Flexible Transparent Films Based on Nanocomposite Networks of Polyaniline and Carbon Nanotubes for High‐Performance Gas Sensing

A flexible, transparent, chemical gas sensor is assembled from a transparent conducting film of carbon nanotube (CNT) networks that are coated with hierarchically nanostructured polyaniline (PANI) nanorods. The nanocomposite film is synthesized by in‐situ, chemical oxidative polymerization of aniline in a functional multiwalled CNT (FMWCNT) suspension and is simultaneously deposited onto a flexible polyethylene terephthalate (PET) substrate. An as‐prepared flexible transparent chemical gas sensor exhibits excellent transparency of 85.0% at 550 nm using the PANI/FMWCNT nanocomposite film prepared over a reaction time of 8 h. The sensor also shows good flexibility, without any obvious decrease in performance after 500 bending/extending cycles, demonstrating high‐performance, portable gas sensing at room temperature. This superior performance could be attributed to the improved electron transport and collection due to the CNTs, resulting in reliable and efficient sensing, as well as the high surface‐to‐volume ratio of the hierarchically nanostructured composites. The excellent transparency, improved sensing performance, and superior flexibility of the device, may enable the integration of this simple, low‐cost, gas sensor into handheld flexible transparent electronic circuitry and optoelectronic devices.     

Rational Design of Nanoporous MoS2/VS2 Heteroarchitecture for Ultrahigh Performance Ammonia Sensors

2D transition metal dichalcogenides (TMDs) have received widespread interest by virtue of their excellent electrical, optical, and electrochemical characteristics. Recent studies on TMDs have revealed their versatile utilization as electrocatalysts, supercapacitors, battery materials, and sensors, etc. In this study, MoS₂ nanosheets are successfully assembled on the porous VS₂ (P‐VS₂) scaffold to form a MoS₂/VS₂ heterostructure. Their gas‐sensing features, such as sensitivity and selectivity, are investigated by using a quartz crystal microbalance (QCM) technique. The QCM results and density functional theory (DFT) calculations reveal the impressive affinity of the MoS₂/VS₂ heterostructure sensor toward ammonia with a higher adsorption uptake than the pristine MoS₂ or P‐VS₂ sensor. Furthermore, the adsorption kinetics of the MoS₂/VS₂ heterostructure sensor toward ammonia follow the pseudo‐first‐order kinetics model. The excellent sensing features of the MoS₂/VS₂ heterostructure render it attractive for high‐performance ammonia sensors in diverse applications.     

Microtopography‐Guided Conductive Patterns of Liquid‐Driven Graphene Nanoplatelet Networks for Stretchable and Skin‐Conformal Sensor Array

Flexible thin‐film sensors have been developed for practical uses in invasive or noninvasive cost‐effective healthcare devices, which requires high sensitivity, stretchability, biocompatibility, skin/organ‐conformity, and often transparency. Graphene nanoplatelets can be spontaneously assembled into transparent and conductive ultrathin coatings on micropatterned surfaces or planar substrates via a convective Marangoni force in a highly controlled manner. Based on this versatile graphene assembled film preparation, a thin, stretchable and skin‐conformal sensor array (144 pixels) is fabricated having microtopography‐guided, graphene‐based, conductive patterns embedded without any complicated processes. The electrically controlled sensor array for mapping spatial distributions (144 pixels) shows high sensitivity (maximum gauge factor ≈1697), skin‐like stretchability (<48%), high cyclic stability or durability (over 10⁵ cycles), and the signal amplification (≈5.25 times) via structure‐assisted intimate‐contacts between the device and rough skin. Furthermore, given the thin‐film programmable architecture and mechanical deformability of the sensor, a human skin‐conformal sensor is demonstrated with a wireless transmitter for expeditious diagnosis of cardiovascular and cardiac illnesses, which is capable of monitoring various amplified pulse‐waveforms and evolved into a mechanical/thermal‐sensitive electric rubber‐balloon and an electronic blood‐vessel. The microtopography‐guided and self‐assembled conductive patterns offer highly promising methodology and tool for next‐generation biomedical devices and various flexible/stretchable (wearable) devices.     

