Soft Fiber Electronics Based on Semiconducting Polymer.

Fibers, originating from nature and mastered by human, have woven their way throughout the entire history of human civilization. Recent developments in semiconducting polymer materials have further endowed fibers and textiles with various electronic functions, which are attractive in applications such as information interfacing, personalized medicine, and clean energy. Owing to their ability to be easily integrated into daily life, soft fiber electronics based on semiconducting polymers have gained popularity recently for wearable and implantable applications. Herein, we present a review of the previous and current progress in semiconducting polymer-based fiber electronics, particularly focusing on smart-wearable and implantable areas. First, we provide a brief overview of semiconducting polymers from the viewpoint of materials based on the basic concepts and functionality requirements of different devices. Then we analyze the existing applications and associated devices such as information interfaces, healthcare and medicine, and energy conversion and storage. The working principle and performance of semiconducting polymer-based fiber devices are summarized. Furthermore, we focus on the fabrication techniques of fiber devices. Based on the continuous fabrication of one-dimensional fiber and yarn, we introduce two- and three-dimensional fabric fabricating methods. Finally, we review challenges and relevant perspectives and potential solutions to address the related problems.

Thiazole Imide-Based All-Acceptor Homopolymer with Branched Ethylene Glycol Side Chains for Organic Thermoelectrics.

n-Type semiconducting polymers with high thermoelectric performance remain challenging due to the scarcity of molecular design strategy, limiting their applications in organic thermoelectric (OTE) devices. Herein, we provide a new approach to enhance the OTE performance of n-doped polymers by introducing acceptor-acceptor (A-A) type backbone bearing branched ethylene glycol (EG) side chains. When doped with 4-(2,3-dihydro-1,3-dimethyl-1H-benzimidazol-2-yl)-N,N-dimethylbenzenamine (N-DMBI), the A-A homopolymer PDTzTI-TEG exhibits n-type electrical conductivity (σ) up to 34 S cm-1 and power factor value of 15.7 µW m-1 K-2 . The OTE performance of PDTzTI-TEG is far greater than that of homopolymer PBTI-TEG (σ=0.27 S cm-1 ), indicating that introducing electron-deficient thiazole units in the backbone further improves the n-doping efficiency. These results demonstrate that developing A-A type polymers with EG side chains is an effective strategy to enhance n-type OTE performance.

Ground-state electron transfer in all-polymer donor-acceptor heterojunctions.

Doping of organic semiconductors is crucial for the operation of organic (opto)electronic and electrochemical devices. Typically, this is achieved by adding heterogeneous dopant molecules to the polymer bulk, often resulting in poor stability and performance due to dopant sublimation or aggregation. In small-molecule donor-acceptor systems, charge transfer can yield high and stable electrical conductivities, an approach not yet explored in all-conjugated polymer systems. Here, we report ground-state electron transfer in all-polymer donor-acceptor heterojunctions. Combining low-ionization-energy polymers with high-electron-affinity counterparts yields conducting interfaces with resistivity values five to six orders of magnitude lower than the separate single-layer polymers. The large decrease in resistivity originates from two parallel quasi-two-dimensional electron and hole distributions reaching a concentration of ∼1013 cm-2. Furthermore, we transfer the concept to three-dimensional bulk heterojunctions, displaying exceptional thermal stability due to the absence of molecular dopants. Our findings hold promise for electro-active composites of potential use in, for example, thermoelectrics and wearable electronics.

Double doping of conjugated polymers with monomer molecular dopants.

Molecular doping is a crucial tool for controlling the charge-carrier concentration in organic semiconductors. Each dopant molecule is commonly thought to give rise to only one polaron, leading to a maximum of one donor:acceptor charge-transfer complex and hence an ionization efficiency of 100%. However, this theoretical limit is rarely achieved because of incomplete charge transfer and the presence of unreacted dopant. Here, we establish that common p-dopants can in fact accept two electrons per molecule from conjugated polymers with a low ionization energy. Each dopant molecule participates in two charge-transfer events, leading to the formation of dopant dianions and an ionization efficiency of up to 200%. Furthermore, we show that the resulting integer charge-transfer complex can dissociate with an efficiency of up to 170%. The concept of double doping introduced here may allow the dopant fraction required to optimize charge conduction to be halved.

