Atomic Layer Deposition of Defective Amorphous TiOx Thin Films with Improved Photoelectrochemical Performance.

A proper control of defects in TiO2 thin films is challenging work for enhancing the photoelectrochemical (PEC) efficiency in water splitting processes. Additionally, a deep understanding of how defects affect the PEC performance of TiO2 thin films is of great interest for achieving better performance. With these aims, we prepared defective amorphous TiOx thin films at various growth temperatures by atomic layer deposition using tetrakis(dimethylamido)titanium as the Ti precursor. Careful X-ray photoelectron spectroscopy and electron spin resonance spectroscopy analyses revealed that the defect concentration in the TiOx thin films can be controlled by adjusting the growth temperature during the ALD process. We also evaluated the light absorption properties of the deposited TiOx thin films using ultraviolet-visible absorption spectroscopy. And it was found that the TiOx thin film deposited at a growth temperature of 200 °C exhibited the highest defect concentration and the highest photocurrent density of 0.051 mA/cm2 at 1.23 V vs reversible hydrogen electrode (RHE) compared to those of the other films. The light absorption efficiency, photogenerated charge separation efficiency, and charge transfer efficiency of defective amorphous TiOx thin films were carefully studied to understand the correlation between the defect concentration in the prepared TiOx thin film and its PEC activity. This study provides insight into the PEC properties of defective amorphous ALD-TiOx thin films.

Direct Printing of Ultrathin Block Copolymer Film with Nano-in-Micro Pattern Structures.

Nanotransfer printing (nTP) is one of the most promising nanopatterning methods given that it can be used to produce nano-to-micro patterns effectively with functionalities for electronic device applications. However, the nTP process is hindered by several critical obstacles, such as sub-20 nm mold technology, reliable large-area replication, and uniform transfer-printing of functional materials. Here, for the first time, a dual nanopatterning process is demonstrated that creates periodic sub-20 nm structures on the eight-inch wafer by the transfer-printing of patterned ultra-thin (<50 nm) block copolymer (BCP) film onto desired substrates. This study shows how to transfer self-assembled BCP patterns from the Si mold onto rigid and/or flexible substrates through a nanopatterning method of thermally assisted nTP (T-nTP) and directed self-assembly (DSA) of Si-containing BCPs. In particular, the successful microscale patternization of well-ordered sub-20 nm SiOx patterns is systematically presented by controlling the self-assembly conditions of BCP and printing temperature. In addition, various complex pattern geometries of nano-in-micro structures are displayed over a large patterning area by T-nTP, such as angular line, wave line, ring, dot-in-hole, and dot-in-honeycomb structures. This advanced BCP-replicated nanopatterning technology is expected to be widely applicable to nanofabrication of nano-to-micro electronic devices with complex circuits.

Activity-Stability Trends of the Sb-SnO2@RuOx Heterostructure toward Acidic Water Oxidation.

Accomplishments of enhanced activity and durability are a major concern in the design of catalysts for acidic water oxidation. To date, most studied supported metal catalysts undergo fast degradation in strongly acidic and oxidative environments due to improper controlling of the interface stability caused by their lattice mismatches. Here, we evaluate the activity-stability trends of in situ crystallized antimony-doped tin oxide (Sb-SnO2)@RuOx (Sb-SnO2@RuOx) heterostructure nanosheets (NSs) for acidic water oxidation. The catalyst prepared by atomic layer deposition of a conformal Ru film on antimony-doped tin sulfide (Sb-SnS2) NSs followed by heat treatment highlights comparable activity but longer stability than that of the ex situ catalyst (where Ru was deposited on Sb-SnO2 followed by heating). Air calcination for in situ crystallization allows the formation of hierarchical mesoporous Sb-SnO2 NSs from as-prepared Sb-SnS2 NSs and parallel in situ transformation from Ru to RuOx, resulting in a compact heterostructure. The significance of this approach significantly resists corrosive dissolution, which is justified by the enhanced oxygen evolution reaction (OER) stability of the catalyst compared to most of the state-of-the-art ruthenium-based catalysts including Carbon@RuOx (which shows ∼10 times higher dissolution) as well as Sb-SnO2@Com. RuOx and Com. RuO2. This study demonstrates the controlled interface stability of heterostructure catalysts toward enhancing OER activity and stability.

