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The study explains the preparation of self-assembled epitaxial nanocomposite BaTi[O.sub.3]=Ni[Fe.sub.2][O.sub.4] by polymer-associated deposition. The discussed composites are found to exhibit ferroelectric, as well as ferromagnetic properties.

The coexistence of nonvolatile and volatile switching modes in a single memristive device provides flexibility to emulate both neuronal and synaptic functions in the brain. Furthermore, such a device structure may eliminate the need for additional circuit elements such as transistor-based selectors, enabling low-power consumption and high-density device integration in fully memristive spiking neural networks. In this work, we report dual resistive switching (RS) modes in VO 2 /La 0.7 Sr 0.3 MnO 3 (LSMO) bilayer memristive devices. Specifically, the nonvolatile RS is driven by the movement of oxygen vacancies (V o ) at the VO 2 /LSMO interface and requires a higher biasing voltage, whereas the volatile RS is controlled by the metal-insulator transition (MIT) of VO 2 under a lower biasing voltage. The simple device structure is electrically driven between the two RS modes and thus can operate as a one selector-one resistor (1S1R) cell, which is a desirable feature in memristive crossbar arrays to avoid the sneak-path current issue. The RS modes are found to be stable and repeatable and can be reconfigured by exploiting the interfacial and phase transition properties, and thus, they hold great promise for applications in memristive neural networks and neuromorphic computing.

Filamentary-type resistive switching devices, such as conductive bridge random-access memory and valence change memory, have diverse applications in memory and neuromorphic computing. However, the randomness in filament formation poses challenges to device reliability and uniformity. To overcome this issue, various defect engineering methods have been explored, including doping, metal nanoparticle embedding, and extended defect utilization. In this study, we present a simple and effective approach using self-assembled uniform Au nanoelectrodes to controll filament formation in HfO 2 resistive switching devices. By concentrating the electric field near the Au nanoelectrodes within the BaTiO 3 matrix, we significantly enhanced the device stability and reduced the threshold voltage by up to 45% in HfO 2 -based artificial neurons compared to the control devices. The threshold voltage reduction is attributed to the uniformly distributed Au nanoelectrodes in the insulating matrix, as confirmed by COMSOL simulation. Our findings highlight the potential of nanostructure design for precise control of filamentary-type resistive switching devices.

Fundamental understanding of the electronic, chemical, and structural properties of uranium oxides requires the synthesis of high-crystalline-quality epitaxial films of different polymorphs of one material or different phases with various oxygen valence states. We report the growth of single-phase epitaxial UO 2 , α-U 3 O 8 , and α-UO 3 thin films using pulsed laser deposition. Both oxygen partial pressure and substrate temperature play critical roles in determining the crystal structure of the uranium oxide films. X-ray diffraction and Raman spectroscopy demonstrate that the films are single phase with excellent crystallinity and epitaxially grown on a variety of substrates. Chemical valance states and optical properties of epitaxial uranium oxide films are studied by X-ray photoelectron spectroscopy and UV-vis spectroscopy, which further confirm the high-quality stoichiometric phase-pure uranium oxide thin films. Epitaxial UO 2 films show a direct band gap of 2.61 eV, while epitaxial α-U 3 O 8 and α-UO 3 films exhibit indirect band gaps of 1.89 and 2.26 eV, respectively. The ability to grow high-quality epitaxy actinide oxide thin films and to access their different phases and polymorphous will have significant benefits to the future applications in nuclear science and technology.