Room temperature high-efficiency welding of an ultra-long silver nanowire network for flexible transparent electrodes.

In the preparation of flexible electronic devices, obtaining a transparent conductive electrode with high electrical conductivity, high transparency, and mechanical flexibility is a significant challenge. This study developed a simple method for preparing ultra-long silver nanowires (ul-AgNWs), obtaining high-purity ul-AgNWs with an average length of 317.66 ± 98.60 µm, an average diameter of 78.06 ± 13.87 nm, and an aspect ratio exceeding 4000. Integrating these ul-AgNWs with a polyethylene terephthalate (PET) film, a flexible transparent electrode (FTE) with Rs = 561 Ω and T = 97% was obtained. The ul-AgNWs were welded by driving the welding liquid to the intersection points through surface tension, resulting in a decrease of Rs to 61 Ω, T = 98.2%, and achieving a FTE with excellent mechanical properties. Furthermore, this FTE was applied in the preparation of OLED devices, showing a turn-on voltage of 2.7 V, and the maximum current efficiency and power efficiency reached 58.6 mA cm-2 and 64.7 lm W-1, respectively, demonstrating its significant potential in flexible optoelectronic devices.

Multimode opto-magnetic dual-responsive actuating fibers and fabrics programmed via direct ink writing.

Current methods lack one-step actuation programming for weave structures that can achieve multimodal motions in fiber and fabric actuators. Fiber and fabric actuators with dual-response to magnetic fields and near-infrared (NIR) light were fabricated via direct ink writing (DIW) in this work, and have 105.3 J kg-1 energy density, enabling multimodal motions including rolling, grasping, and transportation.

Integrated opposite charge grafting induced ionic-junction fiber.

The emergence of ionic-junction devices has attracted growing interests due to the potential of serving as signal transmission and translation media between electronic devices and biological systems using ions. Among them, fiber-shaped iontronics possesses a great advantage in implantable applications owing to the unique one-dimensional geometry. However, fabricating stable ionic-junction on curved surfaces remains a challenge. Here, we developed a polyelectrolyte based ionic-junction fiber via an integrated opposite charge grafting method capable of large-scale continuous fabrication. The ionic-junction fibers can be integrated into functions such as ionic diodes and ionic bipolar junction transistors, where rectification and switching of input signals are implemented. Moreover, synaptic functionality has also been demonstrated by utilizing the fiber memory capacitance. The connection between the ionic-junction fiber and sciatic nerves of the mouse simulating end-to-side anastomosis is further performed to realize effective nerve signal conduction, verifying the capability for next-generation artificial neural pathways in implantable bioelectronics.

Broadband and High-Efficiency Microwave Absorbers Based on Pyramid Structure.

Microwave-absorbing materials with wide bandwidth and high absorptivity are increasingly playing an important role in over-the-air (OTA) testing. In this work, a kind of pyramid absorbing material was prepared using flame-retardant absorbers as the filler. In addition, a coating was used to further improve the flame-retardant properties of the microwave-absorbing material. To obtain excellent microwave absorption performance (MWAP), a high-frequency structure simulator (HFSS) was adopted to design structural materials. Here, the total height, the base height, the decapitation height of the pyramid tip, the distance between the pyramids, and other parameters were analyzed; then, the actual processing and molding were realized. The MWAP of -30 dB was achieved at 2.7-18 GHz, and the MWAP of -10 dB was also met at 2-18 GHz. In particular, the study also investigated the MWAP of large angle, which can meet the MWAP of -10 dB at 2-18 GHz and MWAP of -30 dB at 4-18 GHz. Most importantly, the absorption mechanism of the pyramid structure was explored. The influence of the tip was proved by the distribution of the electromagnetic field in the pyramid. It can be regarded as a multilayer microwave-absorbing material due to the impedance gradient of the pyramid, which can provide an effective research idea and method for future engineering applications.

