All-Polymer Fiber Organic Electrochemical Transistor for Chronic Chemical Detection in the Brain

Continuous and precise monitoring of chemicals in the brain can assist in understanding the working mechanism of the brain and exploring therapeutics for nerve disorders. Organic electrochemical transistors (OECTs) are employed for this purpose due to their high sensitivity from the in situ amplification effect. However, the chronic and stable detection of chemicals in the brain is rarely reported for OECTs. It is possibly due to the chronic inflammation from mechanical mismatch between the device and soft brain tissue as well as the biofouling that hinder the diffusion of chemicals to decrease the sensitivity similar to other implanted devices. Therefore, an all-polymer fiber OECT (PF-OECT) is designed, composed solely of conductive polymers and fluorine rubber. The PF-OECT shows matching modulus with the soft brain tissue and good anti-biofouling performance. It also demonstrates both high sensitivity and electrochemical stability under dynamic deformations and in complex protein solutions. Finally, the PF-OECT is implanted into the mouse brain, achieving a stable 14-day ascorbic acid monitoring. The design strategy of PF-OECT presents a potential avenue for developing more biomedical devices.     

Membrane‐Free Detection of Metal Cations with an Organic Electrochemical Transistor

Alkali‐metal ions, particularly sodium (Na⁺) and potassium (K⁺), are the messengers of living cells, governing a cascade of physiological processes through the action of ion channels. Devices that can monitor, in real time, the concentrations of these cations in aqueous media are in demand not only for the study of cellular machinery, but also to detect conditions in the human body that lead to electrolyte imbalance. In this work, conducting polymers are developed that respond rapidly and selectively to varying concentrations of Na⁺ and K⁺ in aqueous media. These polymer films, bearing crown‐ether‐functionalized thiophene units specific to either Na⁺ or K⁺, generate an electrical output proportional to the cation type and concentration. Using electropolymerization, the ion‐selective polymers are integrated as the gate electrode of an organic electrochemical transistor (OECT). The OECT current changes with respect to the concentration of the ion to which the polymer electrode is selective. Designed as a single, miniaturized chip, the OECT enables the selective detection of the cations within a physiologically relevant range. These electrochemical ion sensors require neither ion‐selective membranes nor a reference electrode to operate and have the potential to surpass existing technologies for the detection of alkali‐metal ions in aqueous media.     

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors

Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs.     

A Roadmap Review of Thermally Conductive Polymer Composites: Critical Factors,Progress, and Prospects

Recently, the need for miniaturization and high integration have steered a strong technical wave in developing (micro-)electronic devices. However, excessive amounts of heat may be generated during operation/charging, severely affecting device performance and leading to life/property loss. Benefiting from their low density, easy processing and low manufacturing cost, thermally conductive polymer composites have become a research hotspot to mitigate the disadvantage of excessive heat, with potential applications in 5G communication, electronic packaging and energy transmission. By far, the reported thermal conductivity coefficient (λ) of thermally conductive polymer composite is far from expectation. Deeper understanding of heat transfer mechanism is desired for developing next generation thermally conductive composites. This review holistically scopes current advances in this field, while giving special attention to critical factors that affect thermal conductivity in polymer composites as well as the thermal conduction mechanisms on how to enhance the λ value. This review covers critical factors such as interfacial thermal resistance, chain structure of polymer, intrinsic λ value of different thermally conductive fillers, orientation/configuration of nanoparticles, 3D interconnected networks, processing technology, etc. The applications of thermally conductive polymer composites in electronic devices are summarized. The existing problems are also discussed, new challenges and opportunities are prospected.     