Synthesis of Yttria-Stabilized Zirconia Nanospheres from Zirconium-Based Metal-Organic Frameworks and the Dielectric Properties.

Yttria-stabilized zirconia (YSZ) nanospheres were synthesized by calcination at 900 °C after the adsorption of Y3+ ions into the pores of a zirconium-based metal-organic framework (MOF). The synthesized 3YSZ (zirconia doped with 3 mol% Y2O3), 8YSZ (8 mol% Y2O3), and 30YSZ (30 mol% Y2O3) nanospheres were found to exhibit uniform sizes and shapes. Complex permittivity and complex permeability were carried out in K-band (i.e., 18-26.5 GHz) to determine their suitability for use as low-k materials in 5G communications. The real and imaginary parts of the permittivity of the sintered 3YSZ were determined to be 21.24 and 0.12, respectively, while those of 8YSZ were 22.80 and 0.16, and those of 30YSZ were 7.16 and 0.38. Control of the real part of the permittivity in the sintered YSZ was facilitated by modifying the Y2O3 content, thereby rendering this material an electronic ceramic with potential for use in high-frequency 5G communications due to its excellent mechanical properties, high chemical resistance, and good thermal stability. In particular, it could be employed as an exterior material for electronic communication products requiring the minimization of information loss.

Small Reduced Graphene Oxides for Highly Efficient Oxygen Reduction Catalysts.

We demonstrated highly efficient oxygen reduction catalysts composed of uniform Pt nanoparticles on small, reduced graphene oxides (srGO). The reduced graphene oxide (rGO) size was controlled by applying ultrasonication, and the resultant srGO enabled the morphological control of the Pt nanoparticles. The prepared catalysts provided efficient surface reactions and exhibited large surface areas and high metal dispersions. The resulting Pt/srGO samples exhibited excellent oxygen reduction performance and high stability over 1000 cycles of accelerated durability tests, especially the sample treated with 2 h of sonication. Detailed investigations of the structural and electrochemical properties of the resulting catalysts suggested that both the chemical functionality and electrical conductivity of these samples greatly influence their enhanced oxygen reduction efficiency.

Cobalt-Iron-Phosphate Hydrogen Evolution Reaction Electrocatalyst for Solar-Driven Alkaline Seawater Electrolyzer.

Seawater splitting represents an inexpensive and attractive route for producing hydrogen, which does not require a desalination process. Highly active and durable electrocatalysts are required to sustain seawater splitting. Herein we report the phosphidation-based synthesis of a cobalt-iron-phosphate ((Co,Fe)PO4) electrocatalyst for hydrogen evolution reaction (HER) toward alkaline seawater splitting. (Co,Fe)PO4 demonstrates high HER activity and durability in alkaline natural seawater (1 M KOH + seawater), delivering a current density of 10 mA/cm2 at an overpotential of 137 mV. Furthermore, the measured potential of the electrocatalyst ((Co,Fe)PO4) at a constant current density of -100 mA/cm2 remains very stable without noticeable degradation for 72 h during the continuous operation in alkaline natural seawater, demonstrating its suitability for seawater applications. Furthermore, an alkaline seawater electrolyzer employing the non-precious-metal catalysts demonstrates better performance (1.625 V at 10 mA/cm2) than one employing precious metal ones (1.653 V at 10 mA/cm2). The non-precious-metal-based alkaline seawater electrolyzer exhibits a high solar-to-hydrogen (STH) efficiency (12.8%) in a commercial silicon solar cell.

Microcellular sensing media with ternary transparency states for fast and intuitive identification of unknown liquids.

Rapid, accurate, and intuitive detection of unknown liquids is greatly important for various fields such as food and drink safety, management of chemical hazards, manufacturing process monitoring, and so on. Here, we demonstrate a highly responsive and selective transparency-switching medium for on-site, visual identification of various liquids. The light scattering­based sensing medium, which is designed to be composed of polymeric interphase voids and hollow nanoparticles, provides an extremely large transmittance window (>95%) with outstanding selectivity and versatility. This sensing medium features ternary transparency states (transparent, semitransparent, and opaque) when immersed in liquids depending on liquid-polymer interactions and diffusion kinetics. Several different types of these transparency-changing media can be configured into an arrayed platform to discriminate a wide variety of liquids and also quantify their mixing ratios. The outstanding versatility and user friendliness of the sensing platform allow the development of a practical tool for discrimination of diverse organic liquids.

