Layer-Structured Anisotropic Metal Chalcogenides: Recent Advances in Synthesis, Modulation, and Applications.

The unique electronic and catalytic properties emerging from low symmetry anisotropic (1D and 2D) metal chalcogenides (MCs) have generated tremendous interest for use in next generation electronics, optoelectronics, electrochemical energy storage devices, and chemical sensing devices. Despite many proof-of-concept demonstrations so far, the full potential of anisotropic chalcogenides has yet to be investigated. This article provides a comprehensive overview of the recent progress made in the synthesis, mechanistic understanding, property modulation strategies, and applications of the anisotropic chalcogenides. It begins with an introduction to the basic crystal structures, and then the unique physical and chemical properties of 1D and 2D MCs. Controlled synthetic routes for anisotropic MC crystals are summarized with example advances in the solution-phase synthesis, vapor-phase synthesis, and exfoliation. Several important approaches to modulate dimensions, phases, compositions, defects, and heterostructures of anisotropic MCs are discussed. Recent significant advances in applications are highlighted for electronics, optoelectronic devices, catalysts, batteries, supercapacitors, sensing platforms, and thermoelectric devices. The article ends with prospects for future opportunities and challenges to be addressed in the academic research and practical engineering of anisotropic MCs.

Hydrogen-doped viscoplastic liquid metal microparticles for stretchable printed metal lines.

Conductive and stretchable electrodes that can be printed directly on a stretchable substrate have drawn extensive attention for wearable electronics and electronic skins. Printable inks that contain liquid metal are strong candidates for these applications, but the insulating oxide skin that forms around the liquid metal particles limits their conductivity. This study reveals that hydrogen doping introduced by ultrasonication in the presence of aliphatic polymers makes the oxide skin highly conductive and deformable. X-ray photoelectron spectroscopy and atom probe tomography confirmed the hydrogen doping, and first-principles calculations were used to rationalize the obtained conductivity. The printed circuit lines show a metallic conductivity (25,000 S cm-1), excellent electromechanical decoupling at a 500% uniaxial stretching, mechanical resistance to scratches and long-term stability in wide ranges of temperature and humidity. The self-passivation of the printed lines allows the direct printing of three-dimensional circuit lines and double-layer planar coils that are used as stretchable inductive strain sensors.

Pseudoequilibrium between Etching and Selective Grain Growth: Chemical Conversion of a Randomly Oriented Au Film into a (111)-Oriented Ultrathin Au Film.

Metal thin films with a specific orientation play vital roles in electronics, catalysts, and epitaxial templates. Although oriented metal films have been produced in the recent years, ultrathin oriented metal films (<10 nm) have not been achieved owing to the interfacial instability of the ultrathin films during the thermal annealing process. This study investigates chemical conversion of randomly oriented multigrain Au ultrathin films into (111)-oriented Au ultrathin films. A novel chemical process, termed pseudoequilibrium of etching and selective grain growth, is presented for the chemical conversion by using a quaternary ammonium halide. The reaction variables (reaction time, reaction temperature, species of halide ions) for the chemical conversion process are systematically investigated. This study reveals the in-plane rotational degeneracy in the Au(111) thin film epitaxially grown on a Si(111) substrate. The chemical process can be applied to a broad range of thicknesses from 9 to 100 nm.

Catalytic topological insulator Bi2Se3 nanoparticles for invivo protection against ionizing radiation.

Bi2Se3 nanoparticles (NPs) have attracted wide interests in biological and medical applications. Layer-like Bi2Se3 with high active surface area is promising for free radical scavenging. Here, we extended the medical applications of Bi2Se3 NPs further to in vivo protection against ionizing radiation based on their superior antioxidant activities and electrocatalytic properties. It was found that Bi2Se3 NPs can significantly increase the surviving fraction of mice after exposure of high-energy radiation of gamma ray. Additionally, the Bi2Se3 NPs can help to recover radiation-lowered red blood cell counts, white blood cell counts and platelet levels. Further investigations revealed that Bi2Se3 NPs behaved as functional free radical scavengers and significantly decreased the level of methylenedioxyamphetamine. In vivo toxicity studies showed that Bi2Se3 NPs did not cause significant side effects in panels of blood chemistry, clinical biochemistry and pathology.

New Approaches to Produce Large-Area Single Crystal Thin Films.