Solid-State Homojunction Electrochemical Transistors and Logic Gates on Plastic

Organic electrochemical transistors (OECTs) have attracted significant attention due to their unique ionic–electronic charge coupling, which holds promise for use in a variety of bioelectronics. However, the typical electronic components of OECTs, such as the rigid metal electrodes and aqueous electrolytes, have limited their application in solid-state bioelectronics that requires design flexibility and a variety of form factors. Here, the fabrication of a solid-state homojunction OECT consisting of a pristine polymer semiconductor channel, doped polymer semiconductor electrodes, and a solid electrolyte is demonstrated. This structure combines the photo-crosslinking of all of the electronic OECT components with the selective doping of the polymer semiconductor. Three Lewis acids (gold (III) chloride (AuCl₃), iron (III) chloride (FeCl₃), and copper (II) chloride (CuCl₂) ) are utilized as dopants for the metallization of the polymer semiconductor. The AuCl₃-doped polymer semiconductor with an electrical conductivity of ≈100 S cm⁻¹ is successfully employed as the source, drain, and gate electrodes for the OECT, which exhibited a high carrier mobility of 3.4 cm² V⁻¹ s⁻¹ and excellent mechanical stability, with negligible degradation in device performance after 5000 cycles of folding at a radius of 0.1 mm. Homojunction OECTs are then successfully assembled to produce NOT, NAND, and NOR logic gates.     

Analysis of the dynamic short-circuit resistance in organic bulk-heterojunction solar cells: relation to the charge carrier collection efficiency

This work studies the charge carrier collection efficiency in organic bulk-heterojunction solar cells based on polymer:fullerene blends. An equivalent circuit with a specific recombination term is proposed to describe the behavior of this type of devices. It is experimentally shown that this recombination term determines the slope of the current–voltage characteristic at the short-circuit condition. The variation of this dynamic resistance with the light intensity can be interpreted considering a dominant first-order recombination process. Finally, an analytical model under a constant electric field approximation is presented that can be used to calculate the charge carrier collection efficiency of the device. This model can be also used to estimate an effective mobility–lifetime product, which is characteristic of the quality of the active layer.     

Branched Oligo(ether) Side Chains: A Path to Enhanced Processability and Elevated Conductivity for Polymeric Semiconductors

Commercialization of stable conjugated polymers (CPs) with tunable electronic properties will remain a challenge without adequate solution processability due to the importance of techniques such as roll-to-roll manufacturing. Consequently, modifying CP backbones with polar side chains has recently resurged as an attractive structural design approach to improve polymer solubility and to provide CPs with the capability of transporting both electrons and ions, which is crucial for applications such as organic electrochemical transistors (OECTs). Here, a new dioxythiophene copolymer comprised of 2,​2'-bis-(3,4-ethylenedioxy)thiophene (biEDOT) and 3,4-propylenedioxythiophene (ProDOT) substituted with branched oligo(ether) side chains (PE₂-biOE2OE3) is synthesized using two direct hereto(arylation) polymerization (DHAP) techniques. The typical DHAP technique results in a lower molecular weight polymer (PE₂-biOE2OE3(L)), which is soluble in acetone and demonstrated a solid-state conductivity after oxidative doping of 55 ± 3 S cm⁻¹. Alternatively, a unique temperature ramp DHAP methodology results in a higher molecular weight polymer (PE₂-biOE2OE3(H)) with an especially high solid-state conductivity of 430 ± 60 S cm⁻¹. Notably, the first OECT fabricated from an acetone-processed polymer is reported, which is stable up to 500 cycles and can provide a pathway for future material design aimed at eliminating the use of toxic chlorinated solvents in OECT active layer processing.     

Negative mold transfer patterned conductive polymer electrode for flexible organic light-emitting diodes

We demonstrate flexible organic light-emitting diodes (FOLEDs) that use flexible conductive polymer electrodes patterned by negative mold transfer printing (nMTP). Because pristine poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is unsuitable for nMTP owing to problems with wettability, additives are used to improve the surface wetting properties of the polymer on the mold to successfully employ nMTP. Moreover, the additives improve the conductivity of the polymer electrode. FOLEDs fabricated with the modified PEDOT:PSS using nMTP exhibit electrical properties comparable to those of a device having an indium tin oxide (ITO) anode. These results show that the highly conductive PEDOT:PSS patterned by nMTP can be used as transparent high-resolution electrodes in low-cost ITO-free FOLEDs.     

