Herein, we report a de novo chemical design of supramolecular polymer materials (SPMs-1–3) by condensation polymerization, consisting of (i) soft polymeric chains (polytetramethylene glycol and ...tetraethylene glycol) and (ii) strong and reversible quadruple H-bonding cross-linkers (from 0 to 30 mol %). The former contributes to the formation of the soft domain of the SPMs, and the latter furnishes the SPMs with desirable mechanical properties, thereby producing soft, stretchable, yet tough elastomers. The resulting SPM-2 was observed to be highly stretchable (up to 17 000% strain), tough (fracture energy ∼30 000 J/m2), and self-healing, which are highly desirable properties and are superior to previously reported elastomers and tough hydrogels. Furthermore, a gold, thin film electrode deposited on this SPM substrate retains its conductivity and combines high stretchability (∼400%), fracture/notch insensitivity, self-healing, and good interfacial adhesion with the gold film. Again, these properties are all highly complementary to commonly used polydimethylsiloxane-based thin film metal electrodes. Last, we proceed to demonstrate the practical utility of our fabricated electrode via both in vivo and in vitro measurements of electromyography signals. This fundamental understanding obtained from the investigation of these SPMs will facilitate the progress of intelligent soft materials and flexible electronics.
Skin-like electronics that can adhere seamlessly to human skin or within the body are highly desirable for applications such as health monitoring, medical treatment, medical implants and biological ...studies, and for technologies that include human-machine interfaces, soft robotics and augmented reality. Rendering such electronics soft and stretchable-like human skin-would make them more comfortable to wear, and, through increased contact area, would greatly enhance the fidelity of signals acquired from the skin. Structural engineering of rigid inorganic and organic devices has enabled circuit-level stretchability, but this requires sophisticated fabrication techniques and usually suffers from reduced densities of devices within an array. We reasoned that the desired parameters, such as higher mechanical deformability and robustness, improved skin compatibility and higher device density, could be provided by using intrinsically stretchable polymer materials instead. However, the production of intrinsically stretchable materials and devices is still largely in its infancy: such materials have been reported, but functional, intrinsically stretchable electronics have yet to be demonstrated owing to the lack of a scalable fabrication technology. Here we describe a fabrication process that enables high yield and uniformity from a variety of intrinsically stretchable electronic polymers. We demonstrate an intrinsically stretchable polymer transistor array with an unprecedented device density of 347 transistors per square centimetre. The transistors have an average charge-carrier mobility comparable to that of amorphous silicon, varying only slightly (within one order of magnitude) when subjected to 100 per cent strain for 1,000 cycles, without current-voltage hysteresis. Our transistor arrays thus constitute intrinsically stretchable skin electronics, and include an active matrix for sensory arrays, as well as analogue and digital circuit elements. Our process offers a general platform for incorporating other intrinsically stretchable polymer materials, enabling the fabrication of next-generation stretchable skin electronic devices.
Soft and conformable wearable electronics require stretchable semiconductors, but existing ones typically sacrifice charge transport mobility to achieve stretchability. We explore a concept based on ...the nanoconfinement of polymers to substantially improve the stretchability of polymer semiconductors, without affecting charge transport mobility. The increased polymer chain dynamics under nanoconfinement significantly reduces the modulus of the conjugated polymer and largely delays the onset of crack formation under strain. As a result, our fabricated semiconducting film can be stretched up to 100% strain without affecting mobility, retaining values comparable to that of amorphous silicon. The fully stretchable transistors exhibit high biaxial stretchability with minimal change in on current even when poked with a sharp object. We demonstrate a skinlike finger-wearable driver for a light-emitting diode.
