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Mixed conductors-materials that can efficiently conduct both ionic and electronic species-are an important class of functional solids. Here we demonstrate an organic nanocomposite that spontaneously forms when mixing an organic semiconductor with an ionic liquid and exhibits efficient room-temperature mixed conduction. We use a polymer known to form a semicrystalline microstructure to template ion intercalation into the side-chain domains of the crystallites, which leaves electronic transport pathways intact. Thus, the resulting material is ordered, exhibiting alternating layers of rigid semiconducting sheets and soft ion-conducting layers. This unique dual-network microstructure leads to a dynamic ionic/electronic nanocomposite with liquid-like ionic transport and highly mobile electronic charges. Using a combination of operando X-ray scattering and in situ spectroscopy, we confirm the ordered structure of the nanocomposite and uncover the mechanisms that give rise to efficient electron transport. These results provide fundamental insights into charge transport in organic semiconductors, as well as suggesting a pathway towards future improvements in these nanocomposites.

Electron-transporting (n-type) conjugated polymers have recently been applied in numerous electrochemical applications, where both ion and electron transport are required. Despite continuous efforts to improve their performance and stability, n-type conjugated polymers with mixed conduction still lag behind their hole-transporting (p-type) counterparts, limiting the functions of electrochemical devices. In this work, we investigate the effect of enhanced backbone coplanarity on the electrochemical activity and mixed ionic-electronic conduction properties of n-type polymers during operation in aqueous media. Through substitution of the widely employed electron-deficient naphthalene diimide (NDI) unit for the core-extended naphthodithiophene diimide (NDTI) units, the resulting polymer shows a more planar backbone with closer packing, leading to an increase in the electron mobility in organic electrochemical transistors (OECTs) by more than two orders of magnitude. The NDTI-based polymer shows a deep-lying lowest unoccupied molecular orbital level, enabling operation of the OECT closer to 0 V vs Ag/AgCl, where fewer parasitic reactions with molecular oxygen occur. Enhancing the backbone coplanarity also leads to a lower affinity toward water uptake during cycling, resulting in improved stability during continuous electrochemical charging and ON-OFF switching relative to the NDI derivative. Furthermore, the NDTI-based polymer also demonstrates near-perfect shelf-life stability over a month-long test, exhibiting a negligible decrease in both the maximum on-current and transconductance. Our results highlight the importance of polymer backbone design for developing stable, high-performing n-type materials with mixed ionic-electronic conduction in aqueous media.

Electrochemical reduction of atmospheric oxygen provides carbon emission-free pathways for the generation of electricity from chemical fuels and for the distributed production of green chemical oxidants like hydrogen peroxide. Recently, organic mixed ionic-electronic conducting polymers (OMIECs) have been reported as a new class of active electrode materials for the oxygen reduction reaction. This work sets out to identify the operative oxygen reduction mechanism of OMIECs through a multi-faceted experimental and theoretical approach. Using a combination of pH-dependent electrochemical characterization, operando UV-Vis and Raman spectroscopy, and ab initio calculations, we find that the n-type OMIEC, p(NDI-T2 P75), displays pH-dependent activity for the selective reduction of oxygen to the 2-electron hydrogen peroxide product. We use microkinetic simulations of the electrochemical behavior to rationalize our experimental observations through a polaron-mediated pathway involving chemical reduction of oxygen to the 1-electron superoxide intermediate followed by pH-dependent catalytic disproportionation to hydrogen peroxide. Finally, this pathway is applied to understand the experimental oxygen reduction reactivity of an expanded set of n- and p-type OMIECs.

Self-doping organic semiconductors provide a promising route to avoid instabilities and morphological issues associated with molecular n-type dopants. Structural characterization of a naphthalenetetracarboxylic diimide (NDI) semiconductor covalently bound to an ammonium hydroxide group is presented. The dopant precursor was found to be the product of an unexpected base catalyzed hydrolysis, which was reversible. The reversible hydrolysis had profound consequences on the chemical composition, morphology, and electronic performance of the doped films. In addition, we investigated the degradation mechanism of the quaternary ammonium group and the subsequent doping of NDI. These findings reveal that the products of more than one chemical reaction during processing of films must be considered when utilizing this promising class of water-soluble semiconductors.

