Transition‐Metal Dichalcogenide NiTe2: An Ambient‐Stable Material for Catalysis and Nanoelectronics

By means of theory and experiments, the application capability of nickel ditelluride (NiTe₂) transition‐metal dichalcogenide in catalysis and nanoelectronics is assessed. The Te surface termination forms a TeO₂ skin in an oxygen environment. In ambient atmosphere, passivation is achieved in less than 30 min with the TeO₂ skin having a thickness of about 7 Å. NiTe₂ shows outstanding tolerance to CO exposure and stability in water environment, with subsequent good performance in both hydrogen and oxygen evolution reactions. NiTe₂‐based devices consistently demonstrate superb ambient stability over a timescale as long as one month. Specifically, NiTe₂ has been implemented in a device that exhibits both superior performance and environmental stability at frequencies above 40 GHz, with possible applications as a receiver beyond the cutoff frequency of a nanotransistor.     

Ionoskins: Nonvolatile,Highly Transparent,Ultrastretchable Ionic Sensory Platforms for Wearable Electronics

The primary technology of next‐generation wearable electronics pursues the development of highly deformable and stable systems. Here, nonvolatile, highly transparent, and ultrastretchable ionic conductors based on polymeric gelators [poly(methyl methacrylate‐ran‐butyl acrylate), PMMA‐r‐PBA] and ionic liquids (IL) are proposed. A crucial strategy in the molecular design of polymer gelators is copolymerization of PMMA and IL‐insoluble low glass transition temperature (T_g) polymers that can be deformed and effectively dissipate applied strains. Highly stretchable (elongation limit ≈850%), mechanically robust (elastic modulus ≈3.1 × 10⁵ Pa), and deformation durable (recovery ratio ≈96.1% after 500 stretching/releasing cycles) gels are obtained by judiciously adjusting the molecular characteristics of polymer gelators and gel composition. An extremely simple “ionic” strain sensory platform is fabricated by directly connecting the stretchable gel and a digital multimeter, exhibiting high sensitivity (gauge factor ≈2.73), stable operation (>13 000 cycles), and nonvolatility (>10 d in air). Moreover, the skin‐type strain sensor, referred to as ionoskin, is demonstrated. The gels are attached to a part of the body (e.g., finger, elbow, knee, or ankle) and various human movements are successfully monitored. The ionoskin renders the opportunity to achieve wearable ubiquitous electronics such as healthcare devices and smart textile systems.     

Thermally Stable,Biocompatible, and Flexible Organic Field‐Effect Transistors and Their Application in Temperature Sensing Arrays for Artificial Skin

Application of degradable organic electronics based on biomaterials, such as polylactic‐co‐glycolic acid and polylactide (PLA), is severely limited by their low thermal stability. Here, a highly thermally stable organic transistor is demonstrated by applying a three‐arm stereocomplex PLA (tascPLA) as dielectric and substrate materials. The resulting flexible transistors are stable up to 200 °C, while devices based on traditional PLA are damaged at 100 °C. Furthermore, charge‐ trapping effect induced by polar groups of the dielectric is also utilized to significantly enhance the temperature sensitivity of the electronic devices. Skin‐like temperature sensor array is successfully demonstrated based on such transistors, which also exhibited good biocompatibility in cytotoxicity measurement. By presenting combined advantages of transparency, flexibility, thermal stability, temperature sensitivity, degradability, and biocompatibility, these organic transistors thus possess a broad applicability such as environment friendly electronics, implantable medical devices, and artificial skin.     

