Micro- and Nanostructure Analysis of Vapor-Phase-Grown AlN on Face-to-Face Annealed Sputtered AlN/Nanopatterned Sapphire Substrate Templates.

Micro- and nanostructures in vapor-phase-grown AlN on face-to-face annealed sputtered AlN (FFA Sp-AlN) templates formed on nanopatterned sapphire substrates (NPSS) were comprehensively analyzed using transmission electron microscopy. The comparison between metal-organic vapor-phase epitaxy-grown AlN/FFA Sp-AlN/hole-type NPSS (Sample MOH) and hydride vapor-phase epitaxy-grown AlN/FFA Sp-AlN/cone-type NPSS (Sample HVC) showed apparent differences in the morphology of dislocation propagation, presence of voids, shape of polarity inversion boundaries, and crystal structure on the slope region of NPSS. Notably, cross-sectional and plan-view observations revealed that the quality of FFA Sp-AlN significantly affects the threading dislocation density in the vapor-phase-grown layer. At the slope region of the AlN/NPSS interface, γ-AlON was observed in the MOH sample, while highly misaligned AlN grains were observed in the HVC sample. These characteristic crystal structures affect the occurrence of dislocations via different mechanisms in each sample. This study provides practical information for strategically controlling the micro- and nanostructures formed in AlN/NPSS structures for high-performance AlGaN-based deep-ultraviolet emitters. Supplementary Information: The online version contains supplementary material available at 10.1007/s11664-023-10348-3.

A new layered iron arsenide superconductor: (Ca,Pr)FeAs2.

A new iron-based superconductor, (Ca,Pr)FeAs2, was discovered. Plate-like crystals of the new phase were obtained, and its crystal structure was investigated by single-crystal X-ray diffraction analysis. The structure was identified as the monoclinic system with space group P21/m, composed of two Ca(Pr) planes, Fe2As2 layers, and As2 zigzag chain layers. Plate-like crystals of the new phase showed superconductivity, with a T(c) of ~20 K in both magnetization and resistivity measurements.

Multivariate statistical characterization of charged and uncharged domain walls in multiferroic hexagonal YMnO3 single crystal visualized by a spherical aberration-corrected STEM.

A state-of-the-art spherical aberration-corrected STEM was fully utilized to directly visualize the multiferroic domain structure in a hexagonal YMnO3 single crystal at atomic scale. With the aid of multivariate statistical analysis (MSA), we obtained unbiased and quantitative maps of ferroelectric domain structures with atomic resolution. Such a statistical image analysis of the transition region between opposite polarizations has confirmed atomically sharp transitions of ferroelectric polarization both in antiparallel (uncharged) and tail-to-tail 180° (charged) domain boundaries. Through the analysis, a correlated subatomic image shift of Mn-O layers with that of Y layers, exhibiting a double-arc shape of reversed curvatures, have been elucidated. The amount of image shift in Mn-O layers along the c-axis is statistically significant as small as 0.016 nm, roughly one-third of the evident image shift of 0.048 nm in Y layers. Interestingly, a careful analysis has shown that such a subatomic image shift in Mn-O layers vanishes at the tail-to-tail 180° domain boundaries. Furthermore, taking advantage of the annular bright field (ABF) imaging technique combined with MSA, the tilting of MnO5 bipyramids, the very core mechanism of multiferroicity of the material, is evaluated.

Fluorine in shark teeth: its direct atomic-resolution imaging and strengthening function.

Atomic-resolution imaging of beam-sensitive biominerals is extremely challenging, owing to their fairly complex structures and the damage caused by electron irradiation. Herein, we overcome these difficulties by performing aberration-corrected electron microscopy with low-dose imaging techniques, and report the successful direct atomic-resolution imaging of every individual atomic column in the complex fluorapatite structure of shark tooth enameloid, which can be of paramount importance for teeth in general. We demonstrate that every individual atomic column in shark tooth enameloid can be spatially resolved, and has a complex fluorapatite structure. Furthermore, ab initio calculations show that fluorine atoms can be covalently bound to the surrounding calcium atoms, which improves understanding of their caries-reducing effects in shark teeth.

High-temperature operation of gallium oxide memristors up to 600 K.

Memristors have attracted much attention for application in neuromorphic devices and brain-inspired computing hardware. Their performance at high temperatures is required to be sufficiently reliable in neuromorphic computing, potential application to power electronics, and the aerospace industry. This work focuses on reduced gallium oxide (GaOx) as a wide bandgap memristive material that is reported to exhibit highly reliable resistive switching operation. We prepared amorphous GaOx films to fabricate Pt/GaOx/indium tin oxide memristors using pulsed laser deposition. Stable resistive switching phenomena were observed in current-voltage properties measured between 300 and 600 K. The conduction mechanism analysis revealed that the resistive switching is caused by the transition between ohmic and space charge limiting current conductions. We elucidated the importance of appropriate control of the density of oxygen vacancies to obtain a high on/off resistance ratio and distinct resistive switching at high temperatures. These results indicate that GaOx is a promising memristor material that can be stably operated even at the record-high temperature of 600 K.