Self‐Healable and Recyclable Tactile Force Sensors with Post‐Tunable Sensitivity

It is challenging to post‐tune the sensitivity of a tactile force sensor. Herein, a facile method is reported to tailor the sensing properties of conductive polymer composites by utilizing the liquid‐like property of dynamic polymer matrix at low strain rates. The idea is demonstrated using dynamic polymer composites (CB/dPDMS) made via evaporation‐induced gelation of the suspending toluene solution of carbon black (CB) and acid‐catalyzed dynamic polydimethylsiloxane (dPDMS). The dPDMS matrices allow CB to redistribute to change the sensitivity of materials at the liquid‐like state, but exhibit typical solid‐like behavior and thus can be used as strain sensors at normal strain rates. It is shown that the gauge factor of the polymer composites can be easily post‐tuned from 1.4 to 51.5. In addition, the dynamic polymer matrices also endow the composites with interesting self‐healing ability and recyclability. Therefore, it is envisioned that this method can be useful in the design of various novel tactile sensing materials for many applications.     

Single-Material OECT-Based Flexible Complementary Circuits Featuring Polyaniline in Both Conducting Channels

The organic electrochemical transistor (OECT) with a conjugated polymer as the active material is the elementary unit of organic bioelectronic devices. Improved functionalities, such as low power consumption, can be achieved by building complementary circuits featuring two or more OECTs. Complementary circuits commonly combine both p- and n-type transistors to reduce power draw. While p-type OECTs are readily available, n-type OECTs are less common mainly due to poor stability of the n-type active channel material in aqueous electrolyte. Here, a complementary circuit is made using a pair of OECTs having polyaniline (PANI) as the channel material in both transistors. PANI, with a finite electrochemical window accessible at voltages lower than 1 V, exhibits a peak in current versus gate voltage when used as an active channel in an OECT. The current peak has two slopes, one n-like and one p-like, which correspond to different electrochemical regimes of the same underlying conjugated polymer. The electrochemistry enables the design of a complementary circuit using only PANI as the channel material. The PANI-based circuit is shown to have excellent performance with gain of ≈7 and is transferred on a flexible biocompatible chitosan substrate with demonstrated operation in aqueous electrolyte.     

Polymer-based non-volatile resistive random-access memory device fabrication with multi-level switching and negative differential resistance state

Resistive random-access memory (RRAM) has been widely considered for its prospective applicability owing to its non-volatile characteristics. In this study, a polymer-based vacuum-free RRAM device fabricated with the conductive polymer, poly(3,4-ethylene-dioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) was proposed. Pristine PEDOT:PSS coated on indium tin oxide (ITO) electrode was used as the active layer, while PEDOT:PSS with 16 vol% ethylene glycol was added for the top electrode. The PEDOT:PSS-based RRAM device demonstrated controlled non-volatile bipolar switching and a good ON/OFF ratio with a negative differential resistance effect in the high-voltage range during the RESET process. Multi-level switching was also accomplished by controlling the voltage, which demonstrated reliable and non-volatile switching. The switching mechanism of this polymer RRAM device can be explained through the electrochemical filamentary formation as well as the current-induced phase segregation of PEDOT:PSS near the anode(ITO)/polymer interface.     

Direct Observation of Ag Filamentary Paths in Organic Resistive Memory Devices

We demonstrate bipolar switching of organic resistive memory devices consisting of Ag/polymer/heavily‐doped p‐type poly Si junctions in an 8 × 8 cross‐bar array structure. The bistable switching mechanism appears to be related to the formation and rupture of highly conductive paths, as shown by a direct observation of Ag metallic bridges using transmission electron microscopy and energy‐dispersive X‐ray spectroscopy. Current images of high‐ and low‐conducting states acquired by conducting atomic force microscopy also support this filamentary switching mechanism. The filamentary formation can be described by an electrochemical redox reaction model of Ag. Our results may also be applied to other kinds of organic materials presenting similar switching properties, contributing to the optimization of device scaling or memory performance improvement.     

Defective Engineering Tuning the Analog Switching Linearity and Symmetry of Two-Terminal Artificial Synapse for Neuromorphic Systems

Neuromorphic computing inspired by memristors has gained considerable attention due to its low power and easy integration. However, state-of-the-art two-terminal resistive switching memristors based on conductive filament formation suffer from high variability and poor controllability. As a three-terminal device operated through electrochemistry and dynamic insertion/extraction of ions, the electrochemical ion synapse demonstrates deterministic control of electron conductivity based on ion doping. But, integrating the electrochemical ion synapse into crossbar arrays will pose higher challenges and lower integration density. Herein, inspired by first-principles calculations, a two-terminal bidirectional plasticity electrochemical artificial synapse with integrated lithium polymer electrolyte and polycrystalline tungsten oxide layer is reported. The linearity and stability of the device weight update are greatly improved by adjusting the defect concentration of the polycrystalline WO₃ layer. Even after 16 000 write-read events in the air, its performance remained almost unchanged. Moreover, it has an over-limit protection mechanism under one-way stimulation that exceeds the normal range. Based on this excellent stability, the authors designed and successfully simulated the “muscle memory” that the programmatical organization of the nervous system leads to proficiency in specific actions.     

