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Ti2O3 exhibits a unique metal-insulator transition (MIT) at approximately 450 K over a wide temperature range of ~ 150 K. This broad MIT accompanied by lattice deformation differs from the sharp MITs observed in most other transition-metal oxides. A long-standing issue is determining the role of electron-electron correlation in the electronic structure and MIT of Ti2O3. However, the lack of information about the band structure of Ti2O3 has hindered investigating the origin of its unusual physical properties. Here, we report the electronic band structure of insulating Ti2O3 films with slight hole doping by angle-resolved photoemission spectroscopy (ARPES). ARPES showed clear band dispersion on the surface of single-crystalline epitaxial films. The experimentally obtained band structures were compared with band-structure calculation results based on density functional theory (DFT) with generalized gradient approximation + U correction. The obtained band structures are in good agreement with the DFT calculations at U = 2.2 eV, suggesting that electron-electron correlation plays an important role in the electronic structure of Ti2O3. Furthermore, the detailed analyses with varying U suggest that the origin of the characteristic MIT in Ti2O3 is a semimetal-semimetal or semimetal-semiconductor transition caused by changes in the Fermi surface due to lattice deformation., Comment: Main manuscript: 30 pages, 4 figures, Supplemental Material: 23 pages, 15 figures

Angle-resolved photoemission spectroscopy using a micro-focused beam spot (micro-ARPES) is becoming a powerful tool to elucidate key electronic states of exotic quantum materials. We have developed a versatile micro-ARPES system based on synchrotron radiation beam focused with a Kirkpatrick-Baez mirror optics. The mirrors are monolithically installed on a stage, which is driven with five-axes motion, and are vibrationally separated from the ARPES measurement system. Spatial mapping of the Auphotolithography pattern on Si signifies the beam spot size of 10 $\mu$m (horizontal) x 12 $\mu$m (vertical) at the sample position, which is well suited to resolve the fine structure in local electronic states. Utilization of the micro beam and the high precision sample motion system enables the accurate spatially resolved band-structure mapping, as demonstrated by the observation of a small band anomaly associated with tiny sample bending near the edge of a cleaved topological insulator single crystal., Comment: 21 pages, 8 figures

This study investigated the electronic structure of SrTi$_{1-x}$V$_x$O$_3$ (STVO) thin films, which are solid solutions of strongly correlated transparent conductive oxide (TCO) SrVO$_3$ and oxide semiconductor SrTiO$_3$, using ${in situ}$ photoemission spectroscopy. STVO is one of the most promising candidates for correlated-metal TCO because it has the capability of optimizing the performance of transparent electrodes by varying ${x}$. Systematic and significant spectral changes were found near the Fermi level (${E_{\rm F}}$) as a function of ${x}$, while the overall electronic structure of STVO is in good agreement with the prediction of band structure calculations. As ${x}$ decreases from 1.0, spectral weight transfer occurs from the coherent band near ${E_{\rm F}}$ to the incoherent states (lower Hubbard band) around 1.0-1.5 eV. Simultaneously, a pseudogap is formed at ${E_{\rm F}}$, indicating a significant reduction in quasiparticle spectral weight within close vicinity of ${E_{\rm F}}$. This pseudogap seems to evolve into an energy gap at ${x}$ = 0.4, suggesting the occurrence of a composition-driven metal-insulator transition. From angle-resolved photoemission spectroscopic results, the carrier concentration ${n}$ changes proportionally as a function of ${x}$ in the metallic range of ${x}$ = 0.6-1.0. In contrast, the mass enhancement factor, which is proportional to the effective mass (${m^*}$), does not change significantly with varying ${x}$. These results suggest that the key factor of ${n/m^*}$ in optimizing the performance of correlated-metal TCO is tuned by ${x}$, highlighting the potential of STVO to achieve the desired TCO performance in the metallic region., Comment: 32 pages, 5 main figures, and 7 supplementary figures

