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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]

A new technique for the fabrication of monodisperse asymmetric colloidal clusters by contact area lithography (CAL) is discussed. The approach is found to be highly site-specific, leading to the formation of several nanoscale arrays.

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]

Bothenhancing the excitons’ lifetime and ingeniously controllingthe spatial charge transfer are the key to the realization of efficientlyphotocatalytic and artificially photosynthetic devices. Nanostructuredmetal/metal-oxide interfaces often exhibit improved energy conversionefficiency. Understanding the surface potential changes of nano-objectsunder light illumination is crucial in photoelectrochemical cells.Under ultraviolet (UV) illumination, here, we directly observed thecharge separation phenomena at the Au-nanoparticle/TiO2-nanotube interfaces by using Kelvin probe force microscopy. Thesurface potential maps of TiO2nanotubes with and withoutAu nanoparticles were compared on the effect of different substrates.We observed that in a steady state, approximately 0.3 electron perAu particle of about 4 nm in diameter is effectively charged and consequentlyscreens the surface potential of the underlying TiO2nanotubes.Our observations should help design improved photoelectrochemicaldevices for energy conversion applications. [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]

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]

We report, for the first time, a novel procedure for fabricating multiwall anatase TiO2nanotubes by utilizing templated atomic layer deposition synthesis in conjunction with alternating TiO2/Al2O3nanolaminate structures. [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]

Cadmium sulfide (CdS) is a semiconducting absorber for photoelectrochemical (PEC) hydrogen production with suitable electronic band structures. However, it suffers from severe photocorrosion and rapid charge recombination during the desired PEC reactions. Herein, we describe the identification of the optimal junction thickness of CdS/MoS 2 core/sheath heterojunction nanostructures by employing atomic layer deposition (ALD) techniques. ALD-grown MoS 2 sheath layers with different thicknesses were realized on single-crystalline CdS nanorod (NR) arrays on transparent conducting oxide substrates. We further monitored the resulting solar H 2 evolution performance with our heterojunction photoanodes. The results showed that the junction thickness of MoS 2 plays a key role in the reduction of photocorrosion and the enhanced photocurrent density by optimizing the charge separation. A better saturation photocurrent (∼46%) was obtained with the 7 nm-thick MoS 2 @CdS NRs than that with the bare CdS NRs. Moreover, the external quantum efficiency was increased twofold over that of the pristine CdS NRs. The ALD-grown MoS 2 @CdS heterojunction structures provides an efficient and versatile platform for hydrogen production when combining ALD-grown MoS 2 with ideal semiconducting absorbers.

Single-crystalline gold nanowires (Au NWs) are directly synthesized by the photocatalytic reduction of an aqueous HAuCl 4 solution inside high-aspect-ratio TiO 2 nanotubes (NTs). Crystalline TiO 2 (anatase) NTs are prepared by the template-assisted atomic layer deposition technique with a subsequent annealing. Under the irradiation of ultraviolet light, photoexcited electrons are formed on the surfaces of TiO 2 NTs and could reduce Au ions to create nuclei without using any surfactant, reducing agent, and/or seed. Once nucleation occurred, high-aspect-ratio Au NWs are grown inside the TiO 2 NTs in a diffusion-controlled manner. As the solution pH increased, the nucleation/growth rate decreased and twin-free (or not observed), single-crystalline Au NWs are formed. At a pH above 6, the nucleation/growth rates increased and Au nanoparticles are observed both inside and outside of the TiO 2 NTs. The confined nanoscale geometries of the interior of the TiO 2 NTs are found to play a key role in the controlled diffusion of Au species and in determining the crystal morphology of the resulting Au NWs.