Preparation of High‐Performance Conductive Polymer Fibers through Morphological Control of Networks Formed by Nanofillers

A general method is described to prepare high‐performance conductive polymer fibers or tapes. In this method, bicomponent tapes/fibers containing two layers of conductive polymer composites (CPCs) filled with multiwall carbon nanotubes (MWNT) or carbon black (CB) based on a lower‐melting‐temperature polymer and an unfilled polymer core with higher melting temperature are fabricated by a melt‐based process. Morphological control of the conductive network formed by nanofillers is realized by solid‐state drawing and annealing. Information on the morphological and electrical change of the highly oriented conductive nanofiller network in CPC bicomponent tapes during relaxation, melting, and crystallization of the polymer matrix is reported for the first time. The conductivity of these polypropylene tapes can be as high as 275 S m^?1 with tensile strengths of around 500 MPa. To the best of the authors' knowledge, it is the most conductive, high‐strength polymer fiber produced by melt‐processing reported in literature, despite the fact that only ～5 wt.% of MWNTs are used in the outer layers of the tape and the overall MWNT content in the bicomponent tape can be much lower (typically ～0.5 wt.%). Their applications could include sensing, smart textiles, electrodes for flexible solar cells, and electromagnetic interference (EMI) shielding. Furthermore, a modeling approach was used to study the relaxation process of highly oriented conductive networks formed by carbon nanofillers.     

Photoluminescence-Based Electron and Lattice Temperature Measurements in GaN-Based HEMTs

Nitride-based semiconductors are gaining importance not only for high-power applications but also for high-temperature electronic devices. Using photoluminescence (PL) techniques, it is now possible to simultaneously determine the temperatures of the lattice and hot electrons in these devices. Therefore, it is possible to use PL mapping measurements to derive temperature profiles for electrons and the lattice in the active region of an operating device with a single set of measurements. This work presents an experimental process to construct such spatially resolved temperature maps for a planar semiconductor device under bias and applies this approach to a specific example using the conductive channels of a biased AlGaN/GaN high-electron-mobility transistor. Studying the temperature distribution inside the conductive channels will help understand how electrons flowing in the device interact with the lattice as well as the process of heat generation within the device.     

Filament diffusion model for simulating reset and retention processes in RRAM

Resistive switching memory (RRAM) devices are attracting an increasing interest as a possible future technology for ultra-scaled, high-density nonvolatile/dynamic memory. Although the RRAM concept is promising from the integration and scaling viewpoints, the switching mechanism and its controllability are still under debate. This paper addresses the modeling of reset and retention processes in unipolar resistive-switching memory devices. Reset transition and data loss are described in terms of the dissolution of a conductive filament, which is modeled by thermally-activated diffusion of defects/dopants. Carrier transport, Joule heating and diffusion of oxygen ions/vacancies during the electrical pulse and/or the annealing are modeled within a 3D numerical solver. The model can account for the observed dependence of reset voltage on the width of the applied triangular pulse and on the initial resistance for NiO-based RRAM devices. Retention simulations as a function of annealing temperature also agree with available data. The model provides a first example of device simulation tool for the design and the exploration of scaling and performance of RRAM cells.     