Hierarchical Nanoporous BiVO4 Photoanodes with High Charge Separation and Transport Efficiency for Water Oxidation.

To fabricate high efficiency photoanodes for water oxidation, it is highly required to engineer their nanoporous architecture and interface to improve the charge separation and transport efficiency. By focusing on this aspect, we developed hierarchical nanoporous BiVO4 (BV) from solution processed two-dimensional BiOI (BI) crystals. The orientation of the BI crystals was controlled by changing the solvent volume ratios of ethylene glycol (EG) to ethanol (ET), which resulted in different hierarchical and planar BV morphologies through a chemical treatment followed by thermal heating. The morphology with optimal particle dimension, connectivity, and porosity can offer a highly enhanced electrochemically active surface area (ECSA). The hierarchical BV owning a maximum ECSA showed the best photoelectrochemical (PEC) performance in terms of the highest photocurrent density and charge separation efficiency. However, to further improve the performance of the electrode, conformal and ultrathin SnO2 underlayers were deposited by a powerful atomic layer deposition technique at the interface to effectively block the defect density, which significantly improved the photocurrents as high as 3.25 mA/cm2 for sulfite oxidation and 2.55 mA/cm2 for water oxidation at 0.6 V versus the reversible hydrogen electrode (RHE). The electrode possessed record charge separation efficiency of 97.1% and charge transfer efficiency of 90.1% at 1.23 VRHE among to-date reported BiVO4-based photoanodes for water oxidation. Furthermore, a maximum applied bias photon-to-current efficiency (ABPE) of 1.61% was found at a potential as low as 0.6 VRHE, which is highly promising to make a tandem cell. These results indicate that the construction of the hierarchical nanoporous photoanode with an enhanced ECSA and its proper interface engineering can significantly improve the PEC performance.

Plasma-Enhanced Atomic Layer Deposition of TiN Thin Films as an Effective Se Diffusion Barrier for CIGS Solar Cells.

Plasma-enhanced atomic layer deposition (PEALD) of TiN thin films were investigated as an effective Se diffusion barrier layer for Cu (In, Ga) Se2 (CIGS) solar cells. Before the deposition of TiN thin film on CIGS solar cells, a saturated growth rate of 0.67 Å/cycle was confirmed using tetrakis(dimethylamido)titanium (TDMAT) and N2 plasma at 200 °C. Then, a Mo (≈30 nm)/PEALD-TiN (≈5 nm)/Mo (≈600 nm) back contact stack was fabricated to investigate the effects of PEALD-TiN thin films on the Se diffusion. After the selenization process, it was revealed that ≈5 nm-thick TiN thin films can effectively block Se diffusion and that only the top Mo layer prepared on the TiN thin films reacted with Se to form a MoSe2 layer. Without the TiN diffusion barrier layer, however, Se continuously diffused along the grain boundaries of the entire Mo back contact electrode. Finally, the adoption of a TiN diffusion barrier layer improved the photovoltaic efficiency of the CIGS solar cell by approximately 10%.

Effect of ZnO and SnO2 Nanolayers at Grain Boundaries on Thermoelectric Properties of Polycrystalline Skutterudites.

Nanostructuring is considered one of the key approaches to achieve highly efficient thermoelectric alloys by reducing thermal conductivity. In this study, we investigated the effect of oxide (ZnO and SnO2) nanolayers at the grain boundaries of polycrystalline In0.2Yb0.1Co4Sb12 skutterudites on their electrical and thermal transport properties. Skutterudite powders with oxide nanolayers were prepared by atomic layer deposition method, and the number of deposition cycles was varied to control the coating thickness. The coated powders were consolidated by spark plasma sintering. With increasing number of deposition cycle, the electrical conductivity gradually decreased, while the Seebeck coefficient changed insignificantly; this indicates that the carrier mobility decreased due to the oxide nanolayers. In contrast, the lattice thermal conductivity increased with an increase in the number of deposition cycles, demonstrating the reduction in phonon scattering by grain boundaries owing to the oxide nanolayers. Thus, we could easily control the thermoelectric properties of skutterudite materials through adjusting the oxide nanolayer by atomic layer deposition method.