Healable,Transparent, Room‐Temperature Electronic Sensors Based on Carbon Nanotube Network‐Coated Polyelectrolyte Multilayers

Transparent and conductive film based electronics have attracted substantial research interest in various wearable and integrated display devices in recent years. The breakdown of transparent electronics prompts the development of transparent electronics integrated with healability. A healable transparent chemical gas sensor device is assembled from layer‐by‐layer‐assembled transparent healable polyelectrolyte multilayer films by developing effective methods to cast transparent carbon nanotube (CNT) networks on healable substrates. The healable CNT network‐containing film with transparency and superior network structures on self‐healing substrate is obtained by the lateral movement of the underlying self‐healing layer to bring the separated areas of the CNT layer back into contact. The as‐prepared healable transparent film is assembled into healable transparent chemical gas sensor device for flexible, healable gas sensing at room temperature, due to the 1D confined network structure, relatively high carrier mobility, and large surface‐to‐volume ratio. The healable transparent chemical gas sensor demonstrates excellent sensing performance, robust healability, reliable flexibility, and good transparency, providing promising opportunities for developing flexible, healable transparent optoelectronic devices with the reduced raw material consumption, decreased maintenance costs, improved lifetime, and robust functional reliability.     

Tuning Excitonic Properties of Monolayer MoS2 with Microsphere Cavity by High‐Throughput Chemical Vapor Deposition Method

Tuning the optical properties of 2D direct bandgap semiconductors is crucial for applications in photonic light source, optical communication, and sensing. In this work, the excitonic properties of molybdenum disulphide (MoS₂) are successfully tuned by directly depositing it onto silica microsphere resonators using chemical vapor deposition method. Multiple whispering gallery mode (WGM) peaks in the emission wavelength range of ≈650–750 nm are observed under continuous wave excitation at room temperature. Time‐resolved photoluminescence (TRPL) and femtosecond transient absorption (TA) spectroscopy are conducted to study light‐matter interaction dynamics of the MoS₂ microcavities. TRPL study suggests radiative recombination rate of carrier‐phonon scattering and interband transition processes in MoS₂ is enhanced by a factor of ≈1.65 due to Purcell effect in microcavities. TA spectroscopy study shows modulation of the interband transition process mainly occurs at PB‐A band with an estimated F ≈ 1.60. Furthermore, refractive index sensing utilizing WGM peaks of MoS₂ is established with sensitivity up to ≈150 nm per refractive index unit. The present work provides a large‐scale and straightforward method for coupling atomically thin 2D gain media with cavities for high‐performance optoelectronic devices and sensors.     

Highly Sensitive and Stretchable Resistive Strain Sensors Based on Microstructured Metal Nanowire/Elastomer Composite Films

High sensitivity and high stretchability are two conflicting characteristics that are difficult to achieve simultaneously in elastic strain sensors. A highly sensitive and stretchable strain sensor comprising a microstructured metal nanowire (mNW)/elastomer composite film is presented. The surface structure is easily prepared by combining an mNW coating and soft‐lithographic replication processes in a simple and reproducible manner. The densely packed microprism‐array architecture of the composite film leads to a large morphological change in the mNW percolation network by efficiently concentrating the strain in the valley regions upon stretching. Meanwhile, the percolation network comprising mNWs with a high aspect ratio is stable enough to prevent electrical failure, even under high strains. This enables the sensor to simultaneously satisfy high sensitivity (gauge factor ≈81 at >130% strain) and high stretchability (150%) while ensuring long‐term reliability (10 000 cycles at 150% strain). The sensor can also detect strain induced by bending and pressure, thus demonstrating its potential as a versatile sensing tool. The sensor is successfully utilized to monitor a wide range of human motions in real time. Furthermore, the unique sensing mechanism is easily extended to detect more complex multiaxial strains by optimizing the surface morphology of the device.     

