SearcharxivSearch

arXiv subjects

Shigeo Mori

Publications and source records attributed to Shigeo Mori.

At least 19 recordsLinked to original sources

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

Time-Temperature-Transformation (TTT) Diagrams to rationalize the nucleation and quenchability of metastable $\alpha$-Li$_3$PS$_4$

$\alpha$-Li$_3$PS$_4$ is a promising solid-state electrolyte with the highest ionic conductivity among its polymorphs. However, its formation presents a thermodynamic paradox: the $\alpha$-phase is the equilibrium phase at high temperature and transforms to the stable $\gamma$-Li$_3$PS$_4$ polymorph when cooled to room temperature; however, $\alpha$-Li$_3$PS$_4$ can be synthesized and quenched in a metastable state via rapid heating at relatively low temperatures. The origin of this synthesizability and anomalous stability has remained elusive. Here, we resolve this paradox by establishing a comprehensive time-temperature-transformation (TTT) diagram, constructed from a computational temperature-size phase diagram and experimental high-time-resolution isothermal measurements. Our density functional theory calculations reveal that at the nanoscale, the $\alpha$-phase is stabilized by its low surface energy, which drastically lowers the nucleation barrier across a wide temperature range. This size-dependent stabilization is directly visualized using in-situ synchrotron X-ray diffraction and electron microscopy, capturing the rapid nucleation of nano-sized $\alpha$-phase and its subsequent slow transformation. This work presents a generalizable framework that integrates thermodynamic and kinetic factors for understanding nucleation and phase transformation mechanisms, providing a rational strategy for the targeted synthesis of functional metastable materials.

cond-mat.mtrl-sci

Characteristic ferroelectric domains and their dynamic behavior in ordered Pb(Sc$_{1/2}$Nb$_{1/2}$)O$_{3}$

Pb-based perovskites with multiple cations are fascinating materials showing various phenomena such as high piezoelectric, electromechanical, and relaxor properties. While chemical disordering accompanied by polar nanoregions and nanosized domains is commonly believed to cause the relaxor nature, little is known about ferroelectric microstructures of chemically ordered Pb-based perovskites. In this study, we discovered intriguing meandering ferroelectric domains in chemically ordered ferroelectric Pb(Sc$_{1/2}$Nb$_{1/2}$)O$_{3}$ using in-situ transmission electron microscopy with dark-field imaging. Observation results demonstrate that electric polarization can fluctuate around the [111] direction despite the formation of long-range ordered rhombohedral domains, which results in unique weak relaxor properties. In-situ imaging upon heating successfully reveals the dynamic behavior of domain-wall movements with lattice distortion and paraelectric-ferroelectric phase coexistence in the vicinity of the Curie temperature, indicating a discontinuous phase transition. Our research provides new insights into the effect of chemical ordering on ferroelectric nanodomains.

cond-mat.mtrl-sci

Impact of in-plane disorders on the thermal conductivity of AgCrSe$_2$

Superionic conductors have recently attracted renewed attention for their use as thermoelectric materials due to their extremely low lattice thermal conductivity. Of central interest is why the superionic conductors exhibit such low thermal conductivity, and competing mechanisms have been proposed thus far. In this study, we investigate the effects of Cu and Au substitution for Ag site on the crystal structure and thermal properties of AgCrSe$_2$, which exhibits superionic conduction of Ag ions. We show that Au substitution significantly reduces the lattice thermal conductivity of AgCrSe$_2$. Powder structure analysis using synchrotron x-ray diffraction reveals that Au substitution increases the anisotropic atomic displacement parameter of Ag ions along the $a$ and $b$ axes. This result indicates that the amplitude of in-plane vibrations is enhanced, which is attributed to increased anharmonicity in the potential energy around Ag ions. The enhanced vibrational amplitude also suggests a reduction in the force constants between Ag ions. Consequently, the enhanced anharmonicity not only shortens the phonon lifetime ($τ$) by increasing phonon-phonon scattering, but also increases the number of low-energy phonons, which further contributes to the reduction of $τ$. This anharmonicity mechanism is applicable to other superionic conductors exhibiting ultra-low thermal conductivity, promoting their widespread use as thermoelectric materials.