OMIECs undergo structural rearrangements to accommodate ions and electronic charge carriers during which percolating networks are formed for efficient electronic charge transport.

A.G. and A.S. acknowledge funding from the TomKat Center for Sustainable Energy at Stanford University and the StorageX initiative. A.S. and S.T.M.T. gratefully acknowledge support from the National Science Foundation Award CBET #1804915. T.J.Q. and G.L. acknowledge support from the NSF Graduate Research Fellowship Program under grant DGE-1656518. Part of this work was performed at the Stanford Nanofabrication Facilities (SNF) and Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation as part of the National Nanotechnology Coordinated Infrastructure under award ECCS-1542152. The authors acknowledge financial support from KAUST, including the Office of Sponsored Research (OSR) award nos. OSR-2018-CRG/CCF-3079, OSR-2019-CRG8-4086, and OSR-2018-CRG7-3749. The authors acknowledge funding from an ERC Synergy Grant SC2 (610115). Use of the Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, is supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-76SF00515.

Conjugated polymers achieve redox activity in electrochemical devices by combining redox-active, electronically conducting backbones with ion-transporting side chains that can be tuned for different electrolytes. In aqueous electrolytes, redox activity can be accomplished by attaching hydrophilic side chains to the polymer backbone, which enables ionic transport and allows volumetric charging of polymer electrodes. While this approach has been beneficial for achieving fast electrochemical charging in aqueous solutions, little is known about the relationship between water uptake by the polymers during electrochemical charging and the stability and redox potentials of the electrodes, particularly for electron-transporting conjugated polymers. We find that excessive water uptake during the electrochemical charging of polymer electrodes harms the reversibility of electrochemical processes and results in irreversible swelling of the polymer. We show that small changes of the side chain composition can significantly increase the reversibility of the redox behavior of the materials in aqueous electrolytes, improving the capacity of the polymer by more than one order of magnitude. Finally, we show that tuning the local environment of the redox-active polymer by attaching hydrophilic side chains can help to reach high fractions of the theoretical capacity for single-phase electrodes in aqueous electrolytes. Our work shows the importance of chemical design strategies for achieving high electrochemical stability for conjugated polymers in aqueous electrolytes.

Exchanging hydrophobic alkyl-based side chains to hydrophilic glycol-based side chains is a widely adopted method for improving mixed-transport device performance, despite the impact on solid state packing and polymer-electrolyte interactions being poorly understood. Presented here is a Molecular Dynamics (MD) force field for modelling alkoxylated and glycolated polythiophenes. The force field is validated against known packing motifs for their monomer crystals. MD simulations, coupled with X-ray Diffraction (XRD), show that alkoxylated polythiophenes will pack with a `tilted stack' and straight interdigitating side chains, whilst their glycolated counterpart will pack with a `deflected stack' and an s-bend side chain configuration. MD simulations reveal water penetration pathways into the alkoxylated and glycolated crystals - through the {\pi}-stack and through the lamellar stack respectively. Finally, the two distinct ways tri-ethylene glycol polymers can bind to cations are revealed, showing the formation of a meta-stable single bound state, or an energetically deep double bound state, both with a strong side chain length dependance. The minimum energy pathways for the formation of the chelates are identified, showing the physical process through which cations can bind to one or two side chains of a glycolated polythiophene, with consequences for ion transport in bithiophene semiconductors., Comment: 10 pages, 4 figures