Extraordinarily Stretchable All‐Carbon Collaborative Nanoarchitectures for Epidermal Sensors

Multifunctional microelectronic components featuring large stretchability, high sensitivity, high signal‐to‐noise ratio (SNR), and broad sensing range have attracted a huge surge of interest with the fast developing epidermal electronic systems. Here, the epidermal sensors based on all‐carbon collaborative percolation network are demonstrated, which consist 3D graphene foam and carbon nanotubes (CNTs) obtained by two‐step chemical vapor deposition processes. The nanoscaled CNT networks largely enhance the stretchability and SNR of the 3D microarchitectural graphene foams, endowing the strain sensor with a gauge factor as high as 35, a wide reliable sensing range up to 85%, and excellent cyclic stability (>5000 cycles). The flexible and reversible strain sensor can be easily mounted on human skin as a wearable electronic device for real‐time and high accuracy detecting of electrophysiological stimuli and even for acoustic vibration recognition. The rationally designed all‐carbon nanoarchitectures are scalable, low cost, and promising in practical applications requiring extraordinary stretchability and ultrahigh SNRs.     

Advances in Rational Design and Materials of High‐Performance Stretchable Electromechanical Sensors

Stretchable and wearable sensor technology has attracted significant interests and created high technological impact on portable healthcare and smart human–machine interfaces. Wearable electromechanical systems are an important part of this technology that has recently witnessed tremendous progress toward high‐performance devices for commercialization. Over the past few years, great attention has been paid to simultaneously enhance the sensitivity and stretchability of the electromechanical sensors toward high sensitivity, ultra‐stretchability, low power consumption or self‐power functionalities, miniaturisation as well as simplicity in design and fabrication. This work presents state‐of‐the‐art advanced materials and rational designs of electromechanical sensors for wearable applications. Advances in various sensing concepts and structural designs for intrinsic stretchable conductive materials as well as advanced rational platforms are discussed. In addition, the practical applications and challenges in the development of stretchable electromechanical sensors are briefly mentioned and highlighted.     

Editable Supercapacitors with Customizable Stretchability Based on Mechanically Strengthened Ultralong MnO2 Nanowire Composite

Although some progress has been made on stretchable supercapacitors, traditional stretchable supercapacitors fabricated by predesigning structured electrodes for device assembling still lack the device‐level editability and programmability. To adapt to wearable electronics with arbitrary configurations, it is highly desirable to develop editable supercapacitors that can be directly transferred into desirable shapes and stretchability. In this work, editable supercapacitors for customizable shapes and stretchability using electrodes based on mechanically strengthened ultralong MnO₂ nanowire composites are developed. A supercapacitor edited with honeycomb‐like structure shows a specific capacitance of 227.2 mF cm^?2 and can be stretched up to 500% without degradation of electrochemical performance, which is superior to most of the state‐of‐the‐art stretchable supercapacitors. In addition, it maintains nearly 98% of the initial capacitance after 10 000 stretch‐and‐release cycles under 400% tensile strain. As a representative of concept for system integration, the editable supercapacitors are integrated with a strain sensor, and the system exhibits a stable sensing performance even under arm swing. Being highly stretchable, easily programmable, as well as connectable in series and parallel, an editable supercapacitor with customizable stretchability is promising to produce stylish energy storage devices to power various portable, stretchable, and wearable devices.     

A General Method for the Chemical Synthesis of Large‐Scale,Seamless Transition Metal Dichalcogenide Electronics

The capability to directly build atomically thin transition metal dichalcogenide (TMD) devices by chemical synthesis offers important opportunities to achieve large‐scale electronics and optoelectronics with seamless interfaces. Here, a general approach for the chemical synthesis of a variety of TMD (e.g., MoS₂, WS₂, and MoSe₂) device arrays over large areas is reported. During chemical vapor deposition, semiconducting TMD channels and metallic TMD/carbon nanotube (CNT) hybrid electrodes are simultaneously formed on CNT‐patterned substrate, and then coalesce into seamless devices. Chemically synthesized TMD devices exhibit attractive electrical and mechanical properties. It is demonstrated that chemically synthesized MoS₂–MoS₂/CNT devices have Ohmic contacts between MoS₂/CNT hybrid electrodes and MoS₂ channels. In addition, MoS₂–MoS₂/CNT devices show greatly enhanced mechanical stability and photoresponsivity compared with conventional gold‐contacted devices, which makes them suitable for flexible optoelectronics. Accordingly, a highly flexible pixel array based on chemically synthesized MoS₂–MoS₂/CNT photodetectors is applied for image sensing.     

