arXiv subjects

H. Sawa

Publications and source records attributed to H. Sawa.

16 recordsLinked to original sources

arXiv2025

Reexamination of the charge-ordered dimer pattern in the spinel compound CuIr2S4 using single-crystal synchrotron x-ray diffraction

We have re-investigated the crystal structure of a spinel type CuIr2S4 at low temperatures using a single-crystal in a synchrotron radiation x-ray diffraction experiment. The crystal structure of the low-temperature phase of CuIr2S4 has been already studied by diffraction experiments using a powder sample, and it has been reported that the formation of dimer molecules accompanied by charge ordering of Ir has been achieved. The crystal structure of the low-temperature phase obtained in our reanalysis was the same as the previously reported structure in that it showed the formation of Ir dimers accompanied by charge ordering, but the charge ordering pattern and arrangement of the dimers in the unit cell were different. We will discuss the validity of the structure obtained in this study and provide the structural parameters revealed in the reanalysis. The results of this study should provide a basis for further studies of the physical properties of CuIr2S4, which are still being actively investigated.

cond-mat.str-el↗

arXiv2024

Metastable ordered states induced by low temperature annealing of δ-Ag2/3V2O5

In δ-Ag2/3V2O5 with charge degrees of freedom in V, it is known that the charge ordering state and physical properties of V that appear at low temperatures depend strongly on the ordering state of Ag. In this study, we focused on the Ag ions in the interlayer and studied the structure using synchrotron radiation powder diffraction in dependence on temperature. We found that when the sample is slowly cooled from room temperature and ordering occurs at the Ag sites, V4+/V5+ charge ordering of V and subsequent V4+-V4+ structural dimers are produced. Although quenching the sample from room temperature suppresses the ordering of Ag, annealing at around 160 K promotes partial ordering of Ag and allows a metastable phase to be realized. This metastable phase is maintained even when the temperature is lowered again, producing a remarkable change in low-temperature properties. These results indicate that the ordered state of Ag, which is the key to control the charge-ordered state and physical properties, can be controlled by low-temperature annealing. The results of this study may provide a methodology for the realization of metastable states in a wide range of material groups of vanadium compounds, where competition among various charge ordered states underlies the physical properties.

cond-mat.str-el↗

arXiv2023

Zigzag chain order of LiVSe$_2$ developing away from the vanadium trimer phase transition boundary

The phenomenon of self-assembly of constituent elements to form molecules at low temperatures appears ubiquitously in transition metal compounds with orbital degrees of freedom. Recent progress in local structure studies using synchrotron radiation x-rays is shifting the interest in structural studies in such molecule-forming systems from the low-temperature ordered phase to the short-range order that appears like a precursor at high temperatures. In this study, we discuss both experimentally and theoretically the relationship between the trimer structure that appears in the layered LiV$X_2$ ($X$ = O, S, Se) system with a two-dimensional triangular lattice of vanadium and the zigzag chain-like local structure that appears near the phase transition boundary where molecular formation occurs. The vanadium trimerization that persistently appears in both low-temperature phases of LiVO$_2$ and LiVS$_2$ disappears in LiVSe$_2$, and a regular triangular lattice is thought to be realized in LiVSe$_2$, but this study reveals that the zigzag chain local distortion appears with a finite correlation length. This zigzag chain state local distortions are similar to the motif of local distortions in the high-temperature phase of LiVS$_2$, indicating that the local distortions are persistent away from the trimer phase transition boundary. On the other hand, it is concluded that the zigzag chain order appearing in LiVSe$_2$ is more stable than that in LiVS$_2$ in terms of the temperature variation of atomic displacement and correlation length. The zigzag chain order is considered to be competitive with the trimer order appearing in the LiV$X_2$ system. In this paper, we discuss the similarities and differences between the parameters that stabilize these electronic phases and the local distortions that appear in other molecular formation systems.

cond-mat.str-el↗

arXiv2023

Observation of local atomic displacements intrinsic to the double zigzag chain structure of 1T-MTe2 (M = V, Nb, Ta)