Donor-acceptor (D-A) polymers are promising materials for organic electrochemical transistors (OECTs), as they minimize detrimental faradaic side-reactions during OECT operation, yet their steady-state OECT performance still lags far behind their all-donor counterparts. Here, we report three D-A polymers based on the diketopyrrolopyrrole unit that afford OECT performances similar to those of all-donor polymers, hence representing a significant improvement to the previously developed D-A copolymers. In addition to improved OECT performance, DFT simulations of the polymers and their respective hole polarons also revealed a positive correlation between hole polaron delocalization and steady-state OECT performance, providing new insights into the design of OECT materials. More importantly, we demonstrate how polaron delocalization can be tuned directly at the molecular level by selection of the building blocks comprising the polymers' conjugated backbone, thus paving the way for the development of even higher performing OECT polymers.

The ability to control the charge density of organic mixed ionic electronic conductors (OMIECs) via reactions with redox-active analytes has enabled applications as electrochemical redox sensors. Their charge density-dependent conductivity can additionally be tuned via charge injection from electrodes, for instance in organic electrochemical transistors (OECTs), where volumetric charging of the OMIEC channel enables excellent transconductance and amplification of low potentials. Recent efforts have combined the chemical detection with the transistor function of OECTs to achieve compact electrochemical sensors. However, these sensors often fall short of the expected amplification performance of OECTs. Here, we investigate the operation mechanism of various OECT architectures to deduce the design principles required to achieve reliable chemical detection and signal amplification. By utilizing a non-polarizable gate electrode and conducting the chemical reaction in a compartment separate from the OECT, the recently developed Reaction Cell OECT achieves reliable modulation of the OECT channel's charge density. This work demonstrates that systematic and rational design of OECT chemical sensors requires understanding the electrochemical processes that result in changes in the potential (charge density) of the channel, the underlying phenomenon behind amplification.

Organic electrochemical transistors (OECTs) have shown promise as transducers and amplifiers of minute electronic potentials due to their large transconductances. Tuning the OECT threshold voltage is important to achieve low-powered devices with amplification properties within the desired operational voltage range. However, traditional design approaches have struggled to decouple channel and materials properties from threshold voltage, thereby compromising on several other OECT performance metrics, such as electrochemical stability, transconductance, and dynamic range. In this work, simple solution-processing methods are utilized to chemically dope polymer gate electrodes, thereby controlling their work function, which in turn tunes the operation voltage range of the OECTs without perturbing their channel properties. Chemical doping of initially air-sensitive polymer electrodes further improves their electrochemical stability in ambient conditions. Thus, OECTs that are simultaneously low-powered and electrochemically resistant to oxidative side reactions under ambient conditions are demonstrated. This approach shows that threshold voltage, which is once interwoven with other OECT properties, can in fact be an independent design parameter, expanding the design space of OECTs.

In the past two decades, organic electronic materials have enabled and accelerated a large and diverse set of technologies, from energy-harvesting devices and electromechanical actuators, to flexible and printed (opto)electronic circuitry. Among organic (semi)conductors, organic mixed ion-electronic conductors (OMIECs) are now at the center of renewed interest in organic electronics, as they are key drivers of recent developments in the fields of bioelectronics, energy storage, and neuromorphic computing. However, due to the relatively slow switching dynamics of organic electronics, their application in microwave technology, until recently, has been overlooked. Nonetheless, other unique properties of OMIECs, such as their substantial electrochemical tunability, charge-modulation range, and processability, make this field of use ripe with opportunities. In this work, the use of a series of solution-processed intrinsic OMIECs is demonstrated to actively tune the properties of metamaterial-inspired microwave devices, including an untethered bioelectrochemical sensing platform that requires no external power, and a tunable resonating structure with independent amplitude- and frequency-modulation. These devices showcase the considerable potential of OMIEC-based metadevices in autonomous bioelectronics and reconfigurable microwave optics.