Stabilizing MoS2 Nanosheets through SnO2 Nanocrystal Decoration for High‐Performance Gas Sensing in Air

The unique properties of MoS₂ nanosheets make them a promising candidate for high‐performance room temperature sensing. However, the properties of pristine MoS₂ nanosheets are strongly influenced by the significant adsorption of oxygen in an air environment, which leads to instability of the MoS₂ sensing device, and all sensing results on MoS₂ reported to date were exclusively obtained in an inert atmosphere. This significantly limits the practical sensor application of MoS₂ in an air environment. Herein, a novel nanohybrid of SnO₂ nanocrystal (NC)‐decorated crumpled MoS₂ nanosheet (MoS₂/SnO₂) and its exciting air‐stable property for room temperature sensing of NO₂ are reported. Interestingly, the SnO₂ NCs serve as strong p‐type dopants for MoS₂, leading to p‐type channels in the MoS₂ nanosheets. The SnO₂ NCs also significantly enhance the stability of MoS₂ nanosheets in dry air. As a result, unlike other MoS₂ sensors operated in an inert gas (e.g. N₂), the nanohybrids exhibit high sensitivity, excellent selectivity, and repeatability to NO₂ under a practical dry air environment. This work suggests that NC decoration significantly tunes the properties of MoS₂ nanosheets for various applications.     

A Novel and Facile Route to Synthesize Atomic‐Layered MoS2 Film for Large‐Area Electronics

High‐quality and large‐area molybdenum disulfide (MoS₂) thin film is highly desirable for applications in large‐area electronics. However, there remains a challenge in attaining MoS₂ film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few‐layered MoS₂ film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)₆) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS₂ film is readily achievable in 20 min. Large‐area MoS₂ field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm² V^?1 s^?1, which is the highest reported for bottom‐gated MoS₂‐FETs fabricated via photolithography with an on/off ratio of ≈10⁵ at room temperature.     

Thin polyaniline and polyaniline/carbon nanocomposite films for gas sensing

We have studied the gas sensing properties of five polyaniline-based materials—thick and thin PANI films, nanocomposite PANI/MWNT and PANI/SWNT films, and PANI nanogranules embedded in a polyvinylpyrrolidone matrix. The films (except for the latter) were deposited within the induction period of the polymerization process on gold interdigitated micro electrodes. Their sensitivity to NH₃, H₂, ethanol, methanol, and acetone was measured. The thin PANI film (~ 100 nm thick) prepared by a lift-off process had the sensitivity to ammonia below 0.5 ppm, which was higher than that of nanocomposite films. Two materials—thick PANI film and nanocomposite PANI/MWNT film—exhibited a shallow minimum in the temperature dependence of resistance (at 313 K and 319 K), which is a feature exploitable in practical applications, since the gas sensors should be insensitive to small temperature fluctuations at these temperatures.     

Mechanics for stretchable sensors

In the past decade, high performance stretchable sensors have found many exciting applications including epidermal and in vivo monitors, minimally invasive surgical tools, as well as deployable structure health monitors (SHM). Although wafer based electronics are known to be rigid and planar, recent advances in manufacture and mechanics have made intrinsically stiff and brittle inorganic electronic materials stretchable and compliant. This review article summarizes the most recent mechanics studies on stretchable sensors composed of ceramic and metallic functional materials. The discussion will focus around the most popular “island plus serpentine” design where active electronic or sensing components are housed on an array of isolated, micro-scale islands which are interconnected by electrically conductive, stretchable, serpentine thin films. The mechanics of polymer supported islands, freestanding serpentines, and polymer supported serpentines will be introduced. The effects of feature geometry and polymer substrate on the stretchability, compliance, as well as functionality of the sensor system will be discussed in details. The tradeoff between mechanics and functionality gives rise to the challenge of simultaneously optimizing the structure and performance of stretchable sensors.     