Wearable Thermoelectric Materials and Devices for Self-Powered Electronic Systems.

The emergence of artificial intelligence and the Internet of Things has led to a growing demand for wearable and maintenance-free power sources. The continual push toward lower operating voltages and power consumption in modern integrated circuits has made the development of devices powered by body heat finally feasible. In this context, thermoelectric (TE) materials have emerged as promising candidates for the effective conversion of body heat into electricity to power wearable devices without being limited by environmental conditions. Driven by rapid advances in processing technology and the performance of TE materials over the past two decades, wearable thermoelectric generators (WTEGs) have gradually become more flexible and stretchable so that they can be used on complex and dynamic surfaces. In this review, the functional materials, processing techniques, and strategies for the device design of different types of WTEGs are comprehensively covered. Wearable self-powered systems based on WTEGs are summarized, including multi-function TE modules, hybrid energy harvesting, and all-in-one energy devices. Challenges in organic TE materials, interfacial engineering, and assessments of device performance are discussed, and suggestions for future developments in the area are provided. This review will promote the rapid implementation of wearable TE materials and devices in self-powered electronic systems.

A high-conductivity n-type polymeric ink for printed electronics.

Conducting polymers, such as the p-doped poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), have enabled the development of an array of opto- and bio-electronics devices. However, to make these technologies truly pervasive, stable and easily processable, n-doped conducting polymers are also needed. Despite major efforts, no n-type equivalents to the benchmark PEDOT:PSS exist to date. Here, we report on the development of poly(benzimidazobenzophenanthroline):poly(ethyleneimine) (BBL:PEI) as an ethanol-based n-type conductive ink. BBL:PEI thin films yield an n-type electrical conductivity reaching 8 S cm-1, along with excellent thermal, ambient, and solvent stability. This printable n-type mixed ion-electron conductor has several technological implications for realizing high-performance organic electronic devices, as demonstrated for organic thermoelectric generators with record high power output and n-type organic electrochemical transistors with a unique depletion mode of operation. BBL:PEI inks hold promise for the development of next-generation bioelectronics and wearable devices, in particular targeting novel functionality, efficiency, and power performance.

Amphipathic Side Chain of a Conjugated Polymer Optimizes Dopant Location toward Efficient N-Type Organic Thermoelectrics.

There is no molecular strategy for selectively increasing the Seebeck coefficient without reducing the electrical conductivity for organic thermoelectrics. Here, it is reported that the use of amphipathic side chains in an n-type donor-acceptor copolymer can selectively increase the Seebeck coefficient and thus increase the power factor by a factor of ≈5. The amphipathic side chain contains an alkyl chain segment as a spacer between the polymer backbone and an ethylene glycol type chain segment. The use of this alkyl spacer does not only reduce the energetic disorder in the conjugated polymer film but can also properly control the dopant sites away from the backbone, which minimizes the adverse influence of counterions. As confirmed by kinetic Monte Carlo simulations with the host-dopant distance as the only variable, a reduced Coulombic interaction resulting from a larger host-dopant distance contributes to a higher Seebeck coefficient for a given electrical conductivity. Finally, an optimized power factor of 18 µW m-1 K-2 is achieved in the doped polymer film. This work provides a facile molecular strategy for selectively improving the Seebeck coefficient and opens up a new route for optimizing the dopant location toward realizing better n-type polymeric thermoelectrics.

Conductive polymer nanoantennas for dynamic organic plasmonics.

Being able to dynamically shape light at the nanoscale is one of the ultimate goals in nano-optics1. Resonant light-matter interaction can be achieved using conventional plasmonics based on metal nanostructures, but their tunability is highly limited due to a fixed permittivity2. Materials with switchable states and methods for dynamic control of light-matter interaction at the nanoscale are therefore desired. Here we show that nanodisks of a conductive polymer can support localized surface plasmon resonances in the near-infrared and function as dynamic nano-optical antennas, with their resonance behaviour tunable by chemical redox reactions. These plasmons originate from the mobile polaronic charge carriers of a poly(3,4-ethylenedioxythiophene:sulfate) (PEDOT:Sulf) polymer network. We demonstrate complete and reversible switching of the optical response of the nanoantennas by chemical tuning of their redox state, which modulates the material permittivity between plasmonic and dielectric regimes via non-volatile changes in the mobile charge carrier density. Further research may study different conductive polymers and nanostructures and explore their use in various applications, such as dynamic meta-optics and reflective displays.