cond-mat.mtrl-sci

Enhanced ionic conductivity through crystallization of glass-Li$_3$PS$_4$ by machine learning molecular dynamics simulations

Understanding the atomistic mechanism of ion conduction in solid electrolytes is critical for the advancement of all-solid-state batteries. Glass-ceramics, which undergo crystallization from a glass state, frequently exhibit unique properties including enhanced ionic conductivities compared to both the original crystalline and glass forms. Despite these distinctive features, specific details regarding the behavior of ion conduction in glass-ceramics, particularly concerning conduction pathways, remain elusive. In this study, we demonstrate the crystallization process of glass-Li$_3$PS$_4$ through molecular dynamics simulations employing machine learning interatomic potentials constructed from first principles calculation data. Our analyses of Li conduction using the obtained partially crystallized structures reveal that the diffusion barriers of Li decrease as the crystallinity in Li$_3$PS$_4$ glass-ceramics increases. Furthermore, Li displacements predominantly occur in the precipitated crystalline portion, suggesting that percolation conduction plays a significant role in enhanced Li conduction. These findings provide valuable insights for the future utilization of glass-ceramic materials.

cond-mat.mtrl-sci

Unusual nanoscale coexistence of polar-nonpolar domains underlying oxygen storage properties in Ho(Mn, Ti)O$_{3+δ}$

Hexagonal manganese oxides RMnO$_3$ show intriguing topological ferroelectric-domain walls with variable conductivity, leading to domain wall engineering. Despite the numerous experimental studies on the polar nanoscale structures, controlling ferroelectric domains has not been sufficiently investigated. Here, we reveal the unprecedented coexistence of polar-nonpolar nanoscale domains that can be formed by substituting Ti ions in HoMnO$_3$. Unusual polar nanoscale domains are embedded in nonpolar domains with different crystallographic symmetry. This polar-nonpolar coexisting structure is naturally assembled by adjusting the lattice length during a solid-state reaction process. Furthermore, the comprehensive study reveals that the reversible microstructural change with a nonpolar-polar transition is strongly correlated with the oxygen storage properties in Ho(Mn, Ti)O$_{3+δ}$. The present results provide important insight into the nanoscale polar-nonpolar domain coexistence in functional rare-earth manganese oxides, RMnO$_3$.

cond-mat.mtrl-sci

Magnetization controlled by crystallization in soft magnetic Fe-Si-B-P-Cu alloys

Soft magnetic materials have low coercive fields and high permeability. Recently, nanocrystalline alloys obtained using annealing amorphous alloys have attracted much interest since nanocrystalline alloys with small grain sizes of tens of nanometers exhibit low coercive fields comparable to that of amorphous alloys. Since nanocrystalline soft magnetic materials attain remarkable soft magnetic properties by controlling the grain size, the crystal grains' microstructure has a substantial influence on the soft magnetic properties. In this research, we examined the magnetic properties of Fe-Si-B-P-Cu nanocrystalline soft magnetic alloys obtained by annealing amorphous alloys. During crystallization, the observation findings reveal the correlation between the generated microstructures and soft magnetic properties.

cond-mat.mtrl-sci

Direct observation of monoclinic polar nanoregions in the relaxor ferroelectric Pb(Yb$_{1/2}$Nb$_{1/2}$)O$_{3}$-PbTiO$_{3}$