Bath Electrospinning of Continuous and Scalable Multifunctional MXene‐Infiltrated Nanoyarns

Electroactive yarns that are stretchable are desired for many electronic textile applications, including energy storage, soft robotics, and sensing. However, using current methods to produce these yarns, achieving high loadings of electroactive materials and simultaneously demonstrating stretchability is a critical challenge. Here, a one‐step bath electrospinning technique is developed to effectively capture Ti₃C₂T_x MXene flakes throughout continuous nylon and polyurethane (PU) nanofiber yarns (nanoyarns). With up to ≈90 wt% MXene loading, the resulting MXene/nylon nanoyarns demonstrate high electrical conductivity (up to 1195 S cm^?1). By varying the flake size and MXene concentration, nanoyarns achieve stretchability of up to 43% (MXene/nylon) and 263% (MXene/PU). MXene/nylon nanoyarn electrodes offer high specific capacitance in saturated LiClO₄ electrolyte (440 F cm^?3 at 5 mV s^?1), with a wide voltage window of 1.25 V and high rate capability (72% between 5 and 500 mV s^?1). As strain sensors, MXene/PU yarns demonstrate a wide sensing range (60% under cyclic stretching), high sensitivity (gauge factor of ≈17 in the range of 20–50% strain), and low drift. Utilizing the stretchability of polymer nanofibers and the electrical and electrochemical properties of MXene, MXene‐based nanoyarns demonstrate potential in a wide range of applications, including stretchable electronics and body movement monitoring.     

A New Strategy for Humidity Independent Oxide Chemiresistors: Dynamic Self‐Refreshing of In2O3 Sensing Surface Assisted by Layer‐by‐Layer Coated CeO2 Nanoclusters

The humidity dependence of the gas sensing characteristics of metal oxide semiconductors has been one of the greatest obstacles for gas sensor applications during the last five decades because ambient humidity dynamically changes with the environmental conditions. Herein, a new and novel strategy is reported to eliminate the humidity dependence of the gas sensing characteristics of oxide chemiresistors via dynamic self‐refreshing of the sensing surface affected by water vapor chemisorption. The sensor resistance and gas response of pure In₂O₃ hollow spheres significantly change and deteriorate in humid atmospheres. In contrast, the humidity dependence becomes negligible when an optimal concentration of CeO₂ nanoclusters is uniformly loaded onto In₂O₃ hollow spheres via layer‐by‐layer (LBL) assembly. Moreover, In₂O₃ sensors LBL‐coated with CeO₂ nanoclusters show fast response/recovery, low detection limit (500 ppb), and high selectivity to acetone even in highly humid conditions (relative humidity 80%). The mechanism underlying the dynamic refreshing of the In₂O₃ sensing surfaces regardless of humidity variation is investigated in relation to the role of CeO₂ and the chemical interaction among CeO₂, In₂O₃, and water vapor. This strategy can be widely used to design high performance gas sensors including disease diagnosis via breath analysis and pollutant monitoring.     

High‐Performance Piezoelectric Nanogenerators with Imprinted P(VDF‐TrFE)/BaTiO3 Nanocomposite Micropillars for Self‐Powered Flexible Sensors

Piezoelectric nanogenerators with large output, high sensitivity, and good flexibility have attracted extensive interest in wearable electronics and personal healthcare. In this paper, the authors propose a high‐performance flexible piezoelectric nanogenerator based on piezoelectrically enhanced nanocomposite micropillar array of polyvinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE))/barium titanate (BaTiO₃) for energy harvesting and highly sensitive self‐powered sensing. By a reliable and scalable nanoimprinting process, the piezoelectrically enhanced vertically aligned P(VDF‐TrFE)/BaTiO₃ nanocomposite micropillar arrays are fabricated. The piezoelectric device exhibits enhanced voltage of 13.2 V and a current density of 0.33 µA cm^?2, which an enhancement by a factor of 7.3 relatives to the pristine P(VDF‐TrFE) bulk film. The mechanisms of high performance are mainly attributed to the enhanced piezoelectricity of the P(VDF‐TrFE)/BaTiO₃ nanocomposite materials and the improved mechanical flexibility of the micropillar array. Under mechanical impact, stable electricity is stably generated from the nanogenerator and used to drive various electronic devices to work continuously, implying its significance in the field of consumer electronic devices. Furthermore, it can be applied as self‐powered flexible sensor work in a noncontact mode for detecting air pressure and wearable sensors for detecting some human vital signs including different modes of breath and heartbeat pulse, which shows its potential applications in flexible electronics and medical sciences.     

