ formation of ferromagnetic Ru clusters at the crystal surface is critical for the outstanding catalytic activity, endowing the single-crystal catalyst with low charge transfer resistance and high wettability for rapid gas bubble removal. Density functional theory calculations indicate that SRO gains electrons from the Ru clusters, thus leading to the thermodynamically favorable hydrogen desorption for the rapidly modified catalysts. More generally, our experiment exemplifies the potential of designing novel HER catalysts that work under industrial-scale current density.

We report on studies of charge carrier plasmon excitations in Sr2RuO4 by transmission Electron Energy-Loss Spectroscopy. In particular, we present results on the plasmon dispersion and its width as a function of momentum transfer. The dispersion can be qualitatively explained in the framework of RPA calculations, using an unrenormalized tight-binding band structure. The constant long-wavelength width of the plasmon indicates, that it is caused by a decay into inter-band transition and not by quantum critical fluctuations. The results from these studies on a prototypical bad metal system show that the long-wavelength plasmon excitations near 1 eV are caused by resilient quasiparticles and are not influenced by correlation effects., Comment: 6 pages, 3 figures

One of the main developments in unconventional superconductivity in the past two decades has been the discovery that most unconventional superconductors form phase diagrams that also contain other strongly correlated states. Many systems of interest are therefore close to more than one instability, and tuning between the resultant ordered phases is the subject of intense research1. In recent years, uniaxial pressure applied using piezoelectric-based devices has been shown to be a particularly versatile new method of tuning, leading to experiments that have advanced our understanding of the fascinating unconventional superconductor Sr$_2$RuO$_4$. Here we map out its phase diagram using high-precision measurements of the elastocaloric effect in what we believe to be the first such study including both the normal and the superconducting states. We observe a strong entropy quench on entering the superconducting state, in excellent agreement with a model calculation for pairing at the Van Hove point, and obtain a quantitative estimate of the entropy change associated with entry to a magnetic state that is observed in proximity to the superconductivity. The phase diagram is intriguing both for its similarity to those seen in other families of unconventional superconductors and for extra features unique, so far, to Sr$_2$RuO$_4$., Comment: 34 pages, 23 figures, published version, manuscript and supplementary information in one document

One of the main developments in unconventional superconductivity in the past two decades has been the discovery that most unconventional superconductors form phase diagrams that also contain other strongly correlated states. Many systems of interest are therefore close to more than one instability, and tuning between the resultant ordered phases is the subject of intense research

This work is supported by a KAKENHI Grants-in-Aids for Scientific Research (Grant Nos. 17H06136, 18K04715, and 21H01033), and Core-to-Core Program (No. JPJSCCA20170002) from the Japan Society for the Promotion of Science (JSPS) and by a JST-Mirai Program (Grant No. JPMJMI18A3), and by the Max Planck Society. We report the magnetocaloric effect of a bilayered perovskite ruthenate Ca3Ru2O7 that has recently been recognized as an antiferromagnetic polar metal. The magnetic entropy change obtained from temperature dependence of the DC magnetization measurements shows peaks and valleys under the magnetic field near metamagnetic transitions, and enable us to map out a thermodynamic field–temperature phase-diagram. The area surrounded by the boundaries agrees well with a novel “metamagnetic texture” with spin modulation observed recently by small angle neutron scattering measurements. We demonstrate that a thermodynamically equilibrium state is realized between the antiferromagnetic and spin-polarized states throughout the metamagnetic transition in this polar metal. Postprint

CaFeAsF is an iron-based superconductor parent compound whose Fermi surface is quasi-two dimensional, composed of Dirac-electron and Schr\"odinger-hole cylinders elongated along the $c$ axis. We measured the longitudinal and Hall resistivities in CaFeAsF with the electrical current in the $ab$ plane in magnetic fields up to 45 T applied along the $c$ axis and obtained the corresponding conductivities via tensor inversion. We found that both the longitudinal and Hall conductivities approached zero above $\sim$40 T as the temperature was lowered to 0.4 K. Our analysis indicates that the Landau-level filling factor is $\nu$ = 2 for both electrons and holes at these high field strengths, resulting in a total filling factor $\nu$ = $\nu_{hole} - \nu_{electron}$ = 0. We therefore argue that the $\nu$ = 0 quantum Hall state emerges under these conditions., Comment: 18 pages, 1 table, 4 figures

