Automated Assembly of Wafer-Scale 2D TMD Heterostructures of Arbitrary Layer Orientation and Stacking Sequence Using Water Dissoluble Salt Substrates.

We report a novel strategy to assemble wafer-scale two-dimensional (2D) transition metal dichalcogenide (TMD) layers of well-defined components and orientations. We directly grew a variety of 2D TMD layers on "water-dissoluble" single-crystalline salt wafers and precisely delaminated them inside water in a chemically benign manner. This manufacturing strategy enables the automated integration of vertically aligned 2D TMD layers as well as 2D/2D heterolayers of arbitrary stacking orders on exotic substrates insensitive to their kind and shape. Furthermore, the original salt wafers can be recycled for additional growths, confirming high process sustainability and scalability. The generality and versatility of this approach have been demonstrated by developing proof-of-concept "all 2D" devices for diverse yet unconventional applications. This study is believed to shed a light on leveraging opportunities of 2D TMD layers toward achieving large-area mechanically reconfigurable devices of various form factors at the industrially demanded scale.

Experimental Realization of Few Layer Two-Dimensional MoS2 Membranes of Near Atomic Thickness for High Efficiency Water Desalination.

A globally imminent shortage of freshwater has been demanding viable strategies for improving desalination efficiencies with the adoption of cost- and energy-efficient membrane materials. The recently explored 2D transition metal dichalcogenides (2D TMDs) of near atomic thickness have been envisioned to offer notable advantages as high-efficiency membranes owing to their structural uniqueness; that is, extremely small thickness and intrinsic atomic porosity. Despite theoretically projected advantages, experimental realization of near atom-thickness 2D TMD-based membranes and their desalination efficiency assessments have remained largely unexplored mainly due to the technical difficulty associated with their seamless large-scale integration. Herein, we report the experimental demonstration of high-efficiency water desalination membranes based on few-layer 2D molybdenum disulfide (MoS2) of only ∼7 nm thickness. Chemical vapor deposition (CVD)-grown centimeter-scale 2D MoS2 layers were integrated onto porous polymeric supports with well-preserved structural integrity enabled by a water-assisted 2D layer transfer method. These 2D MoS2 membranes of near atomic thickness exhibit an excellent combination of high water permeability (>322 L m-2 h-1 bar-1) and high ionic sieving capability (>99%) for various seawater salts including Na+, K+, Ca2+, and Mg2+ with a range of concentrations. Moreover, they present near 100% salt ion rejection rates for actual seawater obtained from the Atlantic coast, significantly outperforming the previously developed 2D MoS2 layer membranes of micrometer thickness as well as conventional reverse osmosis (RO) membranes. Underlying principles behind such remarkably excellent desalination performances are attributed to the intrinsic atomic vacancies inherent to the CVD-grown 2D MoS2 layers as verified by aberration-corrected electron microscopy characterization.

Multifunctional Two-Dimensional PtSe2-Layer Kirigami Conductors with 2000% Stretchability and Metallic-to-Semiconducting Tunability.

Two-dimensional transition-metal dichalcogenide (2D TMD) layers are highly attractive for emerging stretchable and foldable electronics owing to their extremely small thickness coupled with extraordinary electrical and optical properties. Although intrinsically large strain limits are projected in them (i.e., several times greater than silicon), integrating 2D TMDs in their pristine forms does not realize superior mechanical tolerance greatly demanded in high-end stretchable and foldable devices of unconventional form factors. In this article, we report a versatile and rational strategy to convert 2D TMDs of limited mechanical tolerance to tailored 3D structures with extremely large mechanical stretchability accompanying well-preserved electrical integrity and modulated transport properties. We employed a concept of strain engineering inspired by an ancient paper-cutting art, known as kirigami patterning, and developed 2D TMD-based kirigami electrical conductors. Specifically, we directly integrated 2D platinum diselenide (2D PtSe2) layers of controlled carrier transport characteristics on mechanically flexible polyimide (PI) substrates by taking advantage of their low synthesis temperature. The metallic 2D PtSe2/PI kirigami patterns of optimized dimensions exhibit an extremely large stretchability of ∼2000% without compromising their intrinsic electrical conductance. They also present strain-tunable and reversible photoresponsiveness when interfaced with semiconducting carbon nanotubes (CNTs), benefiting from the formation of 2D PtSe2/CNT Schottky junctions. Moreover, kirigami field-effect transistors (FETs) employing semiconducting 2D PtSe2 layers exhibit tunable gate responses coupled with mechanical stretching upon electrolyte gating. The exclusive role of the kirigami pattern parameters in the resulting mechanoelectrical responses was also verified by a finite-element modeling (FEM) simulation. These multifunctional 2D materials in unconventional yet tailored 3D forms are believed to offer vast opportunities for emerging electronics and optoelectronics.

