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Hafnium zirconium oxide (HZO) has been studied intensively due to its potential application to memory and logic devices based on its outstanding dielectric and ferroelectric properties. Because many process factors can significantly impact the properties of HZO thin film, an optimized process or post‐treatment is necessary to ensure its performance. Herein, the effect of hydrogen on HZO thin film can make the film degraded. Analysis of the polarization–voltage hysteresis loops and I–V measurements indicate a leaky behavior in the film. To address this issue, post‐oxygen‐plasma treatment is performed on the film, which results in the decrease in hydrogen ions inside the film and consequently reduces the leakage current density. This finding can provide new insight into the effect of hydrogen incorporation for HZO thin films and methodology to remove leaky components inside ferroelectric films using O2 plasma treatment. [ABSTRACT FROM AUTHOR]

We describe guanidinium-based organic-inorganic hybrid lead triiodides (GAPbI3) as an active layer in resistive switching structures and compare the switching results to those of the conventional compound, MAPbI3. Both the GAPbI3- and MAPbI3-based ReRAM devices showed bistable switching characteristics with a low operating voltage (<0.25 V) and high on/off ratio (∼106). Remarkably, we found that the GAPbI3-based devices exhibited prolonged switching behaviors for over 40 days under ambient conditions (MAPbI3, only 4 days). The GAPbI3 devices lasted for a larger number of cycles (>1900) in an endurance test and exhibited a longer data storage time (>3 × 104 s) in a retention test. Our results suggest that GAPbI3 has stronger hydrogen bonding in the lattice and thus the potential for application in memory devices. [ABSTRACT FROM AUTHOR]

The authors describe the atomic layer deposition (ALD) of titanium oxysulfide films (TiO2−xSx). A new ALD chemistry of tetrakis(dimethylamido)titanium and hydrogen sulfide is proposed for fabricating amorphous titanium sulfide layers. They found that the resulting films subsequently underwent oxidation upon reactions under the ambient condition, resulting in TiO2−xSx. The resultant structures were analyzed by using x-ray diffraction, transmission electron microscopy, and x-ray photoelectron spectroscopy, indicative of the formation of TiO2−xSx. A combined study of Hall effect measurements and Mott–Schottky analysis showed n-type semiconductor behaviors possessing a good conductivity. Optical properties testify that the present system has a moderate bandgap in between the related binary end compounds such as TiS2 and TiO2. [ABSTRACT FROM AUTHOR]

Non-equilibrium fractal growth of MoS2 was induced by establishing an extremely Mo rich chemical vapor deposition (CVD) environment using a rapid heating rate in a confined reaction space. In addition, a detailed shape evolution mechanism was suggested based on the results of thermodynamics and kinetics studies. The extremely Mo rich CVD condition allowed various MoS2 flakes to be synthesized with triangular, star-like, and dendrite-like shapes in series, owing to the thermodynamic preference to increase the number of growth directions. Moreover, numerous small triangular crystals led to the formation of MoS2 flakes with jagged edges, probably as a result of the aggressive nucleation triggered by a fast and abundant supply of MoO3−x vapors. Lastly, using the MoS2 flakes with various fractal shapes, a systematic improvement of the hydrogen evolution reaction performance was demonstrated in accordance with the increase in the surrounding edge length. [ABSTRACT FROM AUTHOR]

We describe a fabrication strategy for preparing yttria-stabilized zirconia nanotube (YSZ-NT) arrays embedded in porous alumina membranes by means of template-directed atomic layer deposition (ALD) technique. The individual YSZ-NTs have a high aspect-ratio of well over 120, about ~ 110 nm in diameter, and ~ 14 µm in length. Interfacing the tube arrays with porous Pt was also introduced on the basis of partial etching technique in order to construct Pt/YSZ-NTs/Pt membrane electrode assembly (MEA) structures. The resulting YSZ-NTs MEAs show a 7 mm in diameter with a roughness factor of ~ 2. Area specific resistance was measured up to 1.84 Ω cm at 400 °C using H as fuel. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2), tin dioxide (SnO2), and heterostructured TiO2/SnO2 nanotube (NT) arrays have been fabricated by template-assisted atomic-layer deposition (ALD) for use as anodes in a lithium-ion battery (LIB). TiO2 NT arrays with 8 nm thick walls showed higher capacity (≈250 mA h g−1 after the 50th cycle at a rate of C/10) than the typical theoretical capacity of bulk TiO2 and a radically improved capacity retention property upon cycling. SnO2 NT arrays with different wall thicknesses (8, 10, 13, and 20 nm) were also fabricated and their electrochemical performances were measured. All of the SnO2 NT arrays showed substantially higher initial irreversible capacity and higher reversible capacity than those of bulk TiO2. Thinner walls of the SnO2 NTs result in better capacity retention. Heterotubular structures of TiO2 (5 nm)/SnO2 (10 nm)/TiO2 (5 nm) were successfully fabricated, and displayed a sufficiently high capacity (≈300 mA h g−1 after 50 cycles) with exceptionally improved cycling performance up to the 50th cycle. [ABSTRACT FROM AUTHOR]