High Thermoelectric Performance in n-Type Perylene Bisimide Induced by the Soret Effect.

Low-cost, non-toxic, abundant organic thermoelectric materials are currently under investigation for use as potential alternatives for the production of electricity from waste heat. While organic conductors reach electrical conductivities as high as their inorganic counterparts, they suffer from an overall low thermoelectric figure of merit (ZT) due to their small Seebeck coefficient. Moreover, the lack of efficient n-type organic materials still represents a major challenge when trying to fabricate efficient organic thermoelectric modules. Here, a novel strategy is proposed both to increase the Seebeck coefficient and achieve the highest thermoelectric efficiency for n-type organic thermoelectrics to date. An organic mixed ion-electron n-type conductor based on highly crystalline and reduced perylene bisimide is developed. Quasi-frozen ionic carriers yield a large ionic Seebeck coefficient of -3021 µV K-1 , while the electronic carriers dominate the electrical conductivity which is as high as 0.18 S cm-1 at 60% relative humidity. The overall power factor is remarkably high (165 µW m-1 K-2 ), with a ZT = 0.23 at room temperature. The resulting single leg thermoelectric generators display a high quasi-constant power output. This work paves the way for the design and development of efficient organic thermoelectrics by the rational control of the mobility of the electronic and ionic carriers.

Complementary Logic Circuits Based on High-Performance n-Type Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) have been the subject of intense research in recent years. To date, however, most of the reported OECTs rely entirely on p-type (hole transport) operation, while electron transporting (n-type) OECTs are rare. The combination of efficient and stable p-type and n-type OECTs would allow for the development of complementary circuits, dramatically advancing the sophistication of OECT-based technologies. Poor stability in air and aqueous electrolyte media, low electron mobility, and/or a lack of electrochemical reversibility, of available high-electron affinity conjugated polymers, has made the development of n-type OECTs troublesome. Here, it is shown that ladder-type polymers such as poly(benzimidazobenzophenanthroline) (BBL) can successfully work as stable and efficient n-channel material for OECTs. These devices can be easily fabricated by means of facile spray-coating techniques. BBL-based OECTs show high transconductance (up to 9.7 mS) and excellent stability in ambient and aqueous media. It is demonstrated that BBL-based n-type OECTs can be successfully integrated with p-type OECTs to form electrochemical complementary inverters. The latter show high gains and large worst-case noise margin at a supply voltage below 0.6 V.

Enhanced n-Doping Efficiency of a Naphthalenediimide-Based Copolymer through Polar Side Chains for Organic Thermoelectrics.

N-doping of conjugated polymers either requires a high dopant fraction or yields a low electrical conductivity because of their poor compatibility with molecular dopants. We explore n-doping of the polar naphthalenediimide-bithiophene copolymer p(gNDI-gT2) that carries oligoethylene glycol-based side chains and show that the polymer displays superior miscibility with the benzimidazole-dimethylbenzenamine-based n-dopant N-DMBI. The good compatibility of p(gNDI-gT2) and N-DMBI results in a relatively high doping efficiency of 13% for n-dopants, which leads to a high electrical conductivity of more than 10-1 S cm-1 for a dopant concentration of only 10 mol % when measured in an inert atmosphere. We find that the doped polymer is able to maintain its electrical conductivity for about 20 min when exposed to air and recovers rapidly when returned to a nitrogen atmosphere. Overall, solution coprocessing of p(gNDI-gT2) and N-DMBI results in a larger thermoelectric power factor of up to 0.4 µW K-2 m-1 compared to other NDI-based polymers.

A Chemically Doped Naphthalenediimide-Bithiazole Polymer for n-Type Organic Thermoelectrics.