Description, A robot learns to follow a path to exit a maze through sensorimotor learning that is induced by an organic neuromorphic circuit., In living organisms, sensory and motor processes are distributed, locally merged, and capable of forming dynamic sensorimotor associations. We introduce a simple and efficient organic neuromorphic circuit for local sensorimotor merging and processing on a robot that is placed in a maze. While the robot is exposed to external environmental stimuli, visuomotor associations are formed on the adaptable neuromorphic circuit. With this on-chip sensorimotor integration, the robot learns to follow a path to the exit of a maze, while being guided by visually indicated paths. The ease of processability of organic neuromorphic electronics and their unconventional form factors, in combination with education-purpose robotics, showcase a promising approach of an affordable, versatile, and readily accessible platform for exploring, designing, and evaluating behavioral intelligence through decentralized sensorimotor integration.

Electroactive polymer thin films undergo repeated reversible structural change during operation in electrochemical applications. While synchrotron X-ray scattering is powerful for the characterization of stand-alone and ex situ organic thin films, in situ/operando structural characterization has been underutilized-in large part due to complications arising from supporting electrolyte scattering. This has greatly hampered the development of application relevant structure property relationships. Therefore, a new methodology for in situ/operando X-ray characterization that separates the incident and scattered X-ray beam path from the electrolyte is developed. As a proof of concept, the operando structural characterization of weakly-scattering, organic mixed conducting thin films in an aqueous electrolyte environment is demonstrated, accessing previously unexplored changes in the π-π peak and diffuse scatter, while capturing the solvent swollen thin film structure which is inaccessible in previous ex situ studies. These in situ/operando measurements improve the sensitivity to structural changes, capturing minute changes not possible ex situ, and have multimodal potential such as combined Raman measurements that also serve to validate the true in situ/operando conditions of the cell. Finally, new directions enabled by this in situ/operando cell design are examined and state of the art measurements are compared.

© Copyright 2019 American Chemical Society. Organic electrochemical transistors (OECTs) composed of organic mixed conductors can operate in aqueous, biological media and translate low-magnitude ionic fluctuations of biological origin into measurable electrical signals. The growing technological interest in these biotransducers makes the fundamental understanding of ion-to-electron coupling extremely important for the design of new materials and devices. One crucial aspect in this process that has been so far disregarded is the water taken up by the film during device operation and its effects on device performance. Here, using a series of the same electrolyte with varying ion concentrations, we quantify the amount of water that is incorporated into a hydrophilic p-type organic semiconductor film alongside the dopant anions and investigate structural and morphological changes occurring in the film upon electrochemical doping. We show that infiltration of the hydrated dopant ions into the film irreversibly changes the polymer structure and negatively impacts the efficiency, reversibility, and speed of charge generation. When less water is injected into the channel, OECTs exhibit higher transconductance and faster switching speeds. Although swelling is commonly suggested to be a necessity for efficient ion-to-electron transduction, this work uncovers the negative impact of a swollen channel material on the performance of accumulation mode OECTs and lays the foundation for future materials design.

Rapid and efficient measurement of sodium ion concentrations will benefit future studies and healthcare due to the importance of sodium to many biological processes. Ratiometric optical probes, where light absorption wavelengths shift according to ion concentration, can be used as a quick measurement method. In contrast to the currently available UV absorbing probes, we have synthesised a series of sensors which absorb in different regions of the visible spectrum. In addition to measurement by conventional UV-Vis spectroscopy, this also enables analysis of sodium ion concentration from colorimetry, opening the door to faster and cheaper analysis. Finally, the optical properties of the dyes were well reproduced by computational methods, with and without the presence of sodium, enabling acceleration of design of future materials.