Atomic Layer Deposition Seeded Growth of Rutile SnO2 Nanowires on Versatile Conducting Substrates.

Extended and oriented rutile nanowires (NWs) hold great promise for numerous applications because of their various tunable physicochemical properties in air and/or solution media, but their direct synthesis on a wide range of conducting substrates remains a significant challenge. Their device performance is governed by relevant NW geometries that cannot be fully controlled to date by varying bulk synthetic conditions. Herein, orientation engineering of rutile SnO2 NWs on a variety of conducting substrates by atomic layer deposition (ALD) seeding has been investigated. The seeded growth controls the nucleation event of the NW, and thicknesses and crystallographic properties of seed layers are the key parameters toward tuning the NW characteristics. The seed layers on carbon cloth produce NWs with highly enhanced electrochemically active surface area, which would show efficient electrochemical CO2 reduction. In addition, the hierarchical architecture resulted from the seeded growth of NWs on SnO2 nanosheets allows thin layers of BiVO4, forming a heterojunction photoanode, which shows a record charge separation efficiency of 96.6% and a charge-transfer efficiency of 90.2% at 1.23 V versus the reversible hydrogen electrode among, to date, the reported BiVO4-based photoanodes for water oxidation. Our study illustrates that such a versatile interfacial engineering effort by the ALD technique would be promising for further wide range of practical applications.

Thermally assisted nanotransfer printing with sub-20-nm resolution and 8-inch wafer scalability.

Nanotransfer printing (nTP) has attracted considerable attention due to its good pattern resolution, process simplicity, and cost-effectiveness. However, the development of a large-area nTP process has been hampered by critical reliability issues related to the uniform replication and regular transfer printing of functional nanomaterials. Here, we present a very practical thermally assisted nanotransfer printing (T-nTP) process that can easily produce well-ordered nanostructures on an 8-inch wafer via the use of a heat-rolling press system that provides both uniform pressure and heat. We also demonstrate various complex pattern geometries, such as wave, square, nut, zigzag, and elliptical nanostructures, on diverse substrates via T-nTP. Furthermore, we demonstrate how to obtain a high-density crossbar metal-insulator-metal memristive array using a combined method of T-nTP and directed self-assembly. We expect that the state-of-the-art T-nTP process presented here combined with other emerging patterning techniques will be especially useful for the large-area nanofabrication of various devices.

Dataset for TiN Thin Films Prepared by Plasma-Enhanced Atomic Layer Deposition Using Tetrakis(dimethylamino)titanium (TDMAT) and Titanium Tetrachloride (TiCl4) Precursor.

A dataset in this report is regarding an article "Ultrathin Effective TiN Protective Films Prepared by Plasma-Enhanced Atomic Layer Deposition for High Performance Metallic Bipolar Plates of Polymer Electrolyte Membrane Fuel Cells" [1]. TiN (Titanium Nitride) thin films were deposited by Plasma-Enhanced Atomic Layer Deposition (PEALD) method using well known two types of precursor: using tetrakis(dimethylamino)titanium (TDMAT) and titanium tetrachloride (TiCl4), and plasma. Summarized reports, growth characteristics (growth rate as a function of each precursor pulse time, plasma power, precursor and plasma purge time, thickness depending on the number of PEALD cycles), each precursor structural information and the atomic force micrographs (AFM) data are herein demonstrated. For TDMAT-TiN, N2 plasma was used as a reactant whereas, H2+N2 plasma was used as TiCl4-TiN reactant. To apply the bipolar plate substrate, two types of TiN thin films were introduced into Stainless steel (SUS) 316L.

Sb2S3 Nanoparticles Anchored or Encapsulated by the Sulfur-Doped Carbon Sheet for High-Performance Supercapacitors.

