Polarity Control of an All-Sputtered Epitaxial GaN/AlN/Al Film on a Si(111) Substrate by Intermediate Oxidization.

The ability to control the polarity of an all-sputtered epitaxial GaN/AlN/Al film on a Si(111) substrate via intermediate oxidization was investigated. A stable surface of GaN on a Si substrate is a N-terminated surface (-c surface); hence, for electric device applications, the Ga-terminated surface (+c surface) is preferable. The GaN/AlN/Al film on Si(111) showed a -c surface, as confirmed by time-of-flight low-energy atom scattering spectroscopy (TOFLAS) and X-ray photoelectron spectroscopy (XPS). The AlN layer was intentionally oxidized via air exposure during film growth. The GaN surface subjected to the oxidization process had the +c surface. Secondary-ion mass spectrometry measurements indicated a high oxygen concentration after the intentional oxidization. However, the intentional oxidization degraded the crystallinity of the GaN/AlN layer. By changing the oxidization point and repeating the GaN/AlN growth, the crystallinity of GaN was recovered. Such polarity control of GaN on Si grown by sputtering shows strong potential for the fabrication of large-diameter +c-GaN template substrates at low cost.

Evidence-based recommender system for high-entropy alloys.

Existing data-driven approaches for exploring high-entropy alloys (HEAs) face three challenges: numerous element-combination candidates, designing appropriate descriptors, and limited and biased existing data. To overcome these issues, here we show the development of an evidence-based material recommender system (ERS) that adopts Dempster-Shafer theory, a general framework for reasoning with uncertainty. Herein, without using material descriptors, we model, collect and combine pieces of evidence from data about the HEA phase existence of alloys. To evaluate the ERS, we compared its HEA-recommendation capability with those of matrix-factorization- and supervised-learning-based recommender systems on four widely known datasets of up-to-five-component alloys. The k-fold cross-validation on the datasets suggests that the ERS outperforms all competitors. Furthermore, the ERS shows good extrapolation capabilities in recommending quaternary and quinary HEAs. We experimentally validated the most strongly recommended Fe-Co-based magnetic HEA (namely, FeCoMnNi) and confirmed that its thin film shows a body-centered cubic structure.

Valence Band Modification of a (GaxIn1-x)2O3 Solid Solution System Fabricated by Combinatorial Synthesis.

The correlation between the crystal structure and valence band structure of a (GaxIn1-x)2O3 solid solution system was investigated by using combinatorial synthesis. At a low Ga content of (GaxIn1-x)2O3 with a single-phase cubic In2O3 crystal structure, a surface electron accumulation layer (SEAL), which is an important electrical phenomenon in In2O3, was confirmed. When the Ga content increased to approximately x = 0.4, mixed crystal structures of Ga2O3 and In2O3 were produced. Above x = 0.5, the dominant valence band structure was attributed to Ga2O3, the SEAL disappeared, and the sheet resistance increased greatly by 5 orders of magnitude or more. The in-gap state and valence band structure of the (GaxIn1-x)2O3 solid solution system were strongly affected by Ga2O3; however, the valence band maximum position shifted to a higher binding energy.

Layer-by-Layer Motif Heteroarchitecturing of N,S-Codoped Reduced Graphene Oxide-Wrapped Ni/NiS Nanoparticles for the Electrochemical Oxidation of Water.

A new heterostructured material is synthesized with lamellar arrangements in nanoscale precision through an innovative synthetic approach. The self-assembled Ni-based cyano-bridged coordination polymer flakes (Ni-CP) and graphene oxide (GO) nanosheets with a layered morphology (Ni-CP/GO) are used as precursors for the synthesis of multicomponent hybrid materials. Annealing of Ni-CP/GO in nitrogen at 450 °C allows the formation of Ni3 C/rGO nanocomposites. Grinding Ni-CP/GO and thiourea and annealing under the same conditions produces N,S-codoped reduced GO-wrapped NiS2 flakes (NiS2 /NS-rGO). Interestingly, further heating up to 550 °C allows the phase transformation of NiS2 into NiS accompanied by the formation of a face-centered cubic (FCC-Ni) metal phase between NS-rGO layers (FCC-Ni-NiS/NS-rGO). Among all the materials, the resulting FCC-Ni-NiS/NS-rGO exhibits good electrocatalytic activity and stability toward the oxygen evolution reaction (OER) owing to the synergistic effect of multiphases, the well-designed alternating layered structures on the nanoscale with abundant active sites.

