arXiv subjects

Hirofumi Ishii

Publications and source records attributed to Hirofumi Ishii.

12 recordsLinked to original sources

arXiv2026

Weak Ferromagnetism in NiS$_2$ under Nanocrystallization

Structurally well-ordered NiS$_2$ nanocrystals with an average diameter of $27.0 \pm 6.5$ nm retain the bulk-like two-step antiferromagnetic transitions, as shown by magnetization and heat-capacity measurements. Below the lower transition, the nanocrystals exhibit a hysteretic ferromagnetic response with large coercivity, exchange bias, and a vertical loop shift after field cooling, whereas the $M$-$H$ response just above the transition is nearly linear. These features are best explained by uncompensated surface moments generated where the low-temperature antiferromagnetic order terminates at the nanocrystal surface. The absence of a clear additional bulk-like weak-ferromagnetic component constrains homogeneous-canting models and indirectly favors a domain-wall scenario for the weak ferromagnetism of bulk NiS$_2$.

cond-mat.str-el↗

arXiv2026

Survival of the metallic state in a single-hole multiband $p$-orbital molecular system

Strong correlations and ferromagnetic Hund's coupling lead to diverse electronic phenomena in transition-metal oxides that sensitively depend on the $d$-orbital electron filling. Fullerides, their $p$-electron counterparts, exhibit effective antiferromagnetic Hund's coupling in a different energy range. At half-filling ($n=3$, three electrons in triply degenerate orbitals), both $d-$ and $p$-electron systems are Mott insulators due to strong correlations and Hund's coupling. Away from half-filling, in single-electron/hole ($n=1,5$) $d$-orbital systems, Hund's coupling opposes the correlations, reducing the Mott gap and allowing survival of metallicity. Here we report a single-hole multiorbital correlated $p$-electron system, orthorhombic-structured Yb$_2$CsC$_{60}$ comprising pentavalent C$_{60}^{5-}$ anions, which also exhibits a robust metallic state with no Mott transition, just like in the metastable single-electron cubic-structured CsC$_{60}$. We assert that particle-hole symmetry holds well in ($n=1,5$) fullerides and that their $p$-electron-derived states are analogous to those in $d$-orbital solids, providing impetus for further study of these correlated systems.

cond-mat.str-el↗

arXiv2026

Robust Metal-Insulator Transition Despite Surface Dead-Layer Growth in Sub-10-nm Cr-Doped V2O3 Nanocrystals

We investigated the size dependence of the metal-insulator transition (MIT) in Cr-doped V2O3 nanocrystals by photoemission spectroscopy using complementary probing depths, together with magnetic susceptibility measurements. Photoemission spectra show that MIT signatures persist down to an average particle size of 5.6 nm, and magnetic susceptibility measurements exhibit a nearly size-invariant transition onset. The contrast between surface-sensitive and deeper-probing photoemission spectra reveals that the transition survives in the nanocrystal interior. At the same time, the spectra indicate a systematic suppression of coherent quasiparticle weight with decreasing size, pointing to the growth of an insulating surface dead layer. These results demonstrate that nanoscaling does not intrinsically eliminate the MIT itself, but progressively enhances the influence of surface-driven insulating behavior, thereby providing insight into the practical limits of miniaturizing Mott-based devices.

cond-mat.str-el↗

arXiv2026

Pressure-induced lattice instabilities and phonon softening in the orthorhombically distorted ferrimagnet Ni4Nb2O9

The ambient- and high-pressure behavior of the ferrimagnet Ni4Nb2O9 (orthorhombically distorted honeycomb structure), is investigated using NMR, Raman spectroscopy, and synchrotron XRD. Ambient-pressure NMR measurements reveal, despite its orthorhombic symmetry, the local environment of Ni4Nb2O9 closely resembles that of its trigonal analogue Mn4Nb2O9. In contrast, substantially different paramagnetic shifts observed in the two compounds reflect their distinct average crystal symmetries, governing orbital overlap and magnetic exchange pathways. Under external pressure, Ni4Nb2O9 exhibits pronounced sensitivity to lattice distortions and phonon instabilities. Three isostructural transitions are identified near 2, 6, and 10 GPa, manifested by mode splitting, frequency shifts, line broadenings, intensity anomalies, and slope changes in the evolution of lattice parameters. At higher pressure, around 13 GPa, signatures of an incipient long-range structural transition from orthorhombic Pbcn to monoclinic P2/c symmetry emerge, signaling the onset of a symmetry-lowering transformation. The anomalous softening of the 192 cm^-1 Raman mode, accompanied by multiple linewidth and spectral-weight anomalies, serve as a key fingerprint of these structural instabilities, linking local symmetry breaking at low pressures to the long-range transition into the P2/c phase. Notably, pronounced linewidth anomalies, strongly anisotropic pressure coefficients, together with a marked enhancement of the intensity of the low-frequency branch over the 2-13 GPa range, point toward a pressure-induced regime influenced by coupled spin, orbital, and lattice degrees of freedom. The close correspondence of transition pressures in Ni4Nb2O9 and those reported for Mn4Nb2O9 highlights a common mechanism rooted in their similar local structural environments, as revealed by NMR.