The specific capacitance and energy density of antimony trisulfide (Sb2S3)@carbon supercapacitors (SCs) have been limited and are in need of significant improvement. In this work, Sb2S3 nanoparticles were selectively encapsulated or anchored in a sulfur-doped carbon (S-carbon) sheet depending on the use of microwave-assisted synthesis. The microwave-triggered Sb2S3 nanoparticle growth resulted in core-shell hierarchical spherical particles of uniform diameter assembled with Sb2S3 as the core and an encapsulated S-carbon layer as the shell (Sb2S3-M@S-C). Without the microwave mediation, the other nanostructure was found to comprise fine Sb2S3 nanoparticles widely anchored in the S-carbon sheet (Sb2S3-P@S-C). Structural and morphological analyses confirmed the presence of encapsulated and anchored Sb2S3 nanoparticles in the carbon. These two materials exhibited higher specific capacitance values of 1179 (0 to +1.0 V) and 1380 F·g-1 (-0.8 to 0 V) at a current density of 1 A·g-1, respectively, than those previously reported for Sb2S3 nanomaterials in considerable SCs. Furthermore, both materials exhibited outstanding reversible capacitance and cycle stability when used as SC electrodes while retaining over 98% of the capacitance after 10 000 cycles, which indicates their long-term stability. Furthermore, a hybrid Sb2S3-M@S-C/Sb2S3-P@S-C device was designed, which delivers a remarkable energy density of 49 W·h·kg-1 at a power density of 2.5 kW·kg-1 with long-term cycle stability (94% over 10 000 cycles) and is comparable to SCs in the recent literature. Finally, a light-emitting diode (LED) panel comprising 32 LEDs was powered using three pencil-type hybrid SCs in series.

Hierarchical multi-level block copolymer patterns by multiple self-assembly.

Uniform, well-ordered sub-20 nm patterns can be generated by the templated self-assembly of block copolymers (BCPs) with a high Flory-Huggins interaction parameter (χ). However, the self-assembled BCP monolayers remain limited in the possible structural geometries. Here, we introduce a multiple self-assembly method which uses di-BCPs to produce diverse morphologies, such as dot, dot-in-honeycomb, line-on-dot, double-dot, pondering, dot-in-pondering, and line-on-pondering patterns. To improve the diversity of BCP morphological structures, we employed sphere-forming and cylinder-forming poly(styrene-block-dimethylsiloxane) (PS-b-PDMS) BCPs with a high χ. The self-assembled mono-layer and double-layer SiOx dot patterns were modified at a high temperature (∼800 °C), showing hexagonally arranged (dot) and double-hexagonally arranged (pondering) SiOx patterns, respectively. We successfully obtained additional new nanostructures (big-dot, dot-in-honeycomb, line-on-dot, pondering, dot-in-pondering, and line-on-pondering types) through a second self-assembly of cylinder-forming BCPs using the dot and pondering patterns as guiding templates. This simple approach can likely be extended to the multiple self-assembly of many other BCPs with good functionality, significantly contributing to the development of various nanodevices.

Effects of Ar Addition to O2 Plasma on Plasma-Enhanced Atomic Layer Deposition of Oxide Thin Films.

A method for significantly increasing the growth rates (GRs) of high- k oxide thin films grown via plasma-enhanced atomic layer deposition (PE-ALD) by enhancing the plasma density through the addition of Ar gas to the O2 plasma oxidant was developed. This approach led to improvements of ∼60% in the saturation GRs of PE-ALD ZrO2, HfO2, and SiO2. Furthermore, despite the significantly higher GR enabled by PE-ALD, the mechanical and dielectric properties of the PE-ALD oxide films were similar or even superior to those of films grown via the conventional O2 plasma process. Optical emission spectroscopy analyses in conjunction with theoretical calculation of the electron energy distribution function revealed that adding Ar gas to the O2 plasma increased the density of high-energy electrons, thereby generating more O2 plasma species, such as ions and radicals, which played a key role in improving the GRs and the properties of the films. This promising approach is expected to facilitate the high-volume manufacturing of films via PE-ALD, especially for use as gate insulators in thin-film transistor-based devices in the display industry.

Facile Fabrication of a Two-Dimensional TMD/Si Heterojunction Photodiode by Atmospheric-Pressure Plasma-Enhanced Chemical Vapor Deposition.