Relaxor ferroelectrics are applied in electronic devices such as actuators and sonars. Morphotrophic phase boundaries (MPBs) with monoclinic structures are known for their high piezoelectricity and electromechanical coupling factors in solid solutions of PbTiO$_{3}$ and relaxor ferroelectrics (Pb(Mg$_{1/3}$, Nb$_{2/3}$)O$_{3}$ or Pb(Zn$_{1/3}$, Nb$_{1/3}$)O$_{3}$). However, the monoclinic structures related to polar nanosize domains (polar nanoregions) exhibiting the relaxor properties of dielectric dispersion have not been reported. Using transmission electron microscopy and synchrotron x-ray scattering, we present the first observations of coexisting monoclinic structures and polar nanoregions near the MPB in Pb(Yb$_{1/2}$Nb$_{1/2}$)O$_{3}$-PbTiO$_{3}$. The polar nanoregions in this material are randomly shaped, unlike the ferroelectric nanodomains of the canonical relaxor Pb(Mg$_{1/3}$, Nb$_{1/3}$)O$_{3}$-PbTiO$_{1/3}$. Furthermore, in situ observations reveal that the monoclinic polar nanoregions grow as the temperature decreases. A pair-distribution function analysis reveals a mixture of monoclinic Pm and Cm structures in the polar nanoregions without the rhombohedral structure of other Pb-based relaxor solid solutions. Owing to the peculiar nature of the coexistence of the relaxor property (polar nanoregions) and high piezoelectricity (monoclinic structure), this material is expected as a new platform for understanding relaxor ferroelectricity.

cond-mat.mtrl-sci

Stabilization of layered perovskite structures via strontium substitution in Ca$_3$Ti$_2$O$_7$ revealed via elemental mapping

Extensive studies have been performed on layered compounds, ranging from layered cuprates to van der Waals materials with critical issues of intergrowths and stacking faults. However, such structures have been studied less because of experimental difficulty. We present characteristic defect structures of intergrowths in the Ruddlesden-Popper Ca$_{2.46}$Sr$_{0.54}$Ti$_2$O$_7$, which is known to exhibit hybrid improper ferroelectricity. Transmission electron microscopy reveals that numerous intergrowths composed of 7 and 15 layers are introduced in the ferroelectric domains. Elemental maps demonstrate that Sr ions are selectively substituted into the perovskite layers of intergrowths. Density functional theory calculations support the site-selective substitution of Sr ions, favorably located in the intergrowths. The stabilization of the Ruddlesden-Popper phase and intergrowths via Sr substitution can be explained by the ionic-radius difference between Ca and Sr ions. The study reveals detailed defect structures originating from the layered perovskite structure of Ca$_{2.46}$Sr$_{0.54}$Ti$_2$O$_7$, and shows the usefulness of elemental mapping in probing the substitution effects in oxides.

cond-mat.mtrl-sci

Two types of magnetic bubbles in MnNiGa observed via Lorentz microscopy

Magnetic bubbles are remarkable spin structures that developed in uniaxial magnets with strong magnetocrystalline anisotropy. Several contradictory reports have been published concerning the magnetic bubble structure in a metallic magnet MnNiGa: Biskyrmions or type-II bubbles. Lorentz microscopy in polycrystalline MnNiGa was used to explain the magnetic bubble structure. Depending on the connection between the magnetic easy axis and the observation plane, two types of magnetic bubbles were formed. Magnetic bubbles with 180° domains were formed if the easy axis was away from the direction perpendicular to the observation plane. The contrast of biskyrmion is reproduced by this form of a magnetic bubble. When the easy axis was approximately perpendicular to the observing plane, type-II bubbles were observed in the same specimen. The findings will fill a knowledge gap between prior reports on magnetic bubbles in MnNiGa.

cond-mat.mtrl-sci

Charged domain boundaries stabilized by translational symmetry breaking in the hybrid improper ferroelectric Ca$_{3-x}$Sr$_x$Ti$_2$O$_7$