Knittable and Washable Multifunctional MXene‐Coated Cellulose Yarns

Textile‐based electronics enable the next generation of wearable devices, which have the potential to transform the architecture of consumer electronics. Highly conductive yarns that can be manufactured using industrial‐scale processing and be washed like everyday yarns are needed to fulfill the promise and rapid growth of the smart textile industry. By coating cellulose yarns with Ti₃C₂T_x MXene, highly conductive and electroactive yarns are produced, which can be knitted into textiles using an industrial knitting machine. It is shown that yarns with MXene loading of ≈77 wt% (≈2.2 mg cm^?1) have conductivity of up to 440 S cm^?1. After washing for 45 cycles at temperatures ranging from 30 to 80 °C, MXene‐coated cotton yarns exhibit a minimal increase in resistance while maintaining constant MXene loading. The MXene‐coated cotton yarn electrode offers a specific capacitance of 759.5 mF cm^?1 at 2 mV s^?1. A fully knitted textile‐based capacitive pressure sensor is also prepared, which offers high sensitivity (gauge factor of ≈6.02), wide sensing range of up to ≈20% compression, and excellent cycling stability (2000 cycles at ≈14% compression strain). This work provides new and practical insights toward the development of platform technology that can integrate MXene in cellulose‐based yarns for textile‐based devices.     

Synthesis of Millimeter‐Scale Transition Metal Dichalcogenides Single Crystals

The emergence of semiconducting transition metal dichalcogenide (TMD) atomic layers has opened up unprecedented opportunities in atomically thin electronics. Yet the scalable growth of TMD layers with large grain sizes and uniformity has remained very challenging. Here is reported a simple, scalable chemical vapor deposition approach for the growth of MoSe₂ layers is reported, in which the nucleation density can be reduced from 10⁵ to 25 nuclei cm^?2, leading to millimeter‐scale MoSe₂ single crystals as well as continuous macrocrystalline films with millimeter size grains. The selective growth of monolayers and multilayered MoSe₂ films with well‐defined stacking orientation can also be controlled via tuning the growth temperature. In addition, periodic defects, such as nanoscale triangular holes, can be engineered into these layers by controlling the growth conditions. The low density of grain boundaries in the films results in high average mobilities, around ≈42 cm² V^?1 s^?1, for back‐gated MoSe₂ transistors. This generic synthesis approach is also demonstrated for other TMD layers such as millimeter‐scale WSe₂ single crystals.     

Control of Switching Modes and Conductance Quantization in Oxygen Engineered HfOx based Memristive Devices

Hafnium oxide (HfO_x)‐based memristive devices have tremendous potential as nonvolatile resistive random access memory (RRAM) and in neuromorphic electronics. Despite its seemingly simple two‐terminal structure, a myriad of RRAM devices reported in the rapidly growing literature exhibit rather complex resistive switching behaviors. Using Pt/HfO_x/TiN‐based metal–insulator–metal structures as model systems, it is shown that a well‐controlled oxygen stoichiometry governs the filament formation and the occurrence of multiple switching modes. The oxygen vacancy concentration is found to be the key factor in manipulating the balance between electric field and Joule heating during formation, rupture (reset), and reformation (set) of the conductive filaments in the dielectric. In addition, the engineering of oxygen vacancies stabilizes atomic size filament constrictions exhibiting integer and half‐integer conductance quantization at room temperature during set and reset. Identifying the materials conditions of different switching modes and conductance quantization contributes to a unified switching model correlating structural and functional properties of RRAM materials. The possibility to engineer the oxygen stoichiometry in HfO_x will allow creating quantum point contacts with multiple conductance quanta as a first step toward multilevel memristive quantum devices.     

Interface‐Engineered Amorphous TiO2‐Based Resistive Memory Devices

Crossbar‐type bipolar resistive memory devices based on low‐temperature amorphous TiO₂ (a‐TiO₂) thin films are very promising devices for flexible nonvolatile memory applications. However, stable bipolar resistive switching from amorphous TiO₂ thin films has only been achieved for Al metal electrodes that can have severe problems like electromigration and breakdown in real applications and can be a limiting factor for novel applications like transparent electronics. Here, amorphous TiO₂‐based resistive random access memory devices are presented that universally work for any configuration of metal electrodes via engineering the top and bottom interface domains. Both by inserting an ultrathin metal layer in the top interface region and by incorporating a thin blocking layer in the bottom interface, more enhanced resistance switching and superior endurance performance can be realized. Using high‐resolution transmission electron microscopy, point energy dispersive spectroscopy, and energy‐filtering transmission electron microscopy, it is demonstrated that the stable bipolar resistive switching in metal/a‐TiO₂/metal RRAM devices is attributed to both interface domains: the top interface domain with mobile oxygen ions and the bottom interface domain for its protection against an electrical breakdown.     

