Large Transconductance of Electrochemical Transistors Based on Fluorinated Donor-Acceptor Conjugated Polymers.

Organic electrochemical transistors (OECTs) have enormous potential for use in biosignal amplifiers, analyte sensors, and neuromorphic electronics owing to their exceptionally large transconductance. However, it is challenging to simultaneously achieve high charge carrier mobility and volumetric capacitance, the two most important figures of merit in OECTs. Herein, a method of achieving high-performance OECT with donor-acceptor conjugated copolymers by introducing fluorine units is proposed. A series of cyclopentadithiophene-benzothiadiazole (CDT-BT) copolymers for use in high-performance OECTs with enhanced charge carrier mobility (from 0.65 to 1.73 cm2·V-1·s-1) and extended volumetric capacitance (from 44.8 to 57.6 F·cm-3) by fluorine substitution is achieved. The increase in the volumetric capacitance of the fluorinated polymers is attributed to either an increase in the volume at which ions can enter the film or a decrease in the effective distance between the ions and polymer backbones. The fluorine substitution increases the backbone planarity of the CDT-BT copolymers, enabling more efficient charge carrier transport. The fluorination strategy of this work suggests the more versatile use of conjugated polymers for high-performance OECTs.

High-Performance Solution-Processed 2D P-Type WSe2 Transistors and Circuits through Molecular Doping.

Semiconducting ink based on 2D single-crystal flakes with dangling-bond-free surfaces enables the implementation of high-performance devices on form-free substrates by cost-effective and scalable printing processes. However, the lack of solution-processed p-type 2D semiconducting inks with high mobility is an obstacle to the development of complementary integrated circuits. Here, a versatile strategy of doping with Br2 is reported to enhance the hole mobility by orders of magnitude for p-type transistors with 2D layered materials. Br2 -doped WSe2 transistors show a field-effect hole mobility of more than 27 cm2  V-1  s-1 , and a high on/off current ratio of ≈107 , and exhibits excellent operational stability during the on-off switching, cycling, and bias stressing testing. Moreover, complementary inverters composed of patterned p-type WSe2 and n-type MoS2 layered films are demonstrated with an ultra-high gain of 1280 under a driving voltage (VDD ) of 7 V. This work unveils the high potential of solution-processed 2D semiconductors with low-temperature processability for flexible devices and monolithic circuitry.

Dynamic tactility by position-encoded spike spectrum.

In fast and transient somatosensory processing, the relative timing of the selected spikes is more important than the spike frequency because the ensemble of the first spikes in the spike trains encodes the dynamic tactile information. Here, inspired by the functional effectiveness of the selected spikes, we propose an artificial dynamic sensory system based on position-encoded spike spectrum. We use a mixed ion-electron conductor to generate a potential spike signal. We design artificial receptors that have different ion relaxation times (τ); thus, a sequence of the spikes from the receptors creates a spike spectrum, providing the spatial information (position and motion trace) and the temporal information (speed and dynamic contact area). The artificial receptors can be incorporated by as much as 132/square centimeters by using only two global signal addressing lines for sensor operation. Structural simplicity of the device opens the possibility of scalable fabrication with dense receptor integration. With computational decoding of the position-encoded spike spectrum, the artificial sensory system can recognize complicated dynamic motions in real time. The high-resolution spatiotemporal tactile perception in the ionic artificial sensory system enables the real-time dynamic robotic manipulation.

High-frequency and intrinsically stretchable polymer diodes.

Skin-like intrinsically stretchable soft electronic devices are essential to realize next-generation remote and preventative medicine for advanced personal healthcare1-4. The recent development of intrinsically stretchable conductors and semiconductors has enabled highly mechanically robust and skin-conformable electronic circuits or optoelectronic devices2,5-10. However, their operating frequencies have been limited to less than 100 hertz, which is much lower than that required for many applications. Here we report intrinsically stretchable diodes-based on stretchable organic and nanomaterials-capable of operating at a frequency as high as 13.56 megahertz. This operating frequency is high enough for the wireless operation of soft sensors and electrochromic display pixels using radiofrequency identification in which the base-carrier frequency is 6.78 megahertz or 13.56 megahertz. This was achieved through a combination of rational material design and device engineering. Specifically, we developed a stretchable anode, cathode, semiconductor and current collector that can satisfy the strict requirements for high-frequency operation. Finally, we show the operational feasibility of our diode by integrating it with a stretchable sensor, electrochromic display pixel and antenna to realize a stretchable wireless tag. This work is an important step towards enabling enhanced functionalities and capabilities for skin-like wearable electronics.

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.

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.

Artificial multimodal receptors based on ion relaxation dynamics.