There is intense interest in utilizing the redox activity of Organic Mixed Ionic Electronic Conductors for faradaic chemical sensing. In particular, the investigation of organic electrochemical transistors (OECTs) as biosensors due to their low operational potentials, ease of fabrication (e.g. by inkjet printing), biocompatibility, and large transconductance. It has become common practice in the OECT community to combine both chemical detection and transistor function within the same compartment, assuming that the sensor signal is amplified seamlessly by the sensing OECT. These devices however routinely encounter several challenges whose origins often remained unclear. Some of these challenges are 1) small changes in drain current, contradicting OECT’s oft-touted current-amplifying abilities. 2) Irreversible chemical changes to the semiconducting polymer electrodes. 3) Parasitic side reactions convoluting the sensing signal, exacerbated by applied voltages. In this manuscript, we show that optimization of OECT-based sensors requires more rigorous characterization of electrode potentials to elucidate electrochemical phenomena, a practice that is often largely absent in current reports. Our analysis of fundamental device physics of various OECT architectures shows that despite what a large fraction of the organic bioelectronics community still believes, amperometric OECTs either 1) do not display any transistor behavior, and in fact operate merely as electrodes or 2) Undergo irreversible changes and are extremely complex to calibrate, or both 1) and 2). Indeed, to fully utilize the OECT’s large transconductance, a separate 2-electrode Reaction Cell which is utilized to gate a separate OECT is needed (RC-OECT). In this manuscript, in addition to showing that the RC-OECT resolves the fundamentally and irreconcilably contradicting design principles of amperometric OECTs, we demonstrate that it provides great device and materials design flexibility. Finally, we elucidate the basic principles on how to further optimize the RC-OECT. We believe that our findings will be of great interest to researchers in the fields of bioelectronics as a call to action to re-evaluate present approaches of utilizing OECTs for chemical detection and to help practitioners select materials and designs to optimize redox sensors based on organic semiconductors.

Ion gels enable temperature-stable and high-performance organic memories for integration into hardware artificial neural networks., Devices with tunable resistance are highly sought after for neuromorphic computing. Conventional resistive memories, however, suffer from nonlinear and asymmetric resistance tuning and excessive write noise, degrading artificial neural network (ANN) accelerator performance. Emerging electrochemical random-access memories (ECRAMs) display write linearity, which enables substantially faster ANN training by array programing in parallel. However, state-of-the-art ECRAMs have not yet demonstrated stable and efficient operation at temperatures required for packaged electronic devices (~90°C). Here, we show that (semi)conducting polymers combined with ion gel electrolyte films enable solid-state ECRAMs with stable and nearly temperature-independent operation up to 90°C. These ECRAMs show linear resistance tuning over a >2× dynamic range, 20-nanosecond switching, submicrosecond write-read cycling, low noise, and low-voltage (±1 volt) and low-energy (~80 femtojoules per write) operation combined with excellent endurance (>109 write-read operations at 90°C). Demonstration of these high-performance ECRAMs is a fundamental step toward their implementation in hardware ANNs.

Electrochemical transistors have recently gained significant attention in the field of bioelectronics. In particular, the organic electrochemical transistor (OECT), a device that employs organic semiconductors as the active material, has been widely investigated as biosensors due to their low operational potentials, ability to operate in aqueous environments, biocompatibility, and the amplification of low-lying biological signals owing to the OECTs’ large transconductance. As such, OECTs have been utilized as biochemical sensors for monitoring of biomarkers or metabolites, with potential application for health monitoring for wearable devices in combination with internet of things (IoT). The current working principle of biosensors based on OECTs relies on the reaction between the channel material and the analyte or intentionally generated intermediates that undergo direct or indirect electron transfer reactions with the channel material. This electron transfer reaction results in changes of the device channel conductivity with respect to the concentration of the analyte in a sample. While recent work has shown progress in development of biosensors based on this approach, it introduces several complications and disadvantages, namely unintended and uncontrolled chemical and electrochemical side reactions. First and foremost, this configuration does not allow the signal amplification one expects from a transistor device, thus invalidating the most often (and we show here erroneously) stated advantages of using OECTs for biosensing. Further, devices designed using this approach can rapidly degrade during the operation but more importantly, the results and their interpretation can lead to incorrect conclusions and render current devices unreliable for applications in health monitoring. Our work addresses these challenges by i) isolating the chemical reaction from the OECT channel on a separate compartment and ii) employing enzymatic reactions to form intermediates that drives a reaction to power the OECT. In addition, this device architecture eliminates the need for an external gate voltage so only a single power source is required to monitor changes of the conductivity of the OECT channel material. Doing so also allows us to truly amplify the reaction current on the fuel cell from µA up to mA across the OECT (with ON/OFF ratios of 104), presenting significant improvements over conventional OECT biosensors that operate in the nA range, thereby eliminating the need for sophisticated measurement instrumentation. Our work goes in depth in elucidating general materials design parameters for the fuel cell OECT. Furthermore, the device operation mechanism was rationalized using electrochemical and electrical measurements of a variety of state-of-the-art materials for OECTs. The development of this new device architecture presents an exciting new direction for sensing of metabolites and a low power, low cost and simple alternative approach to current technologies. Importantly, we also challenge some of the current thinking in the field of OECT-based biosensing. We believe that our findings will be of great interest to researchers in the fields of bioelectronics, biofuel cells and organic electronics. Additionally, our findings shine light on the working mechanism of enzymatic biosensors with OECTs. We believe that our approach will pave the way for implementation of OECT biosensors in real life applications due to the simplification of the backend circuitry that powers and synchronizes the gate and drain voltages.

