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The ligand field (LF) of transition metal ions is a crucial factor in realizing the mechanism of novel physical and chemical properties. However, the low-crystallinity state, including the amorphous state, precludes the clarification of the electronic structural relationship of transition metal ions using crystallographic techniques, ultraviolet and infrared optical methods, and magnetometry. Here, we demonstrate that soft X-ray 2p → 3d core-level absorption spectroscopy (

Amorphous coordination polymers and metal-organic frameworks (MOFs) have attracted much attention owing to their various functionalities. Here, we demonstrate the tunable water adsorption behavior of a series of amorphous cyanide-bridged MOFs with different metals (M[Ni(CN)4]: MNi; M = Mn, Fe, and Co). All three compounds adsorb up to six water molecules at a certain vapor pressure (Pads) and undergo conversion to crystalline Hofmann-type MOFs, M(H2O)2[Ni(CN)4]·4H2O (MNi-H2O; M = Mn, Fe, and Co). The Pads of MnNi, FeNi, and CoNi for water adsorption is P/P0 = 0.4, 0.6, and 0.9, respectively. Although the amorphous nature of these materials prevented structural elucidation using X-ray crystallography techniques, the local-scale structure around the N-coordinated M2+ centers was analyzed using L2,3-, K-edge X-ray absorption fine structure, and magnetic measurements. Upon hydration, the coordination geometry of these metal centers changed from tetrahedral to octahedral, resulting in significant reorganization of the MOF local structure. On the other hand, Ni[Ni(CN)4] (NiNi) containing square-planar Ni2+ centers did not undergo significant structural transformation and therefore abruptly adsorbed H2O in the low-pressure region. We could thus define how changes in the bond lengths and coordination geometry are related to the adsorption properties of amorphous MOF systems.

We have measured the lattice volume of ice VIII in different pressure-temperature pathways and found that the volume depends on the pathway, implying that deviatoric stress makes the volume larger. Dense ice is in the ice VIII phase with the molar volume of 6.56 cm

The relationship between the magnetic interaction and photoinduced dynamics in antiferromagnetic perovskites is investigated in this study. In La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$ thin films, commensurate spin ordering is accompanied by charge disproportionation, whereas SrFeO${}_{3}$ thin films show incommensurate helical antiferromagnetic spin ordering due to increased ferromagnetic coupling compared to La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$. To understand the photoinduced spin dynamics in these materials, we investigate the spin ordering through time-resolved resonant soft X-ray scattering. In La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$, ultrafast quenching of the magnetic ordering within 130 fs through a nonthermal process is observed, triggered by charge transfer between the Fe atoms. We compare this to the photoinduced dynamics of the helical magnetic ordering of SrFeO${}_{3}$. We find that the change in the magnetic coupling through optically induced charge transfer can offer an even more efficient channel for spin-order manipulation., 7 pages, 5 figures

Recently, all-optical magnetization control has been garnering considerable attention in realizing next-generation ultrafast magnetic information devices. Here, employing a magneto-optical Kerr effect (MOKE) microscope, we observed the laser-induced magnetization switching of ferrimagnetic oxide NiCo2O4 (NCO) epitaxial thin films with perpendicular magnetic anisotropy, where the sample was pumped at 1030-nm laser pulses, and magnetic domain images were acquired via the MOKE microscope with a white light emitting diode. Laser pulses irradiated an NCO thin film at various temperatures from 300 K to 400 K while altering the parameters of pulse interval, fluence, and the number of pulses with the absence of the external magnetic field. We observed accumulative all-optical switching at 380 K and above. Our observation of oxide NCO thin films facilitates the realization of chemically stable magnetization switching using ultrafast lasers, and without applying a magnetic field., Comment: 6 pages, 6 figures