BaZrS 3 , a prototypical chalcogenide perovskite, has been shown to possess a direct band gap, an exceptionally strong near band edge light absorption, and good carrier transport. Coupled with its great stability, nontoxicity with earth-abundant elements, it is thus a promising candidate for thin film solar cells. However, its reported band gap in the range of 1.7-1.8 eV is larger than the optimal value required to reach the Shockley-Queisser limit of a single-junction solar cell. Here, we report the synthesis of Ba(Zr 1- x Ti x )S 3 perovskite compounds with a reduced band gap. It is found that Ti-alloying is extremely effective in band gap reduction of BaZrS 3 : a mere 4 atom % alloying decreases the band gap from 1.78 to 1.51 eV, resulting in a theoretical maximum power conversion efficiency of 32%. Higher Ti-alloying concentration is found to destabilize the distorted chalcogenide perovskite phase., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Two-dimensional (2D)-layered semiconducting materials with considerable band gaps are emerging as a new class of materials applicable to next-generation devices. Particularly, black phosphorus (BP) is considered to be very promising for next-generation 2D electrical and optical devices because of its high carrier mobility of 200-1000 cm 2 V -1 s -1 and large on/off ratio of 10 4 to 10 5 in field-effect transistors (FETs). However, its environmental instability in air requires fabrication processes in a glovebox filled with nitrogen or argon gas followed by encapsulation, passivation, and chemical functionalization of BP. Here, we report a new method for reduction of BP-channel devices fabricated without the use of a glovebox by galvanic corrosion of an Al overlayer. The reduction of BP induced by an anodic oxidation of Al overlayer is demonstrated through surface characterization of BP using atomic force microscopy, Raman spectroscopy, and X-ray photoemission spectroscopy along with electrical measurement of a BP-channel FET. After the deposition of an Al overlayer, the FET device shows a significantly enhanced performance, including restoration of ambipolar transport, high carrier mobility of 220 cm 2 V -1 s -1 , low subthreshold swing of 0.73 V/decade, and low interface trap density of 7.8 × 10 11 cm -2 eV -1 . These improvements are attributed to both the reduction of the BP channel and the formation of an Al 2 O 3 interfacial layer resulting in a high- k screening effect. Moreover, ambipolar behavior of our BP-channel FET device combined with charge-trap behavior can be utilized for implementing reconfigurable memory and neuromorphic computing applications. Our study offers a simple device fabrication process for BP-channel FETs with high performance using galvanic oxidation of Al overlayers.

Vanadium dioxide (VO 2 ) is a strong-correlated metal-oxide with a sharp metal-insulator transition (MIT) for a range of applications. However, synthesizing epitaxial VO 2 films with desired properties has been a challenge because of the difficulty in controlling the oxygen stoichiometry of VO x , where x can be in the range of 1 < x < 2.5 and V has multiple valence states. Herein, a unique moisture-assisted chemical solution approach has been developed to successfully manipulate the oxygen stoichiometry, to significantly broaden the growth window, and to significantly enhance the MIT performance of VO 2 films. The obvious broadening of the growth window of stoichiometric VO 2 thin films, from 4 to 36 °C, is ascribed to a self-adjusted process for oxygen partial pressure at different temperatures by introducing moisture. A resistance change as large as 4 orders of magnitude has been achieved in VO 2 thin films with a sharp transition width of less than 1 °C. The much enhanced MIT properties can be attributed to the higher and more uniform oxygen stoichiometry. This technique is not only scientifically interesting but also technologically important for fabricating wafer-scaled VO 2 films with uniform properties for practical device applications.

Black TiO2 nanoparticles with a crystalline core and amorphous-shell structure exhibit superior optoelectronic properties in comparison with pristine TiO2. The fundamental mechanisms underlying these enhancements, however, remain unclear, largely due to the inherent complexities and limitations of powder materials. Here, we fabricate TiO2 homojunction films consisting of an oxygen-deficient amorphous layer on top of a highly crystalline layer, to simulate the structural/functional configuration of black TiO2 nanoparticles. Metallic conduction is achieved at the crystalline-amorphous homointerface via electronic interface reconstruction, which we show to be the main reason for the enhanced electron transport of black TiO2. This work not only achieves an unprecedented understanding of black TiO2 but also provides a new perspective for investigating carrier generation and transport behavior at oxide interfaces, which are of tremendous fundamental and technological interest.

Ordered arrays of metallic nanopillars embedded in a ceramic matrix have recently attracted considerable interest for their multifunctionality in advanced devices. A number of hurdles need to be overcome for achieving practical devices, including selections of metal-ceramic combination, creation of tunable and ordered structure, and control of strain state. In this article, we demonstrate major advances to create such a fine nanoscale structure, i.e., epitaxial self-assembled vertically aligned metal-ceramic composite, in one-step growth using pulsed laser deposition. Tunable diameter and spacing of the nanopillars can be achieved by controlling the growth parameters such as deposition temperature. The magnetic metal-ceramic composite thin films demonstrate uniaxial anisotropic magnetic properties and enhanced coercivity compared to that of bulk metal. The system also presents unique anisotropic electrical transport properties under in-plane and out-of-plane directions. This work paves a new avenue to fabricate epitaxial metal-ceramic nanocomposites, which can simulate broader future explorations in nanocomposites with novel magnetic, optical, electrical, and catalytical properties.

