High-speed and large-scale intrinsically stretchable integrated circuits.

Intrinsically stretchable electronics with skin-like mechanical properties have been identified as a promising platform for emerging applications ranging from continuous physiological monitoring to real-time analysis of health conditions, to closed-loop delivery of autonomous medical treatment1-7. However, current technologies could only reach electrical performance at amorphous-silicon level (that is, charge-carrier mobility of about 1 cm2 V-1 s-1), low integration scale (for example, 54 transistors per circuit) and limited functionalities8-11. Here we report high-density, intrinsically stretchable transistors and integrated circuits with high driving ability, high operation speed and large-scale integration. They were enabled by a combination of innovations in materials, fabrication process design, device engineering and circuit design. Our intrinsically stretchable transistors exhibit an average field-effect mobility of more than 20 cm2 V-1 s-1 under 100% strain, a device density of 100,000 transistors per cm2, including interconnects and a high drive current of around 2 µA µm-1 at a supply voltage of 5 V. Notably, these achieved parameters are on par with state-of-the-art flexible transistors based on metal-oxide, carbon nanotube and polycrystalline silicon materials on plastic substrates12-14. Furthermore, we realize a large-scale integrated circuit with more than 1,000 transistors and a stage-switching frequency greater than 1 MHz, for the first time, to our knowledge, in intrinsically stretchable electronics. Moreover, we demonstrate a high-throughput braille recognition system that surpasses human skin sensing ability, enabled by an active-matrix tactile sensor array with a record-high density of 2,500 units per cm2, and a light-emitting diode display with a high refreshing speed of 60 Hz and excellent mechanical robustness. The above advancements in device performance have substantially enhanced the abilities of skin-like electronics.

Highly stretchable polymer semiconductor thin films with multi-modal energy dissipation and high relative stretchability.

Stretchable polymer semiconductors (PSCs) have seen great advancements alongside the development of soft electronics. But it remains a challenge to simultaneously achieve high charge carrier mobility and stretchability. Herein, we report the finding that stretchable PSC thin films (<100-nm-thick) with high stretchability tend to exhibit multi-modal energy dissipation mechanisms and have a large relative stretchability (rS) defined by the ratio of the entropic energy dissipation to the enthalpic energy dissipation under strain. They effectively recovered the original molecular ordering, as well as electrical performance, after strain was released. The highest rS value with a model polymer (P4) exhibited an average charge carrier mobility of 0.2 cm2V-1s-1 under 100% biaxial strain, while PSCs with low rS values showed irreversible morphology changes and rapid degradation of electrical performance under strain. These results suggest rS can be used as a parameter to compare the reliability and reversibility of stretchable PSC thin films.

Chain-Kinked Design: Improving Stretchability of Polymer Semiconductors through Nonlinear Conjugated Linkers.

The manipulation of the polymer backbone structure has a profound influence on the crystalline behavior and charge transport characteristics of polymers. These strategies are commonly employed to optimize the performance of stretchable polymer semiconductors. However, a universal method that can be applied to conjugated polymers with different donor-acceptor combinations is still lacking. In this study, we propose a universal strategy to boost the stretchability of polymers by incorporating the nonlinear conjugated linker (NCL) into the main chain. Specifically, we incorporate meta-dibromobenzene (MB), characterized by its asymmetric linkage sites, as the NCL into the backbone of diketopyrrolopyrrole-thiophene-based (DPP-based) polymers. Our research demonstrates that the introduction of MB prompts chain-kinking, thereby disrupting the linearity and central symmetry of the DPP conjugated backbone. This modification reshapes the polymer conformation, decreasing the radius of gyration and broadening the free volume, which consequently adjusts the level of crystallinity, leading to a considerable increase in the stretchability of the polymer. Importantly, this method increases stretchability without compromising mobility and exhibits broad applicability across a wide range of donor-acceptor pair polymers. Leveraging this strategy, fully stretchable transistors were fabricated using a DPP polymer that incorporates 10 mol % of MB. These transistors display a mobility of approximately 0.5 cm2 V-1 s-1 and prove remarkably durable, maintaining 90% of this mobility even after enduring 1000 cycles at 25% strain. Overall, we propose a method to systematically control the main-chain conformation, thereby enhancing the stretchability of conjugated polymers in a widely applicable manner.

Stretchable Strain Sensor with Small but Sufficient Adhesion to Skin.

Stretchable strain sensors that use a liquid metal (eutectic gallium-indium alloy; E-GaIn) and flexible silicone rubber (Ecoflex) as the support and adhesive layers, respectively, are demonstrated. The flexibility of Ecoflex and the deformability of E-GaIn enable the sensors to be stretched by 100%. Ecoflex gel has sufficiently large adhesion force to skin, even though the adhesion force is smaller than that for commercially available adhesives. This enables the sensor to be used for non-invasive monitoring of human motion. The mechanical and electrical properties of the sensor are experimentally evaluated. The effectiveness of the proposed sensors is demonstrated by monitoring joint movements, facial expressions, and respiration.