Graphene Heterostructure Integrated Optical Fiber Bragg Grating for Light Motion Tracking and Ultrabroadband Photodetection from 400 nm to 10.768 µm

Integrated photonics and optoelectronics devices based on graphene and related 2D materials are at the core of the future industrial revolution, facilitating compact and flexible nanophotonic devices. Tracking and detecting the motion of broadband light in millimeter to nanometer scale is an unfold science which has not been fully explored. In this work, tracking and detecting the motion of light (millimeter precision) is first demonstrated by integrating graphene with an optical fiber Bragg grating device (graphene‐FBG). When the incident light moves toward and away from the graphene‐FBG device, the Bragg wavelength red‐shifts and blue‐shifts, indicating its light motion tracking ability. Such light tracking capability can be further extended to an ultrabroad wavelength range as all‐optical photodetectors show the robust response from 400 nm to 10.768 µm with a linear optical response. Interestingly, it is found that graphene‐Bi₂Te₃ heterostructure on FBG shows 87% higher photoresponse than graphene‐FBG at both visible and telecom wavelengths, due to stronger phonon‐electron coupling and photo‐thermal conversion in the heterostructure. The device also shows superior stability even after 100 d. This work may open up amazing integrated nanophotonics applications such as astrophysics, optical communication, optical computing, optical logic gating, spectroscopy, and laser biology.     

Fully Printed Light‐Emitting Electrochemical Cells Utilizing Biocompatible Materials

The use of biomaterials and bioinspired concepts in electronics will enable the fabrication of transient and disposable technologies within areas ranging from smart packaging and advertisement to healthcare applications. In this work, the use of a nonhalogenated biodegradable solid polymer electrolyte based on poly(ε‐caprolactone‐co‐trimethylene carbonate) and tetrabutylammonium bis‐oxalato borate in light‐emitting electrochemical cells (LECs) is presented. It is shown that the spin‐cast devices exhibit current efficiencies of ≈2 cd A^?1 with luminance over ≈12 000 cd m^?2, an order of magnitude higher than previous bio‐based LECs. By a combination of industrially relevant techniques (i.e., inkjet printing and blade coating), the fabrication of LEC devices on a cellulose‐based flexible biodegradable substrate showing lifetimes compatible with transient applications is demonstrated. The presented results have direct implications toward the industrial manufacturing of biomaterial‐based light‐emitting devices with potential use in future biodegradable/biocompatible electronics.     

Impact of wide bandgap microwave devices on DoD systems

Radiofrequency (RF) semiconductor electronics enable military systems that operate in the microwave and millimeter wave frequency bands of 1-100 GHz. The performance of numerous electromagnetic systems could be enhanced by the inclusion of wide bandgap (WBG) microwave and millimeter wave devices, either as power amplifier or receiver elements. The demonstrated power performance has generally been six to ten times that of equivalent gallium arsenide or indium phosphide devices up through 20 GHz, with enhanced dynamic range and improved impedance matching. These characteristics provide an opportunity to significantly reduce the number of modules required for many active aperture antenna systems, hence, cost, while enabling new capabilities for shared apertures. Prior to realization of any WBG system deployment, however considerable development and maturation of WBG materials, devices, and circuits must yet ensue.     