Study of layered complex oxides emerge as one of leading topics in fundamental materials science because of the strong interplay among intrinsic charge, spin, orbital, and lattice. As a fundamental basis of heteroepitaxial thin film growth, interfacial strain can be used to design materials that exhibit new phenomena beyond their conventional forms. Here, we report a strain-driven self-assembly of bismuth-based supercell (SC) with a two-dimensional (2D) layered structure. With combined experimental analysis and first-principles calculations, we investigated the full SC structure and elucidated the fundamental growth mechanism achieved by the strain-enabled self-assembled atomic layer stacking. The unique SC structure exhibits room-temperature ferroelectricity, enhanced magnetic responses, and a distinct optical bandgap from the conventional double perovskite structure. This study reveals the important role of interfacial strain modulation and atomic rearrangement in self-assembling a layered singe-phase multiferroic thin film, which opens up a promising avenue in the search for and design of novel 2D layered complex oxides with enormous promise.

Metamaterials made of nanoscale inclusions or artificial unit cells exhibit exotic optical properties that do not exist in natural materials. Promising applications, such as super-resolution imaging, cloaking, hyperbolic propagation, and ultrafast phase velocities have been demonstrated based on mostly micrometer-scale metamaterials and few nanoscale metamaterials. To date, most metamaterials are created using costly and tedious fabrication techniques with limited paths toward reliable large-scale fabrication. In this work, we demonstrate the one-step direct growth of self-assembled epitaxial metal-oxide nanocomposites as a drastically different approach to fabricating large-area nanostructured metamaterials. Using pulsed laser deposition, we fabricated nanocomposite films with vertically aligned gold (Au) nanopillars (∼20 nm in diameter) embedded in various oxide matrices with high epitaxial quality. Strong, broad absorption features in the measured absorbance spectrum are clear signatures of plasmon resonances of Au nanopillars. By tuning their densities on selected substrates, anisotropic optical properties are demonstrated via angular dependent and polarization resolved reflectivity measurements and reproduced by full-wave simulations and effective medium theory. Our model predicts exotic properties, such as zero permittivity responses and topological transitions. Our studies suggest that these self-assembled metal-oxide nanostructures provide an exciting new material platform to control and enhance optical response at nanometer scales.

We design and create a unique cell geometry of templated micrometer-thick epitaxial nanocomposite films which contain ~20 nm diameter yttria-stabilized ZrO2 (YSZ) nanocolumns, strain coupled to a SrTiO3 matrix. The ionic conductivity of these nanocolumns is enhanced by over 2 orders of magnitude compared to plain YSZ films. Concomitant with the higher ionic conduction is the finding that the YSZ nanocolumns in the films have much higher crystallinity and orientation, compared to plain YSZ films. Hence, "oxygen migration highways" are formed in the desired out-of-plane direction. This improved structure is shown to originate from the epitaxial coupling of the YSZ nanocolumns to the SrTiO3 film matrix and from nucleation of the YSZ nanocolumns on an intermediate nanocomposite base layer of highly aligned Sm-doped CeO2 nanocolumns within the SrTiO3 matrix. This intermediate layer reduces the lattice mismatch between the YSZ nanocolumns and the substrate. Vertical ionic conduction values as high as 10(-2) Ω(-1) cm(-1) were demonstrated at 360 °C (300 °C lower than plain YSZ films), showing the strong practical potential of these nanostructured films for use in much lower operation temperature ionic devices.

Heterointerfaces in manganite-based heterostructures in either layered or vertical geometry control their magnetotransport properties. Instead of using spin-polarized tunneling across the interface, a unique approach based on the magnetic exchange coupling along the vertical interface to control the magnetotransport properties has been demonstrated. By coupling ferromagnetic La0.7Sr0.3MnO3 and antiferromagnetic NiO in an epitaxial vertically aligned nanocomposite (VAN) architecture, a dynamic and reversible switch of the resistivity between two distinct exchange biased states has been achieved. This study explores the use of vertical interfacial exchange coupling to tailor magnetotransport properties, and demonstrates their viability for spintronic applications.

There are numerous radio frequency and microwave device applications which require materials with high electrical tunability and low dielectric loss. For phased array antenna applications there is also a need for materials which can operate above room temperature and which have a low temperature coefficient of capacitance. We have created a nanoscaffold composite ferroelectric material containing Ba(0.6)Sr(0.4)TiO(3) and Sm(2)O(3) which has a very high tunability which scales inversely with loss. This behavior is opposite to what has been demonstrated in any previous report. Furthermore, the materials operate from room temperature to above 150 °C, while maintaining high tunability and low temperature coefficient of tunability. This new paradigm in dielectric property control comes about because of a vertical strain control mechanism which leads to high tetragonality (c/a ratio of 1.0126) in the BSTO. Tunability values of 75% (200 kV/cm field) were achieved at room temperature in micrometer thick films, the value remaining to >50% at 160 °C. Low dielectric loss values of <0.01 were also achieved, significantly lower than reference pure films.