Mesostructured HfO2/Al2O3 Composite Thin Films with Reduced Leakage Current for Ion-Conducting Devices.

Mesoporous hafnium dioxide (HfO2) thin films (around 20 nm thick) were fabricated by a sol-gel-based spin-coating process, followed by an annealing process at 600 °C to realize the ion-conducting media for the ionics (e.g., Na+ and K+ for rechargeable ion batteries). Another film of aluminum metal (10 nm thick) was deposited by direct current sputtering to soak into the mesopores. A monitored thermal treatment process at 500 °C in the air yields mesostructured HfO2/Al2O3 composite thin films. However, aluminum dioxide (Al2O3) is formed during annealing as an insulating film to reduce the leakage current while retaining the ionic conductivity. The obtained mesostructured HfO2/Al2O3 films show a leakage current at 3.2 × 10-9 A cm-2, which is significantly smaller than that of the mesoporous HfO2 film (1.37 × 10-5 A cm-2) or HfO2/Al film (0.037 A cm-2) at a bias voltage of 1.0 V, which is enough for ion conduction. In the meantime, among all the thin films, the mesostructured HfO2/Al2O3 composite thin films display the smallest Nyquist arc diameter in 1.0 M KOH electrolyte, implying a lower impedance at the electrode/electrolyte interface and reflecting a better ion diffusion and movement.

Electrical and Structural Properties of the Partial Ternary Thin-Film System Ni-Si-B.

High-throughput and combinatorial materials science methods were used to investigate the dependence of the work function in the Ni-Si system on the B content (0-30 at. %). Alloying of NiSi is used to adapt its properties to suit the needs as a gate electrode material. Thin-film materials libraries were fabricated and investigated with respect to their structural and electrical properties. Further the work function values of selected samples in the region of interest were analyzed. The results show that the work function can be adjusted between 4.86 eV (B = 4.2 at. %) and 5.16 eV (B = 29.2 at. %) for (NiSi)B x.

Synthesis of Hollow Co-Fe Prussian Blue Analogue Cubes by using Silica Spheres as a Sacrificial Template.

Herein, we report a novel method for the formation of hollow Prussian blue analogue (CoFe-PBA) nanocubes, using spherical silica particles as sacrificial templates. In the first step, silica cores are coated by a CoFe-PBA shell and then removed by etching with hydrofluoric acid (HF). The cubic shape of CoFe-PBA is well-retained even after the removal of the silica cores, resulting in the formation of hollow CoFe-PBA cubes. The specific capacity of the hollow CoFe-PBA nanocubes electrodes is about two times higher than that of solid CoFe-PBA nanocubes as storage materials for sodium ions. Such an improvement in the electrochemical properties can be attributed to their hollow internal nanostructure. The hollow architecture can offer a larger interfacial area between the electrolyte and the electrode, leading to an improvement in the electrochemical activity. This strategy can be applied to develop PBAs with hollow interiors for a wide range of applications.

Multi-Valued Logic Circuits Based on Organic Anti-ambipolar Transistors.

Multivalued logic circuits, which can handle more information than conventional binary logic circuits, have attracted much attention as a promising way to improve the data-processing capabilities of integrated circuits. In this study, we developed a ternary inverter based on organic field-effect transistors (OFET) as a potential component of high-performance and flexible integrated circuits. Key elements are anti-ambipolar and n-type OFETs connected in series. First, we demonstrate an organic ternary inverter that exhibits three distinct logic states. Second, the operating voltage was greatly reduced by taking advantage of an Al2O3 gate dielectric. Finally, the operating voltage was finely tuned by the designing of the device geometry. These results are achievable owing to the flexible controllability of the device configuration, suggesting that the organic ternary inverter plays an important role with regard to high-performance organic integrated circuits.

Mn Self-Doping of Orthorhombic RMnO3 Perovskites: (R0.667Mn0.333)MnO3 with R = Er-Lu.