Charged domain walls and boundaries in ferroelectric materials display distinct phenomena, such as an increased conductivity due to the accumulation of bound charges. Here, we report the electron microscopy observations of atomic-scale arrangements at charged domain boundaries in the hybrid improper ferroelectric Ca$_{2.46}$Sr$_{0.54}$Ti$_2$O$_7$. Like in the prototype improper ferroelectric YMnO$_3$, we find that charged domain boundaries in Ca$_{2.46}$Sr$_{0.54}$Ti$_2$O$_7$ correspond to out-of-phase boundaries, which separate adjacent domains with a fractional translational shift of the unit cell. In addition, our results show that strontium ions are located at charged domain boundaries. The out-of-phase boundary structure may decrease the polarization charge at the boundary because of the ferrielectric nature of Ca$_{2.46}$Sr$_{0.54}$Ti$_2$O$_7$, thereby promoting the stabilization of the charged state. By combining atomic-resolution imaging and density-functional theory calculations, this study proposes an unexplored stabilization mechanism of charged domain boundaries and structural defects accompanying out-of-phase translational shifts.

cond-mat.mtrl-sci

Crystallization behaviors in superionic conductor Na$_3$PS$_4$

All-solid-state batteries using sodium are promising candidates for next-generation rechargeable batteries due to the limited lithium resources. A practical sodium battery requires an electrolyte with high conductivity. Cubic Na$_3$PS$_4$ exhibiting high conductivity of over 10$^{-4}$ S cm$^{-1}$ is obtained by crystallizing amorphous Na$_3$PS$_4$ synthesized by ball milling. Amorphous Na$_3$PS$_4$ crystallizes in a cubic structure and then is transformed into a tetragonal phase upon heating. In this study, in situ observation by transmission electron microscopy demonstrates that the crystallite size drastically increases during the transition from the cubic phase to the tetragonal phase. Moreover, an electron diffraction analysis reveals that amorphous domains and nano-sized crystallites coexist in the cubic Na$_3$PS$_4$ specimen, while the tetragonal phase contains micro-sized crystallites. The nano-sized crystallites and the composite formed by crystallites and amorphous domains are most likely responsible for the increase in conductivity in the cubic Na$_3$PS$_4$ specimens.

cond-mat.mtrl-sci

Superconductivity enhanced by abundant low-energy phonons in (Sr$_{1-x}$Ca$_x$)$_3$Rh$_4$Sn$_{13}$

The effects of structural quantum criticality on the strong-coupling superconductivity of (Sr$_{1-x}$Ca$_x$)$_3$Rh$_4$Sn$_{13}$ have been investigated via electrical resistivity and specific heat measurements. We demonstrate that the lattice specific heat at low temperatures considerably increases toward the structural quantum critical point (SQCP), $x_{\rm c}\approx0.9$. The superconducting gap increases with $x$ in the exact same fashion as the low-temperature lattice specific heat, clearly indicating that the abundant low-energy phonons cause strong-coupling superconductivity. Despite the electron-phonon interaction, which is much more enhanced than the electron correlation, the low-temperature electrical resistivity near the SQCP varies as $\propto T^2$. This finding suggests that structural quantum fluctuation affects the power law arising from the electron-phonon scattering.

cond-mat.str-el

Magnetic textures in a hexaferrite thin film and their response to magnetic fields revealed by phase microscopy

We investigated magnetic textures in a Sc-doped hexaferrite film by means of phase microscopy (PM) with a hole-free phase plate in a transmission electron microscope. In a zero magnetic field, the stripe-shaped magnetic domains coexist with magnetic bubbles. The magnetization in both magnetic domains was oriented perpendicular to the film and the domain walls have an in-plane magnetization. In the remnant state at 9.2 mT, several magnetic bubbles were formed with the formation of stripe-shaped magnetic domains, and the out-of-plane component in the stripe-shaped domains gradually appeared as the film thickness increased. As the film thickness increases further, the magnetic bubbles with clockwise or counter-clockwise spin helicities formed a triangular lattice. These results in the remnant state suggest that the domain wall energy in the magnetic bubble domains is lower in the thicker region.

cond-mat.mtrl-sci

Magnetic bubbles in an M-type hexagonal ferrite observed by hollow-cone Foucault imaging and small-angle electron diffraction