Investigation of ultrafast dynamic behaviors can provide novel insights about the coupling mechanisms among multiple degrees of freedom, such as lattice, magnetism and electronic structure, in condensed matters. Here we investigate both the ferromagnetic (FM) and antiferromagnetic (AFM) ultrafast dynamics of a strongly correlated oxide system, GdBaCo2O5.5 thin film by time-resolved x-ray magnetic circular dichroism in reflectivity (XMCDR) and resonant magnetic x-ray diffraction (RMXD). A photo-induced AFM-FM transition characterized by an increase of the transient XMCDR (sensitive to FM order) beyond the unpumped value and a decay of RMXD (sensitive to AFM order) was observed. The photon-energy dependence of the transient XMCDR and reflectivity could be interpreted as a concomitant photo-induced spin-state transition (SST). The AFM-FM transition and SST couple with each other in the time domain, resulting in unusual dynamic behaviors of the magnetism.

We investigate the ultrafast lattice dynamics in ${\mathrm{BaFe}}_{2}{\mathrm{As}}_{2}$ via time-resolved x-ray diffraction measurements using an x-ray free-electron laser at SPring-8 Angstrom Compact free-electron LAser (SACLA). The profile of the Bragg peaks substantially changes after strong photoexcitation, where the $c$ axis length of the lattice initially contracts, followed by expansion. These ultrafast lattice contractions and expansions significantly depend on the pump fluence, and it is suggested that a strong normal stress is applied along the $c$ axis. To obtain a phenomenological understanding of the observed lattice dynamics, we performed calculations based on a two-temperature model and an ultrafast thermoelasticity model. Our results showed that a steep gradient of the electron temperature induced by photoexcitation generates a blast force, which acts as a strong normal stress. We propose that a temporal stress can be applied by a strong optical pump, and this scheme can be another route for the application of uniaxial stress to superconductors.

We report x-ray and optical absorption spectroscopy as well as hard x-ray photoemission spectroscopy on hexagonal ${\mathrm{Ba}}_{3}{\mathrm{CuSb}}_{2}{\mathrm{O}}_{9}$ in which a Cu $3d$ spin-orbital liquid state is suggested from absence of the Jahn-Teller distortion of ${\mathrm{Cu}}^{2+}{\mathrm{O}}_{6}$ octahedra and of the magnetic ordering. The experimental results and their cluster model analysis indicate that O $2p$ holes play a crucial role in realizing the spin-orbital liquid state of hexagonal ${\mathrm{Ba}}_{3}{\mathrm{CuSb}}_{2}{\mathrm{O}}_{9}$. These oxygen holes appear due to the ``reaction'' ${\mathrm{Sb}}^{5+}\ensuremath{\rightarrow}{\mathrm{Sb}}^{3+}\phantom{\rule{4pt}{0ex}}+$ two O $2p$ holes, with these holes being able to attach to Cu ions. The present work opens avenues towards spin-charge-orbital entangled liquid state in transition-metal oxides with small or negative charge transfer energy.

The discoveries of intrinsic ferromagnetism in atomically-thin van der Waals crystals have opened up a new research field enabling fundamental studies on magnetism at two-dimensional (2D) limit as well as development of magnetic van der Waals heterostructures. To date, a variety of 2D ferromagnetism has been explored mainly by mechanically exfoliating 'originally ferromagnetic (FM)' van der Waals crystals, while bottom-up approach by thin film growth technique has demonstrated emergent 2D ferromagnetism in a variety of 'originally non-FM' van der Waals materials. Here we demonstrate that V5Se8 epitaxial thin films grown by molecular-beam epitaxy (MBE) exhibit emergent 2D ferromagnetism with intrinsic spin polarization of the V 3d electrons despite that the bulk counterpart is 'originally antiferromagnetic (AFM)'. Moreover, thickness-dependence measurements reveal that this newly-developed 2D ferromagnet could be classified as an itinerant 2D Heisenberg ferromagnet with weak magnetic anisotropy, broadening a lineup of 2D magnets to those potentially beneficial for future spintronics applications.