Orthorhombic rare-earth trivalent manganites RMnO3 (R = Er-Lu) were self-doped with Mn to form (R0.667Mn0.333)MnO3 compositions, which were synthesized by a high-pressure, high-temperature method at 6 GPa and about 1670 K from R2O3 and Mn2O3. The average oxidation state of Mn is 3+ in (R0.667Mn0.333)MnO3. However, Mn enters the A site in the oxidation state of 2+, creating the average oxidation state of 3.333+ at the B site. The presence of Mn2+ was confirmed by hard X-ray photoelectron spectroscopy measurements. Crystal structures were studied by synchrotron powder X-ray diffraction. (R0.667Mn0.333)MnO3 crystallizes in space group Pnma with a = 5.50348(2) Å, b = 7.37564(1) Å, and c = 5.18686(1) Å for (Lu0.667Mn0.333)MnO3 at 293 K, and they are isostructural with the parent RMnO3 manganites. Compared with RMnO3, (R0.667Mn0.333)MnO3 exhibits enhanced Néel temperatures of about TN1 = 106-110 K and ferrimagnetic or canted antiferromagnetic properties. Compounds with R = Er and Tm show additional magnetic transitions at about TN2 = 9-16 K. (Tm0.667Mn0.333)MnO3 exhibits a magnetization reversal or negative magnetization effect with a compensation temperature of about 16 K.

Interface Engineering for Controlling Device Properties of Organic Antiambipolar Transistors.

The main purpose of this study is to establish a guideline for controlling the device properties of organic antiambipolar transistors. Our key strategy is to use interface engineering to promote carrier injection at channel/electrode interfaces and carrier accumulation at a channel/dielectric interface. The effective use of carrier injection interlayers and an insulator layer with a high dielectric constant (high-k) enabled the fine tuning of device parameters and, in particular, the onset (Von) and offset (Voff) voltages. A well-matched combination of the interlayers and a high-k dielectric layer achieved a low peak voltage (0.25 V) and a narrow on-state bias range (2.2 V), indicating that organic antiambipolar transistors have high potential as negative differential resistance devices for multivalued logic circuits.

Vertical resonant tunneling transistors with molecular quantum dots for large-scale integration.

Quantum molecular devices have a potential for the construction of new data processing architectures that cannot be achieved using current complementary metal-oxide-semiconductor (CMOS) technology. The relevant basic quantum transport properties have been examined by specific methods such as scanning probe and break-junction techniques. However, these methodologies are not compatible with current CMOS applications, and the development of practical molecular devices remains a persistent challenge. Here, we demonstrate a new vertical resonant tunneling transistor for large-scale integration. The transistor channel is comprised of a MOS structure with C60 molecules as quantum dots, and the structure behaves like a double tunnel junction. Notably, the transistors enabled the observation of stepwise drain currents, which originated from resonant tunneling via the discrete molecular orbitals. Applying side-gate voltages produced depletion layers in Si substrates, to achieve effective modulation of the drain currents and obvious peak shifts in the differential conductance curves. Our device configuration thus provides a promising means of integrating molecular functions into future CMOS applications.

Formation of a K-In-Se Surface Species by NaF/KF Postdeposition Treatment of Cu(In,Ga)Se2 Thin-Film Solar Cell Absorbers.

A NaF/KF postdeposition treatment (PDT) has recently been employed to achieve new record efficiencies of Cu(In,Ga)Se2 (CIGSe) thin film solar cells. We have used a combination of depth-dependent soft and hard X-ray photoelectron spectroscopy as well as soft X-ray absorption and emission spectroscopy to gain detailed insight into the chemical structure of the CIGSe surface and how it is changed by different PDTs. Alkali-free CIGSe, NaF-PDT CIGSe, and NaF/KF-PDT CIGSe absorbers grown by low-temperature coevaporation have been interrogated. We find that the alkali-free and NaF-PDT CIGSe surfaces both display the well-known Cu-poor CIGSe chemical surface structure. The NaF/KF-PDT, however, leads to the formation of bilayer structure in which a K-In-Se species covers the CIGSe compound that in composition is identical to the chalcopyrite structure of the alkali-free and NaF-PDT absorber.

Spectroscopic and crystallographic anomalies of (Co1-xZnx)Al2O4 spinel oxide.