A series of glycolated polythiophenes for use in organic electrochemical transistors (OECTs) is designed and synthesized, differing in the distribution of their ethylene glycol chains that are tethered to the conjugated backbone. While side chain redistribution does not have a significant impact on the optoelectronic properties of the polymers, this molecular engineering strategy strongly impacts the water uptake achieved in the polymers. By careful optimization of the water uptake in the polymer films, OECTs with unprecedented steady-state performances in terms of [mu C*] and current retentions up to 98% over 700 electrochemical switching cycles are developed. Funding Agencies|KAUSTKing Abdullah University of Science & Technology; King Abdullah University of Science and Technology Office of Sponsored Research (OSR) [OSR-2018-CARF/CCF-3079, OSR-2015-CRG4-2572, OSR-4106 CPF2019]; EC FP7 Project SC2 [610115]; EC H2020 [643791]; EPSRCEngineering & Physical Sciences Research Council (EPSRC) [EP/G037515/1, EP/M005143/1, EP/L016702/1]; Knut and Alice Wallenberg FoundationKnut & Alice Wallenberg Foundation; Wallenberg Wood Science Center [KAW 2018.0452]; Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [2009-00971]; TomKat Center for Sustainable Energy at Stanford University

Conjugated polymers are promising engineering tools for establishing bilateral electrical communication with living systems. The free energy of their films, the roughness, and charge density play major roles in determining their interactions with lipid bilayers, which form the membrane barrier around every living cell allowing for molecular exchange with the extracellular environment. In this work, we investigate lipid bilayer formation from synthetic lipid vesicles (liposomes) on a series of amphiphilic copolymer films based on naphthalene 1,4,5,8 tetracarboxylic diimide bithiophene (NDI-T2) backbone where the alkyl side chain is gradually exchanged for an ethylene glycol-based side chain. As the concentration of ethylene glycol in the composition changes, the surface energy of the films varies drastically, which, in turn, effects the interactions with liposomes. By imaging the interactions of fluorophore-labeled liposomes with these surfaces via a fluorescence microscope, we show that the films can be cast such that ethylene glycol-rich regions, which liposomes favor, are accumulated on the surface and extract information on the wettability behavior that has not been possible using other surface sensitive techniques. This approach uncovers the solid/liquid interface of a promising class of electron transporting conjugated polymer films and suggests synthetic strategies to maximize the number of lipid-polymer contacts for the formation of supported lipid bilayers.