Perovskite-type manganites, which are well-known for their intriguing physical properties such as colossal magnetoresistance (CMR) and half metalicity, have been considered as candidate materials for spintronics. However, their ferromagnetic (FM) properties are often suppressed in thin films when the thickness is reduced down to several monolayers (MLs). In order to investigate how the magnetic phases evolve near the paramagnetic (PM)-to-FM phase transition boundary, we have performed temperature-dependent x-ray magnetic circular dichroism (XMCD) experiments on a La$_{1-x}$Sr$_{x}$MnO$_3$ (LSMO, $x=0.4$) thin film, whose thickness (8 ML) is close to the boundary between the FM-metallic and the PM-insulating phases. By utilizing the element-selectiveness of XMCD, we have quantitatively estimated the fractions of the PM and superparamagnetic (SPM) phases as well as the FM one as a function of temperature. The results can be reasonably described based on a microscopic phase-separation model., Comment: 6 pages, 3 figures

Magnetic anisotropy of epitaxially grown thin films is affected by the strain from the substrates due to a combined effect of distorted electronic structure and spin-orbit interaction (SOI). As an inverse process, one expects an anisotropy of the electronic structure induced by magnetization in the presence of SOI. We have studied the charge-density anisotropy induced by magnetization in thin films of the ferromagnetic metal La$_{1-x}$Sr$_{x}$MnO$_3$ via x-ray magnetic linear dichroism (XMLD). XMLD measurements on thin films with various thicknesses have shown that the XMLD intensity is proportional to the square of the ferromagnetic moment. Using the XMLD sum rule and cluster-model calculation, it has been shown that more Mn 3$d$ electrons are distributed in orbitals elongated along the direction parallel to the spin polarization than in orbitals elongated in the direction perpendicular to it. The cluster-model calculation has shown that the effect of tensile strain from the SrTiO$_3$ substrate on the XMLD spectra is also consistent with the observed XMLD spectral line shapes., Comment: 12 pages, 4 figures

In CsW2O6, which undergoes a metal-insulator transition (MIT) at 213 K, the emergence of exotic properties associated with rattling motion of Cs is expected owing to its characteristic \beta-pyrochlore-type structure. However, a hurdle for crystal growth hampers elucidation of detailed properties and mechanisms of the MIT. Here we report on the epitaxial growth of \beta-pyrochlore-type CsW2O6 films and their electronic properties across the MIT. Using pulsed-laser deposi-tion technique, we grew single-crystalline CsW2O6 films exhibiting remarkably lower resistivity compared with a poly-crystalline bulk and sharp MIT around 200 K. Negative magnetoresistance and positive Hall coefficient were found, which became pronounced below 200 K. The valence-band and core-levels photoemission spectra indicated the drastic changes across the MIT. In the valence band photoemission spectrum, the finite density of states was observed at the Fermi level in the metallic phase. In contrast, an energy gap appeared in the insulating phase. The split of W 4f core-level spectrum suggested the charge disproportionation of W5+ and W6+ in the insulating phase. The change of spectral shape in the Cs 4d core levels reflected the rattling motion of Cs+ cations. These results strongly suggest that CsW2O6 is a novel material, in which MIT is driven by the charge disproportionation associated with the rattling motion., Comment: 8 pages, 6 figures

Controlling quantum critical phenomena in strongly correlated electron systems, which emerge in the neighborhood of a quantum phase transition, is a major challenge in modern condensed matter physics. Quantum critical phenomena are generated from the delicate balance between long-range order and its quantum fluctuation. So far, the nature of quantum phase transitions has been investigated by changing a limited number of external parameters such as pressure and magnetic field. We propose a new approach for investigating quantum criticality by changing the strength of quantum fluctuation that is controlled by the dimensional crossover in metallic quantum well (QW) structures of strongly correlated oxides. With reducing layer thickness to the critical thickness of metal-insulator transition, crossover from a Fermi liquid to a non-Fermi liquid has clearly been observed in the metallic QW of SrVO$_3$ by \textit{in situ} angle-resolved photoemission spectroscopy. Non-Fermi liquid behavior with the critical exponent ${\alpha} = 1$ is found to emerge in the two-dimensional limit of the metallic QW states, indicating that a quantum critical point exists in the neighborhood of the thickness-dependent Mott transition. These results suggest that artificial QW structures provide a unique platform for investigating novel quantum phenomena in strongly correlated oxides in a controllable fashion., Comment: 6 pages, 3 figures

