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Toshio Kamiya

Publications and source records attributed to Toshio Kamiya.

At least 19 recordsLinked to original sources

Extracting effective solutions hidden in large language models via generated comprehensive specialists: case studies in developing electronic devices

Recently, many studies have increasingly explored the use of large language models (LLMs) to generate research ideas and scientific hypotheses. However, real-world research and development often require solving complex, interdisciplinary challenges where solutions may not be readily found through existing knowledge related to the problem. Therefore, it is desirable to leverage the vast, comprehensive knowledge of LLMs to generate effective, breakthrough solutions by integrating various perspectives from other disciplines. Here, we propose SELLM (Solution Enumeration via comprehensive List and LLM), a framework leveraging LLMs and structured guidance using MECE (Mutually Exclusive, Collectively Exhaustive) principles, such as International Patent Classification (IPC) and the periodic table of elements. SELLM systematically constructs comprehensive expert agents from the list to generate cross-disciplinary and effective solutions. To evaluate SELLM's practicality, we applied it to two challenges: improving light extraction in organic light-emitting diode (OLED) lighting and developing electrodes for next-generation memory materials. The results demonstrate that SELLM significantly facilitates the generation of effective solutions compared to cases without specific customization or effort, showcasing the potential of SELLM to enable LLMs to generate effective solutions even for challenging problems.

cs.CL

Discovery of self-assembled Ru/Si heterostructures with unique periodic nanostripe patterns boosting hydrogen evolution

Two-dimensional (2D) heterostructuring is a versatile methodology for designing nanoarchitecture catalytic systems that allow for reconstruction and modulation of interfaces and electronic structures. However, catalysts with such structures are extremely scarce due to limited synthetic strategies. Here, we report a highly ordered 2D Ru/Si nano-heterostructures (RSHS) by acid etching of the LaRuSi electride. RSHS shows a superior electrocatalytic activity for hydrogen evolution with an overpotential of 14 mV at 10 mA/cm2 in alkaline media. Both experimental analysis and first-principles calculations demonstrate that the electronic states of Ru can be tuned by strong interactions of the interfacial Ru-Si, leading to an optimized hydrogen adsorption energy. Moreover, due to the synergistic effect of Ru and Si, the energy barrier of water dissociation is significantly reduced. The unique nanostripe structure with abundant interfaces in RSHS will provide a paradigm for construction of efficient catalysts with tunable electronic states and dual active sites.

cond-mat.mtrl-sci

Photoinduced Transient States of Antiferromagnetic Orderings in La${}_{1/3}$Sr${}_{2/3}$FeO${}_{3}$ and SrFeO${}_{3}$ Thin Films Observed through Time-resolved Resonant Soft X-ray Scattering

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.

cond-mat.str-el

Crystal structure built from a GeO$_6$-GeO$_5$ polyhedra network with high thermal stability: $β$-SrGe$_2$O$_5$

By tackling the challenge of extending transparent oxide semiconductors to Ge based oxides, we have found a not-yet-reported crystal structure, named $β$-SrGe$_2$O$_5$, which is composed of edge-sharing GeO$_6$ octahedra interconnected by GeO$_5$ bipyramids. Single crystals were successfully grown by the high-pressure flux method. $β$-SrGe$_2$O$_5$ has a band gap of 5.2 eV and a dispersive conduction band with an effective mass as small as 0.34 times the electron rest mass, which originates from the edge-sharing GeO$_6$ octahedra network. Although known compounds with octahedral GeO$_6$ coordination are commonly unstable at atmospheric pressure and elevated temperatures, $β$-SrGe$_2$O$_5$ exhibits thermal stability up to 700 $^\circ$C.

cond-mat.mtrl-sci

Shallow Valence Band of Rutile GeO$_2$ and P-type Doping

GeO$_2$ has an $α$-quartz-type crystal structure with a very wide fundamental band gap of 6.6 eV and is a good insulator. Here we find that the stable rutile-GeO$_2$ polymorph with a 4.6 eV band gap has a surprisingly low $\sim$6.8 eV ionization potential, as predicted from the band alignment using first-principles calculations. Because of the short O$-$O distances in the rutile structure containing cations of small effective ionic radii such as Ge$^{4+}$, the antibonding interaction between O 2p orbitals raises the valence band maximum energy level to an extent that hole doping appears feasible. Experimentally, we report the flux growth of $1.5 \times 1.0 \times 0.8$ mm$^3$ large rutile GeO$_2$ single crystals and confirm the thermal stability for temperatures up to $1021 \pm 10~^\circ$C. X-ray fluorescence spectroscopy shows the inclusion of unintentional Mo impurities from the Li$_2$O$-$MoO$_3$ flux, as well as the solubility of Ga in the r-GeO$_2$ lattice as a prospective acceptor dopant. The resistance of the Ga- and Mo-codoped r-GeO$_2$ single crystals is very high at room temperature, but it decreases by 2-3 orders of magnitude upon heating to 300 $^\circ$C, which is attributed to thermally-activated p-type conduction.