Wafer-scale growth of single crystal thin films of metals, semiconductors, and insulators is crucial for manufacturing high-performance electronic and optical devices, but still challenging from both scientific and industrial perspectives. Recently, unconventional advanced synthetic approaches have been attempted and have made remarkable progress in diversifying the species of producible single crystal thin films. This review introduces several new synthetic approaches to produce large-area single crystal thin films of various materials according to the concepts and principles.

High-Performance Indium-Tin Oxide (ITO) Electrode Enabled by a Counteranion-Free Metal-Polymer Complex.

Although multicomponent inorganic thin films (metal-oxides, -carbides, -nitrides, and -chalcogenides) have been synthesized by polymer-assisted deposition (PAD), synthesis of high-performance transparent conducting oxides (TCOs) has been rarely reported. TCO requires (i) removal of impurities, (ii) high-density oxide film, (iii) homogeneity in crystal structures and film morphology, and (iv) controllable elemental doping. This study performs a systematic investigation on preparation of stable multicomponent metal-polymer complex solutions by removing the counteranions in the solution. This study also proposes accurate acid-base titration for each metal species in order to minimize the amount of PEI, thus maximizing the density of the film. As a representative TCO, Sn-doped In2O3 (ITO) films have been achieved. The ITO film has an excellent sheet resistance (24.5 Ω/sq) at 93% optical transparency, with a figure of merit of 2.1 × 10-2 Ω-1, which is comparable to the best.

Overcoming the strength-formability trade-off in high strength steels via cryogenic treatment.

High strength steels are becoming more important than ever before for automotive applications to reduce the weight of automobiles and to ensure the safety of passengers. Since increased strength usually results in degraded formability, however, cold forming of high strength steels into final shapes remains a challenge to both automotive manufacturers and suppliers. Here we report novel alloy and processing design concepts that can impart high strength to cold-formable steels, which deviates from the traditional approach of improving the formability of high strength steels. Such designed steel subjected to a designed processing route shows an excellent combination of formability and strength as well as crashworthiness, which is crucial for the safety of passengers in the automobiles. The alloy and processing design concepts used in the present study are based on the utilization of thermally induced austenite to martensite transformation, which imparts high strength to cold-formable austenite by cryogenic treatment.

Transparent Omni-Directional Stretchable Circuit Lines Made by a Junction-Free Grid of Expandable Au Lines.

Although various stretchable optoelectronic devices have been reported, omni-directionally stretchable transparent circuit lines have been a great challenge. Cracks are engineered and fabricated to be highly conductive patterned metal circuit lines in which gold (Au) grids are embedded. Au is deposited selectively in the cracks to form a grid without any junction between the grid lines. Since each grid line is expandable under stretching, the circuit lines are stretchable in all the directions. This study shows that a thin coating of aluminum on the oxide surface enables precise control of the cracks (crack density, crack depth) in the oxide layer. High optical transparency and high stretchability can be achieved simultaneously by controlling the grid density in the circuit line. Light-emitting diodes are integrated directly on the circuit lines and stable operation is demonstrated under 100% stretching.

Electroactive 1T-MoS2 Fluoroelastomer Ink for Intrinsically Stretchable Solid-State In-Plane Supercapacitors.

Full advantage of stretchable electronic devices can be taken when utilizing an intrinsically stretchable power source. High-performance stretchable supercapacitors with a simple structure and solid-state operation are good power sources for stretchable electronics. This study suggests a new type of intrinsically stretchable, printable, electroactive ink consisting of 1T-MoS2 and a fluoroelastomer (FE). The active material (1T-MoS2/FE) is made by fluorinating the metallic-phase MoS2 (1T-MoS2) nanosheets with the FE under high-power ultrasonication. The MoS2 in the 1T-MoS2/FE has unconventional crystal structures in which the stable cubic (1T) and distorted 2H structures were mixed. The printed line of the 1T-MoS2/FE on the porous stretchable Au collector electrodes is intrinsically stretchable at more than ε = 50% and has good specific capacitance (28 mF cm-2 at 0.2 mA cm-2) and energy density (3.15 mWh cm-3). The in-plane all-solid-state stretchable supercapacitor is stretchable at ε = 40% and retains its relative capacity (C/Co) by 80%. This printable device platform potentially opens up the in-plane fabrication of stretchable micro-supercapacitor devices for wearable electronic applications.

Bi2Se3 nanoplates for contrast-enhanced photoacoustic imaging at 1064 nm.

