Direct Imaging of Band Structure for Powdered Rhombohedral Boron Monosulfide by Microfocused ARPES.

Boron-based two-dimensional (2D) materials are an excellent platform for nanoelectronics applications. Rhombohedral boron monosulfide (r-BS) is attracting particular attention because of its unique layered crystal structure suitable for exploring various functional properties originating in the 2D nature. However, studies to elucidate its fundamental electronic states have been largely limited because only tiny powdered crystals were available, hindering a precise investigation by spectroscopy such as angle-resolved photoemission spectroscopy (ARPES). Here we report the direct mapping of the band structure with a tiny (∼20 × 20 µm2) r-BS powder crystal by utilizing microfocused ARPES. We found that r-BS is a p-type semiconductor with a band gap of >0.5 eV characterized by the anisotropic in-plane effective mass. The present results demonstrate the high applicability of micro-ARPES to tiny powder crystals and widen an opportunity to access the yet-unexplored electronic states of various novel materials.

Large Perpendicular Magnetic Anisotropy Induced by an Intersite Charge Transfer in Strained EuVO2H Films.

Perovskite oxides ABO3 continue to be a major focus in materials science. Of particular interest is the interplay between A and B cations as exemplified by intersite charge transfer (ICT), which causes novel phenomena including negative thermal expansion and metal-insulator transition. However, the ICT properties were achieved and optimized by cationic substitution or ordering. Here we demonstrate an anionic approach to induce ICT using an oxyhydride perovskite, EuVO2H, which has alternating layers of EuH and VO2. A bulk EuVO2H behaves as a ferromagnetic insulator with a relatively high transition temperature (TC) of 10 K. However, the application of external pressure to the EuIIVIIIO2H bulk or compressive strain from the substrate in the thin films induces ICT from the EuIIH layer to the VIIIO2 layer due to the extended empty V dxy orbital. The ICT phenomenon causes the VO2 layer to become conductive, leading to an increase in TC that is dependent on the number of carriers in the dxy orbitals (up to a factor of 4 for 10 nm thin films). In addition, a large perpendicular magnetic anisotropy appears with the ICT for the films of <100 nm, which is unprecedented in materials with orbital-free Eu2+, opening new perspectives for applications. The present results provide opportunities for the acquisition of novel functions by alternating transition metal/rare earth layers with heteroanions.

Fermiology and Origin of T_{c} Enhancement in a Kagome Superconductor Cs(V_{1-x}Nb_{x})_{3}Sb_{5}.

Kagome metals AV_{3}Sb_{5} (A=K, Rb, and Cs) exhibit a characteristic superconducting ground state coexisting with a charge density wave (CDW), whereas the mechanisms of the superconductivity and CDW have yet to be clarified. Here we report a systematic angle-resolved photoemission spectroscopy (ARPES) study of Cs(V_{1-x}Nb_{x})_{3}Sb_{5} as a function of Nb content x, where isovalent Nb substitution causes an enhancement of superconducting transition temperature (T_{c}) and the reduction of CDW temperature (T_{CDW}). We found that the Nb substitution shifts the Sb-derived electron band at the Γ point downward and simultaneously moves the V-derived band around the M point upward to lift up the saddle point (SP) away from the Fermi level, leading to the reduction of the CDW-gap magnitude and T_{CDW}. This indicates a primary role of the SP density of states to stabilize the CDW. The present result also suggests that the enhancement of superconductivity by Nb substitution is caused by the cooperation between the expansion of the Sb-derived electron pocket and the recovery of the V-derived density of states at the Fermi level.

Design, Synthesis, and Optoelectronic Properties of the High-Purity Phase in Layered AETMN2 (AE = Sr, Ba; TM = Ti, Zr, Hf) Semiconductors.

