The 5d pyrochlore oxide superconductor Cd2Re2O7 (CRO) has attracted significant interest as a spin-orbit-coupled metal (SOCM) that spontaneously undergoes a phase transition to an odd-parity multipole phase by breaking the spatial inversion symmetry due to the Fermi liquid instability caused by strong spin-orbit coupling. Despite the significance of structural information during the transition, previous experimental results regarding lattice deformation have been elusive. We have conducted ultra-high resolution synchrotron radiation x-ray diffraction experiments on a high-quality CRO single crystal. The temperature-dependent splitting of the 0 0 16 and 0 0 14 reflections, which are allowed and forbidden, respectively, in the high-temperature cubic phase I (space group Fd-3m), has been clearly observed and reveals the following significant facts: inversion symmetry breaking and tetragonal distortion occur simultaneously at Ts1 = 201.5(1) K; the previously believed first-order transition between phase II (I-4m2) and phase III (I4122) at Ts2 ~ 120 K consists of two close second-order transitions at Ts2 = 115.4(1) K and Ts3 ~ 100 K; there is a new orthorhombic phase XI (F222) in between. The order parameters (OPs) of these continuous transitions are uniquely represented by a two-dimensional irreducible representation Eu of the Oh point group, and the OPs of phase XI are a linear combination of those of phases II and III. Each phase is believed to correspond to a distinct odd-parity multipole order, and the complex successive transitions observed may be the result of an electronic phase transition that resolves the Fermi liquid instability in the SOCM.
The 31P-NMR (nuclear magnetic resonance) measurements of the filled skutterudite SmRu4P12 have been carried out in several applied magnetic fields. The line width of the 31P-NMR spectrum rapidly increases below the metal-insulator transition temperature TMI, which indicates the appearance of an internal field below the temperature. Though no distinct anomaly was observed below TMI in low fields, a complicated structure was observed between the Neel temperature TN and TMI (TN < TMI) above 70 kOe. The spin-lattice relaxation rate 1/T1 is almost independent of temperature above TMI, and rapidly d…
We report thermoelectric measurements of the low carrier heavy fermion compound URu2Si2 at high fields up to 34T and at low temperatures down to 500mK. The field dependence of the thermoelectric power (TEP) and the Nernst signal shows successive anomalies deep inside the hidden order (HO) phase. The field position of these anomalies correspond to different changes in the Shubnikov-de Haas frequencies and effective masses around 12 T, 17 T, 23 T and 30 T. These results indicate successive reconstructions of the Fermi surface, which imply electronic phase transitions well within the HO phase.
The crystal and magnetic structures of the spinel compounds ZnCr$_2$S$_4$ and ZnCr$_2$Se$_4$ were investigated by high resolution powder synchrotron and neutron diffraction. ZnCr$_2$Se$_4$ exhibits a first order phase transition at $T_N=21$ K into an incommensurate helical magnetic structure. Magnetic fluctuations above $T_N$ are coupled to the crystal lattice as manifested by negative thermal expansion. Both, the complex magnetic structure and the anomalous structural behavior can be related to magnetic frustration. Application of an external magnetic field shifts the ordering temperature and…
A synchrotron x-ray diffraction study of the crystallographic structure of PrO2 in the Jahn-Teller distorted phase is reported. The distortion of the oxygen sublattice, which was previously ambiguous, is shown to be a chiral structure in which neighbouring oxygen chains have opposite chiralities. A temperature dependent study of the magnetic excitation spectrum, probed by neutron inelastic scattering, is also reported. Changes in the energies and relative intensities of the crystal field transitions provide an insight into the interplay between the static and dynamic Jahn-Teller effects.