Human skin has different types of tactile receptors that can distinguish various mechanical stimuli from temperature. We present a deformable artificial multimodal ionic receptor that can differentiate thermal and mechanical information without signal interference. Two variables are derived from the analysis of the ion relaxation dynamics: the charge relaxation time as a strain-insensitive intrinsic variable to measure absolute temperature and the normalized capacitance as a temperature-insensitive extrinsic variable to measure strain. The artificial receptor with a simple electrode-electrolyte-electrode structure simultaneously detects temperature and strain by measuring the variables at only two measurement frequencies. The human skin-like multimodal receptor array, called multimodal ion-electronic skin (IEM-skin), provides real-time force directions and strain profiles in various tactile motions (shear, pinch, spread, torsion, and so on).

A bioinspired stretchable membrane-based compliance sensor.

Compliance sensation is a unique feature of the human skin that electronic devices could not mimic via compact and thin form-factor devices. Due to the complex nature of the sensing mechanism, up to now, only high-precision or bulky handheld devices have been used to measure compliance of materials. This also prevents the development of electronic skin that is fully capable of mimicking human skin. Here, we developed a thin sensor that consists of a strain sensor coupled to a pressure sensor and is capable of identifying compliance of touched materials. The sensor can be easily integrated into robotic systems due to its small form factor. Results showed that the sensor is capable of classifying compliance of materials with high sensitivity allowing materials with various compliance to be identified. We integrated the sensor to a robotic finger to demonstrate the capability of the sensor for robotics. Further, the arrayed sensor configuration allows a compliance mapping which can enable humanlike sensations to robotic systems when grasping objects composed of multiple materials of varying compliance. These highly tunable sensors enable robotic systems to handle more advanced and complicated tasks such as classifying touched materials.

Liquid Metal Covered with Thermoplastic Conductive Composites for High Electrical Stability and Negligible Electromechanical Coupling at Large Strains.

Stretchable electrode is an essential part of soft electronic devices. Practical stretchable electrodes must meet the following requirements: metallic conductivity and no resistance change in various situations such as repeated large deformation, toxic environment, and large temperature change. This study suggests a simple electrode design that meets all of these requirements simultaneously. The electrode consists of a liquid metal (LM) mesh pattern that is sandwiched between a thermoplastic block copolymer (BCP) film and a BCP/Ag flake composite film with a microfibril network structure on its surface. The electrode has a high conductivity (1.2 × 104 S/cm) and is stretchable up to 600% uniaxial strain (ε). Its resistance remains unchanged during repeated stretching cycles at ε = 300% (ΔR < 0.04 Ω) as well as under simultaneous situation of large deformation (ε = 400%) and large temperature change (20-70 °C). The electrode is anticorrosive in an acidic solution owing to the hydrophobic BCP layer that protects the LM from being etched. This study shows the connection of two separate electrodes and complete healing of scratched electrodes by finger pressing. In addition, it demonstrates the fabrication of superstretchable electroluminescence display as an example of potential uses of the electrode.

Ag nanowire-based transparent stretchable tactile sensor recognizing strain directions and pressure.

In the last decade, extensive studies have been conducted to realize the functions of human skin based on stretchable electronics. An artificial skin, recognizing complex mechanical stimulation including pressure, strain and shear, and composed of transparent material, is an essential goal but has hardly been achieved. We fabricated a transparent integrated sensor system that can sense the strain direction and normal pressure of applied mechanical stimulation. Each sensor is composed of micropatterned Ag nanowire, forming a composite stretchable conductor with a block copolymer elastomer. The micropatterning and transfer process using thermoplastic elastomer facilitates the transparent conductor to show high transmittance with low sheet resistance at the same time. The designed transparent strain sensor responds linearly to strain, but does not respond to the orthogonal direction, which enables it to have strain-directionality. The applied mechanical signal, comprising normal force and directional strain, can be interpreted through the electrical signal observed from integrated sensors.

Block Copolymer Elastomers for Stretchable Electronics.

As industrial needs for healthcare sensors, electronic skin, and flexible/stretchable displays increase, interest in stretchable materials is increasing as well. In recent years, the studies on stretchable materials have spread to various pivot components, such as electrodes, circuits, substrates, semiconductors, dielectric layers, membranes, and active nanocomposite films. The block copolymer (BC) elastomers have been playing considerable role in the development of stretchable materials. Since BCs are soft elastomers based on physical cross-links, they show differences in physical properties from normal elastomers formed with chemical cross-linking. BC elastomers does not require additional chemical cross-linking procedure, so they can be easily processed after dissolved in various solvents. Their viscoelasticity and thermoplasticity enable the BCs to become moldable and sticky. Although their unique physical properties may serve as disadvantages in some cases, they have been actively applied to create various stretchable electronic materials and their uses are expected to be enlarged more than ever. In this Account, we summarize recent successful applications of BCs for the stretchable electronic devices and discuss the possibility of further uses and the challenges to be addressed for practical uses. Studies on BC-based stretchable materials have focused initially on the fabrication process of stretchable conductors; mixing conductive fillers physically with BCs, infiltrating BCs in a conductive filler layer, and converting metal precursors into metal nanoparticles inside BCs. When conductive fillers with high aspect ratios, such as nanowires or nanosheets are used, the fillers can be infiltrated by the BCs after deposited. Since the contacts between the fillers are maintained during the infiltration process, even thin composite films possess high conductivity and stretchability. The metal precursor solution printing is suggested as a promising approach because it is compatible with traditional printing techniques without clogging the nozzles and allows high filler loading efficiency. When using a BC as a substrate, it is advisable to use a BC/PDMS double layer because of viscoelastic and thermoplastic properties of BCs. If BC/PDMS double layer is used with much thicker PDMS layer instead of viscoelastic BC alone, the double layer substrate can show a perfect elastomeric behavior, and the advantages of the BC substrate are preserved. Additionally, the use of conventional manufacturing techniques is important for commercialization of the stretchable devices. BC substrates having preformed microfibril network on their surfaces facilitate the fabrication of high-resolution circuitry by directly depositing metals through a mask on the substrate. Recent successes of fabricating stretchable organic transistors were obtained based on in situ phase separation of polymer semiconductors to form nanofibril bundles on the surface of a BC substrate. They have led to the achievement of high resolution transistor array printed in large area. BCs are expected to expand their applicability, including stretchable batteries, since they make it feasible to fabricate various hybrid nanocomposites, pore size-controlled membranes, and microstructured surfaces. However, it is necessary to secure long-term stability under heat, solvent, and UV; in addition, there is a need for the synthesis of functional BCs for use in stretchable implanted biomedical 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.