Nanotubes of TiO2 (anatase) and their ordered arrays are emerging, promising candidates as efficient host materials in many applications such as photovoltaic cells, batteries, sensors and catalysts/catalytic supports, but the interplay between these structures and their transport properties has been reported only rarely. Monodisperse, stoichiometric TiO2 nanotubes with smooth morphology and controlled wall thickness were fabricated by template-directed low-temperature atomic layer deposition (ALD), followed by annealing at elevated temperatures. We present a study on the wall thickness-dependent crystallization behaviors due to physical and/or self-confinement, as well as on the corresponding electrical properties. Over certain wall thicknesses, unexpectedly, our TiO2 nanotubes were found to be a new type of mesoporous wide gap semiconductor in which they possess similar porosity, but in terms of conductivity differ from previously known mesoporous photoanodes (i.e., anodized surfaces of Ti films and sintered films consisting of TiO2 nanoparticles). These results were ascribed to the large, elongated anatase domains (by a factor of up to 15–40 wall thicknesses) that developed via boosted crystal growth on porous alumina templates (physical confinement) as well as to the highly curved tubular shape (self-confinement). Indeed, nanotube arrays with walls thicker than 10 nm exhibited an enhancement in conductivity, by more than three orders of magnitude, compared to sintered, mesoporous TiO2 (anatase) particles, approaching the bulk value. The nearly single-crystalline TiO2 nanotubes presented here should allow for a good model system to study TiO2-based surface chemistry and have potential for many applications in photovoltaic and/or catalytic systems. [ABSTRACT FROM AUTHOR]

Atomic layer deposition (ALD) not only presents a direct way to prepare nanomaterials when combined with templates, but also allows surface engineering to fine-tune the properties of the material. Here, we review recent progress in the field of nanostructured materials and devices that have been fabricated by ALD. Various materials, including semiconducting, magnetic, noble metallic, and insulating materials, can be used to form three-dimensional (3D), complex nanostructures with controlled composition and physical properties. We begin this review with ALD nanomaterials that can be prepared from porous templates with a 2D pore arrangement, such as anodic aluminum oxide, and advance toward opal structures with a 3D pore arrangement. We also discuss surface engineering by ALD on existing nanowires/nanotubes, devices, and chemical patterns that has the potential for application in high-performance transistors, sensors, and green energy conversion. Finally, we provide perspectives for future device applications that could arise from ALD nanomaterials. [ABSTRACT FROM AUTHOR]

We describe a procedure for one-step patterning and transfer of self-assembled organic monolayers (SAMs) on SiO2/Si substrates. This procedure was inspired from an idea of pattern formation at contact area, which realizes high patterning fidelity, and enables a universal approach for the micro/nanometre scale patterning of SAMs. [ABSTRACT FROM AUTHOR]

Nanostructured electrodes and their flexible integrated systems have great potential for many applications, including electrochemical energy storage, electrocatalysis and solid-state memory devices, given their ability to improve faradaic reaction sites by large surface area. Although many processing techniques have been employed to fabricate nanostructured electrodes onto flexible substrates, these present limitations in terms of achieving flexible electrodes with high mechanical stability. In this study, the adhesion, mechanical properties and flexibility of TiN nanotube arrays on a Pt substrate were improved using a Ti interlayer. Highly ordered and well-aligned TiN nanotube arrays were fabricated on a Pt substrate using a template-assisted method with an anodic aluminum oxide (AAO) template and atomic layer deposition (ALD) system. We show that with the use of a Ti interlayer between the TiN nanotube arrays and Pt substrate, the TiN nanotube arrays could perfectly attach to the Pt substrate without delamination and faceted phenomena. Furthermore, the I-V curve measurements confirmed that the electric contact between the TiN nanotube arrays and substrate for use as an electrode was excellent, and its flexibility was also good for use in flexible electronic devices. Future efforts will be directed toward the fabrication of embedded electrodes in flexible plastic substrates by employing the concepts demonstrated in this study. [ABSTRACT FROM AUTHOR]