cond-mat.mtrl-sci

Phonon scattering limited mobility in the representative cubic perovskite semiconductors SrGeO$_3$, BaSnO$_3$ and SrTiO$_3$

Cubic perovskite oxides are emerging high-mobility transparent conducting oxides (TCOs), but Ge-based TCOs had not been known until the discovery of metastable cubic SrGeO$_3$. $0.5 \times 0.4 \times 0.2$-mm$^3$ large single crystals of the cubic SrGeO$_3$ perovskite were successfully synthesized employing the high-pressure flux method. The phonon spectrum is determined from the IR optical reflectance and Raman-scattering analysis to evaluate the electron transport governed by optical phonon scattering. A calculated room-temperature mobility on the order of $3.9 \times 10^2$ cm$^2$V$^{-1}$s$^{-1}$ is obtained, identifying cubic SrGeO$_3$ as one of the most promising TCOs. Employing classical phonon theory and a combined experimental-theoretical approach, a comprehensive analysis of the intrinsic electron mobility in the cubic perovskite semiconductors SrGeO$_3$, BaSnO$_3$, and SrTiO$_3$ is provided based on the magnitude of polarization and eigenfrequency of optically active phonons.

cond-mat.mtrl-sci

Particulate Generation on Surface of Iron Selenide Films by Air Exposure

Nanometer-sized particular structures are generated on the surfaces of FeSe epitaxial films directly after exposure to air; this phenomenon was studied in the current work because these structures are an obstacle to field-induced superconductivity in electric double-layer transistors using FeSe channel layers. Chemical analyses using field-effect scanning Auger electron spectroscopy revealed no clear difference in the chemical composition between the particular structures and the other flat surface region. This observation limits the possible origins of the particulate formation to light elements in air such as O, C, H, and N.

cond-mat.supr-con

Insulator-like behavior coexisting with metallic electronic structure in strained FeSe thin films grown by molecular beam epitaxy

This paper reports that ~10-nm-thick FeSe thin films exhibit insulator-like behavior in terms of the temperature dependence of their electrical resistivity even though bulk FeSe has a metallic electronic structure that has been confirmed by photoemission spectroscopy and first-principles calculations. This apparent contradiction is explained by potential barriers formed in the conduction band. Very thin FeSe epitaxial films with various [Fe]/[Se] were fabricated by molecular beam epitaxy and classified into two groups with respect to lattice strain and electrical properties. Lattice parameter a increased and lattice parameter c decreased with increasing [Fe]/[Se] up to 1.1 and then a levelled off and c began to decrease at higher [Fe]/[Se]. Consequently, the FeSe films had the most strained lattice when [Fe]/[Se] was 1.1, but these films had the best quality with respect to crystallinity and surface flatness. All the FeSe films with [Fe]/[Se] of 0.8-1.9 exhibited insulator-like behavior, but the temperature dependences of their electrical resistivities exhibited different activation energies Ea between the Se-rich and Fe-rich regions; i.e., Ea were small (a few meV) up to [Fe]/[Se]=1.1 but jumped up to ~25 meV at higher [Fe]/[Se]. The film with [Fe]/[Se]=1.1 had the smallest Ea of 1.1 meV and exhibited an insulator-superconducting transition at 35 K with zero resistance under gate bias. The large Ea of the Fe-rich films was attributed to the unusual lattice strain with tensile in-plane and relaxed out-of-plane strains. The large Ea of films with [Fe]/[Se]>1.1 resulted in low mobility with a high potential barrier of ~50 meV in the conduction band for percolation carrier conduction compared with that of the [Fe]/[Se]=1.1 film (~17 meV). Therefore, the Fe-rich films exhibited remarkable insulator-like behavior similar to a semiconductor despite their metallic electronic structure.

cond-mat.str-el

BaFe2(As1-xPx)2 (x = 0.22-0.42) thin films grown on practical metal-tape substrates and their critical current densities

We optimized the substrate temperature (Ts) and phosphorus concentration (x) of BaFe2(As1-xPx)2 films on practical metal-tape substrates for pulsed laser deposition from the viewpoints of crystallinity, superconductor critical temperature (Tc), and critical current density (Jc). It was found that the optimum Ts and x values are 1050 degree C and x = 0.28, respectively. The optimized film exhibits Tc_onset = 26.6 and Tc_zero = 22.4 K along with a high self-field Jc at 4 K (~1 MA/cm2) and relatively isotropic Jc under magnetic fields up to 9 T. Unexpectedly, we found that lower crystallinity samples, which were grown at a higher Ts of 1250 degree C than the optimized Ts = 1050 degree C, exhibit higher Jc along the ab plane under high magnetic fields than the optimized samples. The presence of horizontal defects that act as strong vortex pinning centers, such as stacking faults, are a possible origin of the high Jc values in the poor crystallinity samples.