A Hemispherical Image Sensor Array Fabricated with Organic Photomemory Transistors.

Hemispherical image sensors simplify lens designs, reduce optical aberrations, and improve image resolution for compact wide-field-of-view cameras. To achieve hemispherical image sensors, organic materials are promising candidates due to the following advantages: tunability of optoelectronic/spectral response and low-temperature low-cost processes. Here, a photolithographic process is developed to prepare a hemispherical image sensor array using organic thin film photomemory transistors with a density of 308 pixels per square centimeter. This design includes only one photomemory transistor as a single active pixel, in contrast to the conventional pixel architecture, consisting of select/readout/reset transistors and a photodiode. The organic photomemory transistor, comprising light-sensitive organic semiconductor and charge-trapping dielectric, is able to achieve a linear photoresponse (light intensity range, from 1 to 50 W m-2 ), along with a responsivity as high as 1.6 A W-1 (wavelength = 465 nm) for a dark current of 0.24 A m-2 (drain voltage = -1.5 V). These observed values represent the best responsivity for similar dark currents among all the reported hemispherical image sensor arrays to date. A transfer method was further developed that does not damage organic materials for hemispherical organic photomemory transistor arrays. These developed techniques are scalable and are amenable for other high-resolution 3D organic semiconductor devices.

Tough-interface-enabled stretchable electronics using non-stretchable polymer semiconductors and conductors.

Semiconducting polymer thin films are essential elements of soft electronics for both wearable and biomedical applications1-11. However, high-mobility semiconducting polymers are usually brittle and can be easily fractured under small strains (<10%)12-14. Recently, the improved intrinsic mechanical properties of semiconducting polymer films have been reported through molecular design15-18 and nanoconfinement19. Here we show that engineering the interfacial properties between a semiconducting thin film and a substrate can notably delay microcrack formation in the film. We present a universal design strategy that involves covalently bonding a dissipative interfacial polymer layer, consisting of dynamic non-covalent crosslinks, between a semiconducting thin film and a substrate. This enables high interfacial toughness between the layers, suppression of delamination and delocalization of strain. As a result, crack initiation and propagation are notably delayed to much higher strains. Specifically, the crack-onset strain of a high-mobility semiconducting polymer thin film improved from 30% to 110% strain without any noticeable microcracks. Despite the presence of a large mismatch in strain between the plastic semiconducting thin film and elastic substrate after unloading, the tough interface layer helped maintain bonding and exceptional cyclic durability and robustness. Furthermore, we found that our interfacial layer reduces the mismatch of thermal expansion coefficients between the different layers. This approach can improve the crack-onset strain of various semiconducting polymers, conducting polymers and even metal thin films.

A flexible electronic strain sensor for the real-time monitoring of tumor regression.

Assessing the efficacy of cancer therapeutics in mouse models is a critical step in treatment development. However, low-resolution measurement tools and small sample sizes make determining drug efficacy in vivo a difficult and time-intensive task. Here, we present a commercially scalable wearable electronic strain sensor that automates the in vivo testing of cancer therapeutics by continuously monitoring the micrometer-scale progression or regression of subcutaneously implanted tumors at the minute time scale. In two in vivo cancer mouse models, our sensor discerned differences in tumor volume dynamics between drug- and vehicle-treated tumors within 5 hours following therapy initiation. These short-term regression measurements were validated through histology, and caliper and bioluminescence measurements taken over weeklong treatment periods demonstrated the correlation with longer-term treatment response. We anticipate that real-time tumor regression datasets could help expedite and automate the process of screening cancer therapies in vivo.

High-brightness all-polymer stretchable LED with charge-trapping dilution.

Next-generation light-emitting displays on skin should be soft, stretchable and bright1-7. Previously reported stretchable light-emitting devices were mostly based on inorganic nanomaterials, such as light-emitting capacitors, quantum dots or perovskites6-11. They either require high operating voltage or have limited stretchability and brightness, resolution or robustness under strain. On the other hand, intrinsically stretchable polymer materials hold the promise of good strain tolerance12,13. However, realizing high brightness remains a grand challenge for intrinsically stretchable light-emitting diodes. Here we report a material design strategy and fabrication processes to achieve stretchable all-polymer-based light-emitting diodes with high brightness (about 7,450 candela per square metre), current efficiency (about 5.3 candela per ampere) and stretchability (about 100 per cent strain). We fabricate stretchable all-polymer light-emitting diodes coloured red, green and blue, achieving both on-skin wireless powering and real-time displaying of pulse signals. This work signifies a considerable advancement towards high-performance stretchable displays.