Highly stretchable and tough hydrogels.

Hydrogels are used as scaffolds for tissue engineering, vehicles for drug delivery, actuators for optics and fluidics, and model extracellular matrices for biological studies. The scope of hydrogel applications, however, is often severely limited by their mechanical behaviour. Most hydrogels do not exhibit high stretchability; for example, an alginate hydrogel ruptures when stretched to about 1.2 times its original length. Some synthetic elastic hydrogels have achieved stretches in the range 10-20, but these values are markedly reduced in samples containing notches. Most hydrogels are brittle, with fracture energies of about 10 J m(-2) (ref. 8), as compared with ∼1,000 J m(-2) for cartilage and ∼10,000 J m(-2) for natural rubbers. Intense efforts are devoted to synthesizing hydrogels with improved mechanical properties; certain synthetic gels have reached fracture energies of 100-1,000 J m(-2) (refs 11, 14, 17). Here we report the synthesis of hydrogels from polymers forming ionically and covalently crosslinked networks. Although such gels contain ∼90% water, they can be stretched beyond 20 times their initial length, and have fracture energies of ∼9,000 J m(-2). Even for samples containing notches, a stretch of 17 is demonstrated. We attribute the gels' toughness to the synergy of two mechanisms: crack bridging by the network of covalent crosslinks, and hysteresis by unzipping the network of ionic crosslinks. Furthermore, the network of covalent crosslinks preserves the memory of the initial state, so that much of the large deformation is removed on unloading. The unzipped ionic crosslinks cause internal damage, which heals by re-zipping. These gels may serve as model systems to explore mechanisms of deformation and energy dissipation, and expand the scope of hydrogel applications.

Centimeter-Scale 2D van der Waals Vertical Heterostructures Integrated on Deformable Substrates Enabled by Gold Sacrificial Layer-Assisted Growth.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) such as molybdenum or tungsten disulfides (MoS2 or WS2) exhibit extremely large in-plane strain limits and unusual optical/electrical properties, offering unprecedented opportunities for flexible electronics/optoelectronics in new form factors. In order for them to be technologically viable building-blocks for such emerging technologies, it is critically demanded to grow/integrate them onto flexible or arbitrary-shaped substrates on a large wafer-scale compatible with the prevailing microelectronics processes. However, conventional approaches to assemble them on such unconventional substrates via mechanical exfoliations or coevaporation chemical growths have been limited to small-area transfers of 2D TMD layers with uncontrolled spatial homogeneity. Moreover, additional processes involving a prolonged exposure to strong chemical etchants have been required for the separation of as-grown 2D layers, which is detrimental to their material properties. Herein, we report a viable strategy to universally combine the centimeter-scale growth of various 2D TMD layers and their direct assemblies on mechanically deformable substrates. By exploring the water-assisted debonding of gold (Au) interfaced with silicon dioxide (SiO2), we demonstrate the direct growth, transfer, and integration of 2D TMD layers and heterostructures such as 2D MoS2 and 2D MoS2/WS2 vertical stacks on centimeter-scale plastic and metal foil substrates. We identify the dual function of the Au layer as a growth substrate as well as a sacrificial layer which facilitates 2D layer transfer. Furthermore, we demonstrate the versatility of this integration approach by fabricating centimeter-scale 2D MoS2/single walled carbon nanotube (SWNT) vertical heterojunctions which exhibit current rectification and photoresponse. This study opens a pathway to explore large-scale 2D TMD van der Waals layers as device building blocks for emerging mechanically deformable electronics/optoelectronics.

Promotion of resin bonding to dental zirconia ceramic using plasma deposition of tetramethylsilane and benzene.