cond-mat.mtrl-sci↗

arXiv2026

Pressure Induced 18 K Superconductivity and Two Superconducting Phases in CuIr2S4

We report pressure-induced superconductivity in the spinel CuIr$_{2}$S$_{4}$ with a transition temperature ($T_{\text{c}}$) reaching \textbf{18.2 K}, establishing a new record for this class of materials and surpassing the decades-old limit of 13.7 K. Our electrical transport and synchrotron X-ray diffraction studies up to 224 GPa reveal the emergence of \textbf{two distinct superconducting phases} from a charge-ordered insulating state. The first phase (SC-I) appears around 18 GPa, and forms a dome-shaped superconducting region in which the resistivity exhibits a pronounced, field- and current-sensitive drop without reaching strict zero above our base temperature. Above 111.8 GPa, a second, lower-$T_{\text{c}}$ phase (SC-II) emerges and coexists with SC-I over a broad pressure range, and SC-II ultimately develops a true zero-resistance state above 122.2 GPa. These superconducting phases are intimately linked to a cascade of structural transitions that systematically distort the frustrated pyrochlore lattice of Ir atoms. Our results expand the potential for superconductivity in spinels and demonstrate a pathway to high-$T_{\text{c}}$ pairing directly from a correlated insulating state driven by lattice tuning.

cond-mat.supr-con↗

arXiv2024

Narrowing band gap chemically and physically: Conductive dense hydrocarbon

Band gap energy of an organic molecule can be reduced by intermolecular interaction enhancement, and thus, certain polycyclic aromatic hydrocarbons (PAHs), which are insulators with wide band gaps, are expected to undergo insulator-metal transitions by simple compression. Such a pressure-induced electronic transition can be exploited to transform non-metallic organic materials into states featuring intriguing electronic characteristics such as high-temperature superconductivity. Numerous attempts have been made to metalize various small PAHs, but so far only pressure-induced amorphization well below the megabar region was observed. The wide band gap energy of the small PAHs and low chemical stability under simple compression are the bottlenecks. We have investigated the band gap energy evolution and the crystal structural compression of the large PAH molecules, where the band gap energy is significantly reduced by increasing the number of π-electrons and improved chemical stability with fully benzenoid molecular structure. Herein, we present a pressure-induced transition in dicoronylene, C48H20, an insulator at ambient conditions that transforms into a semi-metallic state above 23.0 GPa with a three-order-of-magnitude reduction in resistivity. In-situ UV-visible absorption, transport property measurement, Raman spectroscopy, X-ray diffraction and density functional theory calculations were performed to provide tentative explanations to the alterations in its electronic structure at high pressure. The discovery of an electronic transition at pressures well below the megabar is a promising step towards realization of a single component purely hydrocarbon molecular metal in the near future.

cond-mat.mtrl-sci↗

arXiv2023

Variation of Pressure-Induced Valence Transition with Approximation Degree in Yb-Based Quasicrystalline Approximants

We have synthesized new Tsai-type Yb-based intermediate-valence approximant crystals (ACs) with different degree of approximation to quasicrystal, Zn--Au--Yb 1/1 and 2/1 AC, and studied the external pressure effect on their Yb mean-valence $ν$. Whereas 1/1 AC distinctly exhibits a first-order-like jump in $ν$ at a transition pressure $P_{\rm v}$, 2/1 AC only shows an indistinct anomaly at $P_{\rm v}$. We have also studied the pressure dependence of the $ν$ of Au--Al--Yb 1/1 AC, which is a prototypal AC exhibiting pressure-induced quantum criticality. It shows a continuous valence anomaly at a critical pressure $P_{\rm c}$ where the magnetic susceptibility diverges toward zero temperature, in contrast to the valence jump in the Zn--Au--Yb 1/1 AC. These results are discussed based on a theoretical model of quantum critical valence fluctuation.

cond-mat.str-el↗

arXiv2021

Robustness of superconductivity to external pressure in high-entropy-alloy-type metal telluride AgInSnPbBiTe5