We report the synthesis and optoelectronic properties of high phase-purity (>94 mol %) bulk polycrystals of KCoO2-type layered nitrides AETMN2 (AE = Sr, Ba; and TM = Ti, Zr, Hf), which are expected to exhibit unique electron transport properties originating from their natural two-dimensional (2D) electronic structure, but high-purity intrinsic samples have yet been reported. The bulks were synthesized using a solid-state reaction between AENH and TMN precursors with NaN3 to achieve high N chemical potential during the reaction. The AETMN2 bulks are n-type semiconductors with optical band gaps of 1.63 eV for SrTiN2, 1.97 eV for BaZrN2, and 2.17 eV for BaHfN2. SrTiN2 and BaZrN2 bulks show degenerated electron conduction due to the natural high-density electron doping and paramagnetic behavior in all of the temperature ranges examined, while such unintentional carrier generation is largely suppressed in BaHfN2, which exhibits nondegenerated electron conduction. The BaHfN2 sample also exhibits weak ferromagnetic behavior at temperatures lower than 35 K. Density functional theory calculations suggest that the high-density electron carriers in SrTiN2 come from oxygen impurity substitution at the N site (ON) acting as a shallow donor even if the high-N chemical potential synthesis conditions are employed. On the other hand, the formation energy of ON becomes larger in BaHfN2 because of the stronger TM-N chemical bonds. Present results demonstrate that the easiness of impurity incorporation is designed by density functional calculations to produce a more intrinsic semiconductor in wider chemical conditions, opening a way to cultivating novel functional materials that are sensitive to atmospheric impurities and defects.

Large phonon drag thermopower boosted by massive electrons and phonon leaking in LaAlO3/LaNiO3/LaAlO3 heterostructure.

An unusually large thermopower (S) enhancement is induced by heterostructuring thin films of the strongly correlated electron oxide LaNiO3. The phonon-drag effect, which is not observed in bulk LaNiO3, enhances S for thin films compressively strained by LaAlO3 substrates. By a reduction in the layer thickness down to three unit cells and subsequent LaAlO3 surface termination, a 10 times S enhancement over the bulk value is observed due to large phonon drag S (Sg), and the Sg contribution to the total S occurs over a much wider temperature range up to 220 K. The Sg enhancement originates from the coupling of lattice vibration to the d electrons with large effective mass in the compressively strained ultrathin LaNiO3, and the electron-phonon interaction is largely enhanced by the phonon leakage from the LaAlO3 substrate and the capping layer. The transition-metal oxide heterostructures emerge as a new playground to manipulate electronic and phononic properties in the quest for high-performance thermoelectrics.

Bipolar Semiconducting Properties in α-SnWO4 Based on the Characteristic Defect Structure.

Diodes, memories, logic circuits, and most other current information technologies rely on the combined use of p- and n-type semiconductors. Although oxide semiconductors have many technologically attractive functionalities, such as transparency and high dopability to enable their use as conducting films, they typically lack bipolar conductivity. In particular, the absence of p-type semiconducting properties owing to the innate electronic structures of oxides represents a bottleneck for the development of practical devices. Here, bipolar semiconducting properties are demonstrated in α-SnWO4 within a 100 °C temperature window after appropriate thermal treatment. Comprehensive spectroscopic observations reveal that Sn4+ is present in p-type α-SnWO4 in a notably greater quantity than in n-type. This result strongly suggests that the Sn4+ substitutional defects on the W6+ sites contribute to hole-carrier generation in α-SnWO4. We also find that oxygen vacancies are initially formed in Sn-O-W bonds and migrate to W-O-W bonds with changes in semiconducting properties from p-type to n-type. These findings suggest useful strategies for exploring p-type oxide semiconductors and controlling their carrier type by utilizing the octahedral structure.

Observation of Chiral Fermions with a Large Topological Charge and Associated Fermi-Arc Surface States in CoSi.

Topological semimetals materialize a new state of quantum matter where massless fermions protected by a specific crystal symmetry host exotic quantum phenomena. Distinct from well-known Dirac and Weyl fermions, structurally chiral topological semimetals are predicted to host new types of massless fermions characterized by a large topological charge, whereas such exotic fermions are yet to be experimentally established. Here, by using angle-resolved photoemission spectroscopy, we experimentally demonstrate that a transition-metal silicide CoSi hosts two types of chiral topological fermions, a spin-1 chiral fermion and a double Weyl fermion, in the center and corner of the bulk Brillouin zone, respectively. Intriguingly, we found that the bulk Fermi surfaces are purely composed of the energy bands related to these fermions. We also find the surface states connecting the Fermi surfaces associated with these fermions, suggesting the existence of the predicted Fermi-arc surface states. Our result provides the first experimental evidence for the chiral topological fermions beyond Dirac and Weyl fermions in condensed-matter systems, and paves the pathway toward realizing exotic electronic properties associated with unconventional chiral fermions.