Unambiguous identification of the superconducting order parameter symmetry of Sr$_2$RuO$_4$ has remained elusive for more than a quarter century. While a chiral $p$-wave ground state analogue to superfluid $^3$He-$A$ was ruled out only very recently, other proposed $p$-wave scenarios are still viable. Here, field-dependent $^{17}$O Knight shift measurements are compared to corresponding specific heat measurements, previously reported. We conclude that the shift results can be accounted for by the expected field-induced quasiparticle response only. An upper bound for the condensate magnetic response of $, Main Article: 4 pages 3 figures Supplement: 6 pages 4 figures

There is considerable evidence that the superconducting state of Sr2RuO4 breaks time reversal symmetry. In the experiments showing time reversal symmetry breaking, its onset temperature, TTRSB, is generally found to match the critical temperature, Tc, within resolution. In combination with evidence for even parity, this result has led to consideration of a dxz ± idyz order parameter. The degeneracy of the two components of this order parameter is protected by symmetry, yielding TTRSB = Tc, but it has a hard-to-explain horizontal line node at kz = 0. Therefore, s ± id and d ± ig order parameters are also under consideration. These avoid the horizontal line node, but require tuning to obtain TTRSB ≈ Tc. To obtain evidence distinguishing these two possible scenarios (of symmetry-protected versus accidental degeneracy), we employ zero-field muon spin rotation/relaxation to study pure Sr2RuO4 under hydrostatic pressure, and Sr1.98La0.02RuO4 at zero pressure. Both hydrostatic pressure and La substitution alter Tc without lifting the tetragonal lattice symmetry, so if the degeneracy is symmetry-protected, TTRSB should track changes in Tc, while if it is accidental, these transition temperatures should generally separate. We observe TTRSB to track Tc, supporting the hypothesis of dxz ± idyz order., Nature Communications, 12 (1), ISSN:2041-1723

A key question regarding the unconventional superconductivity of Sr$_2$RuO$_4$ remains whether the order parameter is single- or two-component. Under a hypothesis of two-component superconductivity, uniaxial pressure is expected to lift their degeneracy, resulting in a split transition. The most direct and fundamental probe of a split transition is heat capacity. Here, we report measurement of heat capacity of samples subject to large and highly homogeneous uniaxial pressure. We place an upper limit on the heat-capacity signature of any second transition of a few per cent of that of the primary superconducting transition. The normalized jump in heat capacity, $\Delta C/C$, grows smoothly as a function of uniaxial pressure, favouring order parameters which are allowed to maximize in the same part of the Brillouin zone as the well-studied van Hove singularity. Thanks to the high precision of our measurements, these findings place stringent constraints on theories of the superconductivity of Sr$_2$RuO$_4$., Comment: This manuscript is an extended version of the scientific part of arXiv:1906.07597, which is being split into two separate papers. An extended discussion on the experimental methods can be found at arXiv:2009.03125. It includes supplemental material

This work has been financially supported by the Deutsche Forschungsgemeinschaft (GR 4667/1, GRK 1621 and SFB 1143 projects C02 and C09) and the Max Planck Society. Y.M., T.M. and J.S.B. acknowledge the financial support of JSPS Kakenhi (JP15H5852, JP15K21717 and JP17H06136) and the JSPS Core-to-Core Program. N.K. acknowledges the financial support from JSPS Kakenhi (no. JP18K04715) and JST-Mirai Program (no. JPMJMI18A3). A.N. acknowledges funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement no. 701647. Strontium ruthenate (Sr2RuO4) continues to present an important test of our understanding of unconventional superconductivity, because while its normal-state electronic structure is known with precision, its superconductivity remains unexplained. There is evidence that its order parameter is chiral, but reconciling this with recent observations of the spin part of the pairing requires an order parameter that is either finely tuned or implies a new form of pairing. Therefore, a definitive resolution of whether the superconductivity of Sr2RuO4 is chiral is important for the study of superconductivity. Here we report the measurement of zero-field muon spin relaxation—a probe sensitive to weak magnetism—on samples under uniaxial stresses. We observe stress-induced splitting between the onset temperatures of superconductivity and time-reversal symmetry breaking—consistent with the qualitative expectations for a chiral order parameter—and argue that this observation cannot be explained by conventional magnetism. In addition, we report the appearance of bulk magnetic order under higher uniaxial stress, above the critical pressure at which a Lifshitz transition occurs in Sr2RuO4. Postprint