High-entropy-alloy (HEA) superconductors are a new class of disordered superconductors. In this study, we investigate the robustness of superconducting states in HEA-type metal telluride (MTe; M = Ag, In, Sn, Pb, Bi) under high pressure. PbTe exhibits a structural transition from a NaCl-type to an orthorhombic Pnma structure at low pressures, and further transitions to a CsCl-type structure at high pressures. When the superconductivity of the CsCl-type PbTe is observed, it is found that its superconducting transition temperature (Tc) decreases with pressure. However, in the HEA-type AgInSnPbBiTe5, Tc is almost independent of pressure, for pressures ranging from 13.0 to 35.1 GPa. This trend is quite similar to that observed in an HEA superconductor (TaNb)0.67(HfZrTi)0.33, which shows that the robustness of superconductivity to external pressure is a universal feature in HEA-type superconductors. To clarify the effects of the modification of the configurational entropy of mixing on the crystal structure, superconducting states, and electronic structure of MTe, electrical resistance measurements, synchrotron X-ray diffraction, and synchrotron X-ray absorption spectroscopy with partial fluorescence mode (PFY-XAS) for three MTe polycrystalline samples of PbTe, AgPbBiTe3, and AgInSnPbBiTe5 with different configurational entropies of mixing at the M site were performed.

cond-mat.supr-con↗

arXiv2020

Stabilization of Nonmagnetic Hexagonal Close-Packed Phase in Nanocrystalline Nickel Metal with a Giant Volume Expansion

Nanocrystalline Ni can adopt a hexagonal close-packed (hcp) structure,which does not appear in a bulk form under any conditions.Structural studies found its $>$ 20% expansion of volume per atom compared with face-centered cubic (fcc) Ni.Hard x-ray photoemission spectroscopy of the hcp phase revealed a $>$ 0.14 valence electron transfer from 3$d$ to 4$s$ and 4$p$ orbitals and a 0.25 eV reduction in band energy per electron compared with the fcc phase.Its nonmagnetic nature was attributed to a low density of states at the Fermi level.Thermodynamic stability of the hcp phase can be explained by the band energy gain and the electrostatic potential energy loss as related to the large lattice expansion.

cond-mat.mtrl-sci↗

arXiv2016

Origin of Pressure-induced Superconducting Phase in K$_{x}$Fe$_{2-y}$Se$_{2}$ studied by Synchrotron X-ray Diffraction and Spectroscopy

Pressure dependence of the electronic and crystal structures of K$_{x}$Fe$_{2-y}$Se$_{2}$, which has pressure-induced two superconducting domes of SC I and SC II, was investigated by x-ray emission spectroscopy and diffraction. X-ray diffraction data show that compressibility along the c-axis changes around 12 GPa, where a new superconducting phase of SC II appears. This suggests a possible tetragonal to collapsed tetragonal phase transition. X-ray emission spectroscopy data also shows the change in the electronic structure around 12 GPa. These results can be explained by the scenario that the two SC domes under pressure originate from the change of Fermi surface topology. Present results here show that the nesting condition plays a key role in stabilizing the superconducting state helping to address outstanding fundamental question as to why the SC II appears under pressure.

cond-mat.supr-con↗

arXiv2013

Unified understanding of the valence transition in the rare-earth monochalcogenides under pressure

Valence instability is a key ingredient of the unusual properties of f electron materials, yet a clear understanding is lacking as it involves a complex interplay between f electrons and conduc- tion states. Here we propose a unified picture of pressure-induced valence transition in Sm and Yb monochalcogenides, considered as model system for mixed valent 4f-electron materials. Using high-resolution x-ray absorption spectroscopy, we show that the valence transition is driven by the promotion of a 4f electron specifically into the lowest unoccupied (LU) 5d t2g band. We demonstrate with a promotional model that the nature of the transition at low pressures is intimately related to the density of states of the LU band, while at high pressures it is governed by the hybridization strength. These results set a new standard for the generic understanding of valence fluctuations in f-electron materials.

cond-mat.str-el↗

arXiv2010

High pressure evolution of Fe$_{2}$O$_{3}$ electronic structure revealed by X-ray absorption

We report the first high pressure measurement of the Fe K-edge in hematite (Fe$_2$O$_3$) by X-ray absorption spectroscopy in partial fluorescence yield geometry. The pressure-induced evolution of the electronic structure as Fe$_2$O$_3$ transforms from a high-spin insulator to a low-spin metal is reflected in the x-ray absorption pre-edge. The crystal field splitting energy was found to increase monotonically with pressure up to 48 GPa, above which a series of phase transitions occur. Atomic multiplet, cluster diagonalization, and density-functional calculations were performed to simulate the pre-edge absorption spectra, showing good qualitative agreement with the measurements. The mechanism for the pressure-induced phase transitions of Fe$_2$O$_3$ is discussed and it is shown that ligand hybridization significantly reduces the critical high-spin/low-spin pressure.

cond-mat.str-el↗