Polymer-assisted deposition (PAD) technique was developed to fabricate ferroelectric BaTiO(3) (BTO) thin films directly on polycrystalline nickel foils. The growth dynamics was systematically studied to optimize the single-phase BTO films with good dielectric properties. It is critical to pretreat nickel foils with hydrogen peroxide (H(2)O(2)) solution to form thin nickel oxide layers on the surfaces for the growth of BTO films. Both the concentration of H(2)O(2) solution and the pretreated time were found to strongly affect the dielectric constant of BTO films, which may be associated with the oxygen diffusion from nickel oxide buffer layers to BTO layers during annealing. The BTO thin films with optimized growth conditions have good crystal structure and electrical properties, suggesting that the as-grown BTO films by PAD technique can be utilized for new devices development and energy storage applications.

The synthesis of pure δ-MoN with desired superconducting properties usually requires extreme conditions, such as high temperature and high pressure, which hinders its fundamental studies and applications. Herein, by using a chemical solution method, epitaxial δ-MoN thin films have been grown on c-cut Al(2)O(3) substrates at a temperature lower than 900 °C and an ambient pressure. The films are phase pure and show a T(c) of 13.0 K with a sharp transition. In addition, the films show a high critical field and excellent current carrying capabilities, which further prove the superior quality of these chemically prepared epitaxial thin films., (© 2011 American Chemical Society)

Monolayer graphene is one of the most interesting materials applicable to next-generation electronic devices due to its transport properties. However, realization of graphene devices requires suitable nanoscale lithography as well as a method to open a band gap in monolayer graphene. Nanoscale hydrogenation and oxidation are promising methods to open an energy band gap by modification of surface structures and to fabricate nanostructures such as graphene nanoribbons (GNRs). Until now it has been difficult to fabricate nanoscale devices consisting of both hydrogenated and oxidized graphene because the hydrogenation of graphene requires a complicated process composed of large-scale chemical modification, nanoscale patterning, and etching. We report on nanoscale hydrogenation and oxidation of graphene under normal atmospheric conditions and at room temperature without etching, wet process, or even any gas treatment by controlling just an external bias through atomic force microscope lithography. Both the lithographically defined nanoscale hydrogenation and oxidation have been confirmed by micro-Raman spectroscopy measurements. Patterned hydrogenated and oxidized graphene show insulating behaviors, and their friction values are several times larger than those of graphene. These differences can be used for fabricating electronic or electromechanical devices based on graphene., (© 2011 American Chemical Society)

Carbide films exhibit many unique properties. The development of a versatile and simple technique for the deposition of carbide films will enable a wide range of technological applications. Here we report a cost-effective chemical solution deposition or polymer-assisted deposition method for growing epitaxial carbide (including TiC, VC, and TaC) films. These epitaxial carbide films exhibit structural and physical properties similar to the films grown by vapor deposition methods.

Directly spinning carbon nanotube (CNT) fibers from vertically aligned CNT arrays is a promising way for the application of CNTs in the field of high-performance materials. However, most of the reported CNT arrays are not spinnable. In this work, by controlling catalyst pretreatment conditions, we demonstrate that the degree of spinnability of CNTs is closely related to the morphology of CNT arrays. Shortest catalyst pretreatment time led to CNT arrays with the best spinnability, while prolonged pretreatment resulted in coarsening of catalyst particles and nonspinnable CNTs. By controlling the coalescence of catalyst particles, we further demonstrate the growth of undulating CNT arrays with uniform and tunable waviness. The CNT arrays can be tuned from well-aligned, spinnable forests to uniformly wavy, foam-like films. To the best of our knowledge, this is the first systematical study on the correlation between catalyst pretreatment, CNT morphology, and CNT spinnability.

It is indispensable to use thin films for many technological applications. This is the first report of epitaxial growth of ternary nitride AMN2 films. Epitaxial tetragonal SrTiN2 films have been successfully prepared by a chemical solution approach, polymer-assisted deposition. The structural, electrical, and optical properties of the films are also investigated.

Epitaxial anatase thin films were grown on single-crystal LaAlO3 substrates by a sol-gel process. The epitaxial relationship between TiO2 and LaAlO3 was found to be [100]TiO2||[100]LaAlO3 and (001)TiO2||(001)LaAlO3 based on X-ray diffraction and a high-resolution transmission electron microscopy. The epitaxial anatase films show significantly improved photocatalytic properties, compared with polycrystalline anatase film on fused silica substrate. The increase in the photocatalytic activity of epitaxial anatase films is explained by enhanced charge carrier mobility, which is traced to the decreased grain boundary density in the epitaxial anatase film.