In this sturdy, we determine the roles of two successive phase transitions in the new spin-Peierls system TiOBr by electron and synchrotron X-ray diffraction analyses. Results show an incommensurate superstructure along the h- and k-directions between Tc1=27K and Tc2=47K, and a twofold superstructure which is related to a spin-Peierls lattice distortion below Tc1. The diffuse scattering observed above Tc2 indicates that a structural correlation develops at a high temperature. We conclude that Tc2 is a second-order lock-in temperature, which is related to the spin-Peierls lattice distortion wit…
The 5d-transition metal pyrochlore oxide Cd2Re2O7, which was recently suggested to be a prototype of the spin-orbit-coupled metal [Phys. Rev. Lett. 115, 026401 (2015)], exhibits an inversion-symmetry breaking (ISB) transition at 200 K and a subsequent superconductivity below 1 K at ambient pressure. We study the crystal structure at high pressures up to 5 GPa by means of synchrotron X-ray powder diffraction. A rich structural phase diagram is obtained, which contains at least seven phases and is almost consistent with the electronic phase diagram determined by previous resistivity measurements…
The University of Tokyo（东京大学）；Nagoya University（名古屋大学）；Japan Synchrotron Radiation Research Institute (JASRI)（日本同步辐射研究所）；RIKEN Center for Emergent Matter Science (CEMS)（理化学研究所 新兴物质科学中心）
We report the optimized conditions for growing the high quality single crystals of candidate quantum spin-ice Pr2Hf2O7 using the optical floating-zone method. Large single crystals of Pr2Hf2O7 have been grown under different growth conditions using a four-mirror type optical floating-zone furnace and their microscopic structural differences have been probed by high-resolution synchrotron x-ray diffraction (SXRD). The SXRD data reveal that the crystals grown under fowing argon (~ 2 L/h) atmosphere with slightly off-stoichiometric (optimized) starting composition yields the highest quality cryst…
Synchrotron X-ray diffraction patterns were measured and analyzed for a polycrystalline sample of the room-temperature ferromagnet Sr3.12Er0.88Co4O10.5 from 300 to 650 K, from which two structural phase transitions were found to occur successively. The higher-temperature transition at 509 K is driven by ordering of the oxygen vacancies, which is closely related to the metallic state at high temperatures. The lower-temperature transition at 360 K is of first order, at which the ferromagnetic state suddenly appears with exhibiting a jump in magnetization and resistivity. Based on the refined str…
Real-space determination of orbital states driving successive phase transitions in FeV2O4
The University of Tokyo（东京大学）；Institute for Materials Research (IMR), Tohoku University（东北大学物质材料研究所）；International Quantum Materials Center (Q²), Advanced Institute for Materials Research (WPI-AIMR), Tohoku University（东北大学量子材料国际中心（WPI-AIMR））；Japan Synchrotron Radiation Research Institute (JASRI), SPring-8（日本同步辐射研究所（SPring-8））；Department of Physics, Tohoku University（东北大学物理学系）；Department of Physics, Okayama University（冈山大学物理学系）；Department of Applied Physics and Physico-Informatics, Keio University（庆应义塾大学应用物理与物理信息学系）；RIKEN Center for Emergent Matter Science (CEMS)（理化学研究所涌现物质科学中心）；Nagoya Industrial Science Research Institute（名古屋市工业科学研究所以）
The ground state of the spin-Peierls system TiOCl was probed using synchrotron x-ray diffraction on a single-crystal sample at T = 6 K. We tracked the evolution of the structural superlattice peaks associated with the dimerized ground state as a function of pressure. The dimerization along the b axis is rapidly suppressed in the vicinity of a first-order structural phase transition at Pc = 13.1(1) GPa. The high-pressure phase is characterized by an incommensurate charge density wave perpendicular to the original spin chain direction. These results show that the electronic ground state undergoe…
DyB4 has a two-dimensional Shastry-Sutherland (Sh-S) lattice with strong Ising character of the Dy ions. Despite the intrinsic frustrations, surprisingly, it undergoes two successive transitions: a magnetic ordering at TN = 20K, and a quadrupole ordering at TQ=12.5 K. From high-resolution neutron and synchrotron X-ray powder diffraction studies, we have obtained full structural information on this material in all phases, and demonstrate that structural modifications occurring at quadrupolar transition lead to the lifting of frustrations inherent in the Sh-S model. Our study thus provides a com…
In electronic solids with strong spin-orbit interactions (SOIs), the spin and orbital degrees of freedom of an electron are quantum mechanically entangled, which may result in an exotic multipolar order instead of a conventional dipolar order such as a magnetic order. Such a higher-degree order is called "hidden order" because of difficulties in experimental detection. Moreover, the number of candidate compounds is limited, especially rare in d electron systems, in which an interplay between SOIs and Coulomb interactions is expected to cause rich physics. Here, we employ state-of-the-art synch…
