Surface Diffusion and Epitaxial Self-Planarization for Wafer-Scale Single-Grain Metal Chalcogenide Thin Films.

Although wafer-scale single-grain thin films of 2D metal chalcogenides (MCs) have been extensively sought after during the last decade, the grain size of the MC thin films is still limited in the sub-millimeter scale. A general strategy of synthesizing wafer-scale single-grain MC thin films by using commercial wafers (Si, Ge, GaAs) both as metal source and epitaxial collimator is presented. A new mechanism of single-grain thin-film formation, surface diffusion, and epitaxial self-planarization is proposed, where chalcogen elements migrate preferentially along substrate surface and the epitaxial crystal domains flow to form an atomically smooth thin film. Through synchrotron X-ray diffraction and high-resolution scanning transmission electron microscopy, the formation of single-grain Si2 Te3 , GeTe, GeSe, and GaTe thin films on (111) Si, Ge, and (100) GaAs is verified. The Si2 Te3 thin film is used to achieve transfer-free fabrication of a high-performance bipolar memristive electrical-switching device.

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.

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.

Fabrication of Foldable Metal Interconnections by Hybridizing with Amorphous Carbon Ultrathin Anisotropic Conductive Film.

With the advent of foldable electronics, it is necessary to develop a technology ensuring foldability when the circuit lines are placed on the topmost substrate rather than in the neutral plane used in the present industry. Considering the potential technological impacts, conversion of the conventional printed circuit boards to foldable ones is most desirable to achieve the topmost circuitry. This study realizes this unconventional conversion concept by coating an ultrathin anisotropic conductive film (UACF) on a printed metal circuit board. This study presents rapid large-area synthesis of hydrogenated amorphous carbon (a-C:H) thin films and their use as the UACF. Since the synthesized a-C:H thin film has electrical transparency, the metal/a-C:H hybrid board reflects the complexity of the underlying metal circuit board. The a-C:H thin film electrically connects the cracked area of the metal line; thus, the hybrid circuit board is foldable without resistance change during repeated folding cycles. The metal/UACF hybrid circuit board can be applied to the fabrication of various foldable electronic devices.

Hygroscopic Auxetic On-Skin Sensors for Easy-to-Handle Repeated Daily Use.

Despite the advance of on-skin sensors over the last decade, a sensor that solves simultaneously the critical issues for using in everyday life, such as stable performance in various environments, use over a long period of time, and repeated use by easy handling, has not yet been achieved. Here, we introduce an auxetic hygroscopic sensor that simultaneously meets all of the conditions. The auxetic structure with a negative Poisson's ratio matches with deformation of the skin in ankles; hence, a conformal contact between the sensor and the skin could be maintained during repeated movements. Sweat was absorbed in the auxetic electrode made of a hydrogel pattern coated with Ag nanowires and evaporated quickly; such hygroscopic characteristic led to excellent breathability. An electrocardiogram sensor and a haptic device were fabricated according to the proposed design for a sensor electrode. The sensors provide stable detecting performance in various environments, such as exercising, submersion in water, exposure to concentrated salt water, and continuous wearing for long time (7 days). Also, the sensors could be manually attached repeatedly without degrading the performance. This study provides new structural insights for on-skin sensors and presents future research directions.

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.

Nonstoichiometric nucleation and growth of multicomponent nanocrystals in solution.

The ability to assemble nanoscale functional building blocks is a useful and modular way for scientists to design valuable materials with specific physical and chemical properties. Chemists expect multicomponent, heterostructured nanocrystals to show unique electrical, thermal, and optical properties not seen in homogeneous, single-phase nanocrystals. Although researchers have made remarkable advances in heterogeneous nucleation and growth, design of synthetic conditions for obtaining nanocrystals with a target composition and shape is still a big challenge. There are several outstanding issues that chemists need to address before they can successfully carry out the design-based synthesis of multicomponent nanocrystals. For instance, small changes in the reaction parameters, such as the precursor, solvent, surfactant, reducing agent, and the reaction temperature, often result in changes in the structure and chemical composition of the final product. Although scientists do not fully understand the mechanisms underlying the nucleation and growth processes involved in the synthesis of these multicomponent nanocrystals, recent progress in understanding of the thermodynamic and kinetic factors have improved our control over their final structure and chemical composition. In this Account, we summarize our recent advances in understanding of the nucleation and growth mechanisms involved in the solution-based synthesis of multicomponent nanocrystals. We also discuss the various challenges encountered in their synthesis, emphasizing what still needs special consideration. We first discuss the three different nucleation paths from a thermodynamics perspective: amorphous nucleation, crystalline nucleation, and two-step nucleation. Amorphous nucleation and two-step nucleation involve the generation of nonstoichiometric nuclei. We initiate this process mainly by introducing an imbalance in the concentrations of the reduced elements. When the nonstoichiometric nuclei grow, we can add secondary elements to the growing nonstoichiometric nuclei. This leads to either the physical deposition or atomic mixture formation through the diffusion and rearrangement of constituents. The processes of mixture formation and the physical deposition of the secondary constituent element also compete and determine the shape and chemical composition of the final product. If the free energy change by mixture formation is positive (ΔGAB ≥ 0), physical deposition takes place predominantly, and the spreading coefficient (S) determines the structure of the nanocrystals. However, when mixture formation is highly spontaneous (ΔGAB < -ξ), the chemical composition of the final product is usually stoichiometric, and its shape then depends on the size of the primary nanocrystals. When the mixture formation and physical deposition are in competition (-ξ ≤ ΔGAB < 0), as commonly seen for many nanoalloy systems, both the chemical composition and the structure are determined by the size of the primary nanocrystals as well as the degree of mixture formation at the interface of the constituent components. Finally, we discuss the challenges and caveats that one needs to take into account when synthesizing multicomponent nanocrystals.