Sensitive and Ultrabroadband Phototransistor Based on Two‐Dimensional Bi2O2Se Nanosheets

Bi₂O₂Se, a high‐mobility and air‐stable 2D material, has attracted substantial attention for application in integrated logic electronics and optoelectronics. However, achieving an overall high performance over a wide spectral range for Bi₂O₂Se‐based devices remains a challenge. A broadband phototransistor with high photoresponsivity (R) is reported that comprises high‐quality large‐area ( ≈ 180 µm) Bi₂O₂Se nanosheets synthesized via a modified chemical vapor deposition method with a face‐down configuration. The device covers the ultraviolet (UV), visible (Vis), and near‐infrared (NIR) wavelength ranges (360–1800 nm) at room temperature, exhibiting a maximum R of 108 696 A W^?1 at 360 nm. Upon illumination at 405 nm, the external quantum efficiency, R, and detectivity (D*) of the device reach up to 1.5 × 10⁷%, 50055 A W^?1, and 8.2 × 10¹² Jones, respectively, which is attributable to a combination of the photogating, photovoltaic, and photothermal effects. The devices reach a ?3 dB bandwidth of 5.4 kHz, accounting for a fast rise time (τ_rise) of 32 µs. The high sensitivity, fast response time, and environmental stability achieved simultaneously in these 2D Bi₂O₂Se phototransistors are promising for high‐quality UV and IR imaging applications.     

Analog Circuit Applications Based on All‐2D Ambipolar ReSe2 Field‐Effect Transistors

Complementary circuits based on 2D materials show great promise for next‐generation electronics. An ambipolar all‐2D ReSe₂ field‐effect transistor (FET) with a hexagonal boron nitride gate dielectric is fabricated and its electronic characteristics are comprehensively studied by temperature dependence and noise measurements. Ambipolar transfer characteristics are achieved owing to the tunable Fermi level of the graphene contact and negligible and 30 meV Schottky barrier heights for the n‐ and p‐channel regimes, respectively. An inverter is also fabricated to demonstrate ambipolar ReSe₂ FET operation in a logic circuit. Furthermore, a p/n switchable unipolar FET is designed and shows potential for building complimentary circuits from a signal device. This work demonstrates the potential of all‐2D ReSe₂ FETs and makes available new approaches for designing next‐generation devices.     

Ultrasensitive Room‐Temperature Terahertz Direct Detection Based on a Bismuth Selenide Topological Insulator

Despite their huge application capabilities, millimeter‐ and terahertz‐wave photodetectors still face challenges in the detection scheme. Topological insulators (TIs) are predicted to be promising candidates for long‐wavelength photodetection, due to the presence of Dirac fermions in their topologically protected surface states. However, photodetection based on TIs is usually hindered by the large dark current, originating from the mixing of bulk states with topological surface states (TSSs) in most realistic samples of TIs. Here millimeter and terahertz detectors based on a subwavelength metal–TI–metal (MTM) heterostructure are demonstrated. The achieved photoresponse stems from the asymmetric scattering of TSS, driven by the localized surface plasmon‐induced terahertz field, which ultimately produces direct photocarriers beyond the interband limit. The device enables high responsivity in both the self‐powered and bias modes even at room temperature. The achieved responsivity is over 75 A/W, with response time shorter than 60 ms in the self‐powered mode. Remarkably, the responsivity increases by several orders of magnitude in the biased configuration, with the noise‐equivalent power (NEP) of 3.6 × 10^?13 W Hz^?1/2 and a detectivity of 2.17 × 10¹¹ cm Hz^?1/2 W^?1 at room temperature. The detection performances open a way toward realistic exploitation of TIs for large‐area, real‐time imaging within long‐wavelength optoelectronics.     