We describe the existence of local distortion discovered in the synchrotron x-ray single-crystal structure analysis of layered ditelluride 1T-MTe2 (M = V, Nb, Ta). In 1T-TaTe2, the double zigzag chain structure of Ta is deformed at about 170 K, and heptamer molecules are formed periodically at low temperatures. We found that some of the Ta atoms that compose the double zigzag chain structure appearing at high temperatures are locally displaced, resulting in local dimerization. This tendency weakens when Ta is replaced by V or Nb. Our results indicate that the local distortion persistently survives in these ditellurides, where the electronic degrees of freedom, including orbitals, are weakened. We further discuss the origin of local distortion in these ditellurides, which is different from many usual material systems where molecular formation occurs at low temperatures.

cond-mat.str-el↗

arXiv2023

Short-range order and increased transition temperature in LiVO2 with weakened trimer frustration

Vanadium atoms in layered LiVO2 form in-plane periodic vanadium trimers at low temperatures, but the trimers appear randomly in the stacking direction because there are many trimer configurations with comparable lattice energy. We detailed an original modeling scheme to represent glassy states with a completely disordered trimer configuration in the stacking structure. Through PDF analysis using this model, we show that the synthesis method can yield two types of low-temperature stacking structures: a completely disordered stacking structure and a short-range order in the stacking structure. The phase transition temperature of the former sample is about 15 K lower than that of the latter. We discuss that this is due to the strong trimer frustration that appears in the sample without short-range order, which suppresses the phase transition temperature, similar to the frustration effect in conventional spin systems.

cond-mat.str-el↗

arXiv2022

Pressure suppression of the excitonic insulator state in Ta2NiSe5 observed by optical conductivity

The layered chalcogenide Ta2NiSe5 has recently attracted much interest as a strong candidate for the long sought excitonic insulator (EI). Since the physical properties of an EI are expected to depend sensitively on the external pressure, it is important to clarify the pressure evolution of microscopic electronic state in Ta2NiSe5. Here we report the optical conductivity [s(w)] of Ta2NiSe5 measured at high pressures to 10 GPa and at low temperatures to 8 K. With cooling at ambient pressure, s(w) develops an energy gap of about 0.17 eV and a pronounced excitonic peak at 0.38 eV, as already reported in the literature. Upon increasing pressure, the energy gap becomes narrower and the excitonic peak is broadened. Above a structural transition at Ps~3 GPa, the energy gap becomes partially filled, indicating that Ta2NiSe5 is a semimetal after the EI state is suppressed by pressure. At higher pressures, s(w) exhibits metallic characteristics with no energy gap. The detailed pressure evolution of s(w) is presented, and discussed mainly in terms of a weakening of excitonic correlation with pressure.

cond-mat.str-el↗

arXiv2020

Robust atomic orbital in the cluster magnet LiMoO2

In this study, we present a rutile-related material, LiMoO2, that becomes a cluster magnet and exhibits a spin singlet formation on a preformed molybdenum dimer upon cooling. Unlike ordinary cluster magnets, the atomic dyz orbital robustly survives despite the formation of molecular orbitals, thereby affecting the magnetic properties of the selected material. Such hybrid cluster magnets with the characters of molecular and atomic orbitals realize multiple independent spins on an isolated cluster, leading to an ideal platform to study the isolated spin dimers physics.

cond-mat.str-el↗

arXiv2019

Vanadium trimers randomly aligned along the c-axis direction in layered LiVO2

Herein, we discuss the identification of vanadium trimers in layered LiVO2 and its sulfide analog of LiVS2 with two-dimensional triangular lattices. Our comprehensive structural studies using synchrotron X-ray diffraction experiments clarified that vanadium trimers are randomly aligned along the c-axis direction in LiVO2, while the long-range ordering of vanadium trimers along the c-axis direction appears in LiVS2. Our results solve the longstanding issue of cluster patterns in LiVO2 and provide an experimental basis for identifying the mechanism of trimer formation.