cond-mat.supr-con

Electron effective mass and mobility limits in degenerate perovskite stannate BaSnO$_3$

The high room temperature mobility and the electron effective mass in BaSnO$_3$ are investigated in depth by evaluation of the free carrier absorption observed in infrared spectra for epitaxial films with free electron concentrations from $8.3 \times 10^{18}$ to $7.3 \times 10^{20}$~cm$^{-3}$. Both the optical band gap widening by conduction band filling and the carrier scattering mechanisms in the low and high doping regimes are consistently described employing parameters solely based on the intrinsic physical properties of BaSnO$_3$. The results explain the current mobility limits in epitaxial films and demonstrate the potential of BaSnO$_3$ to outperform established wide band gap semiconductors also in the moderate doping regime.

cond-mat.mtrl-sci

Enhanced critical-current in P-doped BaFe2As2 thin films on metal substrates arising from poorly aligned grain boundaries

Thin films of the iron-based superconductor BaFe2(As1-xPx)2 (Ba122:P) were fabricated on polycrystalline metal-tape substrates with two kinds of in-plane grain boundary alignments (well aligned (4 deg.) and poorly aligned (8 deg.)) by pulsed laser deposition. The poorly aligned substrate is not applicable to cuprate-coated conductors because the in-plane alignment >4 deg. results in exponential decay of the critical current density (Jc). The Ba122:P film exhibited higher Jc at 4 K when grown on the poorly aligned substrate than on the well-aligned substrate even though the crystallinity was poorer. It was revealed that the misorientation angles of the poorly aligned samples were less than 6 deg., which are less than the critical angle of an iron-based superconductor, cobalt-doped BaFe2As2 (~9 deg.), and the observed strong pinning in the Ba122:P is attributed to the high-density grain boundaries with the misorientation angles smaller than the critical angle. This result reveals a distinct advantage over cuprate-coated conductors because well-aligned metal-tape substrates are not necessary for practical applications of the iron-based superconductors.

cond-mat.supr-con

Novel solid-phase epitaxy for multi-component materials with extremely high vapor pressure elements: An application to KFe2As2

We propose a novel solid-phase epitaxy technique applicable to high annealing temperatures up to 1000 C without re-vaporization of alkali metal elements with high vapor pressures. This technique is demonstrated through the successful growth of high-quality KFe2As2 epitaxial films. The key factors are employing a custom-designed alumina vessel/cover and sealing it in a stainless tube with a large amount of atmospheric KFe2As2 powder in tightly closed sample spaces. This technique can also be effective for other materials composed of elements with very high vapor pressures, such as alkali metals, and can lead to the realization of spintronics devices in the future using KFe2As2.

cond-mat.mtrl-sci

Electric field-induced superconducting transition of insulating FeSe thin film at 35 K

It is thought that strong electron correlation in an insulating parent phase would enhance a critical temperature (Tc) of superconductivity in a doped phase via enhancement of the binding energy of a Cooper pair as known in high-Tc cuprates. To induce a superconductor transition in an insulating phase, injection of a high density of carriers is needed (e.g., by impurity doping). An electric double-layer transistor (EDLT) with an ionic liquid gate insulator enables such a field-induced transition to be investigated and is expected to result in a high Tc because it is free from deterioration in structure and carrier transport that are in general caused by conventional carrier doping (e.g., chemical substitution). Here, for insulating epitaxial thin films (~10 nm thick) of FeSe, we report a high Tc of 35 K, which is four times higher than that of bulk FeSe, using an EDLT under application of a gate bias of +5.5 V. Hall effect measurements under the gate bias suggest that highly accumulated electron carrier in the channel, whose area density is estimated to be 1.4x10^15 cm-2 (the average volume density of 1.7x10^21 cm-3), is the origin of the high-Tc superconductivity. This result demonstrates that EDLTs are useful tools to explore the ultimate Tc for insulating parent materials.