In-gap state generated by La-on-Sr substitutional defects within the bulk of SrTiO3.

Local distortion in the conduction pathway has a significant influence on the conducting properties of oxides. The electronic states induced in the band gap of SrTiO3 by La doping were investigated using photoemission spectroscopy (PES) and soft X-ray emission spectroscopy (SXES); moreover, the local distortion in the conduction pathway was examined using extended X-ray absorption fine structure (EXAFS). An itinerant state and a localized state were observed as a metallic state and an in-gap state, respectively, in the PES spectra and as inelastic peaks in the SXES spectra. This implied that the itinerant state and the in-gap state coexisted within the bulk. From EXAFS results, it was observed that La doped into SrTiO3 substituted Sr and locally distorted the conduction pathway. The results showed that some electrons doped by La-on-Sr substitution are trapped/localized by the local distortion in the conduction pathway, whereas the remaining doped electrons itinerate in the pristine conduction pathway with no distortion.

Origins of Thermal Spin Depolarization in Half-Metallic Ferromagnet CrO_{2}.

Using high-resolution spin-resolved photoemission spectroscopy, we observe a thermal spin depolarization to which all spin-polarized electrons contribute. Furthermore, we observe a distinct minority spin state near the Fermi level and a corresponding depolarization that seldom contributes to demagnetization. The origin of this depolarization has been identified as the many-body effect characteristic of half-metallic ferromagnets. Our investigation opens an experimental field of itinerant ferromagnetic physics focusing on phenomena with sub-meV energy scale.

Quasiparticle Interference on Cubic Perovskite Oxide Surfaces.

We report the observation of coherent surface states on cubic perovskite oxide SrVO_{3}(001) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a d_{xy}-derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO_{2} plane play a critical role in controlling the coherent surface state via modulating orbital state.

Dirac Fermions in Borophene.

Honeycomb structures of group IV elements can host massless Dirac fermions with nontrivial Berry phases. Their potential for electronic applications has attracted great interest and spurred a broad search for new Dirac materials especially in monolayer structures. We present a detailed investigation of the ß_{12} sheet, which is a borophene structure that can form spontaneously on a Ag(111) surface. Our tight-binding analysis revealed that the lattice of the ß_{12} sheet could be decomposed into two triangular sublattices in a way similar to that for a honeycomb lattice, thereby hosting Dirac cones. Furthermore, each Dirac cone could be split by introducing periodic perturbations representing overlayer-substrate interactions. These unusual electronic structures were confirmed by angle-resolved photoemission spectroscopy and validated by first-principles calculations. Our results suggest monolayer boron as a new platform for realizing novel high-speed low-dissipation devices.

Isotropic Kink and Quasiparticle Excitations in the Three-Dimensional Perovskite Manganite La_{0.6}Sr_{0.4}MnO_{3}.

In order to reveal the many-body interactions in three-dimensional perovskite manganites that show colossal magnetoresistance, we performed an in situ angle-resolved photoemission spectroscopy on La_{0.6}Sr_{0.4}MnO_{3} and investigated the behavior of quasiparticles. We observed quasiparticle peaks near the Fermi momentum in both the electron and the hole bands, and clear kinks throughout the entire hole Fermi surface in the band dispersion. This isotropic behavior of quasiparticles and kinks suggests that polaronic quasiparticles produced by the coupling of electrons with Jahn-Teller phonons play an important role in the colossal magnetoresistance properties of the ferromagnetic metallic phase of three-dimensional manganites.

Enhanced electrical transparency by ultrathin LaAlO3 insertion at oxide metal/semiconductor heterointerfaces.