We report resistance and elastoresistance measurements on $({\mathrm{Ba}}_{0.5}{\mathrm{K}}_{0.5}){\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$, ${\mathrm{CaKFe}}_{4}{\mathrm{As}}_{4}$, and ${\mathrm{KCa}}_{2}{\mathrm{Fe}}_{4}{\mathrm{As}}_{4}{\mathrm{F}}_{2}$. The Fe-site symmetry is ${D}_{2d}$ in the first compound but ${C}_{2v}$ in the latter two, which lifts the degeneracy of the Fe ${d}_{xz}$ and ${d}_{yz}$ orbitals. The temperature dependence of the resistance and elastoresistance is similar between the three compounds. Especially, the [110] elastoresistance is enhanced with decreasing temperature irrespective of the Fe-site symmetry. This appears to be in conflict with recent Raman scattering studies on ${\mathrm{CaKFe}}_{4}{\mathrm{As}}_{4}$, which suggest the absence of nematic fluctuations. We consider possible ways of reconciliation and suggest that the present result is important in elucidating the origin of in-plane resistivity anisotropy in iron-based superconductors.

The interplay between spin–orbit coupling and structural inversion symmetry breaking in solids has generated much interest due to the nontrivial spin and magnetic textures which can result. Such studies are typically focused on systems where large atomic number elements lead to strong spin–orbit coupling, in turn rendering electronic correlations weak. In contrast, here we investigate the temperature-dependent electronic structure of [Formula: see text] , a [Formula: see text] oxide metal for which both correlations and spin–orbit coupling are pronounced and in which octahedral tilts and rotations combine to mediate both global and local inversion symmetry-breaking polar distortions. Our angle-resolved photoemission measurements reveal the destruction of a large hole-like Fermi surface upon cooling through a coupled structural and spin-reorientation transition at 48 K, accompanied by a sudden onset of quasiparticle coherence. We demonstrate how these result from band hybridization mediated by a hidden Rashba-type spin–orbit coupling. This is enabled by the bulk structural distortions and unlocked when the spin reorients perpendicular to the local symmetry-breaking potential at the Ru sites. We argue that the electronic energy gain associated with the band hybridization is actually the key driver for the phase transition, reflecting a delicate interplay between spin–orbit coupling and strong electronic correlations and revealing a route to control magnetic ordering in solids.

The cubic Kondo lattice ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ is one of the heaviest known Fermi liquids. We have measured the low-temperature electrical resistivity $\ensuremath{\rho}(T)$, magnetic susceptibility $\ensuremath{\chi}(T)$, and heat capacity $C(T)$ in single crystals of $\mathrm{Yb}{({\mathrm{Co}}_{1\ensuremath{-}x}{\mathrm{Ni}}_{x})}_{2}{\mathrm{Zn}}_{20}$ ($x\ensuremath{\le}0.126$) and $\mathrm{Yb}{({\mathrm{Co}}_{1\ensuremath{-}x}{\mathrm{Fe}}_{y})}_{2}{\mathrm{Zn}}_{20}$ ($y\ensuremath{\le}0.07$). While pure ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ displays maxima in $\ensuremath{\rho}(T)$ and $\ensuremath{\chi}(T)$, ascribed to an enhanced crystal electric field (CEF) degeneracy, the maxima are suppressed by small amounts ($\ensuremath{\approx}6$ at.%) of substitutions of the Co atoms. This goes along with a suppression of superheavy Fermi liquid behavior as manifested in the divergence of $C/T$. We ascribe the observations to local distortions at the Yb site due to the chemical disorder in the environment, rather than to a chemical pressure effect. This fragileness to the local distortion indicates that superheavy Fermion behavior in ${\mathrm{YbCo}}_{2}{\mathrm{Zn}}_{20}$ is closely linked to an enhanced CEF degeneracy.