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.

A design strategy for high mobility stretchable polymer semiconductors.

As a key component in stretchable electronics, semiconducting polymers have been widely studied. However, it remains challenging to achieve stretchable semiconducting polymers with high mobility and mechanical reversibility against repeated mechanical stress. Here, we report a simple and universal strategy to realize intrinsically stretchable semiconducting polymers with controlled multi-scale ordering to address this challenge. Specifically, incorporating two types of randomly distributed co-monomer units reduces overall crystallinity and longer-range orders while maintaining short-range ordered aggregates. The resulting polymers maintain high mobility while having much improved stretchability and mechanical reversibility compared with the regular polymer structure with only one type of co-monomer units. Interestingly, the crystalline microstructures are mostly retained even under strain, which may contribute to the improved robustness of our stretchable semiconductors. The proposed molecular design concept is observed to improve the mechanical properties of various p- and n-type conjugated polymers, thus showing the general applicability of our approach. Finally, fully stretchable transistors fabricated with our newly designed stretchable semiconductors exhibit the highest and most stable mobility retention capability under repeated strains of 1,000 cycles. Our general molecular engineering strategy offers a rapid way to develop high mobility stretchable semiconducting polymers.

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).

An artificial sensory neuron with visual-haptic fusion.

Human behaviors are extremely sophisticated, relying on the adaptive, plastic and event-driven network of sensory neurons. Such neuronal system analyzes multiple sensory cues efficiently to establish accurate depiction of the environment. Here, we develop a bimodal artificial sensory neuron to implement the sensory fusion processes. Such a bimodal artificial sensory neuron collects optic and pressure information from the photodetector and pressure sensors respectively, transmits the bimodal information through an ionic cable, and integrates them into post-synaptic currents by a synaptic transistor. The sensory neuron can be excited in multiple levels by synchronizing the two sensory cues, which enables the manipulating of skeletal myotubes and a robotic hand. Furthermore, enhanced recognition capability achieved on fused visual/haptic cues is confirmed by simulation of a multi-transparency pattern recognition task. Our biomimetic design has the potential to advance technologies in cyborg and neuromorphic systems by endowing them with supramodal perceptual capabilities.

Locally coupled electromechanical interfaces based on cytoadhesion-inspired hybrids to identify muscular excitation-contraction signatures.

Coupling myoelectric and mechanical signals during voluntary muscle contraction is paramount in human-machine interactions. Spatiotemporal differences in the two signals intrinsically arise from the muscular excitation-contraction process; however, current methods fail to deliver local electromechanical coupling of the process. Here we present the locally coupled electromechanical interface based on a quadra-layered ionotronic hybrid (named as CoupOn) that mimics the transmembrane cytoadhesion architecture. CoupOn simultaneously monitors mechanical strains with a gauge factor of ~34 and surface electromyogram with a signal-to-noise ratio of 32.2 dB. The resolved excitation-contraction signatures of forearm flexor muscles can recognize flexions of different fingers, hand grips of varying strength, and nervous and metabolic muscle fatigue. The orthogonal correlation of hand grip strength with speed is further exploited to manipulate robotic hands for recapitulating corresponding gesture dynamics. It can be envisioned that such locally coupled electromechanical interfaces would endow cyber-human interactions with unprecedented robustness and dexterity.

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.

All-nanofiber-based, ultrasensitive, gas-permeable mechanoacoustic sensors for continuous long-term heart monitoring.

The prolonged and continuous monitoring of mechanoacoustic heart signals is essential for the early diagnosis of cardiovascular diseases. These bodily acoustics have low intensity and low frequency, and measuring them continuously for long periods requires ultrasensitive, lightweight, gas-permeable mechanoacoustic sensors. Here, we present an all-nanofiber mechanoacoustic sensor, which exhibits a sensitivity as high as 10,050.6 mV Pa-1 in the low-frequency region (<500 Hz). The high sensitivity is achieved by the use of durable and ultrathin (2.5 µm) nanofiber electrode layers enabling a large vibration of the sensor during the application of sound waves. The sensor is ultralightweight, and the overall weight is as small as 5 mg or less. The devices are mechanically robust against bending, and show no degradation in performance even after 1,000-cycle bending. Finally, we demonstrate a continuous long-term (10 h) measurement of heart signals with a signal-to-noise ratio as high as 40.9 decibels (dB).

Decoupling of mechanical properties and ionic conductivity in supramolecular lithium ion conductors.