This work investigates the spectroscopic properties of (Co1-xZnx)Al2O4 with a range of x of 0 ≤ x ≤ 1. Spectroscopic and crystallographic evaluations using XRD, Raman, FT-IR and UV-Vis spectroscopy reveal that Zn(2+) substitution systematically changes the lattice constant, which mainly depends on the Co-O bonds, and the related optical characteristics of this material. The x dependence of these properties shows two trends, and the mutation point seems to be at x ≈ 0.5. This implies that the electronic structure of (Co1-xZnx)Al2O4 is not changed monotonically by Zn(2+) substitution. Interestingly, some of the optical phenomena observed in this study become prominent for samples with x ≥ 0.5. That is, we observed sideband peaks near the main peaks in the Raman spectra, and their relative intensities systematically and significantly increased with increasing Zn(2+) substitution. The rates of increase are not constant, and are fast for samples with x ≥ 0.5. The sideband peaks are considered to reflect the unique changes in the local electronic structure of (Co1-xZnx)Al2O4, and they are useful for evaluating the substitution level without the influence of the site change phenomenon. Thus, clarifying them is expected to be important for understanding and controlling the electronic structure of the spinel oxide. On the other hand, investigation of the visible light absorption due to the d-d transition of Co(2+) reveals that the efficiency is also high for samples with high Zn(2+) substitution (x ≥ 0.5). This is also considered to be valuable information for investigation of the optical properties and/or the catalytic function of the spinel oxide. Moreover, the fluorescence of the (Co1-xZnx)Al2O4 samples is also identified as a novel functional property of this material. The intensity of the fluorescence peak also dramatically increases for samples with x ≥ 0.7. The effect of Zn(2+) substitution on the local electronic structure of (Co1-xZnx)Al2O4 has not been clarified yet. However, some of the interesting characteristics reviewed in this study are worth investigating from the viewpoint of materials science and applications.

Optically controllable dual-gate organic transistor produced via phase separation between polymer semiconductor and photochromic spiropyran molecules.

We produced an optically controllable dual-gate organic field-effect transistor by a simple one-step spin-coating of a mixed solution of photochromic spiropyran (SP) and poly(3-hexylthiophene) (P3HT). Postannealing enhanced polymer chain ordering of P3HT to induce phase separation into an SP-rich lower layer and an SP-free upper layer. These layers worked independently as transistor channels with distinct optical responsivity. The top channel was optically inactive, but the bottom channel was optically active, because of the photoisomerization of SP. These results demonstrate the potential of our technique to produce a multifunctional photoactive organic transistor by a simple process.

Diffusion barrier and adhesion properties of SiO(x)N(y) and SiO(x) layers between Ag/polypyrrole composites and Si substrates.

This paper describes the interface reactions and diffusion between silver/polypyrrole (Ag/PPy) composite and silicon substrate. This composite material can be used as a novel technique for 3D-LSI (large-scale integration) by the fast infilling of through-silicon vias (TSV). By immersion of the silicon wafer with via holes into the dispersed solution of Ag/PPy composite, the holes are filled with the composite. It is important to develop a layer between the composite and the Si substrate with good diffusion barrier and adhesion characteristics. In this paper, SiOx and two types of SiOxNy barrier layers with various thicknesses were investigated. The interface structure between the Si substrate, the barrier, and the Ag/PPy composite was characterized by transmission electron microscopy. The adhesion and diffusion properties of the layers were established for Ag/PPy composite. Increasing thickness of SiOx proved to permit less Ag to transport into the Si substrate. SiOxNy barrier layers showed very good diffusion barrier characteristics; however, their adhesion depended strongly on their composition. A barrier layer composition with good adhesion and Ag barrier properties has been identified in this paper. These results are useful for filling conductive metal/polymer composites into TSV.

Photoisomerization-induced manipulation of single-electron tunneling for novel Si-based optical memory.

We demonstrated optical manipulation of single-electron tunneling (SET) by photoisomerization of diarylethene molecules in a metal-insulator-semiconductor (MIS) structure. Stress is placed on the fact that device operation is realized in the practical device configuration of MIS structure and that it is not achieved in structures based on nanogap electrodes and scanning probe techniques. Namely, this is a basic memory device configuration that has the potential for large-scale integration. In our device, the threshold voltage of SET was clearly modulated as a reversible change in the molecular orbital induced by photoisomerization, indicating that diarylethene molecules worked as optically controllable quantum dots. These findings will allow the integration of photonic functionality into current Si-based memory devices, which is a unique feature of organic molecules that is unobtainable with inorganic materials. Our proposed device therefore has enormous potential for providing a breakthrough in Si technology.