We investigated systematic evolutions of structural and electronic properties of LixWO3 films, induced by Li-ion electrochemical reactions. Chronoamperometric Li-ion intercalation could control the amount of Li content up to x ~ 0.5. The resistivity abruptly decreased with increasing x and the films underwent an insulator to metal transition (IMT) within a range of 0.2 < x < 0.24, which was consistent with IMT of cubic NaxWO3. The X-ray diffraction analyses revealed the coexistence of tetragonal and cubic phases across IMT, suggesting that the alkaline-ion content was a primary factor for metallic conductivity in the ReO3-type WO3 system., Comment: 18 pages, 5 figures

We report epitaxial synthesis of superconducting CsxWO3 (x = 0.11, 0.20, 0.31) films on Y-stabilized ZrO2 (111) substrates. The hexagonal crystal structure was verified not only for composition within the stable region of bulk (x = 0.20, 0.31), but also for the out-of-range composition (x = 0.11). The onset of superconducting transition temperature (TC) was recorded 5.8 K for x = 0.11. We found strong correlation between TC and c-axis length, irrespective of the Cs content. The results indicate that hidden superconducting phase region of hexagonal tungsten bronze is accessible by using epitaxial synthesis of lightly doped films., Comment: 17 pages, 4 figures

In order to reveal many-body interactions in the three-dimensional (3D) perovskite manganite, we have performed an $in$ $situ$ angle-resolved photoemission spectroscopy (ARPES) on La$_{0.6}$Sr$_{0.4}$MnO$_3$ (LSMO) and investigated the behaviors of quasiparticles. We observe quasiparticle peaks around the Fermi momentum, both in the electron and the hole bands, and clear kinks throughout the hole Fermi surface in the ARPES band dispersion. The isotropic behavior sharply contrasts to the strong anisotropic quasiparticle excitation observed in layered manganites. These results suggest that polaronic quasiparticles by coupling of the electrons with Jahn-Teller phonons play an important role in the physical properties of the ferromagnetic metallic phase in 3D manganite LSMO., Comment: 13 pages, 4 figures

$In$ $situ$ angle-resolved photoemission spectroscopy (ARPES) has been performed on SrVO$_3$ ultrathin films, which show metallic quantum well (QW) states, to unveil the origin of the anomalous mass enhancement in the QW subbands. The line-shape analysis of the ARPES spectra reveals that the strength of the electron correlation increases as the subband bottom energy approaches the Fermi level. These results indicate that the anomalous subband-dependent mass enhancement mainly arises from the quasi-one-dimensional character of confined V $3d$ states as a result of their orbital-selective quantization., Comment: 6 pages, 3 figures

Metallic transition-metal oxides undergo a metal-to-insulator transition (MIT) as the film thickness decreases across a ritical thickness of several monolayers (MLs), but its driving mechanism remains controversial. We have studied the thickness-dependent MIT of the ferromagnetic metal La$_{0.6}$Sr$_{0.4}$MnO$_3$ by x-ray absorption spectroscopy and x-ray magnetic circular dichroism. As the film thickness was decreased across the critical thickness of the MIT (6-8 ML), a gradual decrease of the ferromagnetic signals and a concomitant increase of paramagnetic signals were observed, while the Mn valence abruptly decreased towards Mn$^{3+}$. These observations suggest that the ferromagnetic phase gradually and most likely inhomogeneously turns into the paramagnetic phase and both phases abruptly become insulating at the critical thickness., Comment: 12 pages, 3 figures

Synthesizing metastable phase often opens new functions in materials but is a challenging topic. Thin film techniques have advantages to form materials which do not exist in nature since nonequilibrium processes are frequently utilized. In this study, we successfully synthesize epitaxially stabilized new compound of perovskite Eu2+Mo4+O3 as a thin film form by a pulsed laser deposition. Analogous perovskite SrMoO3 is a highly conducting paramagnetic material, but Eu2+ and Mo4+ are not compatible in equilibrium and previous study found more stable pyrochlore Eu23+Mo24+O7 prefers to form. By using isostructural perovskite substrates, the gain of the interface energy between the film and the substrate stabilizes the matastable EuMoO3 phase. This compound exhibits high conductivity and large magnetic moment, originating from Mo 4d2 electrons and Eu 4f7 electrons, respectively. Our result indi-cates the epitaxial stabilization is effective not only to stabilize crystallographic structures but also to from a new compound which contains unstable combinations of ionic valences in bulk form., Comment: 7 pages, 9 figures