Control of the polarization of an X-ray free-electron laser (XFEL) has been performed using an X-ray phase retarder (XPR) in combination with an arrival timing diagnostic on BL3 of the SPring-8 Angstrom Compact free-electron LAser (SACLA). To combine with the timing diagnostic, a pink beam was incident on the XPR crystal and then monochromated in the vicinity of samples. A high degree of circular polarization of ∼97% was obtained experimentally at 11.567 keV, which agreed with calculations based on the dynamical theory of X-ray diffraction. This system enables pump–probe experiments to be operated using circular polarization with a time resolution of 40 fs to investigate ultrafast magnetic phenomena.

A new perovskite-type cuprate PrCuO3 has been synthesized by high-pressure oxygen annealing. Synchrotron X-ray powder diffraction and absorption spectroscopy revealed that PrCuO3 crystallizes in the GdFeO3-type structure with cooperative Jahn–Teller distortion, forming one-dimensional chains of corner-shared CuO4 plaquettes with nearly divalent Cu ions.

Using a time-resolved magneto-optical Kerr effect (TR-MOKE) microscope, we observed ultrafast demagnetization of inverse-spinel-type NiCo2O4 (NCO) epitaxial thin films of the inverse spinel type ferrimagnet NCO with perpendicular magnetic anisotropy. This microscope uses a pump-probe method, where the sample is pumped at 1030 nm, and magnetic domain images are acquired via MOKE microscopy at 515 nm (the second harmonic). We successfully observed the dynamics of the magnetic domain of the NCO thin film via laser irradiation, and obtained a demagnetization time constant of approximately 0.4 ps. This time constant was significantly smaller than the large time constants reported for other half-metallic oxides. These results, combined with the results of our x-ray photoemission spectroscopy study, indicate that this NCO thin film is a ferrimagnetic metal whose electronic structure deviates from the theoretically predicted half-metallic one., 5 pages, 5 figures

We demonstrate that total reflection hard x-ray photoelectron spectroscopy (TR-HAXPES) is a versatile method for elucidating a difference between surface and bulk electronic states of strongly correlated electron systems, complementing conventional bulk sensitive hard x-ray photoelectron spectroscopy (HAXPES). To demonstrate the experimental feasibility of the method, we investigated ${\mathrm{La}}_{0.6}{\mathrm{Sr}}_{0.4}{\mathrm{MnO}}_{3}$ and the electron-doped high-${T}_{\mathrm{C}}$ superconductor ${\mathrm{La}}_{1.9}{\mathrm{Ce}}_{0.1}{\mathrm{CuO}}_{4}$. From the incident angle dependence of the spectral line shapes, we found that the surface-sensitive TR-HAXPES measurement equivalent to soft x-ray photoelectron spectroscopy is possible in the total reflection condition. The results strongly suggest that this method allows us to measure both surface and bulk electronic states without making any changes to experimental setup such as the energy resolution, x-ray energy, and the beamline.

The strain effect from a substrate is an important experimental route to control electronic and magnetic properties in transition-metal oxide (TMO) thin films. Using hard x-ray photoemission spectroscopy, we investigate the strain dependence of the valence states in LaNiO$_{3}$ thin films, strongly correlated perovskite TMO, grown on four substrates: LaAlO$_{3}$, (LaAlO$_{3}$)$_{0.3}$(SrAl$_{0.5}$Ta$_{0.5}$O$_{3}$)$_{0.7}$, SrTiO$_{3}$, and DyScO$_{3}$. A Madelung potential analysis of core-level spectra suggests that the point-charge description is valid for the La ions while it breaks down for Ni and O ions due to a strong covalent bonding between the two. A clear x-ray photon-energy dependence of the valence spectra is analyzed by the density functional theory, which points to a presence of the La 5$p$ state near the Fermi level., 6 pages, 4 figures, and 2 tables