A growth technique to directly prepare two-dimensional (2D) materials onto conventional semiconductor substrates, enabling low-temperature, high-throughput, and large-area capability, is needed to realize competitive 2D transition-metal dichalcogenide (TMD)/three-dimensional (3D) semiconductor heterojunction devices. Therefore, we herein successfully developed an atmospheric-pressure plasma-enhanced chemical vapor deposition (AP-PECVD) technique, which could grow MoS2 and WS2 multilayers directly onto PET flexible substrate as well as 4-in. Si substrates at temperatures of <200 °C. The as-fabricated MoS2/Si and WS2/Si heterojunctions exhibited large and fast photocurrent responses under illumination of a green light. The measured photocurrent was linearly proportional to the laser power, indicating that trapping and detrapping of the photogenerated carriers at defect states could not significantly suppress the collection of photocarriers. All the results demonstrated that our AP-PECVD method could produce high-quality TMD/Si 2D-3D heterojunctions for optoelectronic applications.

Influence of Surface Defects and Size on Photochemical Properties of SnO2 Nanoparticles.

We report the successful synthesis of surface defective small size (SS) SnO2 nanoparticles (NPs) by adopting a low temperature surfactant free solution method. The structural properties of the NPs were analyzed using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). The presence of surface defects, especially oxygen vacancies, in the sample were characterized using micro-Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence emission. The Brunauer⁻Emmet⁻Teller (BET) nitrogen adsorption⁻desorption isotherms demonstrated the superior textural properties (high surface area and uniform pore size) of SS SnO2 compared to large size (LS) SnO2. A comparable study was drawn between SS SnO2 and LS SnO2 NPs and a significant decrease in the concentration of surface defects was observed for the LS sample. The results showed that surface defects significantly depend upon the size of the NPs. The surface defects formed within the band gap energy level of SnO2 significantly participated in the recombination process of photogenerated charge carriers, improving photochemical properties. Moreover, the SS SnO2 showed superior photoelectrochemical (PEC) and photocatalytic activities compared to the LS SnO2. The presence of a comparatively large number of surface defects due to its high surface area may enhance the photochemical activity by reducing the recombination rate of the photogenerated charges.

Self-Formed Channel Devices Based on Vertically Grown 2D Materials with Large-Surface-Area and Their Potential for Chemical Sensor Applications.

2D layered materials with sensitive surfaces are promising materials for use in chemical sensing devices, owing to their extremely large surface-to-volume ratios. However, most chemical sensors based on 2D materials are used in the form of laterally defined active channels, in which the active area is limited to the actual device dimensions. Therefore, a novel approach for fabricating self-formed active-channel devices is proposed based on 2D semiconductor materials with very large surface areas, and their potential gas sensing ability is examined. First, the vertical growth phenomenon of SnS2 nanocrystals is investigated with large surface area via metal-assisted growth using prepatterned metal electrodes, and then self-formed active-channel devices are suggested without additional pattering through the selective synthesis of SnS2 nanosheets on prepatterned metal electrodes. The self-formed active-channel device exhibits extremely high response values (>2000% at 10 ppm) for NO2 along with excellent NO2 selectivity. Moreover, the NO2 gas response of the gas sensing device with vertically self-formed SnS2 nanosheets is more than two orders of magnitude higher than that of a similar exfoliated SnS2 -based device. These results indicate that the facile device fabrication method would be applicable to various systems in which surface area plays an important role.

Enhanced Electron Transfer Mediated by Conjugated Polyelectrolyte and Its Application to Washing-Free DNA Detection.

Direct electron transfer between a redox label and an electrode requires a short working distance (<1-2 nm), and in general an affinity biosensor based on direct electron transfer requires a finely smoothed Au electrode to support efficient target binding. Here we report that direct electron transfer over a longer working distance is possible between (i) an anionic π-conjugated polyelectrolyte (CPE) label having many redox-active sites and (ii) a readily prepared, thin polymeric monolayer-modified indium-tin oxide electrode. In addition, the long CPE label (∼18 nm for 10 kDa) can approach the electrode within the working distance after sandwich-type target-specific binding, and fast CPE-mediated oxidation of ammonia borane along the entire CPE backbone affords high signal amplification.