Polar distortions in solids give rise to the well-known functionality of switchable macroscopic polarisation in ferroelectrics and, when combined with strong spin-orbit coupling, can mediate giant spin splittings of electronic states. While typically found in insulators, ferroelectric-like distortions can remain robust against increasing itineracy, giving rise to so-called "polar metals". Here, we investigate the temperature-dependent electronic structure of Ca$_3$Ru$_2$O$_7$, a correlated oxide metal in which octahedral tilts and rotations combine to mediate pronounced polar distortions. Our angle-resolved photoemission measurements reveal the destruction of a large hole-like Fermi surface upon cooling through a coupled structural and spin-reorientation transition at 48 K, accompanied by a sudden onset of quasiparticle coherence. We demonstrate how these result from band hybridisation mediated by a hidden Rashba-type spin-orbit coupling. This is enabled by the bulk structural distortions and unlocked when the spin reorients perpendicular to the local symmetry-breaking potential at the Ru sites. We argue that the electronic energy gain associated with the band hybridisation is actually the key driver for the phase transition, reflecting a delicate interplay between spin-orbit coupling and strong electronic correlations, and revealing a new route to control magnetic ordering in solids., Comment: Contains 6+5 pages, including supplementary information

Sr2RuO4 has stood as the leading candidate for a spin-triplet superconductor for 26 years1. However, recent NMR experiments have cast doubt on this candidacy2,3 and it is difficult to find a theory of superconductivity that is consistent with all experiments. The order parameter symmetry for this material therefore remains an open question. Symmetry-based experiments are needed that can rule out broad classes of possible superconducting order parameters. Here, we use resonant ultrasound spectroscopy to measure the entire symmetry-resolved elastic tensor of Sr2RuO4 through the superconducting transition. We observe a thermodynamic discontinuity in the shear elastic modulus c66, which implies that the superconducting order parameter has two components. A two-component p-wave order parameter, such as px + ipy, naturally satisfies this requirement. As this order parameter appears to have been precluded by recent NMR experiments, we suggest that two other two-component order parameters, namely $$\{{d}_{xz},{d}_{yz}\}$$ and $$\{{d}_{{x}^{2}-{y}^{2}},{g}_{xy({x}^{2}-{y}^{2})}\}$$ , are now the prime candidates for the order parameter of Sr2RuO4. Ultrasound measurements show that the superconducting order parameter in strontium ruthenate must have two components.

We report the magnetocaloric effect of the Tsai-type 1/1 quasicrystal approximants Au64Al22R14 (R = Gd, Tb, and Dy) with the space group of Im 3 . These approximants with the electron-per-atom (e/a) ratio of 1.72 exhibit a ferromagnetic transition in bulk at the Curie temperatures of 27, 15, and 9.5 K for R = Gd, Tb, and Dy, respectively, as confirmed by both magnetic susceptibility and specific heat measurements. The magnetic entropy change (ΔSM) of the materials for a field change of 7 T are 6.3, 4.4, and 4.8 J/K mol-R for R = Gd, Tb, and Dy, respectively. Other parameters related to the magnetocaloric effect, the adiabatic temperature change (ΔTad) and the relative cooling power (RCP) are also evaluated. We also discuss the obtained magnetocaloric effect of the approximants with relation to the recently reported unique magnetic order formed on the icosahedral clusters, a building unit of the Tsai-type 1/1 quasicrystal approximants.

