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We demonstrate that hole carrier density of α-SnWO4 can be tuned by controlling the annealing process. Hole carrier density increased by two orders of magnitude and achieved a value close to 1019 cm−3 at an optimum O2 gas concentration.

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.

A layered semiconductor, SrTiN2, has an interesting crystal structure as a two-dimensional (2D) electron system embedded in a three-dimensional bulk periodic structure because it has alternate stacking of a SrN blocking layer and a TiN conduction layer, in which the Ti 3dxy orbital forms the conduction band minimum (CBM) similar to the SrTiO3-based thin-film heterostructure. However, SrTiN2 has been reported to exhibit nearly degenerate conduction, but we reported that it would be due to the easy formation of nitrogen vacancies and oxygen impurities from air. In this paper, we extend the materials to family compounds, alkaline earth (AE) ion-substituted, AETiN2 (AE = Ca, Sr, and Ba), and investigated how we can suppress the defect formation by (hybrid) density functional theory calculations. All AETiN2 compounds possess thermodynamic stability in the wide nitrogen (N) chemical potential window. Especially, CaTiN2 is the most stable even against N-poor conditions. Unintentional carrier generation occurs due to the nitrogen vacancies (VN), oxygen substitution (ON), and hydrogen anion substitution (HN) at the nitrogen sites. The VN and HN impurities can be suppressed under N-moderate and N-rich conditions. The ON defect is easily formed in SrTiN2 and also in BaTiN2 under N-rich conditions, but its formation can be suppressed in CaTiN2. Present results suggest that high-purity CaTiN2 can be obtained under wider N chemical conditions, which would lead to the realization of the novel functional properties originating from Ti 3dxy 2D bands embedded in the bulk crystal structure.

Metastable cubic (Sn

We propose a unique strategy to apply stronger strain at heterointerfaces than conventional epitaxial strain methods to extract hidden attractive physical/chemical properties in materials. This strategy involves precisely accounting for the epitaxial strain induced by lattice mismatch as well as the differences in the thermal expansion coefficients and compressibilities of epitaxial films and substrates. We selected optimally cobalt-doped BaFe2As2(Ba122:Co), an iron-based superconductor with a bulk critical temperature (Tc) of 22 K, as a model material and four types of single-crystal substrates. Ba122:Co was selected because its Tc is robust to hydrostatic pressure but sensitive to epitaxial strain (i.e., one of the anisotropic strains), and the selected substrates entirely cover the positive/negative lattice mismatches, thermal expansion coefficients, and compressibilities with respect to Ba122:Co. With strong anisotropic strain successfully induced by film growth, external hydrostatic pressurizing, and cooling processes, we observed unique carrier transport properties in Ba122:Co epitaxial films on CaF2 and BaF2 substrates including (i) upturn behavior in the temperature dependence of the longitudinal resistivity, (ii) negative magnetoresistance, (iii) large enhancement of anomalous Hall effects in the epitaxial films on CaF2, and (iv) enhancement of Tc to 27 K in the epitaxial films on BaF2. These results demonstrate the effectiveness of our strategy, and this approach can be further extended to other inorganic materials in thin-film form.

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

Owing to the recent discovery of the current-induced metal-insulator transition and unprecedented electronic properties of the concomitant phases of calcium ruthenate Ca2RuO4, it is emerging as an important material. To further explore the properties, the growth of epitaxial thin films of Ca2RuO4 is receiving more attention, as high current densities can be applied to thin-film samples and the amount can be precisely controlled in an experimental environment. However, it is difficult to grow high-quality thin films of Ca2RuO4 due to the easy formation of the crystal defects originating from the sublimation of RuO4; therefore, the metal-insulator transition of Ca2RuO4 is typically not observed in the thin films. Herein, a stable current-induced metal-insulator transition is achieved in the high-quality thin films of Ca2RuO4 grown by solid-phase epitaxy under high growth temperatures and pressures. In the Ca2RuO4 thin films grown by ex situ annealing at >1200 °C and 1.0 atm, continuous changes in the resistance of over 2 orders of magnitude are induced by currents with a precise dependence of the resistance on the current amplitude. A hysteretic, abrupt resistive transition is also observed in the thin films from the resistance-temperature measurements conducted under constant-voltage (variable-current) conditions with controllability of the transition temperature. A clear resistive switching by the current-induced transition is demonstrated in the current-electric-field characteristics, and the switching currents and fields are shown to be very stable. These results represent a significant step toward understanding the high-current-density properties of Ca2RuO4 and the future development of Mott-electronic devices based on electricity-driven transitions.