cond-mat.str-el↗

arXiv2019

Thermal conductivity of the quantum spin liquid candidate EtMe3Sb[Pd(dmit)2]2: No evidence of mobile gapless excitations

The thermal conductivity $κ$ of the quasi-2D organic spin-liquid candidate EtMe$_3$Sb[Pd(dmit)$_2$]$_2$ (dmit-131) was measured at low temperatures, down to 0.07 K. We observe a vanishingly small residual linear term $κ_0/T$, in $κ/T$ vs $T$ as $T \to 0$. This shows that the low-energy excitations responsible for the sizeable residual linear term $γ$ in the specific heat $C$, seen in $C/T$ vs $T$ as $T \to 0,$ are localized. We conclude that there are no mobile gapless excitations in this spin liquid candidate, in contrast with a prior study of dmit-131 that reported a large $κ_0/T$ value [Yamashita et al., Science 328, 1246 (2010)]. Our study shows that dmit-131 is in fact similar to $κ$-(BEDT-TTF)$_2$Cu$_2$(CN)$_3$, another quasi-2D organic spin-liquid candidate where a vanishingly small $κ_0/T$ and a sizeable $γ$ are seen. We attribute heat conduction in these organic insulators without magnetic order to phonons undergoing strong spin-phonon scattering, as observed in several other spin-liquid materials.

cond-mat.str-el↗

arXiv2018

Large entropy change derived from the orbitally assisted three-centered two-electron σ bond formation in a metallic Li0.33VS2

We discuss herein the emergence of a large entropy change in metallic Li0.33VS2 derived from the orbitally assisted loose σ bond formation. Comprehensive structural studies based on synchrotron x-ray and neutron diffraction analyses clarify the fabrication of ribbon chains at 375 K, consisting of multiple three-centered two-electron σ bonds based on the viewpoint of local chemical bonding. Although the metallic conductivity persists down to the lowest temperature measured, exceptionally large entropy change as a metal, as much as ΔS = 6.6 J/mol K, appears at the transition. Emergence of a large entropy change in a metallic state expects us the possible novel functional materials, such as a heat-storage material with rapid thermal response.

cond-mat.str-el↗

arXiv2014

Absence of Jahn-Teller transition in the hexagonal Ba3CuSb2O9 single crystal

We present a comprehensive structural study on perovskite-type 6H-Ba3CuSb2O9, which exhibits a spin-orbital short-range ordering on a honeycomb-based lattice. By combining synchrotron x-ray diffraction, electron spin resonance, ultrasound measurement and Raman spectroscopy, we found that the static Jahn-Teller distortion is absent down to the lowest temperature in the present material, indicating orbital ordering is strongly suppressed. We discuss such an unusual state is realized with the help of spin degree of freedom, leading to a spin-orbital entangled liquid state.

cond-mat.str-el↗

arXiv2011

Crystallographic and superconducting properties of the fully-gapped noncentrosymmetric 5d-electron superconductors CaMSi3 (M=Ir, Pt)

We report crystallographic, specific heat, transport, and magnetic properties of the recently discovered noncentrosymmetric 5d-electron superconductors CaIrSi3 (Tc = 3.6 K) and CaPtSi3 (Tc = 2.3 K). The specific heat suggests that these superconductors are fully gapped. The upper critical fields are less than 1 T, consistent with limitation by conventional orbital depairing. High, non-Pauli-limited μ0 Hc2 values, often taken as a key signature of novel noncentrosymmetric physics, are not observed in these materials because the high carrier masses required to suppress orbital depairing and reveal the violated Pauli limit are not present.

cond-mat.supr-con↗

arXiv2011

Magnetic and transport properties of the spin-state disordered oxide La0.8Sr0.2Co_{1-x}Rh_xO_{3-δ}