Diketopyrrolopyrrole (DPP)-based donor–acceptor conjugated polymers, with increasing amount of weak H-bonding units, namely 2,6-pyridinedicarboxamide (PDCA), inserted as end groups in alkyl side ...chains were prepared and investigated. In contrast to previously reported DPP polymers containing PDCA units as conjugation breakers along the polymer backbone, PDCA in the alkyl side chains readily produced almost quantitative formation of intermolecular H-bonding even at low PDCA unit content (<10 mol %) as shown by Fourier transform infrared spectroscopy (FTIR). The efficient intermolecular H-bonding was further supported by the appearance of a pronounced vibronic shoulder in the UV–vis spectra and a reduction of interlamellar spacing (from 24.02 to 22.87 Å) compared to the neat DPP polymer. Increasing mol % of PDCA units in side chains of DPP conjugated polymers also has a clear effect on the thermal and mechanical properties of the films as investigated by dynamic mechanical analysis (DMA). Polymers with a high loading of PDCA showed a linear increase in both tan delta intensity and temperature at which softening of film cross-linking occurs. In particular, at a comparable mol %, polymers with PDCA units along the conjugated backbone showed a lower transition intensity and on average a 10–20 °C higher temperature required for H-bonding breaking. FTIR coupled with crack onset measurements showed that H-bonding breaking during tensile deformation happens only at strains close to crack onset. All these observations suggest that molecular engineering of conjugated polymers bearing H-bonding units has a strong influence on microstructure, thermal and mechanical properties of solution processed films, and final energy dissipation mechanisms in stretchable electronics applications.
Deformable electronic devices that are impervious to mechanical influence when mounted on surfaces of dynamically changing soft matters have great potential for next‐generation implantable ...bioelectronic devices. Here, deformable field‐effect transistors (FETs) composed of single organic nanowires (NWs) as the semiconductor are presented. The NWs are composed of fused thiophene diketopyrrolopyrrole based polymer semiconductor and high‐molecular‐weight polyethylene oxide as both the molecular binder and deformability enhancer. The obtained transistors show high field‐effect mobility >8 cm2 V−1 s−1 with poly(vinylidenefluoride‐co‐trifluoroethylene) polymer dielectric and can easily be deformed by applied strains (both 100% tensile and compressive strains). The electrical reliability and mechanical durability of the NWs can be significantly enhanced by forming serpentine‐like structures of the NWs. Remarkably, the fully deformable NW FETs withstand 3D volume changes (>1700% and reverting back to original state) of a rubber balloon with constant current output, on the surface of which it is attached. The deformable transistors can robustly operate without noticeable degradation on a mechanically dynamic soft matter surface, e.g., a pulsating balloon (pulse rate: 40 min−1 (0.67 Hz) and 40% volume expansion) that mimics a beating heart, which underscores its potential for future biomedical applications.
Deformable organic nanowire (NW) field‐effect transistors (FETs) with mechanical reliability are demonstrated with highly ductile and deformable NWs as the semiconductor. The NWs maintain a continuous structure under 100% strain in both channel length and width directions of the transistors. Stretchable FETs with single NWs are operated stably on a 3D soft matter substrate with dynamic volume expansion and contraction that mimics a beating heart.
Emulation of human sensory and motor functions becomes a core technology in bioinspired electronics for next-generation electronic prosthetics and neurologically inspired robotics. An electronic ...synapse functionalized with an artificial sensory receptor and an artificial motor unit can be a fundamental element of bioinspired soft electronics. Here, we report an organic optoelectronic sensorimotor synapse that uses an organic optoelectronic synapse and a neuromuscular system based on a stretchable organic nanowire synaptic transistor (s-ONWST). The voltage pulses of a self-powered photodetector triggered by optical signals drive the s-ONWST, and resultant informative synaptic outputs are used not only for optical wireless communication of human-machine interfaces but also for light-interactive actuation of an artificial muscle actuator in the same way that a biological muscle fiber contracts. Our organic optoelectronic sensorimotor synapse suggests a promising strategy toward developing bioinspired soft electronics, neurologically inspired robotics, and electronic prostheses.