The aim of this study was to investigate the effects of plasma-enhanced deposition of an organosilane and benzene on resin bonding to a dental zirconia ceramic. A total of 70 zirconia specimens, which were polished before sintering, were randomly divided into five groups according to surface treatments before applying a dental adhesive (each group, n = 14): group 1, no previous treatment (control); group 2, plasma deposition with tetramethylsilane (TMS); group 3, plasma deposition with benzene; group 4, sequential plasma deposition with TMS and benzene; and group 5, a zirconia primer (Z-Prime Plus). A dental adhesive (Scotchbond Multi-Purpose adhesive) was applied to the surface-treated zirconia, and resin composite rods were built in to enable shear bond-strength testing. The sequential deposition of TMS and benzene showed the highest bond strength [22.7 ± 3.7 MPa (mean ± SD)], approximately twice that of Z-Prime Plus (10.3 ± 3.2 MPa). The plasma deposition with either TMS or benzene also significantly improved bond-strength values compared with the negative-control group, and their effects were not statistically different from that of Z-Prime Plus. Following plasma deposition with TMS, the introduction of silicon-oxygen-zirconium (Si-O-Zr) bonds on the zirconia surface was confirmed via X-ray photoelectron spectroscopy (XPS) analysis. Transmission electron microscopy and energy dispersive X-ray spectroscopy showed that a silica-like layer and a polymerizable carbon-rich layer were formed through sequential deposition with TMS and benzene.

Interface-enhanced Li ion conduction in a LiBH4-SiO2 solid electrolyte.

We have developed a fast solid state Li ion conductor composed of LiBH4 and SiO2 by means of interface engineering. A composite of LiBH4-SiO2 was simply synthesized by high energy ball-milling, and two types of SiO2 (MCM-41 and fumed silica) having different specific surface areas were used to evaluate the effect of the LiBH4/SiO2 interface on the ionic conductivity enhancement. The ionic conductivity of the ball-milled LiBH4-MCM-41 and LiBH4-fumed silica mixture is as high as 10(-5) S cm(-1) and 10(-4) S cm(-1) at room temperature, respectively. In particular, the conductivity of the latter is comparable to the LiBH4 melt-infiltrated into MCM-41. The conductivities of the LiBH4-fumed silica mixtures at different mixing ratios were analyzed employing a continuum percolation model, and the conductivity of the LiBH4/SiO2 interface layer is estimated to be 10(5) times higher than that of pure bulk LiBH4. The result highlights the importance of the interface and indicates that significant enhancement in ionic conductivity can be achieved via interface engineering.

Promotion of adhesive penetration and resin bond strength to dentin using non-thermal atmospheric pressure plasma.

Non-thermal atmospheric pressure plasmas (NT-APPs) have been shown to improve the bond strength of resin composites to demineralized dentin surfaces. Based on a wet-bonding philosophy, it is believed that a rewetting procedure is necessary after treatment with NT-APP because of its air-drying effect. This study investigated the effect of 'plasma-drying' on the bond strength of an etch-and-rinse adhesive to dentin by comparison with the wet-bonding technique. Dentin surfaces of human third molars were acid-etched and divided into four groups according to the adhesion procedure: wet bonding, plasma-drying, plasma-drying/rewetting, and dry bonding. In plasma treatment groups, the demineralized dentin surfaces were treated with a plasma plume generated using a pencil-type low-power plasma torch. After the adhesion procedures, resin composite/dentin-bonded specimens were subjected to a microtensile bond-strength test. The hybrid layer formation was characterized by micro-Raman spectroscopy and scanning electron microscopy. The plasma-drying group presented significantly higher bond strength than the wet-bonding and dry-bonding groups. Micro-Raman spectral analysis indicated that plasma-drying improved the penetration and polymerization efficacy of the adhesive. Plasma-drying could be a promising method to control the moisture of demineralized dentin surfaces and improve the penetration of adhesive and the mechanical property of the adhesive/dentin interface.

A Shear Strain Route Dependency of Martensite Formation in 316L Stainless Steel.