We report a comprehensive experimental and theoretical study of the quasi-one-dimensional quantum magnet CuNCN. Based on magnetization measurements above room temperature as well as muon spin rotation and electron spin resonance measurements, we unequivocally establish the localized Cu+2-based magnetism and the magnetic transition around 70 K, both controversially discussed in the previous literature. Thermodynamic data conform to the uniform-spin-chain model with a nearest-neighbor intrachain coupling of about 2300 K, in remarkable agreement with the microscopic magnetic model based on densit…
Through powder x-ray diffraction we have investigated the structural behavior of SmVO3, in which orbital and magnetic degrees of freedom are believed to be closely coupled to the crystal lattice. We have found, contrary to previous reports, that SmVO3 exists in a single, monoclinic, phase below 200 K. The associated crystallographic distortion is then stabilized through the magnetostriction that occurs below 134 K. The crystal structure has been refined using synchrotron x-ray powder diffraction data measured throughout the structural phase diagram, showing a substantial Jahn-Teller distortion…
The "devil's staircase" type phase transition in the quarter-filled spin-ladder compound NaV2O5 has been discovered at low temperature and high pressure by synchrotron radiation x-ray diffraction. A large number of transitions are found to successively take place among higher-order commensurate phases with 2a * 2b * zc type superstructures. The observed temperature and pressure dependence of modulation wave number qc, defined by 1/z, is well reproduced by the Axial Next Nearest Neighbor Ising (ANNNI) model. The qc is suggested to reflect atomic displacements coupled with charge ordering in thi…
Crystal structure, electronic structure, and magnetic behavior of the spin-1/2 quantum magnet Na1.5VOPO4F0.5 are reported. The disorder of Na atoms leads to a sequence of structural phase transitions revealed by synchrotron x-ray powder diffraction and electron diffraction. The high-temperature second-order alpha <--> beta transition at 500 K is of the order-disorder type, whereas the low-temperature beta <--> gamma+gamma' transition around 250 K is of the first order and leads to a phase separation toward the polymorphs with long-range (gamma) and short-range (gamma') order of Na. Despite the…
Realizing a quantum spin liquid (QSL) ground state in a real material is a leading issue in condensed matter physics research. In this pursuit, it is crucial to fully characterize the structure and influence of defects, as these can significantly affect the fragile QSL physics. Here, we perform a variety of cutting-edge synchrotron X-ray scattering and spectroscopy techniques, and we advance new methodologies for site-specific diffraction and L-edge Zn absorption spectroscopy. The experimental results along with our first-principles calculations address outstanding questions about the local an…
The crystal lattice of Sr$_2$IrO$_4$ is investigated with synchrotron X-ray powder diffraction under hydrostatic pressures up to $P=43$ GPa and temperatures down to $20$ K. The tetragonal unit cell is maintained over the whole investigated pressure range, within our resolution and sensitivity. The $c$-axis compressibility $κ_c(P,T) \equiv -({1} / {c}) ({d c} / {d P})$ presents an anomaly with pressure at $P_1=17$ GPa at fixed $T=20$ K that is not observed at $T=300$ K, whereas $κ_a(P,T)$ is nearly temperature-independent and shows a linear behavior with $P$. The anomaly in $κ_c(P,T)$ is associ…
Two-dimensional iron-chalcogenide intercalates display a remarkable correlation of the interlayer spacing with the enhancement of the superconducting critical temperature ($T_c$). In this work, synchrotron x-ray absorption ($XAS$, at Fe and Se K edges) and emission ($XES$) spectroscopies, allow to discuss how the important rise of $T_c$ (44 K) in the molecule intercalated $\rm Li_x(C_5H_5N)_yFe_{2-z}Se_2$ relates to the electronic and local structure changes felt by the inorganic host upon doping ($x$). $XES$ shows that widely-separated layers of edge-sharing $\rm FeSe_4$ tetrahedra, carry low…
Neutron and synchrotron resonant X-ray magnetic scattering (RXMS) complemented by heat capacity and resistivity measurements reveal the evolution of the magnetic structures of Fe and Ce sublattices in single crystal CeFeAsO. The RXMS of magnetic reflections at the Ce $L_{\rm II}$-edge shows a magnetic transition that is specific to the Ce antiferromagnetic long-range ordering at $T_\texttt{Ce}\approx$ 4 K with short-range Ce ordering above $T_\texttt{Ce}$, whereas neutron diffraction measurements of a few magnetic reflections indicate a transition at $T^{*}\approx$ 12 K with unusual order para…
We report $^{139}$La and $^{63}$Cu NMR investigation of the successive charge order, spin order, and superconducting transitions in super-oxygenated La$_2$CuO$_{4+y}$ single crystal with stage-4 excess oxygen order at $T_{stage}\simeq 290$ K. We show that the stage-4 order induces tilting of CuO$_6$ octahedra below $T_{stage}$, which in turn causes $^{139}$La NMR line broadening. The structural distortion continues to develop far below $T_{stage}$, and completes at $T_{charge}\simeq 60$ K, where charge order sets in. This sequence is reminiscent of the the charge order transition in Nd co-dope…