We demonstrate that the electrical conductivity of metal/semiconductor oxide heterojunctions can be increased over 7 orders of magnitude by inserting an ultrathin layer of LaAlO3. This counterintuitive result, that an interfacial barrier can be driven transparent by inserting a wide-gap insulator, arises from the large internal electric field between the two polar LaAlO3 surfaces. This field modifies the effective band offset in the device, highlighting the ability to design the electrostatic boundary conditions with atomic precision.

Origin of the Anomalous Mass Renormalization in Metallic Quantum Well States of Strongly Correlated Oxide SrVO_{3}.

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.

Inverse-Perovskite Ba3 BO (B = Si and Ge) as a High Performance Environmentally Benign Thermoelectric Material with Low Lattice Thermal Conductivity.

High energy-conversion efficiency (ZT) of thermoelectric materials has been achieved in heavy metal chalcogenides, but the use of toxic Pb or Te is an obstacle for wide applications of thermoelectricity. Here, high ZT is demonstrated in toxic-element free Ba3 BO (B = Si and Ge) with inverse-perovskite structure. The negatively charged B ion contributes to hole transport with long carrier life time, and their highly dispersive bands with multiple valley degeneracy realize both high p-type electronic conductivity and high Seebeck coefficient, resulting in high power factor (PF). In addition, extremely low lattice thermal conductivities (κlat ) 1.0-0.4 W m-1  K-1 at T = 300-600 K are observed in Ba3 BO. Highly distorted O-Ba6 octahedral framework with weak ionic bonds between Ba with large mass and O provides low phonon velocities and strong phonon scattering in Ba3 BO. As a consequence of high PF and low κlat , Ba3 SiO (Ba3 GeO) exhibits rather high ZT = 0.16-0.84 (0.35-0.65) at T = 300-623 K (300-523 K). Finally, based on first-principles carrier and phonon transport calculations, maximum ZT is predicted to be 2.14 for Ba3 SiO and 1.21 for Ba3 GeO at T = 600 K by optimizing hole concentration. Present results propose that inverse-perovskites would be a new platform of environmentally-benign high-ZT thermoelectric materials.

Surface terminations control charge transfer from bulk to surface states in topological insulators.

Topological insulators (TI) hold significant potential for various electronic and optoelectronic devices that rely on the Dirac surface state (DSS), including spintronic and thermoelectric devices, as well as terahertz detectors. The behavior of electrons within the DSS plays a pivotal role in the performance of such devices. It is expected that DSS appear on a surface of three dimensional(3D) TI by mechanical exfoliation. However, it is not always the case that the surface terminating atomic configuration and corresponding band structures are homogeneous. In order to investigate the impact of surface terminating atomic configurations on electron dynamics, we meticulously examined the electron dynamics at the exfoliated surface of a crystalline 3D TI (Bi 2 Se 3 ) with time, space, and energy resolutions. Based on our comprehensive band structure calculations, we found that on one of the Se-terminated surfaces, DSS is located within the bulk band gap, with no other surface states manifesting within this region. On this particular surface, photoexcited electrons within the conduction band effectively relax towards DSS and tend to linger at the Dirac point for extended periods of time. It is worth emphasizing that these distinct characteristics of DSS are exclusively observed on this particular surface.

Berry curvature contributions of kagome-lattice fragments in amorphous Fe-Sn thin films.

Amorphous semiconductors are widely applied to electronic and energy-conversion devices owing to their high performance and simple fabrication processes. The topological concept of the Berry curvature is generally ill-defined in amorphous solids, due to the absence of long-range crystalline order. Here, we demonstrate that the Berry curvature in the short-range crystalline order of kagome-lattice fragments effectively contributes to the anomalous electrical and magneto-thermoelectric properties in Fe-Sn amorphous films. The Fe-Sn films on glass substrates exhibit large anomalous Hall and Nernst effects comparable to those of the single crystals of topological semimetals Fe3Sn2 and Fe3Sn. With modelling, we reveal that the Berry curvature contribution in the amorphous state likely originates from randomly distributed kagome-lattice fragments. This microscopic interpretation sheds light on the topology of amorphous materials, which may lead to the realization of functional topological amorphous electronic devices.