The authors would like to acknowledge the financial support from the Max-Planck Society. E.H. and M.N. acknowledge support from Deutsche Forschungsgemeinschaft (DFG) through the Project No. 107745057 (TRR80: From Electronic Correlations to Functionality). This work is also supported by JSPS KAKENHI (No. 18K04715). A portion of this work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreements No. DMR-1157490 and No. DMR-1644779 and the State of Florida. The delafossite series of layered oxides includes some of the highest conductivity metals ever discovered. Of these, PtCoO2, with a room-temperature resistivity of 1.8 μΩcm for in-plane transport, is the most conducting of all. The high conduction takes place in triangular lattice Pt layers, separated by layers of Co-O octahedra, and the electronic structure is determined by the interplay of the two types of layers. We present a detailed study of quantum oscillations in PtCoO2, at temperatures down to 35 mK and magnetic fields up to 30 T. As for PdCoO2 and PdRhO2, the Fermi surface consists of a single cylinder with mainly Pt character and an effective mass close to the free-electron value. Due to Fermi-surface warping, two close-lying high frequencies are observed. Additionally, a pronounced difference frequency appears. By analyzing the detailed angular dependence of the quantum-oscillation frequencies, we establish the warping parameters of the Fermi surface. We compare these results to the predictions of first-principles electronic-structure calculations including spin-orbit coupling on Pt and Co and on-site correlation U on Co, and hence demonstrate that electronic correlations in the Co-O layers play an important role in determining characteristic features of the electronic structure of PtCoO2. Publisher PDF

Phases of matter are usually identified through spontaneous symmetry breaking, especially regarding unconventional superconductivity and the interactions from which it originates. In that context, the superconducting state of the quasi-two-dimensional and strongly correlated perovskite Sr2RuO4 is considered to be the only solid-state analogue to the superfluid 3He-A phase1,2, with an odd-parity order parameter that is unidirectional in spin space for all electron momenta and breaks time-reversal symmetry. This characterization was recently called into question by a search for an expected ‘split’ transition in a Sr2RuO4 crystal under in-plane uniaxial pressure, which failed to find any such evidence; instead, a dramatic rise and a peak in a single-transition temperature were observed3,4. Here we use nuclear magnetic resonance (NMR) spectroscopy of oxygen-17, which is directly sensitive to the order parameter via hyperfine coupling to the electronic spin degrees of freedom, to probe the nature of superconductivity in Sr2RuO4 and its evolution under strain. A reduction of the Knight shift is observed for all strain values and at temperatures below the critical temperature, consistent with a drop in spin polarization in the superconducting state. In unstrained samples, our results contradict a body of previous NMR work reporting no change in the Knight shift5 and the most prevalent theoretical interpretation of the order parameter as a chiral p-wave state. Sr2RuO4 is an extremely clean layered perovskite and its superconductivity emerges from a strongly correlated Fermi liquid, and our work imposes tight constraints on the order parameter symmetry of this archetypal system. Postprint

This work was supported in part by the Laboratory Directed Research and Development (LDRD) program of Los Alamos National Laboratory under Project No. 20170204ER. Y. L. acknowledges partial support through the LDRD and 1000 Youth Talents Plan of China. N. K. acknowledges the support from JSPS KAKNHI (Grant No. 18K04715). I. I.M. is supported by ONR through the NRL basic research program. This work is supported in part by the National Science Foundation (Grants No. DMR-1410343 and No. DMR-1709304).

Nonequilibrium steady state conditions induced by a dc current can alter the physical properties of strongly correlated electron systems. In this regard, it was recently shown that dc current can trigger novel electronic states, such as current-induced diamagnetism, which cannot be realized in equilibrium conditions. However, reversible control of diamagnetism has not been achieved yet. Here, we demonstrate reversible in situ control between a Mott insulating state and a diamagnetic semimetal-like state by a dc current in the Ti-substituted bilayer ruthenate ${\mathrm{Ca}}_{3}({\mathrm{Ru}}_{1\ensuremath{-}x}{\mathrm{Ti}}_{x}{)}_{2}{\mathrm{O}}_{7}$ ($x=0.5%$). By performing simultaneous magnetic and resistive measurements, we map out the temperature vs current-density phase diagram in the nonequilibrium steady state of this material. The present results open up the possibility of creating novel electronic states in a variety of strongly correlated electron systems under dc current.