We report hollow-cone imaging and small-angle electron diffraction of nanoscale magnetic textures such as magnetic-striped domains and magnetic bubbles of M-type hexagonal ferrite BaFe$_{10.35}$Sc$_{1.6}$Mg$_{0.05}$O$_{19}$. The advantage of the hollow-cone Foucault method is that magnetic domains with various directions of magnetization can be visualized under an infocus condition. Moreover, the contrast of magnetic domain walls in magnetic bubbles depends on the inclination angle of the illumination beam. The combination of small-angle electron diffraction and hollow-cone Foucault imaging proves that magnetization at domain walls exhibits in-plane directions in the magnetic-striped domains and magnetic bubbles.

cond-mat.mtrl-sci

Observation of magnetic domains in uniaxial magnets via small-angle electron diffraction and Foucault imaging

Observation of magnetic domains is important in understanding the magnetic properties of magnetic materials and devices. In this study, we report that the magnetic domains of M-type hexaferrites with uniaxial anisotropy can be visualized via small-angle electron diffraction and Foucault imaging. The position of the diffraction pattern spots has the same period as that of magnetic domains in a Sc-substituted hexaferrite (BaFe$_{12-x-δ}$Sc$_x$Mg$_δ$O$_{19}$). Conversely, the spots were observed four times longer than the period of magnetic domains in hexaferrite without substitution (BaFe$_{12}$O$_{19}$), demonstrating the long-range order of the Bloch walls. When the specimen was tilted, the magnetic deflection effect, as well as the periodic spots of magnetic domains, occurred. Thus, we were able to visualize the magnetic domains with different magnetization directions and domain orientations by selecting deflection spots. The results indicate that the technique utilized in this study is useful in observing the magnetic materials with uniaxial anisotropy.

cond-mat.mes-hall

Foucault imaging and small-angle electron diffraction in controlled external magnetic fields

We report a method for acquiring Foucault images and small-angle electron diffraction patterns in external magnetic fields using a conventional transmission electron microscope without any modification. In the electron optical system that we have constructed, external magnetic fields parallel to the optical axis can be controlled using the objective lens pole piece under weak excitation conditions in the Foucault mode and the diffraction mode. We observe two ferromagnetic perovskite-type manganese oxides, La$_{0.7}$Sr$_{0.3}$MnO$_{3}$ and Nd$_{0.5}$Sr$_{0.5}$MnO$_{3}$, in order to visualize magnetic domains and their magnetic responses to external magnetic fields. In rhombohedral-structured La$_{0.7}$Sr$_{0.3}$MnO$_{3}$, pinning of magnetic domain walls at crystallographic twin boundaries was found to have a strong influence on the generation of new magnetic domains in external applied magnetic fields.

cond-mat.mtrl-sci

Electron diffraction covering a wide angular range from Bragg diffraction to small-angle diffraction

We construct an electron optical system to investigate Bragg diffraction (the crystal lattice plane, $10^{-2}$-$10^{-3}$ rad) with the objective lens turned off by adjusting the current in the intermediate lenses. A crossover was located on the selected-area aperture plane. Thus, the dark-field imaging can be performed by using a selected-area aperture to select Bragg diffraction spots. The camera length can be controlled in the range of 0.8 to 4 m without exciting the objective lens. Furthermore, we can observe the magnetic-field dependence of electron diffraction using the objective lens under weak excitation conditions. The diffraction mode for Bragg diffraction can be easily switched to a small-angle electron diffraction mode having a camera length of more than 100 m. We propose this experimental method to acquire electron diffraction patterns that depict an extensive angular range from 10$^{-2}$ to 10$^{-7}$ rad. This method is applied to analyze the magnetic microstructures in three distinct magnetic materials, i.e., a uniaxial magnetic structure of BaFe$_{10.35}$Sc$_{1.6}$Mg$_{0.05}$O$_{19}$, a martensite of a Ni-Mn-Ga alloy, and a helical magnetic structure of Ba$_{0.5}$Sr$_{1.5}$Zn$_{2}$Fe$_{12}$O$_{22}$.

cond-mat.mtrl-sci