Tailoring the Surface Chemical Reactivity of Transition‐Metal Dichalcogenide PtTe2 Crystals

PtTe₂ is a novel transition‐metal dichalcogenide hosting type‐II Dirac fermions that displays application capabilities in optoelectronics and hydrogen evolution reaction. Here it is shown, by combining surface science experiments and density functional theory, that the pristine surface of PtTe₂ is chemically inert toward the most common ambient gases (oxygen and water) and even in air. It is demonstrated that the creation of Te vacancies leads to the appearance of tellurium‐oxide phases upon exposing defected PtTe₂ surfaces to oxygen or ambient atmosphere, which is detrimental for the ambient stability of uncapped PtTe₂‐based devices. On the contrary, in PtTe₂ surfaces modified by the joint presence of Te vacancies and substitutional carbon atoms, the stable adsorption of hydroxyl groups is observed, an essential step for water splitting and the water–gas shift reaction. These results thus pave the way toward the exploitation of this class of Dirac materials in catalysis.     

Atomic‐Level Coupled Interfaces and Lattice Distortion on CuS/NiS2 Nanocrystals Boost Oxygen Catalysis for Flexible Zn‐Air Batteries

The exploration of highly efficient nonprecious metal bifunctional electrocatalysts to boost oxygen evolution reaction and oxygen reduction reaction is critical for development of high energy density metal‐air batteries. Herein, a class of CuS/NiS₂ interface nanocrystals (INs) catalysts with atomic‐level coupled nanointerface, subtle lattice distortion, and plentiful vacancy defects is reported. The results from temperature‐dependent in situ synchrotron‐based X‐ray absorption fine spectroscopy and electron spin resonance spectroscopy demonstrate that the lattice distortion of 14.7% in CuS/NiS₂ caused by the strong Jahn–Teller effect of Cu, the strong atomic‐level coupled interface of CuS and NiS₂ domains, and distinct vacancy defects can provide numerous effective active sites for their excellent bifunctional performance. A liquid Zn‐air battery with the CuS/NiS₂ INs as air electrode displays a large peak power density (172.4 mW cm^?2), a high specific capacity (775 mAh g_Zn^?1), and long cycle life (up to 83 h), making the CuS/NiS₂ INs among the best bifunctional catalysts for Zn‐air battery. More remarkably, the flexible CuS/NiS₂ INs‐based solid‐state Zn‐air batteries can power the LED after twisting, making them be promising in portable and wearable electronic devices.     

Multifunctional Mo–N/C@MoS2 Electrocatalysts for HER,OER, ORR,and Zn–Air Batteries

Replacement of noble‐metal platinum catalysts with cheaper, operationally stable, and highly efficient electrocatalysts holds huge potential for large‐scale implementation of clean energy devices. Metal–organic frameworks (MOFs) and metal dichalcogenides (MDs) offer rich platforms for design of highly active electrocatalysts owing to their flexibility, ultrahigh surface area, hierarchical pore structures, and high catalytic activity. Herein, an advanced electrocatalyst based on a vertically aligned MoS₂ nanosheet encapsulated Mo–N/C framework with interfacial Mo–N coupling centers is reported. The hybrid structure exhibits robust multifunctional electrocatalytic activity and stability toward the hydrogen evolution reaction, oxygen evolution reaction, and oxygen reduction reaction. Interestingly, it further displays high‐performance of Zn–air batteries as a cathode electrocatalyst with a high power density of ≈196.4 mW cm^?2 and a voltaic efficiency of ≈63 % at 5 mA cm^?2, as well as excellent cycling stability even after 48 h at 25 mA cm^?2. Such outstanding electrocatalytic properties stem from the synergistic effect of the distinct chemical composition, the unique three‐phase active sites, and the hierarchical pore framework for fast mass transport. This work is expected to inspire the design of advanced and performance‐oriented MOF/MD hybrid‐based electrocatalysts for wider application in electrochemical energy devices.     