Photoacoustic (PA) imaging is a high-resolution biomedical imaging modality, which can be used to visualize biological tissues located beyond the limited penetration depth of existing optical imaging techniques. An optical wavelength of 1064 nm is of great interest in PA imaging due to low intrinsic absorption at this wavelength. Reduced absorption implies an increased depth of imaging, which enables several new clinical applications such as bladder imaging, gastrointestinal (GI) imaging, and sentinel lymph node (SLN) imaging. In addition, a 1064 nm Nd:YAG laser system enables a high power, cost-effective, and compact laser-based PA imaging system. However, at this wavelength, due to low intrinsic contrast, high absorption exogenous PA contrast agents are necessary for imaging. To this end, we present new Bi2Se3 nanoplates as PA contrast agents at 1064 nm wavelength for PA imaging. We successfully synthesized Bi2Se3 nanoplates and they exhibited relatively strong PA signals at 1064 nm. We confirmed the increased imaging depth of penetration by imaging the Bi2Se3-containing tube located 4.6 cm deep in biological tissues. We present in vivo PA imaging of the bladder, GI tract, and SLN in mice using a Bi2Se3 contrast agent establishing the clinical feasibility of these agents with a clinical photoacoustic/ultrasound imaging system. Our results confirm that Bi2Se3 nanoplates are promising PA contrast agents at 1064 nm that offer a high optical absorbance in the second NIR region providing a high contrast imaging and increased depth of penetration.

Synthesis of 2D Metal Chalcogenide Thin Films through the Process Involving Solution-Phase Deposition.

2D metal chalcogenide thin films have recently attracted considerable attention owing to their unique physicochemical properties and great potential in a variety of applications. Synthesis of large-area 2D metal chalcogenide thin films in controllable ways remains a key challenge in this research field. Recently, the solution-based synthesis of 2D metal chalcogenide thin films has emerged as an alternative approach to vacuum-based synthesis because it is relatively simple and easy to scale up for high-throughput production. In addition, solution-based thin films open new opportunities that cannot be achieved from vacuum-based thin films. Here, a comprehensive summary regarding the basic structures and properties of different types of 2D metal chalcogenides, the mechanistic details of the chemical reactions in the synthesis of the metal chalcogenide thin films, recent successes in the synthesis by different reaction approaches, and the applications and potential uses is provided. In the last perspective section, the technical challenges to be overcome and the future research directions in the solution-based synthesis of 2D metal chalcogenides are discussed.

Fully Elastic Conductive Films from Viscoelastic Composites.

We investigated, for the first time, the conditions where a thermoplastic conductive composite can exhibit completely reversible stretchability at high elongational strains (ε = 1.8). We studied a composite of Au nanosheets and a polystyrene-block-polybutadiene-block-polystyrene block copolymer as an example. The composite had an outstandingly low sheet resistance (0.45 Ω/sq). We found that when a thin thermoplastic composite film is placed on a relatively thicker chemically cross-linked elastomer film, it can follow the reversible elastic behavior of the bottom elastomer. Such elasticity comes from the restoration of the block copolymer microstructure. The strong adhesion of the thermoplastic polymer to the metallic fillers is advantageous in the fabrication of mechanically robust, highly conductive, stretchable electrodes. The chemical stability of the Au composite was used to fabricate high luminescence, stretchable electrochemiluminescence displays with a conventional top-bottom electrode setup and with a horizontal electrode setup.

Synthesis of Multishell Nanoplates by Consecutive Epitaxial Growth of Bi2Se3 and Bi2Te3 Nanoplates and Enhanced Thermoelectric Properties.

We herein demonstrate the successive epitaxial growth of Bi2Te3 and Bi2Se3 on seed nanoplates for the scalable synthesis of heterostructured nanoplates (Bi2Se3@Bi2Te3) and multishell nanoplates (Bi2Se3@Bi2Te3@Bi2Se3, Bi2Se3@Bi2Te3@Bi2Se3@Bi2Te3). The relative dimensions of the constituting layers are controllable via the molar ratios of the precursors added to the seed nanoplate solution. Reduction of the precursors produces nanoparticles that attach preferentially to the sides of the seed nanoplates. Once attached, the nanoparticles reorganize epitaxially on the seed crystal lattices to form single-crystalline core-shell nanoplates. The nanoplates, initially 100 nm wide, grew laterally to 620 nm in the multishell structure, while their thickness increased more moderately, from 5 to 20 nm. The nanoplates were pelletized into bulk samples by spark plasma sintering and their thermoelectric properties are compared. A peak thermoelectric figure of merit (ZT) ∼0.71 was obtained at 450 K for the bulk of Bi2Se3@Bi2Te3 nanoplates by simultaneous modulation of electronic and thermal transport in the presence of highly dense grain and phase boundaries.