We investigate near-Fermi-energy (${E}_{F}$) element-specific electronic and spin states of ferromagnetic van der Waals (vdW) metal ${\mathrm{Fe}}_{5}\mathrm{Ge}{\mathrm{Te}}_{2}$. The soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) measurement provides spectroscopic evidence of localized Fe $3d$ band. We also find prominent hybridization between the localized Fe $3d$ band and the delocalized Ge/Te $p$ bands. This picture is strongly supported from direct observation of the remarkable spin polarization of the ligand $p$ bands near ${E}_{F}$, using x-ray magnetic circular dichroism (XMCD) measurements. The strength of XMCD signal from ligand element Te shows the highest value, as far as we recognize, among literature reporting finite XMCD signal for nonmagnetic element in any systems. Combining SX-ARPES and elemental selective XMCD measurements, we collectively point to an important role of giant spin polarization of the delocalized ligand Te states for realizing itinerant long-range ferromagnetism in ${\mathrm{Fe}}_{5}\mathrm{Ge}{\mathrm{Te}}_{2}$. Our finding provides a fundamental elemental selective viewpoint for understanding mechanism of itinerant ferromagnetism in low-dimensional compounds, which also leads to insight for designing exotic magnetic states by interfacial band engineering in heterostructures.

Magnetocrystalline anisotropy, a key ingredient for establishing long-range order in a magnetic material down to the two-dimensional (2D) limit, is generally associated with spin-orbit interaction (SOI) involving a finite orbital angular momentum. Here we report strong out-of-plane magnetic anisotropy without orbital angular momentum, emerging at the interface between two different van der Waals (vdW) materials, an archetypal metallic vdW material NbSe2 possessing Zeeman-type SOI and an isotropic vdW ferromagnet V5Se8. We found that the Zeeman SOI in NbSe2 induces robust out-of-plane magnetic anisotropy in V5Se8 down to the 2D limit with a more than 2-fold enhancement of the transition temperature. We propose a simple model that takes into account the energy gain in NbSe2 in contact with a ferromagnet, which naturally explains our observations. Our results demonstrate a conceptually new magnetic proximity effect at the vdW interface, expanding the horizons of emergent phenomena achievable in vdW heterostructures.

The interface properties of strongly correlated electron system/band semiconductor junctions were investigated in the La1−xSrxVO3/p-Si(100) structure. Spectroscopic observations show that the electronic structure of the interface is typical of insulator/semiconductor junctions for x ≤ 0.2 and Schottky junctions for x ≥ 0.25. For the forward current density–bias voltage (J–V) characteristics, energy barriers that were otherwise unexplainable by spectroscopy were estimated from the thermionic emission model fitting of the J–V characteristics, indicating that the injected carriers from Si to La1−xSrxVO3 can also feel the correlation force of Coulomb repulsion at the interface.

Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.

This work explores the mechanism of interfacial coupling in LaMnO${}_{3}$/SrIrO${}_{3}$ superlattices by x-ray spectroscopies and first-principles calculations. The superlattice-period dependent properties of the Ir magnetic moments can be attributed to the realignment of electron spin during the formation of the interfacial molecular orbital.

SmO thin film is a new Kondo system showing a resistivity upturn around 10 K and was theoretically proposed to have a topologically nontrivial band structure. We perform hard x-ray and soft x-ray photoemission spectroscopy to elucidate the electronic structure of SmO. From the Sm $3d$ core-level spectra, we estimate the valence of Sm to be $\ensuremath{\sim}2.96$, proving that the Sm has a mixed valence. The valence-band photoemission spectra exhibit a clear Fermi edge originating from the Sm $5d$-derived band. The present finding is consistent with the theory suggesting a possible topological state in SmO and show that rare-earth monoxides or their heterostructures can be a new playground for the interplay of strong electron correlation and spin-orbit coupling.