The {100}-oriented (CaxSr1-x)Si2 thin films have been prepared by co-sputtering method at various deposition temperatures. Constituent phase of the films primarily depends on the deposition temperature and the composition x. Although CaSi2 films consisted of layered structure regardless of deposition temperature, the phase was changed by the deposition temperature: the majority phases of the film deposited at 600°C, 650°C and 700°C were 1T layered structure, 1T layered structure + 2H layered structure and 1T layered structure + 6R layered structure, respectively. When the (CaxSr1-x)Si2 films deposited at 700°C, the α-SrSi2-type phase was mainly confirmed below x = 0.17, which is the most stable phase of SrSi2. However, the main phase of all CaxSr1-xSi2 films deposited at 600°C changed to be 1T-type layered structure. Substitution with Ca below x = 0.50 in the film deposited at 600°C led to the decrease in the electrical resistivity compared with that of pure SrSi2.

We confirmed that quantum confinement effects are clearly observed even in a disordered material. Employing amorphous In–Ga–Zn–O ( a-IGZO) thin-film transistors (TFTs) with quantum well channels, it was observed that field-effect mobility–gate voltage relations exhibited plateaus when the well thickness was 5 nm or less. Device simulation incorporating the quantum confinement effects reproduced the well-thickness dependence of the plateau onset voltage, verifying that the quantized electronic levels in the a-IGZO well dominate the TFT characteristics and, thus, the electron transport is free electron like with a coherent length of ∼5 nm. The field-effect mobility did not exceed the drift mobility of bulk a-IGZO, which is different from amorphous silicon superlattice TFT.

In this study, we fabricated light-emitting diodes (LEDs) on glass substrates at a maximum process temperature of 200 °C using amorphous oxide semiconductor (AOS) materials as emission layers. Amorphous gallium oxide films doped with rare-earth elements (Eu, Pr, and Tb) were employed as AOS emission layers, and the LEDs emitted clear red, green, and pink luminescence upon direct-current application even in the ambient environment. Resonance photoelectron spectroscopy revealed the difference in the electronic structure of the films for each rare-earth dopant, suggesting different emission mechanisms, viz., electron–hole recombination and impact excitation. Although it is widely believed that amorphous materials are unsuitable for use as emission layers of LEDs because of their high concentrations of mid-gap states and defects, the developed rare-earth-doped AOS materials show good performance as emission layers. This study provides opportunities for the advancement of flexible display technologies operating in harsh environments.

A layered semiconductor, SrTiN

Among the intermetallics and alloys, YCu is an unusual material because it displays negative thermal expansion without spin ordering. The mechanism behind this behavior that is caused by the structural phase transition of YCu has yet to be fully understood. To gain insight into this mechanism, we experimentally examined the crystal structure of the low-temperature phase of YCu and discuss the origin of the phase transition with the aid of thermodynamics calculations. The result shows that the high-temperature (cubic CsCl-type) to low-temperature (orthorhombic FeB-type) structural phase transition is driven by the rearrangement of three covalent bonds, namely, Y-Cu, Y-Y, and Cu-Cu, which compete for the bonding energy and phonon entropy. At low temperatures, the mixing of Y and Cu does not take place easily because of the weak attractive force between these atoms expected from the small negative mixing enthalpy. This causes all three interactions to take part in the bonding, and Y and Cu are segregated to form an FeB-type structure, which is stabilized by internal energy. At higher temperatures, Cu ions are bound loosely with Y ions due to the large Y-Cu distance (3.01 Å), which results in large vibration entropy and stabilizes a CsCl-type crystal structure. In addition, the CsCl-type structure is reinforced by the Y-Y interaction between next-nearest neighbors, resulting in a smaller unit cell volume. The crystal structure has the simple cubic framework of Y containing Cu ions bound loosely at the cavity sites. The calculated frequency of the Y-like phonon modes is much higher than that of the Cu-like modes, indicating the presence of Y-Y covalent interactions in the CsCl-type phase.

SrTiN2 is expected to exhibit unique carrier transport properties since it has a two-dimensional (2D) electron transport layer in its natural layered crystal structure, and its conduction band mini...

Layered Ruddlesden–Popper (RP) perovskites have good moisture- and photostability. However, thermal stability of the RP perovskites is still a challenge. In this work, through a joint theoretical a...

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

3D-2D structural phase transition is artificially induced to invoke giant electronic modulation in nonequilibrium (Pb1−xSnx)Se., Material properties depend largely on the dimensionality of the crystal structures and the associated electronic structures. If the crystal-structure dimensionality can be switched reversibly in the same material, then a drastic property change may be controllable. Here, we propose a design route for a direct three-dimensional (3D) to 2D structural phase transition, demonstrating an example in (Pb1−xSnx)Se alloy system, where Pb2+ and Sn2+ have similar ns2 pseudo-closed shell configurations, but the former stabilizes the 3D rock-salt-type structure while the latter a 2D layered structure. However, this system has no direct phase boundary between these crystal structures under thermal equilibrium. We succeeded in inducing the direct 3D-2D structural phase transition in (Pb1−xSnx)Se alloy epitaxial films by using a nonequilibrium growth technique. Reversible giant electronic property change was attained at x ~ 0.5 originating in the abrupt band structure switch from gapless Dirac-like state to semiconducting state.