We describe the direct preparation of crystalline Ni 3 S 2 thin films via atomic layer deposition (ALD) techniques at temperatures as low as 250 °C without postthermal treatments. A new ALD chemistry is proposed using bis(1-dimethylamino-2-methyl-2-butoxy) nickel(II) [Ni(dmamb) 2 ] and H 2 S as precursors. Homogeneous and conformal depositions of Ni 3 S 2 films were achieved on 4 in. wafers (both metal and oxide substrates, including Au and SiO 2 ). The resulting crystalline Ni 3 S 2 layers exhibited highly efficient and stable performance as electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in alkaline solutions, with a low overpotential of 300 mV and a high turnover frequency for HER and an overpotential of 400 mV for OER (at a current density of 10 mA/cm 2 ). Using our Ni 3 S 2 films as both the cathode and the anode, two-electrode full-cell electrolyzers were constructed, which showed stable operation for 100 h at a current density of 10 mA/cm 2 . The proposed ALD electrocatalysts on planar surfaces exhibited the best performance among Ni 3 S 2 materials for overall water splitting recorded to date.

We describe the spontaneous formation of composite chalcogenide materials that consist of two-dimensional (2D) materials dispersed in bulk and their unusual charge transport properties for application in hydrogen evolution reactions (HERs). When MoS 2 as a representative 2D material is deposited on transition metals (such as Cu) in a controlled manner, the sulfidation reactions also occur with the metal. This process results in remarkably unique structures, that is, bulk layered heterojunctions (BLHJs) of Cu-Mo-S that contain MoS 2 flakes inside, which are uniformly dispersed in the Cu 2 S matrix. The resulting structures were expected to induce asymmetric charge transfer via layered frameworks and tested as electrocatalysts for HERs. Upon suitable thermal treatments, the BLHJ surfaces exhibited the efficient HER performance of approximately 10 mA/cm 2 at a potential of -0.1 V versus a reversible hydrogen electrode. The Tafel slope was approximately 30 to 40 mV per decade. The present strategy was further generalized by demonstrating the formation of BLHJs on other transition metals, such as Ni. The resulting BLHJs of Ni-Mo-S also showed the remarkable HER performance and the stable operation over 10 days without using Pt counter electrodes by eliminating any possible issues on the Pt contamination.

An innovative atomic layer deposition (ALD) concept, with which nanostructures of water condensates with high aspect ratio at equilibrium in cylindrical nanopores can be transformed uniformly into silica (SiO2) at near room temperature and ambient pressure, has been demonstrated for the first time. As a challenging model system, we first prove the conversion of cylindrical water condensates in porous alumina membranes to silica nanotubes (NTs) by introducing SiCl4 as a metal reactant without involving any catalytic reaction. Surprisingly, the water NTs reproducibly transformed into silica NTs, where the wall thickness of the silica NTs deposited per cycle was found to be limited by the amount of condensed water, and it was on the orders of ten nanometers per cycle (i.e., over 50 times faster than that of conventional ALD). More remarkably, the reactions only took place for 10-20 minutes or less without vacuum-related equipment. The thickness of initially adsorbed water layers in cylindrical nanopores was indirectly estimated from the thickness of formed SiO2 layers. With systematic experimental designs, we tackle the classical Kelvin equation in the nanosized pores, and the role of van der Waals forces in the nanoscale wetting phenomena, which is a long-standing issue lacking experimental insight. Moreover, we show that the present strategy is likely generalized to other oxide systems such as TiO2. Our approach opens up a new avenue for ultra-simple preparation of porous oxides and allows for the room temperature formation of dielectric layers toward organic electronic and photovoltaic applications.

Surface decoration strategy for one-dimensional nanostructures will improve their electrical, optical, mechanical, and electrochemical performances dramatically. Heterogeneous growth/deposition on surfaces, however, may create undesired junction interfaces in the system. Here we report a procedure during which amorphous titania nanotubes are readily self-branched with crystalline titanate nanorods at room temperature. The starting amorphous titania nanotubes were prepared by low-temperature atomic layer deposition combined with the template-directed approach. We routinely observed the self-branching phenomenon of crystalline titanate nanorods with a few nanometers in diameter onto the surfaces of the amorphous titania nanotubes in mild alkali solutions. The resulting structures were analyzed by field-emission scanning electron microscopy, high-resolution transmission electron microscopy, and electron energy loss spectroscopy. The reactivity of the hierarchical titania nanotube arrays was observed to be improved as a Li secondary battery electrode. Upon complete consumption of the amorphous body of titania nanotubes, in addition, titanate nanosheets/layers consisting of single TiO(2) layers with unit-cell thickness were obtained, elucidating the formation mechanism of layered titanate materials by alkali treatment.