Comprehensive analysis of current leakage at individual screw and mixed threading dislocations in freestanding GaN substrates.

The electrical characteristics of Schottky contacts on individual threading dislocations (TDs) with a screw-component in GaN substrates and the structures of these TDs were investigated to assess the effects of such defects on reverse leakage currents. Micrometer-scale platinum/GaN Schottky contacts were selectively fabricated on screw- and mixed-TD-related etch pits classified based on the pit size. Current-voltage (I-V) data acquired using conductive atomic force microscopy showed that very few of the screw TDs generated anomalously large reverse leakage currents. An analysis of the temperature dependence of the I-V characteristics established that the leakage current conduction mechanisms for the leaky screw TDs differed from those for the other screw and mixed TDs. Specifically, anomalous current leakage was generated by Poole-Frenkel emission and trap-assisted tunneling via distinctive trap states together with Fowler-Nordheim tunneling, with the mechanism changing according to variations in temperature and applied voltage. The leaky TDs were identified as Burgers vector b = 1c closed-core screw TDs having a helical morphology similar to that of other screw TDs generating small leakage currents. Based on the results, we proposed that the atomic-scale modification of the dislocation core structure related to interactions with point defects via dislocation climbing caused different leakage characteristics of the TDs.

Molecular beam homoepitaxy of N-polar AlN: Enabling role of aluminum-assisted surface cleaning.

N-polar aluminum nitride (AlN) is an important building block for next-generation high-power radio frequency electronics. We report successful homoepitaxial growth of N-polar AlN by molecular beam epitaxy (MBE) on large-area, cost-effective N-polar AlN templates. Direct growth without any in situ surface cleaning leads to films with inverted Al polarity. It is found that Al-assisted cleaning before growth enables the epitaxial film to maintain N-polarity. The grown N-polar AlN epilayer with its smooth, pit-free surface duplicates the structural quality of the substrate, as evidenced by a clean and smooth growth interface with no noticeable extended defects generation. Near band-edge photoluminescence peaks are observed at room temperature on samples with MBE-grown layers but not on the bare AlN templates, implying the suppression of nonradiative recombination centers in the epitaxial N-polar AlN.

Breaking of Thermopower-Conductivity Trade-Off in LaTiO3 Film around Mott Insulator to Metal Transition.

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 (=S2 σ) is significantly enhanced to 300 µW m- 1 K-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.

Origins of hole doping and relevant optoelectronic properties of wide gap p-type semiconductor, LaCuOSe.

LaCuOSe is a wide band gap (∼2.8 eV) semiconductor with unique optoelectronic properties, including room-temperature stable excitons, high hole mobility ∼8 cm(2)/(Vs), and the capability of high-density hole doping (up to 1.7 × 10(21) cm(-3) using Mg). Moreover, its carrier transport and doping behaviors exhibit nonconventional results, e.g., the hole concentration increases with decreasing temperature and the high hole doping does not correlate with other properties such as optical absorption. Herein, secondary ion mass spectroscopy and photoemission spectroscopy reveal that aliovalent ion substitution of Mg at the La site is not the main source of hole doping and the Fermi level does not shift even in heavily doped LaCuOSe:Mg. As the hole concentration increases, the subgap optical absorption becomes more intense, but the increase in intensity does not correlate quantitatively. Transmission electron microscopy indicates that planar defects composed of Cu and Se deficiencies are easily created in LaCuOSe. These observations can be explained via the existence of a degenerate low-mobility layer and formation of complex Cu and Se vacancy defects with the assistance of generalized gradient approximation band calculations.

Author Correction: Gate Tuning of Synaptic Functions Based on Oxygen Vacancy Distribution Control in Four-Terminal TiO2-x Memristive Devices.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Gate Tuning of Synaptic Functions Based on Oxygen Vacancy Distribution Control in Four-Terminal TiO2-x Memristive Devices.