In this study, the effect of simple shearing on microstructure evolution and mechanical properties of 316L austenitic stainless steel were investigated. Two different shear strain routes were obtained by twisting cylindrical specimens in the forward and backward directions. The strain-induced martensite phase was effectively obtained by alteration of the routes. Formation of the martensite phase clearly resulted in significant hardening of the steel. Grain-size reduction and strain-induced martensitic transformation within the deformed structures of the strained specimens were characterized by scanning electron microscopy - electron back-scattered diffraction, X-ray diffraction, and the TEM-ASTAR (transmission electron microscopy - analytical scanning transmission atomic resolution, automatic crystal orientation/phase mapping for TEM) system. Significant numbers of twin networks were formed by alteration of the shear strain routes, and the martensite phases were nucleated at the twin interfaces.

Microstructural characterization of dehydrogenated products of the LiBH4-YH3 composite.

The dehydrogenated microstructure of the lithium borohydride-yttrium hydride (LiBH4-YH3) composite obtained at 350°C under 0.3 MPa of hydrogen and static vacuum was investigated by transmission electron microscopy combined with a focused ion beam technique. The dehydrogenation reaction between LiBH4 and YH3 into LiH and YB4 takes place under 0.3 MPa of hydrogen, which produces YB4 nano-crystallites that are uniformly distributed in the LiH matrix. This microstructural feature seems to be beneficial for rehydrogenation of the dehydrogenation products. On the other hand, the dehydrogenation process is incomplete under static vacuum, leading to the unreacted microstructure, where YH3 and YH2 crystallites are embedded in LiBH4 matrix. High resolution imaging confirmed the presence of crystalline B resulting from the self-decomposition of LiBH4. However, Li2B12H12, which is assumed to be present in the LiBH4 matrix, was not clearly observed.

Strain-induced large exciton energy shifts in buckled CdS nanowires.

Strain engineering can be utilized to tune the fundamental properties of semiconductor materials for applications in advanced electronic and photonic devices. Recently, the effects of large strain on the properties of nanostructures are being intensely investigated to further expand our insights into the physics and applications of such materials. In this Letter, we present results on controllable buckled cadmium-sulfide (CdS) optical nanowires (NWs), which show extremely large energy bandgap tuning by >250 meV with applied strains within the elastic deformation limit. Polarization and spatially resolved optical measurements reveal characteristics related to both compressive and tensile regimes, while microreflectance spectroscopy clearly demonstrates the effect of strain on the different types of excitons in CdS. Our results may enable strained NWs-based optoelectronic devices with tunable optical responses.

Geometry-induced dislocations in coaxial heterostructural nanotubes.

Highly localized dislocations in GaN/ZnO hetero-nanostructures are generated from the residual strain field by lattice mismatches at two interfaces: between the substrate and hetero-nanostructures, and between the ZnO core and GaN shell. The local strain field is measured using tranmission electron microscopy, and the relationship between the nanostructure morphology and the highly localized dislocations is analyzed by a finite element method.

Statistical analysis on static recrystallization texture evolution in cold-rolled AZ31 magnesium alloy sheet.

Cast AZ31B-H24 magnesium alloy, comprising Mg with 3.27 wt% Al and 0.96 wt% Zn, was cold rolled and subsequently annealed. Global texture evolutions in the specimens were observed by X-ray diffractometry after the thermomechanical processing. Image-based microstructure and texture for the deformed, recrystallized, and grown grains were observed by electron backscattered diffractometry. Recrystallized grains could be distinguished from deformed ones by analyzing grain orientation spread. Split basal texture of ca. ±10-15° in the rolling direction was observed in the cold-rolled sample. Recrystallized grains had widely spread basal poles at nucleation stage; strong {0001} basal texture developed with grain growth during annealing.

A quantitative evaluation of microstructure by electron back-scattered diffraction pattern quality variations.

Band contrast (BC) is a qualitative measure of electron back-scattered diffraction (EBSD), which is derived from the intensity of the Kikuchi bands. The BC is dependent upon several factors including scanning electron microscope measurement parameters, EBSD camera setup, and the specimen itself (lattice defect and grain orientation). In this study, the effective factors for BC variations and the feasibility of using BC variations for the quantification of microstructure evolutions have been investigated. In addition, the effects of the lattice defect and the grain orientation on the BC variations are studied. Next, a shear-deformed microstructure of 316L stainless steel, which contains nanosized grains and a large portion of twin boundaries, is revealed by BC map and histogram. Recovery and recrystallization of shear-deformed 316L stainless steel are displayed by BC variations during isothermal annealing at 700 and 800°C, respectively. It is observed that the BC turns bright as the shear-deformed crystal structure is recovered or recrystallized.