Organic stretchable electronics have attracted extensive scientific and industrial interest because they can be stretched, twisted, or compressed, enabling the next-generation of organic electronics ...for human/machine interfaces. These electronic devices have already been described for applications such as field-effect transistors, photovoltaics, light-emitting diodes, and sensors. High-performance stretchable electronics, however, currently still involve complicated processing steps to integrate the substrates, semiconductors, and electrodes for effective performance. Herein, we describe a facile method to efficiently identify suitable semiconducting polymers for organic stretchable transistors using soft contact lamination. In our method, the various polymers investigated are first transferred on an elastomeric poly(dimethylsiloxane) (PDMS) slab and subsequently stretched (up to 100%) along with the PDMS. The polymer/PDMS matrix is then laminated on source/drain electrode-deposited Si substrates equipped with a PDMS dielectric layer. Using this device configuration, the polymer semiconductors can be repeatedly interrogated with laminate/delaminate cycles under different amounts of tensile strain. From our obtained electrical characteristics, e.g., mobility, drain current, and on/off ratio, the strain limitation of semiconductors can be derived. With a facile soft contact lamination testing approach, we can thus rapidly identify potential candidates of semiconducting polymers for stretchable electronics.
Investigation of robust and efficient pathways to build DNA−organic molecule hybrid structures is fundamentally important to realize controlled placement of single molecules for potential ...applications, such as single-molecule electronic devices. Herein, we report a systematic investigation of synthetic processes for preparing organic molecule−DNA building blocks and their subsequent elongation to generate precise micrometer-sized structures. Specifically, optimal cross-coupling routes were identified to enable chemical linkages between three different organic molecules, namely, polyethylene glycol (PEG), poly(p-phenylene ethynylene) (PPE), and benzenetricarboxylate, with single-stranded (ss) DNA. The resulting DNA−organic molecule hybrid building blocks were purified and characterized by both denaturing gel electrophoresis and electrospray ionization mass spectrometry (ESI-MS). The building blocks were subsequently elongated through both the DNA hybridization and ligation processes to prepare micrometer-sized double-stranded (ds) DNA−organic molecule hybrid structures. The described synthetic procedures should facilitate future syntheses of various hybrid DNA-based organic molecular structures.
The design of polymer semiconductors possessing high charge transport performance, coupled with good ductility, remains a challenge. Understanding the distribution and behavior of both crystalline ...domains and amorphous regions in conjugated polymer films, upon an applied stress, shall provide general guiding principles to design stretchable organic semiconductors. Structure–property relationships (especially in both side chain and backbone engineering) are investigated for a series of poly(tetrathienoacene‐diketopyrrolopyrrole) polymers. It is observed that the fused thiophene diketopyrrolopyrrole‐based polymer, when incorporated with branched side chains and an additional thiophene spacer in the backbone, exhibits improved mechanical endurance and, in addition, does not show crack propagation until 40% strain. Furthermore, this polymer exhibits a hole mobility of 0.1 cm2 V−1 s−1 even at 100% strain or after recovered from strain, which reveals prominent continuity and viscoelasticity of the polymer thin film. It is also observed that the molecular packing orientations (either edge‐on or face‐on) significantly affect the mechanical compliance of the polymer films. The improved stretchability of the polymers is attributed to both the presence of soft amorphous regions and the intrinsic packing arrangement of its crystalline domains.
Stretchable polymer electronics are regarded as the next generation of soft electronic devices. Structure–property relationships of conjugated poly(tetrathienoacene‐diketopyrrolopyrrole) polymers with molecular structure modification are demonstrated. The physical, electrical, and morphological properties of conjugated polymers are characterized to elucidate how the thin film behavior under various stretching conditions.
Precise electrical contact between single-molecule and electrodes is a first step to study single-molecule electronics and its application such as (bio)sensors and nanodevices. To realize a reliable ...electrical contact, we can use DNA as a template in the field of nanoelectronics because of its micrometer-scaled length with the thickness of nanometer-scale. In this paper, we studied the reactivity of the amide-coupling reaction to tether oligodeoxynucleotides (ODNs) to organic molecules and the elongation of the ODNs by the polymerase chain reaction (PCR) to synthesize 1.5 kbp dsDNA-organic molecule-1.5 kbp dsDNA (DOD) triblock architecture. The successful amide-coupling reactions were confirmed by electrospray ionization mass spectrometry (ESI-MS), and the triblock architectures were characterized by 1% agarose gel electrophoresis and atomic force microscope (AFM). Our result shows that this strategy is simple and makes it easy to construct DNA−organic molecule−DNA triblock architectures and potentially provides a platform to prepare and investigate single molecule electronics.
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