Effect of ion migration in electro-generated chemiluminescence depending on the luminophore types and operating conditions.

Electro-generated chemiluminescence (ECL) has attracted increasing attention as a new platform for light-emitting devices; in particular, the use of mechanically stretchable ECL gels opens up the opportunity to achieve deformable displays. The movements of radical ions under an external electric field include short-range diffusion near the electrodes and long-distance migration between the electrodes. So far, only the diffusion of radical ions has been considered as the operating principle behind ECL. In this study, electrochemical and optical analysis was performed systematically to investigate the role of ion migration in ECL devices. This study reveals that long-distance migration of radical ions can be a key variable in ECL at low frequencies and that this effect depends on the type of ion species and the operating conditions (e.g. voltage and frequency). We also report that the emissions from the two electrodes are not identical, and the emission behaviors are different in the optimal operating conditions for the red, green, and blue ECL emissions.

Conductive magnetic-patchy colloidal microparticles for a high performance pressure sensor.

A robust and straightforward approach for fabrication of a new type of colloidal pressure sensor was proposed. For this purpose, we synthesized uniform conductive magnetic-patchy microparticles using a microfluidic technique and then coated them with poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) layers using the layer-by-layer deposition. Finally we showed that the magnetic-patchy conductive microparticles could be positioned on the target sites while precisely detecting pressure changes with excellent sensitivity.

Stretchable E-Skin Apexcardiogram Sensor.

A new strategy to measure the apex cardiogram with electronic skin technology is presented. An electronic skin apexcardiogram sensor, which can compensate the conventional electrocardiogram for cardiac diagnosis, is demonstrated through a highly sensitive and stretchable strain sensor with gold-nanoparticle composites.

Interfacing liquid metals with stretchable metal conductors.

Highly stretchable conductors are essential components in deformable electronics. Owing to their high stretchability and conductivity, liquid metals have attracted significant attention for use as circuits and interconnections. However, their poor wettability to stretchable metal electrodes prevents the formation of stable electrical connections. This study examined two approaches for creating a stable interface between a liquid metal (EGaIn) and stretchable metal electrodes via: (i) the use of honeycomb-structured stretchable metal electrodes and (ii) the addition of a conducting polymer interlayer. The line width of the honeycomb had a significant influence on the formation of a stable interface. The liquid metal formed a stable film layer on honeycomb metal electrodes, which have line widths of less than 50 µm. Coating PEDOT: PSS with a nonionic surfactant lowered the interfacial energy of EGaIn with flat stretchable metal surfaces; hence EGaIn was coated uniformly on the stretchable metal surfaces. Strain sensors were fabricated as a demonstrative example of an application that utilizes the stable interface.

Material approaches to stretchable strain sensors.

With the recent progress made in wearable electronics, devices now require high flexibility and stretchability up to large strain levels (typically larger than 30 % strain). Wearable strain sensors or deformable strain sensors have been gaining increasing research interest because of the rapid development of electronic skins and robotics and because of their biomedical applications. Conventional brittle strain sensors made of metals and piezoresistors are not applicable for such stretchable sensors. This Review summarizes recent advances in stretchable sensors and focuses on material aspects for high stretchability and sensitivity. It begins with a brief introduction to the Wheatstone bridge circuit of conventional resistive strain sensors. Then, studies on the manipulation of materials are reviewed, including waved structural approaches for making metals and semiconductors stretchable, the use of liquid metals, and conductive filler/elastomer composites by using percolation among the fillers. For capacitive strain sensors, the constant conductivity of the electrode is a key factor in obtaining reliable sensors. Possible approaches to developing capacitive strain sensors are presented. This Review concludes with a discussion on the major challenges and perspectives related to stretchable strain sensors.