The synthesis of a novel naphthalenediimide (NDI)-bithiazole (Tz2)-based polymer [P(NDI2OD-Tz2)] is reported, and structural, thin-film morphological, as well as charge transport and thermoelectric properties are compared to the parent and widely investigated NDI-bithiophene (T2) polymer [P(NDI2OD-T2)]. Since the steric repulsions in Tz2 are far lower than in T2, P(NDI2OD-Tz2) exhibits a more planar and rigid backbone, enhancing π-π chain stacking and intermolecular interactions. In addition, the electron-deficient nature of Tz2 enhances the polymer electron affinity, thus reducing the polymer donor-acceptor character. When n-doped with amines, P(NDI2OD-Tz2) achieves electrical conductivity (≈0.1 S cm-1 ) and a power factor (1.5 µW m-1 K-2 ) far greater than those of P(NDI2OD-T2) (0.003 S cm-1 and 0.012 µW m-1 K-2 , respectively). These results demonstrate that planarized NDI-based polymers with reduced donor-acceptor character can achieve substantial electrical conductivity and thermoelectric response.

Rosin-enabled ultraclean and damage-free transfer of graphene for large-area flexible organic light-emitting diodes.

The large polymer particle residue generated during the transfer process of graphene grown by chemical vapour deposition is a critical issue that limits its use in large-area thin-film devices such as organic light-emitting diodes. The available lighting areas of the graphene-based organic light-emitting diodes reported so far are usually <1 cm2. Here we report a transfer method using rosin as a support layer, whose weak interaction with graphene, good solubility and sufficient strength enable ultraclean and damage-free transfer. The transferred graphene has a low surface roughness with an occasional maximum residue height of about 15 nm and a uniform sheet resistance of 560 Ω per square with about 1% deviation over a large area. Such clean, damage-free graphene has produced the four-inch monolithic flexible graphene-based organic light-emitting diode with a high brightness of about 10,000 cd m-2 that can already satisfy the requirements for lighting sources and displays.

Thermoelectric Properties of Solution-Processed n-Doped Ladder-Type Conducting Polymers.

Ladder-type "torsion-free" conducting polymers (e.g., polybenzimidazobenzophenanthroline (BBL)) can outperform "structurally distorted" donor-acceptor polymers (e.g., P(NDI2OD-T2)), in terms of conductivity and thermoelectric power factor. The polaron delocalization length is larger in BBL than in P(NDI2OD-T2), resulting in a higher measured polaron mobility. Structure-function relationships are drawn, setting material-design guidelines for the next generation of conducting thermoelectric polymers.

Achieving Extreme Utilization of Excitons by an Efficient Sandwich-Type Emissive Layer Architecture for Reduced Efficiency Roll-Off and Improved Operational Stability in Organic Light-Emitting Diodes.

It has been demonstrated that the efficiency roll-off is generally caused by the accumulation of excitons or charge carriers, which is intimately related to the emissive layer (EML) architecture in organic light-emitting diodes (OLEDs). In this article, an efficient sandwich-type EML structure with a mixed-host EML sandwiched between two single-host EMLs was designed to eliminate this accumulation, thus simultaneously achieving high efficiency, low efficiency roll-off and good operational stability in the resulting OLEDs. The devices show excellent electroluminescence performances, realizing a maximum external quantum efficiency (EQE) of 24.6% with a maximum power efficiency of 105.6 lm W(-1) and a maximum current efficiency of 93.5 cd A(-1). At the high brightness of 5,000 cd m(-2), they still remain as high as 23.3%, 71.1 lm W(-1), and 88.3 cd A(-1), respectively. And, the device lifetime is up to 2000 h at initial luminance of 1000 cd m(-2), which is significantly higher than that of compared devices with conventional EML structures. The improvement mechanism is systematically studied by the dependence of the exciton distribution in EML and the exciton quenching processes. It can be seen that the utilization of the efficient sandwich-type EML broadens the recombination zone width, thus greatly reducing the exciton quenching and increasing the probability of the exciton recombination. It is believed that the design concept provides a new avenue for us to achieve high-performance OLEDs.