Unique device operations by combining optical-memory effect and electrical-gate modulation in a photochromism-based dual-gate transistor.

We demonstrate a new device that combines a light-field effect and an electrical-gate effect to control the drain current in a dual-gate transistor. We used two organic layers, photochromic spiropyran (SP)-doped poly(triarylamine) (PTAA) and pristine PTAA, as top and bottom channels, respectively, connected to common source and drain electrodes. The application of voltage to the top and bottom gates modulated the drain current through each layer independently. UV irradiation suppressed the drain current through the top channel. The suppressed current was then maintained even after the UV light was turned off because of an optical memory effect induced by photoisomerization of SP. In contrast, UV irradiation did not change the drain current in the bottom channel. Our dual-gate transistor thus has two organic channels with distinct photosensitivities: an optically active SP-PTAA film and an optically inactive PTAA film. This device configuration allows multi-level switching via top- and bottom-gate electrical fields with an optical-memory effect.

Combinatorial synthesis of Cu/(Ta(x)Nb(1-x))2O5 stack structure for nanoionics-type ReRAM device.

Resistive random access memory (ReRAM) has been proposed as a new application for oxide materials. We have proposed a Cu electrode/dielectric oxide/bottom electrode stack structure as a potential ReRAM material that is compatible with the LSI process. Control of the switching voltage and the initial conductive filament formation process is beneficial for actual applications. To control the switching property by controlling the valence state of metals, we investigated the Ta-Nb binary oxide ((TaxNb1-x)2O5) system as a dielectric oxide layer using a combinatorial method. A combinatorial pulsed laser deposition method was used to fabricate the (TaxNb1-x)2O5 system systematically on a Pt/Si substrate. X-ray photoelectron spectroscopy revealed defect formation relating to Ta and the compensation of oxygen vacancies caused by a change in the valence number of Nb. As the Ta content decreased, there were a decrease in the threshold voltage of the low resistive state and an enhancement of the leakage current, meaning that the switching properties can be controlled by controlling the (TaxNb1-x)2O5 system.

Optically and electrically driven organic thin film transistors with diarylethene photochromic channel layers.

We achieved drain-current switching of diarylethene-channel field-effect transistors with light- and electric-field effects. The drain current was reversibly changed by alternating ultraviolet and visible light irradiation. Stress is placed on the fact that the on/off ratio realized by light irradiation was 1 × 10(2) (1 × 10(4)%) and this value is much larger than those in other photochromism-based transistors. These results indicate that the drain current was effectively controlled by light irradiation. Furthermore, the on and off states modulated by light were maintained without light irradiation even after 1 week, exhibiting that our transistor works as an optical memory. We clarified that the light-driven modulation can be attributed to the transformation in the π-conjugation system accompanied by photoisomerization. These findings have the potential to attain high-performance optoelectrical organic devices including optical sensors, optical memory, and photoswitching transistors.

Molecular alignment and energy-level diagram at heteromolecular interface of quaterrylene and terrylene-3,4,11,12-tetracarboximide.

Heteromolecular layers consisting of quaterrylene (QT) and terrylene-3,4,11,12-tetracarboximide (TTCDI-C12) were prepared on SiO2 surfaces and the electronic energy level alignment at TTCDI-C12/QT interface was examined. TTCDI-C12 layers were grown in nearly perpendicular orientation on QT layers by an ultraslow deposition technique, thereby achieving formation of a well-defined TTCDI-C12/QT interface. Atomic force microscopy (AFM) measurements ensured excellent surface flatness of each layer, surface roughnesses of which were comparable to that of pristine SiO2. Energy level alignment at the heteromolecular interface was evaluated by using ultraviolet photoelectron spectroscopy (UPS) and optical absorption measurements. No shift in energy level was served at the heteromolecular interface, indicating that charge transfer does not occur and a dipole moment is not formed at the well-defined TTCDI-C12/QT interface.