cond-mat.supr-con

Intrinsic defects in photovoltaic perovskite variant Cs2SnI6

Note: This paper has been published in Physical Chemistry Chemical Physics, which can be viewed at the following URL: http://doi.org/10.1039/C5CP03102H Cs2SnI6, a rarely studied perovskite variant material, is recently gaining a lot of interest in the field of photovoltaics owing to its nontoxity, air-stability and promissing photovoltaic properties. In this work, we report intrinsic defects in Cs2SnI6 using first-principles density functional theory calculations. It is revealed that iodine vacancy and tin interstitial are the dominant defects that are responsible for the intrinsic n-type conduction in Cs2SnI6. Tin vacancy has a very high formation energy (>3.6 eV) due to the strong covalency in the Sn-I bonds and is hardly generated for p-type doping. All the dominant defects in Cs2SnI6 have deep transition levels in the band gap. It is suggested that the formation of the deep defects can be suppressed significantly by employing an I-rich synthesis condition, which is inevitable for photovoltaic and other semiconductor applications.

physics.comp-ph

Ligand-Hole in SnI6 Unit and Origin of Band Gap in Photovoltaic Perovskite Variant Cs2SnI6

This paper has been published in Bulletin of the Chemical Society of Japan, which can be viewed at the following URL: http://doi.org/10.1246/bcsj.20150110 Cs2SnI6, a variant of perovskite CsSnI3, is expected for a photovoltaic material. Based on a simple ionic model, it is expected that Cs2SnI6 is composed of Cs+, I-, and Sn4+ ions and that the band gap is primarily made of occupied I- 5p6 valence band maximum (VBM) and unoccupied Sn4+ 5s conduction band minimum (CBM) similar to SnO2. In this work, we performed density functional theory (DFT) calculations and revealed that the real oxidation state of the Sn ion in Cs2SnI6 is +2 similar to CsSnI3. The +2 oxidation state of Sn originates from 2 ligand holes in the [SnI6]2- octahedron unit, where the ligand [I6] cluster has the apparent [I66-L+2]4- oxidation state, because the band gap is formed mainly by occupied I 5p VBM and unoccupied I 5p CBM. The +2 oxidation state of Sn and the band gap are originated from the intracluster hybridization and stabilized by the strong covalent interaction between Sn and I.

physics.chem-ph

Narrow Bandgap in beta-BaZn2As2 and Its Chemical Origins

Beta-BaZn2As2 is known to be a p-type semiconductor with the layered crystal structure similar to that of LaZnAsO, leading to the expectation that beta-BaZn2As2 and LaZnAsO have similar bandgaps; however, the bandgap of beta-BaZn2As2 (previously-reported value ~0.2 eV) is one order of magnitude smaller than that of LaZnAsO (1.5 eV). In this paper, the reliable bandgap value of beta-BaZn2As2 is determined to be 0.23 eV from the intrinsic region of the tem-perature dependence of electrical conductivity. The origins of this narrow bandgap are discussed based on the chemi-cal bonding nature probed by 6 keV hard X-ray photoemission spectroscopy, hybrid density functional calculations, and the ligand theory. One origin is the direct As-As hybridization between adjacent [ZnAs] layers, which leads to a secondary splitting of As 4p levels and raises the valence band maximum. The other is that the non-bonding Ba 5dx2-y2 orbitals form unexpectedly deep conduction band minimum (CBM) in beta-BaZn2As2 although the CBM of LaZnAsO is formed mainly of Zn 4s. These two origins provide a quantitative explanation for the bandgap difference between beta-BaZn2As2 and LaZnAsO.

physics.chem-ph

n-type conversion of SnS by isovalent ion substitution: Geometrical doping as a new doping route

Tin monosulfide (SnS) is a naturally p-type semiconductor with a layered crystal structure, but no reliable n-type SnS has been obtained by conventional aliovalent ion substitution. In this work, carrier polarity conversion to n-type was achieved by isovalent ion substitution for polycrystalline SnS thin films on glass substrates. Substituting Pb2+ for Sn2+ converted the majority carrier from hole to electron, and the free electron density ranged from 1012 to 1015 cm-3 with the largest electron mobility of 7.0 cm2/(Vs). The n-type conduction was confirmed further by the position of the Fermi level (EF) based on photoemission spectroscopy and electrical characteristics of pn heterojunctions. Density functional theory calculations reveal that the Pb substitution invokes a geometrical size effect that enlarges the interlayer distance and subsequently reduces the formation energies of Sn and Pb interstitials, which work as electron donors.

cond-mat.mtrl-sci

High critical-current density with less anisotropy in BaFe2(As,P)2 epitaxial thin films: Effect of intentionally grown c-axis vortex-pinning centers

We report herein a high and isotropic critical-current density Jc for BaFe2(As,P)2 epitaxial films. The isotropy of Jc with respect to the magnetic-field direction was improved significantly by decreasing the film growth rate to 2.2 Å/s. The low growth rate served to preferentially align dislocations along the c-axis, which work well as c-axis vortex-pinning centers. Because of the intentional introduction of effective pinning, the absolute Jc at 9 T was larger than that obtained for other iron-based superconductors and conventional alloy superconducting wires.

cond-mat.supr-con