Recent developments in artificial intelligence technology has facilitated advances in neuromorphic computing. Electrical elements mimicking the role of synapses are crucial building blocks for neuromorphic computers. Although various types of two-terminal memristive devices have emerged in the mainstream of synaptic devices, a hetero-synaptic artificial synapse, i.e., one with modulatable plasticity induced by multiple connections of synapses, is intriguing. Here, a synaptic device with tunable synapse plasticity is presented that is based on a simple four-terminal rutile TiO2-x single-crystal memristor. In this device, the oxygen vacancy distribution in TiO2-x and the associated bulk carrier conduction can be used to control the resistance of the device. There are two diagonally arranged pairs of electrodes with distinct functions: one for the read/write operation, the other for the gating operation. This arrangement enables precise control of the oxygen vacancy distribution. Microscopic analysis of the Ti valence states in the device reveals the origin of resistance switching phenomena to be an electrically driven redistribution of oxygen vacancies with no changes in crystal structure. Tuning protocols for the write and the gate voltage applications enable high precision control of resistance, or synaptic plasticity, paving the way for the manipulation of learning efficiency through neuromorphic devices.

Demonstrative operation of four-terminal memristive devices fabricated on reduced TiO2 single crystals.

Resistive switching (RS) was demonstrated in four-terminal planar memristive devices fabricated on reduced TiO2 (TiO2-x) single crystal substrates. In the device, a pair of diagonally opposing electrode terminals is used to modify the distribution of oxygen vacancies in the region between another pair of diagonally opposing electrode terminals. This allowed microscopic visual observations of the oxygen vacancy distribution based on electrocoloring. The visual contrast observed in the TiO2-x reflects the oxygen vacancy concentration in the electrically active zone of the device, which can be modified by application of various external voltages to the electrodes. The current that flows in the device is significantly dependent on the modified oxygen vacancy distribution and the resultant resistance is switchable when the polarization of the applied external voltage is reversed. The crystallographic orientation of the TiO2-x substrate has a strong influence on the reversible RS phenomenon. Mechanisms behind the voltage-driven resistance change are elaborated with the aid of microscopic analysis for both crystalline and electronic structures in the electrically active zone of the device. Suppression of the formation of irreversible conductive structures comprised of accumulated oxygen vacancies is a key to establishing reversible RS in the device.

Atomic structures of a liquid-phase bonded metal/nitride heterointerface.

Liquid-phase bonding is a technologically important method to fabricate high-performance metal/ceramic heterostructures used for power electronic devices. However, the atomic-scale mechanisms of how these two dissimilar crystals specifically bond at the interfaces are still not well understood. Here we analyse the atomically-resolved structure of a liquid-phase bonded heterointerface between Al alloy and AlN single crystal using aberration corrected scanning transmission electron microscopy (STEM). In addition, energy-dispersive X-ray microanalysis, using dual silicon drift X-ray detectors in STEM, was performed to analyze the local chemistry of the interface. We find that a monolayer of MgO is spontaneously formed on the AlN substrate surface and that a polarity-inverted monolayer of AlN is grown on top of it. Thus, the Al alloy is bonded with the polarity-inverted AlN monolayer, creating a complex atomic-scale layered structure, facilitating the bonding between the two dissimilar crystals during liquid-phase bonding processes. Density-functional-theory calculations confirm that the bonding stability is strongly dependent on the polarity and stacking of AlN and MgO monolayers. Understanding the spontaneous formation of layered transition structures at the heterointerface will be key in fabricating very stable Al alloy/AlN heterointerface required for high reliability power electronic devices.

Large magnetoelectric coupling in magnetically short-range ordered Bi5Ti3FeO15 film.

Multiferroic materials, which offer the possibility of manipulating the magnetic state by an electric field or vice versa, are of great current interest. However, single-phase materials with such cross-coupling properties at room temperature exist rarely in nature; new design of nano-engineered thin films with a strong magneto-electric coupling is a fundamental challenge. Here we demonstrate a robust room-temperature magneto-electric coupling in a bismuth-layer-structured ferroelectric Bi5Ti3FeO15 with high ferroelectric Curie temperature of ~1000 K. Bi5Ti3FeO15 thin films grown by pulsed laser deposition are single-phase layered perovskit with nearly (00l)-orientation. Room-temperature multiferroic behavior is demonstrated by a large modulation in magneto-polarization and magneto-dielectric responses. Local structural characterizations by transmission electron microscopy and Mössbauer spectroscopy reveal the existence of Fe-rich nanodomains, which cause a short-range magnetic ordering at ~620 K. In Bi5Ti3FeO15 with a stable ferroelectric order, the spin canting of magnetic-ion-based nanodomains via the Dzyaloshinskii-Moriya interaction might yield a robust magneto-electric coupling of ~400 mV/Oe·cm even at room temperature.

Chain-like nanostructures from anisotropic self-assembly of semiconducting metal oxide nanoparticles with a block copolymer.

A facile method is reported for the preparation of chain-like nanostructures by anisotropic self-assembly of TiO(2) and SnO(2) nanoparticles with the aid of a block copolymer in an aqueous medium. Well-defined crystallographic orientations between neighbouring nanoparticles are observed in TiO(2) nanochains, which is important for tailoring the grain boundaries and thus enhancing charge transport.