Pressure‐Tunable Ambipolar Conduction and Hysteresis in Thin Palladium Diselenide Field Effect Transistors

Few‐layer palladium diselenide (PdSe₂) field effect transistors are studied under external stimuli such as electrical and optical fields, electron irradiation, and gas pressure. The ambipolar conduction and hysteresis are observed in the transfer curves of the as‐exfoliated and unprotected PdSe₂ material. The ambipolar conduction and its hysteretic behavior in the air and pure nitrogen environments are tuned. The prevailing p‐type transport observed at atmospheric pressure is reversibly turned into a dominant n‐type conduction by reducing the pressure, which can simultaneously suppress the hysteresis. The pressure control can be exploited to symmetrize and stabilize the transfer characteristics of the device as required in high‐performance logic circuits. The transistors are affected by trap states with characteristic times in the order of minutes. The channel conductance, dramatically reduced by the electron irradiation during scanning electron microscope imaging, is restored after an annealing of several minutes at room temperature. The work paves the way toward the exploitation of PdSe₂ in electronic devices by providing an experiment‐based and deep understanding of charge transport in PdSe₂ transistors subjected to electrical stress and other external agents.     

Nonvolatile Floating‐Gate Memories Based on Stacked Black Phosphorus–Boron Nitride–MoS2 Heterostructures

Research on van der Waals heterostructures based on stacked 2D atomic crystals is intense due to their prominent properties and potential applications for flexible transparent electronics and optoelectronics. Here, nonvolatile memory devices based on floating‐gate field‐effect transistors that are stacked with 2D materials are reported, where few‐layer black phosphorus acts as channel layer, hexagonal boron nitride as tunnel barrier layer, and MoS₂ as charge trapping layer. Because of the ambipolar behavior of black phosphorus, electrons and holes can be stored in the MoS₂ charge trapping layer. The heterostructures exhibit remarkable erase/program ratio and endurance performance, and can be developed for high‐performance type‐switching memories and reconfigurable inverter logic circuits, indicating that it is promising for application in memory devices completely based on 2D atomic crystals.     

Foldable All‐Solid‐State Supercapacitors Integrated with Photodetectors

Recent development in flexible electronics has promoted the increasing demand for their energy storage systems that will be lightweight, thin, flexible, and even foldable. Although various flexible supercapacitors recently have been successfully developed, the design and assembly of highly foldable supercapacitors have received less attention. Furthermore, foldable supercapacitors are in general operated independently with other electronics, resulting in some space and energy consumption from the external connection system. Therefore, the authors fabricate the foldable all‐solid‐state integrated devices with supercapacitor and photodetector functions in a simplified and compact configuration based on single‐walled carbon nanotube films and TiO₂ nanoparticles. The integrated devices not only retain the intrinsic capacitance behavior but also show excellent sensitivity of detecting white light. More importantly, the capacitance behavior of integrated devices remains almost unchanged and the photodetector behavior is quite stable even folded by 180° due to their unique integrated configuration. Such rational design of all‐solid‐state integrated devices will pave the way for assembling energy storage devices and other electronics into highly flexible and foldable integrated devices.     

Distinctive Performance of Terahertz Photodetection Driven by Charge‐Density‐Wave Order in CVD‐Grown Tantalum Diselenide

The quantum behavior of carriers in solid is the foundation of modern electronic and optoelectronic technology, but it is still facing huge challenges within inherited single‐particle quantum processes working at the millimeter wave/terahertz (THz) band. Here, a straightforward strategy for the direct detection of millimeter wave/THz photons in a sub‐wavelength metal‐TaSe₂‐metal structure under strong interaction with a localized field of surface plasmon is proposed. By breaking the inversion symmetry under the perturbations of electric field and atomic reconstruction from van der Waals integration, the nonequilibrium electronic states under a radiant field can be manipulated in a collective fashion, leading to a large photocurrent responsivity over 40 A W^?1 and noise equivalent power less than 1 pW Hz^?1/2 even at room temperature. A more than 40‐fold enhancement in responsivity is achieved when transitioning from the normal phase to the CDW phase. The findings shed fresh light on the understanding of the delicate balance in the charge‐ordered phase, and facilitate the exploitation of a correlated electron system for optoelectronic applications in fields of security, remote sensing, and imaging.