The emergence of wearable electronics puts batteries closer to the human skin, exacerbating the need for battery materials that are robust, highly ionically conductive, and stretchable. Herein, we introduce a supramolecular design as an effective strategy to overcome the canonical tradeoff between mechanical robustness and ionic conductivity in polymer electrolytes. The supramolecular lithium ion conductor utilizes orthogonally functional H-bonding domains and ion-conducting domains to create a polymer electrolyte with unprecedented toughness (29.3 MJ m-3) and high ionic conductivity (1.2 × 10-4 S cm-1 at 25 °C). Implementation of the supramolecular ion conductor as a binder material allows for the creation of stretchable lithium-ion battery electrodes with strain capability of over 900% via a conventional slurry process. The supramolecular nature of these battery components enables intimate bonding at the electrode-electrolyte interface. Combination of these stretchable components leads to a stretchable battery with a capacity of 1.1 mAh cm-2 that functions even when stretched to 70% strain. The method reported here of decoupling ionic conductivity from mechanical properties opens a promising route to create high-toughness ion transport materials for energy storage applications.

Conjugated Carbon Cyclic Nanorings as Additives for Intrinsically Stretchable Semiconducting Polymers.

Molecular additives are often used to enhance dynamic motion of polymeric chains, which subsequently alter the functional and physical properties of polymers. However, controlling the chain dynamics of semiconducting polymer thin films and understanding the fundamental mechanisms of such changes is a new area of research. Here, cycloparaphenylenes (CPPs) are used as conjugated molecular additives to tune the dynamic behaviors of diketopyrrolopyrrole-based (DPP-based) semiconducting polymers. It is observed that the addition of CPPs results in significant improvement in the stretchability of the DPP-based polymers without adversely affecting their mobility, which arises from the enhanced polymer dynamic motion and reduced long-range crystalline order. The polymer films retain their fiber-like morphology and short-range ordered aggregates, which leads to high mobility. Fully stretchable transistors are subsequently fabricated using CPP/semiconductor composites as active layers. These composites are observed to maintain high mobilities when strained and after repeated applied strains. Interestingly, CPPs are also observed to improve the contact resistance and charge transport of the fully stretchable transistors. ln summary, these results collectively indicate that controlling the dynamic motion of polymer semiconductors is proved to be an effective way to improve their stretchability.

Highly Durable Nanofiber-Reinforced Elastic Conductors for Skin-Tight Electronic Textiles.

Soft and stretchable electrodes are essential components for skin-tight wearable devices, which can provide comfortable, unobtrusive, and accurate physiological monitoring and physical sensing for applications such as healthcare, medical treatment, and human-machine interfaces. Metal-elastomer nanocomposites are a promising approach, enabling high conductivity and stretchability derived from metallic conduction and percolation networks of metal nano/micro fillers. However, their practical application is still limited by their inferior cyclic stability and long-term durability. Here, we report on a highly durable nanofiber-reinforced metal-elastomer composite consisting of (i) metal fillers, (ii) an elastomeric binder matrix, and (iii) electrospun polyvinylidene fluoride nanofibers for enhancing both cyclic stability and conductivity. Embedded polyvinylidene fluoride (PVDF) nanofibers enhance the toughness and suppress the crack growth by providing a fiber reinforcing effect. Furthermore, the conductivity of nanofiber-reinforced elastic conductor is four times greater than the pristine material because the silver-rich layer is self-assembled on the top surface by a filtering effect. As a result, a stretchable electrode made from nanofiber-reinforced elastic conductors and wrinkled structures has both excellent cyclic durability and high conductivity and is stretchable up to 800%. The cyclic degradation (ΔR/R0) remains at 0.56 after 5000 stretching cycles (50% strain), whereas initial conductivity and sheet resistance are 9903 S cm-1 and 0.047 Ω sq-1, respectively. By utilizing a highly conductive and durable elastic conductor as sensor electrodes and wirings, a skin-tight multimodal physiological sensing suit is demonstrated. Continuous long-term monitoring of electrocardiogram, electromyogram, and motions during weight-lifting exercises are successfully demonstrated without significant degradation of signal quality.

Materials and structural designs of stretchable conductors.

Stretchable conductors are essential building blocks for stretchable electronic devices used in next-generation wearables and soft robotics. Over 10 years of research in stretchable electronics has produced stretchable sensors, circuits, displays, and energy harvesters, mostly enabled by unique stretchable conductors. This review covers recent advances in stretchable conductors, which have been achieved by engineering their structures, materials, or both. Advantages, mechanisms, and limitations of the different classes of stretchable conductors are discussed to provide insight into which class of stretchable conductor is suitable for fabrication of various stretchable electronic devices. The significantly improved electronic performance and wide variety of stretchable conductors are creating a new paradigm in stretchable electronics.