Measurement of Electrophysiological Signals In Vitro Using High-Performance Organic Electrochemical Transistors

Biological environments use ions in charge transport for information transmission. The properties of mixed electronic and ionic conductivity in organic materials make them ideal candidates to transduce physiological information into electronically processable signals. A device proven to be highly successful in measuring such information is the organic electrochemical transistor (OECT). Previous electrophysiological measurements performed using OECTs show superior signal-to-noise ratios than electrodes at low frequencies. Subsequent development has significantly improved critical performance parameters such as transconductance and response time. Here, interdigitated-electrode OECTs are fabricated on flexible substrates, with one such state-of-the-art device achieving a peak transconductance of 139 mS with a 138 µs response time. The devices are implemented into an array with interconnects suitable for micro-electrocorticographic application and eight architecture variations are compared. The two best-performing arrays are subject to the full electrophysiological spectrum using prerecorded signals. With frequency filtering, kHz-scale frequencies with 10 µV-scale voltages are resolved. This is supported by a novel quantification of the noise, which compares the gate voltage input and drain current output. These results demonstrate that high-performance OECTs can resolve the full electrophysiological spectrum and suggest that superior signal-to-noise ratios could be achieved in high frequency measurements of multiunit activity.     

Thermal Transport in Conductive Polymer–Based Materials

The demand for flexible conductive materials has motivated many recent studies on conductive polymer–based materials. However, the thermal conductivity of conductive polymers is relatively low, which may lead to serious heat dissipation problems for device applications. This review provides a summary of the fundamental principles for thermal transport in conductive polymers and their composites, and recent advancements in regulating their thermal conductivity. The thermal transport mechanisms in conductive polymer–based materials and up‐to‐date experimental approaches for measuring thermal conductivity are first summarized. Effective approaches for the regulation of thermal conductivity are then discussed. Finally, thermal‐related applications and future perspectives are given for conductive polymers and their composites.     

Mixed Conduction in an N-Type Organic Semiconductor in the Absence of Hydrophilic Side-Chains

Organic electrochemical transistors (OECTs) are the building blocks of biosensors, neuromorphic devices, and complementary circuits. One rule in the materials design for OECTs is the inclusion of a hydrophilic component in the chemical structure to enable ion transport in the film. Here, it is shown that the ladder-type, side-chain free polymer poly(benzimidazobenzophenanthroline) (BBL) performs significantly better in OECTs than the donor–acceptor type copolymer bearing hydrophilic ethylene glycol side chains (P-90). A combination of electrochemical techniques reveals that BBL exhibits a more efficient ion-to-electron coupling and higher OECT mobility than P-90. In situ atomic force microscopy scans evidence that BBL, which swells negligibly in electrolytes, undergoes a drastic and permanent change in morphology upon electrochemical doping. In contrast, P-90 substantially swells when immersed in electrolytes and shows moderate morphology changes induced by dopant ions. Ex situ grazing incidence wide-angle X-ray scattering suggests that the particular packing of BBL crystallites is minimally affected after doping, in contrast to P-90. BBL's ability to show exceptional mixed transport is due to the crystallites’ connectivity, which resists water uptake. This side chain-free route for the design of mixed conductors could bring the n-type OECT performance closer to the bar set by their p-type counterparts.     

Ion transport in encapsulants used in microcircuit packaging

Most semiconductor devices are encapsulated in epoxy molding compounds. These molding compounds contain ionic contaminants including chloride ions from epichlorohydrin used in the epoxidation of the resin and bromine ions incorporated into the resin as a flame retardant. Chloride ions are known to break down the protective oxide on the surface of aluminum metallization and accelerate corrosion. The encapsulant material is hydrophilic and will absorb moisture from the environment. When the absorbed moisture is combined with ions, there is an opportunity for electrolytic corrosion to occur on the metal surfaces of the device and package elements. However, the rate of corrosion in an encapsulated microcircuit may be expected to depend upon the rate of ion transport through the encapsulant. This paper evaluates two techniques for the measurement of ion diffusion in epoxy molding compounds used for microelectronic encapsulation. The data suggests that ion diffusion rates vary with molding compound formulation, the solution pH and the ion concentration. SEM-EDX analysis and TOF-SIMS analysis indicate that the mode of diffusion of ions in the encapsulants is primarily through the polymer resin matrix as opposed to diffusion at the interface of the resin and the filler particles. Calculated diffusion coefficients were slower than the literature values for moisture diffusion or the diffusion of gases. In fact, under basic conditions, the ions tend to diffuse through the molding compound almost as a front suggesting that the ions bind to the encapsulant and that the diffusion of ions in molding compounds can be modeled using a Type II non-Fickian model.