Effect of the applied power of atmospheric pressure plasma on the adhesion of composite resin to dental ceramic.

PURPOSE: To evaluate the effect of applied power on dental ceramic bonding of composite resin using nonthermal atmospheric pressure plasma (APP). MATERIALS AND METHODS: A pencil-type APP torch was used to modify the surface chemical composition and hydrophilicity of dental ceramic and to improve the adhesion of composite resin to the surface. The effect of the applied power on chemical changes of the plasma polymer on a ceramic surface and the adhesive strength between the composite resin and feldspathic porcelain were examined. Adhesion was evaluated by comparing shear bond strengths (SBS) using the iris method. The chemical composition of the plasma polymer deposited on the ceramic surface was evaluated using x-ray photoelectron spectroscopy (XPS). Hydrophilicity was evaluated by contact angle measurements. The fracture mode at the interface was also evaluated. RESULTS: The APP treatment was effective and the SBS of the experimental groups were significantly higher than those of the negative control group (p < 0.05). Moreover, the SBS obtained with the APP treatment at the highest input voltage was statistically similar to the gold standard of HF etching and silane coupling-agent coating. Two-thirds of the fractures observed in the specimens bonded with application of APP were mixed and cohesive fractures. CONCLUSION: Application of APP enhanced adhesion by producing carboxyl groups on the ceramic surface and as a result by improving surface hydrophilicity. The carboxyl group contents in the plasma polymer on the ceramic surface increased as the applied power increased.

Peel-and-Stick Integration of Atomically Thin Nonlayered PtS Semiconductors for Multidimensionally Stretchable Electronic Devices.

Various near-atom-thickness two-dimensional (2D) van der Waals (vdW) crystals with unparalleled electromechanical properties have been explored for transformative devices. Currently, the availability of 2D vdW crystals is rather limited in nature as they are only obtained from certain mother crystals with intrinsically possessed layered crystallinity and anisotropic molecular bonding. Recent efforts to transform conventionally non-vdW three-dimensional (3D) crystals into ultrathin 2D-like structures have seen rapid developments to explore device building blocks of unique form factors. Herein, we explore a "peel-and-stick" approach, where a nonlayered 3D platinum sulfide (PtS) crystal, traditionally known as a cooperate mineral material, is transformed into a freestanding 2D-like membrane for electromechanical applications. The ultrathin (∼10 nm) 3D PtS films grown on large-area (>cm2) silicon dioxide/silicon (SiO2/Si) wafers are precisely "peeled" inside water retaining desired geometries via a capillary-force-driven surface wettability control. Subsequently, they are "sticked" on strain-engineered patterned substrates presenting prominent semiconducting properties, i.e., p-type transport with an optical band gap of ∼1.24 eV. A variety of mechanically deformable strain-invariant electronic devices have been demonstrated by this peel-and-stick method, including biaxially stretchable photodetectors and respiratory sensing face masks. This study offers new opportunities of 2D-like nonlayered semiconducting crystals for emerging mechanically reconfigurable and stretchable device technologies.

Strain Concentration Ratio Analysis of Different Waterproofing Materials during Concrete Crack Movement.

When a crack occurs under an installed waterproofing material and moves due to environmental effects (freeze-thaw, settlement, vibration, dead load, etc.), waterproofing materials without adequate elongation or tensile strength properties may break and tear. To enable the selection of materials with proper response against the strain that occur during crack movement, this study proposes and demonstrates a new evaluation method for determining and comparing strain concentration of waterproofing materials under the effect of concrete crack movement. For the proposed testing method and demonstration, three common types of waterproofing material types were selected for testing, poly-urethane coating (PUC), self-adhesive asphalt sheet (SAS) and composite asphalt sheet (CAS). Respective materials are installed with strain gauges and applied onto a specimen with a separated joint that undergoes concrete crack movement simulation. Each specimen types are subject to repeated movement cycles, whereby strain occurring directly above the moving joint is measured and compared with the strain occurring at the localized sections (comparison ratio which is hereafter referred to as strain concentration ratio). Specimens are tested under four separate movement length conditions, 1.5 mm, 3.0 mm, 4.5 mm and 6.0 mm, and the results are compared accordingly. Experimental results show that materials with strain concentration ratio from highest to lowest are as follows: PUC, SAS and CAS.