We report measurements and analysis of magnetization, resistivity and thermopower of polycrystalline samples of the perovskite-type Co/Rh oxide La$_{0.8}$Sr$_{0.2}$Co$_{1-x}$Rh$_x$O$_{3-δ}$. This system constitutes a solid solution for a full range of $x$,in which the crystal structure changes from rhombohedral to orthorhombic symmetry with increasing Rh content $x$. The magnetization data reveal that the magnetic ground state immediately changes upon Rh substitution from ferromagnetic to paramagnetic with increasing $x$ near 0.25, which is close to the structural phase boundary. We find that one substituted Rh ion diminishes the saturation moment by 9 $μ_B$, which implies that one Rh$^{3+}$ ion makes a few magnetic Co$^{3+}$ ions nonmagnetic (the low spin state), and causes disorder in the spin state and the highest occupied orbital. In this disordered composition ($0.05\le x \le 0.75$), we find that the thermopower is anomalously enhanced below 50 K. In particular, the thermopower of $x$=0.5 is larger by a factor of 10 than those of $x$=0 and 1, and the temperature coefficient reaches 4 $μ$V/K$^2$ which is as large as that of heavy-fermion materials such as CeRu$_2$Si$_2$.

cond-mat.str-el↗

arXiv2009

Size of Orbital Ordering Domain Controlled by the Itinerancy of the 3d Electrons in a Manganite Thin Film

An electronic effect on a macroscopic domain structure is found in a strongly correlated half-doped manganite film Nd$_{0.5}$Sr$_{0.5}$MnO3 grown on a (011) surface of SrTiO3. The sample has a high-temperature (HT) phase free from distortion above 180K and two low-temperature (LT) phases with a large shear-mode strain and a concomitant twin structure. One LT phase has a large itinerancy (A-type), and the other has a small itinerancy (CE-type), while the lattice distortions they cause are almost equal. Our x ray diffraction measurement shows that the domain size of the LT phase made by the HT-CE transition is much smaller than that by the HT-A transition, indicating that the difference in domain size is caused by the electronic states of the LT phases.

cond-mat.str-el↗

arXiv2007

Orbital Ordering Structures in (Nd,Pr)0.5Sr0.5MnO3 Manganite Thin Films on Perovskite (011) Substrates

Structural study of orbital-ordered manganite thin films has been conducted using synchrotron radiation, and a ground state electronic phase diagram is made. The lattice parameters of four manganite thin films, Nd0.5Sr0.5MnO3 (NSMO) or Pr0.5Sr0.5MnO3 (PSMO) on (011) surfaces of SrTiO3 (STO) or [(LaAlO3){0.3}(SrAl0.5Ta0.5O3){0.7}] (LSAT), were measured as a function of temperature. The result shows, as expected based on previous knowledge of bulk materials, that the films' resistivity is closely related to their structures. Observed superlattice reflections indicate that NSMO thin films have an antiferro-orbital-ordered phase as their low-temperature phase while PSMO film on LSAT has a ferro-orbital-ordered phase, and that on STO has no orbital-ordered phase. A metallic ground state was observed only in films having a narrow region of A-site ion radius, while larger ions favor ferro-orbital-ordered structure and smaller ions stabilize antiferro-orbital-ordered structure. The key to the orbital-ordering transition in (011) film is found to be the in-plane displacement along [0-1 1] direction.

cond-mat.str-el↗

arXiv2005

Novel Orbital Ordering induced by Anisotropic Stress in a Manganite Thin Film

We performed resonant and nonresonant x-ray diffraction studies of a Nd0.5Sr0.5MnO3 thin film that exhibits a clear first-order transition. Lattice parameters vary drastically at the metal-insulator transition at 170K (=T_MI), and superlattice reflections appear below 140K (=T_CO). The electronic structure between T_MI and T_CO is identified as A-type antiferromagnetic with the d_{x2-y2} ferroorbital ordering. Below T_CO, a new type of antiferroorbital ordering emerges. The accommodation of the large lattice distortion at the first-order phase transition and the appearance of the novel orbital ordering are brought about by the anisotropy in the substrate, a new parameter for the phase control.

cond-mat.str-el↗