Two-dimensional heavy fermion in a monoatomic-layer Kondo lattice YbCu2.

The Kondo effect between localized f-electrons and conductive carriers leads to exotic physical phenomena. Among them, heavy-fermion (HF) systems, in which massive effective carriers appear due to the Kondo effect, have fascinated many researchers. Dimensionality is also an important characteristic of the HF system, especially because it is strongly related to quantum criticality. However, the realization of the perfect two-dimensional (2D) HF materials is still a challenging topic. Here, we report the surface electronic structure of the monoatomic-layer Kondo lattice YbCu2 on a Cu(111) surface observed by synchrotron-based angle-resolved photoemission spectroscopy. The 2D conducting band and the Yb 4f state, located very close to the Fermi level, are observed. These bands are hybridized at low-temperature, forming the 2D HF state, with an evaluated coherence temperature of about 30 K. The effective mass of the 2D state is enhanced by a factor of 100 by the development of the HF state. Furthermore, clear evidence of the hybridization gap formation in the temperature dependence of the Kondo-resonance peak has been observed below the coherence temperature. Our study provides a new candidate as an ideal 2D HF material for understanding the Kondo effect at low dimensions.

Te concentration dependent photoemission and inverse-photoemission study of FeSe1-xTex.

We have characterized the electronic structure of FeSe1-x Te x for various x values using soft x-ray photoemission spectroscopy (SXPES), high-resolution photoemission spectroscopy (HRPES) and inverse photoemission spectroscopy (IPES). The SXPES valence band spectral shape shows that the 2 eV feature in FeSe, which was ascribed to the lower Hubbard band in previous theoretical studies, becomes less prominent with increasing x. HRPES exhibits systematic x dependence of the structure near the Fermi level (EF): its splitting near EF and filling of the pseudogap in FeSe. IPES shows two features, near EF and approximately 6 eV above EF; the former may be related to the Fe 3d states hybridized with chalcogenide p states, while the latter may consist of plane-wave-like and Se d components. In the incident electron energy dependence of IPES, the density of states near EF for FeSe and FeTe has the Fano lineshape characteristic of resonant behavior. These compounds exhibit different resonance profiles, which may reflect the differences in their electronic structures. By combining the PES and IPES data the on-site Coulomb energy was estimated at 3.5 eV for FeSe.

High-Mobility Metastable Rock-Salt Type (Sn,Ca)Se Thin Film Stabilized by Direct Epitaxial Growth on a YSZ (111) Single-Crystal Substrate.

Metastable cubic (Sn1-xPbx)Se with x ≥ 0.5 is expected to be a high mobility semiconductor due to its Dirac-like electronic state, but it has an excessively high carrier concentration of ∼1019 cm-3 and is not suitable for semiconductor device applications such as thin film transistors and solar cells. Further, thin films of (Sn1-xPbx)Se require a complicated synthesis process because of the high vapor pressure of Pb. We herein report the direct growth of metastable cubic (Sn1-xCax)Se films alloyed with CaSe, which has a wider bandgap and lower vapor pressure than PbSe. The cubic (Sn1-xCax)Se epitaxial films with x = 0.4-0.8 are stabilized on YSZ (111) single crystalline substrates by pulsed laser deposition. (Sn1-xCax)Se has a direct-transition-type bandgap, and the bandgap energy can be varied from 1.4 eV (x = 0.4) to 2.0 eV (x = 0.8) by changing x. These films with x = 0.4-0.6 show p-type conduction with low hole carrier concentrations of ∼1017 cm-3. Hall mobility analysis suggests that the hole transport would be dominated by 180° rotational domain structures, which is specific to (111) oriented epitaxial films. However, it, in turn, clarifies that the in-grain carrier mobility in the (Sn0.6Ca0.4)Se film is as high as 322 cm2/(Vs), which is much higher than those in thermodynamically stable layered SnSe and other Sn-based layered semiconductor films at room temperature. Therefore, the present results prove the potential of high mobility (Sn1-xCax)Se films for semiconductor device applications via a simple thin-film deposition process.