Crack-Bridging Property Evaluation of Synthetic Polymerized Rubber Gel (SPRG) through Yield Stress Parameter Identification.

Yield stress parameter derivation was conducted by stress-strain curve analysis on four types of grout injection leakage repair materials (GILRM); acrylic, epoxy, urethane and SPRG grouts. Comparative stress-strain curve analysis results showed that while the yield stress point was clearly distinguishable, the strain ratio of SPRG reached up to 664% (13 mm) before material cohesive failure. A secondary experimental result comprised of three different common component ratios of SPRG was conducted to derive and propose an averaged yield stress curve graph, and the results of the yield stress point (180% strain ratio) were set as the basis for repeated stress-strain curve analysis of SPRGs of up to 15 mm displacement conditions. Results showed that SPRG yield stress point remained constant despite repeated cohesive failure, and the modulus of toughness was calculated to be on average 53.1, 180.7, and 271.4 N/mm2, respectively, for the SPRG types. The experimental results of this study demonstrated that it is possible to determine the property limits of conventional GILRM (acrylic, epoxy and urethane grout injection materials) based on yield stress. The study concludes with a proposal on potential application of GILRM toughness by finite element analysis method whereby strain of the material can be derived by hydrostatic pressure. Comparative analysis showed that the toughness of SPRG materials tested in this study are all able to withstand hydrostatic pressure range common to underground structures (0.2 N/mm2). It is expected that the evaluation method and model proposed in this study will be beneficial in assessing other GILRM materials based on their toughness values.

Mechanically rollable photodetectors enabled by centimetre-scale 2D MoS2 layer/TOCN composites.

Two-dimensional (2D) molybdenum disulfide (MoS2) layers are suitable for visible-to-near infrared photodetection owing to their tunable optical bandgaps. Also, their superior mechanical deformability enabled by an extremely small thickness and van der Waals (vdW) assembly allows them to be structured into unconventional physical forms, unattainable with any other materials. Herein, we demonstrate a new type of 2D MoS2 layer-based rollable photodetector that can be mechanically reconfigured while maintaining excellent geometry-invariant photo-responsiveness. Large-area (>a few cm2) 2D MoS2 layers grown by chemical vapor deposition (CVD) were integrated on transparent and flexible substrates composed of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibers (TOCNs) by a direct solution casting method. These composite materials in three-dimensionally rollable forms exhibited a large set of intriguing photo-responsiveness, well preserving intrinsic opto-electrical characteristics of the integrated 2D MoS2 layers; i.e., light intensity-dependent photocurrents insensitive to illumination angles as well as highly tunable photocurrents varying with the rolling number of 2D MoS2 layers, which were impossible to achieve with conventional photodetectors. This study provides a new design principle for converting 2D materials to three-dimensional (3D) objects of tailored functionalities and structures, significantly broadening their potential and versatility in futuristic devices.

Direct recovery of spilled oil using hierarchically porous oil scoop with capillary-induced anti-oil-fouling.

The pitcher plant has evolved its hierarchically grooved peristome to enhance a water-based slippery system for capturing insects with oil-covered footpads. Based on this, we proposed a hierarchically porous oil scoop (HPOS) with capillary-induced oil peel-off ability for repeatable spilled oil recovery. As the HPOS scoops oil-water mixture, water passes through the hole while the oil is confined within a curved geometry. The filter in HPOS has three levels of porous structures; (1) 3D-printed mesh structure with sub-millimeter scale hole to filter out oil from an oil-water mixture, (2) internal micropore in fibers enhancing capillarity and water transport, (3) O2 plasma-induced high-aspect-ratio nanopillar structures imposing anti-oil-fouling property with capillary-induced oil peeling. As the oil-contaminated HPOS makes contact with water, water meniscus rises and peels off the oil immediately at the air-water interface. The oil-peel-off ability of the HPOS would prevent pores from clogging by oils for reuse. The study demonstrated that the HPOS recovers highly viscous oil (up to 5000 mm2·s-1) with a high recovery rate (>95%), leaving the filtered water with low oil content (<10 ppm), which satisfies the discharge criterion of 15 ppm.