By tackling the challenge of extending transparent oxide semiconductors to Ge based oxides, we have found a not-yet-reported crystal structure, named $\beta$-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. $\beta$-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, $\beta$-SrGe$_2$O$_5$ exhibits thermal stability up to 700 $^\circ$C., Comment: 23 pages, 8 figures

Amorphous oxide semiconductors (AOSs) represented by amorphous In-Ga-Zn-O have been applied for state-of-the-art flat panel displays as thin-film transistor backplane since 2012. Understanding defects in AOS is critically important for controlling the instability of TFTs. It is found in the past decades that many AOS defects are related to oxygen and hydrogen impurities, though oxygen is the major constituent of AOS and hydrogen is not intentionally incorporated.

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 ${\mathrm{SrGeO}}_{3}$. $0.5\ifmmode\times\else\texttimes\fi{}0.4\ifmmode\times\else\texttimes\fi{}0.2\text{\ensuremath{-}}\mathrm{m}{\mathrm{m}}^{3}$ large single crystals of the cubic ${\mathrm{SrGeO}}_{3}$ 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 $3.9\ifmmode\times\else\texttimes\fi{}{10}^{2}\phantom{\rule{0.16em}{0ex}}\mathrm{c}{\mathrm{m}}^{2}\phantom{\rule{0.16em}{0ex}}{\mathrm{V}}^{\ensuremath{-}1}\phantom{\rule{0.16em}{0ex}}{\mathrm{s}}^{\ensuremath{-}1}$ is obtained, identifying cubic ${\mathrm{SrGeO}}_{3}$ 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 ${\mathrm{SrGeO}}_{3}$, ${\mathrm{BaSnO}}_{3}$, and ${\mathrm{SrTiO}}_{3}$ is provided based on the magnitude of polarization and eigenfrequency of optically active phonons.

GeO$_2$ has an $\alpha$-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.

We report the synthesis and characterizations of a new FeSe-based compound CsFe4−δSe4, which is closely related to alkali intercalated FeSe superconductors while exhibits distinct features. It does not undergo phase separation and antiferromagnetic transition. Powder neutron diffractions, electron microscopy and high-angle annular-dark-field images confirm that CsFe4−δSe4 possesses an ordered Cs arrangement as √2 × √2 superstructure, evidencing a B-centered orthorhombic lattice with a space group of Bmmm. The temperature-dependent powder neutron diffractions indicate no structural and magnetic transition from 320 to 5 K. In contrast to the symmetry-breaking in FeSe, this phase naturally possesses the orthorhombic symmetry even at room temperature. DFT calculations and transport measurements reveal a novel Fermi surface geometry with two electron-like sheets centered on Γ point and intermediate density of states at the Fermi level comparing with the value of FeSe and the superconducting AxFe2Se2.

The bandgap is the most important physical property that determines the potential of semiconductors for photovoltaic (PV) applications. This Minireview discusses the parameters affecting the bandgap of perovskite semiconductors that are being widely studied for PV applications, and the recent progress in the optimization of the bandgaps of these materials. Perspectives are also provided for guiding future research in this area.

Introducing artificial strain in epitaxial thin films is an effective strategy to alter electronic structures of transition metal oxides (TMOs) and to induce novel phenomena and functionalities not realized in bulk crystals. This study reports a breaking of the conventional trade‐off relation in thermopower (S)–conductivity (σ) and demonstrates a 2 orders of magnitude enhancement of power factor (PF) in compressively strained LaTiO3 (LTO) films. By varying substrates and reducing film thickness down to 4 nm, the out‐of‐plane to the in‐plane lattice parameter ratio is controlled from 0.992 (tensile strain) to 1.034 (compressive strain). This tuning induces the electronic structure change from a Mott insulator to a metal and leads to a 103‐fold increase in σ up to 2920 S cm−1. Concomitantly, the sign of S inverts from positive to negative, and both σ and S increase and break the trade‐off relation between them in the n‐type region. As a result, the PF (=S2σ) is significantly enhanced to 300 µW m−1K−2, which is 102 times larger than that of bulk LTO. Present results propose epitaxial strain as a means to finely tune strongly correlated TMOs close to their Mott transition, and thus to harness the hidden large thermoelectric PF.

Although metal halide double perovskites A2B(I)B(III)X6 are expected as nontoxic alternatives for lead halide perovskites, recent studies have shown that only Tl(I)–Bi(III) and In(I)–Bi(III) bromides are thermodynamically stable and possess optoelectronic properties suitable for photovoltaic absorbers. Here, we show, through density functional theory calculations, that Tl–Bi and In–Bi bromide double perovskites exhibit significantly different semiconducting behaviors due to the different energy levels of the highest-occupied pseudoclosed s2 orbitals of Tl(I) and In(I). While Tl–Bi double perovskites can exhibit semiconducting p-type properties, In–Bi bromide double perovskites exhibit metallic p-type ones regardless of the synthesis condition due to the extremely low formation energy of In vacancy. Such difference makes Tl–Bi bromide double perovskites suitable for optoelectronic applications, but not In–Bi bromide double perovskites. Furthermore, there is a high probability for In to substitute a Bi site...