An Ultrasensitive Organic Semiconductor NO2 Sensor Based on Crystalline TIPS‐Pentacene Films

Organic semiconductor gas sensor is one of the promising candidates of room temperature operated gas sensors with high selectivity. However, for a long time the performance of organic semiconductor sensors, especially for the detection of oxidizing gases, is far behind that of the traditional metal oxide gas sensors. Although intensive attempts have been made to address the problem, the performance and the understanding of the sensing mechanism are still far from sufficient. Herein, an ultrasensitive organic semiconductor NO₂ sensor based on 6,13‐bis(triisopropylsilylethynyl)­pentacene (TIPS‐petacene) is reported. The device achieves a sensitivity over 1000%/ppm and fast response/recovery, together with a low limit of detection (LOD) of 20 ppb, all of which reach the level of metal oxide sensors. After a comprehensive analysis on the morphology and electrical properties of the organic films, it is revealed that the ultrahigh performance is largely related to the film charge transport ability, which was less concerned in the studies previously. And the combination of efficient charge transport and low original charge carrier concentration is demonstrated to be an effective access to obtain high performance organic semiconductor gas sensors.     

Microstructure,electrical and humidity sensing properties of TiO<Subscript>2</Subscript>/polyaniline nanocomposite films prepared by sol–gel spin coating technique

High sensitive resistive type humidity sensor based titanium oxide/polyaniline (TiO₂/PANI) nanocomposite thin films prepared by a sol–gel spin coating technique on an alumina substrate. The resultant nanocomposites were characterized by using X-ray diffraction (XRD), Field emission electron microscopy, Fourier transform infrared spectroscopy (FTIR), UV–Vis absorbance and energy dispersive spectra analysis. In the XRD patterns of both pure and TiO₂/PANI composite confirms the deposition of PANI on TiO₂ and the average size of the composite particle was found to be 32 nm. Large number of nano grain surface being covered by PANI, which agrees very well with the results obtained by XRD studies. FTIR and UV–Vis spectra reveal that the PANI component undergoes an electronic structure modification as a result of the TiO₂ and PANI interaction. The room temperature resistivity was found to be for TiO₂ and TiO₂/PANI nanocomposite films 1.42?×?10⁶ and 2.56?×?10³ Ω cm respectively. The obtained TiO₂/PANI nanocomposites sensor exhibited higher humidity sensing performance such as high sensitivity, fast response (20 s) and recovery time (15 s) and high stability.     

Ultrasensitive Strain Sensor Based on Separation of Overlapped Carbon Nanotubes

Although there have been remarkable improvements in stretchable strain sensors, the development of strain sensors with scalable fabrication techniques and which both high sensitivity and stretchability simultaneously is still challenging. In this work, a stretchable strain sensor based on overlapped carbon nanotube (CNT) bundles coupled with a silicone elastomer is presented. The strain sensor with overlapped CNTs is prepared by synthesizing line‐patterned vertically aligned CNT bundles and rolling and transferring them to the silicone elastomer. With the sliding and disconnection of the overlapped CNTs, the strain sensor performs excellently with a broad sensing range (≥145% strain), ultrahigh sensitivity (gauge factor of 42 300 at a strain of 125–145%), high repeatability, and durability. The performance of the sensor is also tunable by controlling the overlapped area of CNT bundles. Detailed mechanisms of the sensor and its applications in human motion detection are also further investigated. With the novel structure and mechanism, the sensor can detect a wide range of strains with high sensitivity, demonstrating the potential for numerous applications including wearable healthcare devices.