In the photoelectrochemical (PEC) water splitting (WS) reactions, a photon is absorbed by a semiconductor, generating electron-hole pairs which are transferred across the semiconductor/electrolyte interface to reduce or oxidize water into oxygen or hydrogen. Catalytic junctions are commonly combined with semiconductor absorbers, providing electrochemically active sites for charge transfer across the interface and increasing the surface band bending to improve the PEC performance. In this review, we focus on transition metal (di)chalcogenide [TM(D)C] catalysts in conjunction with silicon photoelectrode as Earth-abundant materials systems. Surprisingly, there is a limited number of reports in Si/TM(D)C for PEC WS in the literature. We provide almost a complete survey on both layered TMDC and non-layered transition metal dichalcogenides (TMC) co-catalysts on Si photoelectrodes, mainly photocathodes. The mechanisms of the photovoltaic power conversion of silicon devices are summarized with emphasis on the exact role of catalysts. Diverse approaches to the improved PEC performance and the proposed synergetic functions of catalysts on the underlying Si are reviewed. Atomic layer deposition of TM(D)C materials as a new methodology for directly growing them and its implication for low-temperature growth on defect chemistry are featured. The multi-phase TM(D)C overlayers on Si and the operation principles are highlighted. Finally, challenges and directions regarding future research for achieving the theoretical PEC performance of Si-based photoelectrodes are provided. [ABSTRACT FROM AUTHOR]

We describe the direct formation of mixed-phase (1T and 2H) MoS2 layers on Si as a photocathode via atomic layer deposition (ALD) for application in the photoelectrochemical (PEC) reduction of water to hydrogen. Without typical series-metal interfaces between Si and MoS2, our p-Si/SiOx/MoS2 photocathode showed efficient and stable operation in hydrogen evolution reactions (HERs). The resulting performance could be explained by spatially genuine device architectures in three dimensions (i.e., laterally homo and vertically heterojunction structures). The ALD-grown MoS2 overlayer with the mixed-phase 1T and 2H homojunction passivates light absorber and surface states and functions as a monolithic structure for effective charge transport within MoS2. It is also beneficial in the operation of p-i-n heterojunctions with inhomogeneous barrier heights due to the presence of mixed-phase cocatalysts. The effective barrier heights reached up to 0.8 eV with optimized MoS2 thicknesses, leading to a 670 mV photovoltage enhancement without employing buried Si p-n junctions. The fast-transient behaviors via light illumination show that the mixed-phase layered chalcogenides can serve as efficient cocatalysts by depinning the Fermi levels at the interfaces. A long-term operation of ~70 h was also demonstrated in a 0.5 M H2SO4 solution. [ABSTRACT FROM AUTHOR]

Rational synthesis of coordinated spherical colloids is reported by site-selective growth of secondary hemispherical patches on primary spherical particles with quasi-defined coordination numbers and positions. We clarify the importance of mass transport phenomena on the site-specific secondary nucleation/growth in nanoparticulate colloidal systems. By comparing ultrasonic and conventional agitation during patch growth, we found that enhanced mass transfer is the key to controlled, homogeneous transport of the molecular precursors in a solvent onto the nanoparticles. With chemically defined nucleation sites, the surfaces of spherical silica particles were modified for use as a new kind of colloid with patches at desired coordination positions. Our observations represent a significant breakthrough in colloidal chemistry and self-assembly. [ABSTRACT FROM AUTHOR]

We report on the interplay between nanostructuring and defect activation in dense polycrystalline Bi2Te3 thin films in terms of the thermopower engineering. The Bi2Te3 thin films were prepared at relatively low temperatures (100–160 °C) by atomic layer deposition and their grains showed different sizes in the range of 50–200 nm according to the deposition temperatures. We monitored the conductivity, Seebeck coefficient, and power factor of all samples from the temperature of 50–400 K. By increasing the growth temperature, remarkably, we observed the gradual defect activation from the nominal p-type to n-type in our binary end compound, Bi2Te3 without any alloying. The present results give us an insight on the optimization of thermoelectric materials not only by nanostructuring (i.e., phonon engineering) but also by controlled defect activation (i.e., electron engineering). [ABSTRACT FROM AUTHOR]

We report visualization of three-dimensional domain structures in ferroelectric PbTiO3 (PTO) nanotubes (NTs) using piezoresponse force microscopy (PFM). The domain distributions of the x, y, and z-axes in PTO NTs were separately measured out-of and in-planes at angles of 0° and 90° by vertical and lateral PFM. The separately obtained PFM images were combined to reconstruct the complex domain structures based on some basic assumptions and finite element modeling. The cross-sectional domain configurations of the PTO NTs were visualized by the proposed approach. The results can provide insight into complex domain configurations of ferroelectric nanostructures. [ABSTRACT FROM AUTHOR]