Perovskite rhodates are characterized by intermediate strengths of both electronic correlation as well as spin-orbit coupling (SOC) and usually behave as moderately correlated metals. A recent publication [Phys. Rev. B 95, 245121 (2017)] on epitaxial ${\mathrm{SrRhO}}_{3}$ thin films reported a bad-metallic behavior and suggested the occurrence of antiferromagnetism below 100 K. We have further studied this ${\mathrm{SrRhO}}_{3}$ thin film by hard x-ray photoemission spectroscopy and found a very small density of states (DOS) at the Fermi level (${E}_{F}$), which is consistent with the previously reported bad-metallic behavior. However, the absence of DOS persists up to room temperature, which contradicts the explanation of antiferromagnetic transition at $\ensuremath{\sim}100$ K. We also employed electronic structure calculations within the framework of density functional theory and dynamical mean-field theory. In contrast to the photoemission results, our calculations indicate metallic behaviors of both bulk ${\mathrm{SrRhO}}_{3}$ and the ${\mathrm{SrRhO}}_{3}$ thin film, and a stronger correlation effect was observed in the thin film than that in the bulk. The calculated uniform magnetic susceptibility is substantially larger in the thin film than that in the bulk. We also investigated the role of SOC and found only a moderate modulation of the band structure. Hence SOC is not expected to significantly affect the electronic correlation in ${\mathrm{SrRhO}}_{3}$. Extrinsic effects of finite-thickness effects beyond our calculations and localization effects may play important roles to induce the negligible spectral weight at ${E}_{F}$.

Hematite, α-Fe2O3, is an important semiconductor for photoelectrochemical water splitting. Its low charge carrier mobility and the presence of midgap states provide favourable conditions for electron-hole recombination, hence affecting the semiconductor's photoelectrochemical efficiency. The nature of the excited state and charge carrier transport in hematite is strongly debated. In order to further understand the fundamental properties of the hematite photoexcited state, we conducted femtosecond 2p (L3) X-ray absorption (XAS) and 2p3d resonant inelastic scattering (RIXS) measurements on hematite thin-films at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). The observed spectral changes and kinetic processes are in agreement with previous 3p XAS reports. The potential additional information that could be acquired from 2p3d RIXS experiments is also discussed.

The discoveries of intrinsic ferromagnetism in atomically thin van der Waals crystals have opened a new research field enabling fundamental studies on magnetism at two-dimensional (2D) limit as well as development of magnetic van der Waals heterostructures. Currently, a variety of 2D ferromagnetism has been explored mainly by mechanically exfoliating "originally ferromagnetic (FM)" van der Waals crystals, while a bottom-up approach by thin-film growth technique has demonstrated emergent 2D ferromagnetism in a variety of "originally non-FM" van der Waals materials. Here we demonstrate that V

Recently, hole-doped superconducting cuprates with the T'-structure La1.8-xEu0.2SrxCuO4 (LESCO) have attracted a lot of attention. We have performed x-ray photoemission and absorption spectroscopy measurements on as-grown and reduced T0-LESCO. Results show that electrons and holes were doped by reduction annealing and Sr substitution, respectively. However, it is shown that the system remains on the electron-doped side of the Mott insulator or that the charge-transfer gap is collapsed in the parent compound., Comment: 2 pages, 2 figures

The photoinduced valence dynamics of ${\mathrm{EuNi}}_{2}{({\mathrm{Si}}_{0.21}{\mathrm{Ge}}_{0.79})}_{2}$ were investigated using time-resolved x-ray absorption spectroscopy for Eu ${M}_{5}$ edge. Through the pump-probe technique with synchrotron x-ray and Ti:sapphire laser pulses, a photoinduced valence transition was observed from ${\mathrm{Eu}}^{3+}$ to ${\mathrm{Eu}}^{2+}$. Because the lifetime of a photoinduced state can be up to 3 ns, a metastable state is considered to be realized. By comparing the experimental results with the theoretical calculations, the photoinduced valence transition between Eu $4f$ and conduction electrons was quantitatively evaluated.