We perform de Haas-van Alphen measurements and quasiparticle self-consistent \textit{GW} (QS\textit{GW}) calculations on FeS. The calculated Fermi surface (FS) consists of two hole and two electron cylinders. We observe all the eight predicted FS cross sections experimentally. With momentum-independent band-energy adjustments of less than 0.1 eV, the maximum deviation between the calculated and observed cross sections is less than 0.2\% of the Brillouin zone area for $B \parallel c$. The carrier density is $\sim$0.5 carriers/Fe. The mass enhancements are nearly uniform across the FS cylinders and moderate, $\sim$2. The absence of a third hole cylinder with $d_{xy}$ character is favorable for the formation of a nodal superconducting gap., 7 pages, 3 figures

Pressure represents a clean tuning parameter for traversing the complex phase diagrams of interacting electron systems, and as such has proved of key importance in the study of quantum materials. Application of controlled uniaxial pressure has recently been shown to more than double the transition temperature of the unconventional superconductor Sr2RuO4, leading to a pronounced peak in Tc versus strain whose origin is still under active debate. Here we develop a simple and compact method to passively apply large uniaxial pressures in restricted sample environments, and utilise this to study the evolution of the electronic structure of Sr2RuO4 using angle-resolved photoemission. We directly visualise how uniaxial stress drives a Lifshitz transition of the γ-band Fermi surface, pointing to the key role of strain-tuning its associated van Hove singularity to the Fermi level in mediating the peak in Tc. Our measurements provide stringent constraints for theoretical models of the strain-tuned electronic structure evolution of Sr2RuO4. More generally, our experimental approach opens the door to future studies of strain-tuned phase transitions not only using photoemission but also other experimental techniques where large pressure cells or piezoelectric-based devices may be difficult to implement.

We report magnetic torque measurements on iron-pnictide superconductors ${\mathrm{Ba}}_{1\ensuremath{-}x}{\mathrm{K}}_{x}{\mathrm{Fe}}_{2}{\mathrm{As}}_{2}$ ($x\ensuremath{\approx}$ 0.69 and 0.76) to an applied field of ${B}_{a}=45$ T. The peak effect is observed in torque-vs-field curves below the irreversibility field. It is enhanced and becomes asymmetric as the field is tilted from the $c$ axis. For field directions close to the $ab$ plane, increasing- and decreasing-field curves peak at markedly different fields and exhibit a sharp jump, suggestive of a first-order phase transition, on the high- and the low-field sides of the peak, respectively. Complicated history dependence of the torque is observed in the peak-effect region. We construct and discuss the temperature-- ($T$) applied-magnetic-field (${B}_{a}$) phase diagram. Since the upper critical field for the $ab$-plane direction is comparable to the Pauli limit, we also consider possible influence of the spin paramagnetic effect on the anomalous peak effect.

Nonequilibrium steady state conditions induced by a dc current can alter the physical properties of strongly correlated electron systems. In this regard, it was recently shown that dc current can trigger novel electronic states, such as current-induced diamagnetism, which cannot be realized in equilibrium conditions. However, reversible control of diamagnetism has not been achieved yet. Here, we demonstrate reversible in situ control between a Mott insulating state and a diamagnetic semimetal-like state by a dc current in the Ti-substituted bilayer ruthenate Ca_{3}(Ru_{1-x}Ti_{x})_{2}O_{7} (x=0.5%). By performing simultaneous magnetic and resistive measurements, we map out the temperature vs current-density phase diagram in the nonequilibrium steady state of this material. The present results open up the possibility of creating novel electronic states in a variety of strongly correlated electron systems under dc current.

To investigate the electronic state of CeRu2Al10, which exhibits an unusual antiferromagnetic order below TN = 27 K, we measured the electrical resistivity ρ, the transverse magnetoresistance (TMR)...

Magnetic properties of an Yb-based semiconductor YbCuS2 with a zigzag chain of Yb3+ ions were studied. The Curie–Weiss behavior of the magnetic susceptibility χ(T) indicates antiferromagnetic inter...