The lipid bilayer is the elemental structure of a cell membrane, forming a stable barrier between the interior and exterior of the cell while hosting membrane proteins that enable selective transport of biologically important compounds and cellular recognition. Monitoring the quality and function of lipid bilayers is thus essential and can be performed using electrically active substrates that allow for transduction of signals. Such a promising electronic transducer material is the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate) (PEDOT:PSS) which has provided a plethora of novel bio transducing architectures. The challenge is, however, in assembling a bilayer on the conducting polymer surface, which is defect-free and has high mobility. Herein, we investigate the fusion of zwitterionic vesicles not only on a variety of PEDOT:PSS films, but also on an electron transporting, negatively charged organic semiconductor, in order to understand the surface properties that trigger vesicle fusion. The PEDOT:PSS films are prepared from dispersions containing different concentrations of ethylene glycol included as a formulation additive, which gives a handle to modulate the surface physicochemical properties without a compromise on the chemical composition. A strong correlation between the polarity of the surface, the fusion of the vesicles and the mobility of the resulting bilayer aids in extracting the design principles for the development of future conducting polymers that will enable the formation of lipid bilayers.

Liquid electrolyte-gated organic field effect transistors and organic electrochemical transistors have recently emerged as powerful technology platforms for sensing and simulation of living cells and organisms. For such applications, the transistors are operated at a gate voltage around or below 0.3 V because prolonged application of a higher voltage bias can lead to membrane rupturing and cell death. This constraint often prevents the operation of the transistors at their maximum transconductance or most sensitive regime. Here, we exploit a solid-liquid dual-gate organic transistor structure, where the threshold voltage of the liquid-gated conduction channel is controlled by an additional gate that is separated from the channel by a metal-oxide gate dielectric. With this design, the threshold voltage of the "sensing channel" can be linearly tuned in a voltage window exceeding 0.4 V. We have demonstrated that the dual-gate structure enables a much better sensor response to the detachment of human mesenchymal stem cells. In general, the capability of tuning the optimal sensing bias will not only improve the device performance but also broaden the material selection for cell-based organic bioelectronics.

Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of reactive side‑products. This is particularly important for bioelectronic devices which are designed to operate in biological systems. While redox‑active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‑reactions with molecular oxygen during device operation. We show that this electrochemical side reaction yields hydrogen peroxide (H2O2), a reactive side‑product, which may be harmful to the local biological environment and may also accelerate device degradation. We report a design strategy for the development of redox-active organic semiconductors based on donor-acceptor copolymers that prevent the formation of H2O2 during device operation. This study elucidates the previously overlooked side-reactions between redox-active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‑gated devices in application-relevant environments.

Conjugated polymers exhibit electrically driven volume changes when included in electrochemical devices via the exchange of ions and solvent. So far, this volumetric change is limited to 40% and 100% for reversible and irreversible systems, respectively, thus restricting potential applications of this technology. A conjugated polymer that reversibly expands by about 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000–10 000%, depending on the voltage applied is reported. From experimental and theoretical studies, it is found that this large and reversible volumetric switching is due to reorganization of the polymer during swelling as it transforms between a solid‐state phase and a gel, while maintaining percolation for conductivity. The polymer is utilized as an electroactive cladding to reduce the void sizes of a porous carbon filter electrode by 85%., Conjugated polymers exhibit electrically driven volume changes when electrochemically switched. Here, a thiophene‐based polymer reversibly expands by 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000–10 000%, depending on the applied voltage. Molecular dynamics reveal that the polymer transforms between a solid state to gelled state.

We report the development of redox-active conjugated polymers with potential application to electrochemical energy storage. Side chain engineering enables processing of the polymer electrodes from solution, stability in aqueous electrolytes and efficient transport of ionic and electronic charge carriers. We synthesized a 3,3' dialkoxybithiophene homo polymer (p type polymer) with glycol side chains and prepared naphthalene 1,4,5,8-tetracarboxylic-diimide-dialkoxybithiophene (NDI gT2) copolymers (n type polymer) with either a glycol or zwitterionic side chain on the NDI unit. For the latter, we developed a post-functionalization synthesis to attach the polar zwitterion side chains to the polymer backbone to avoid challenges of purifying polar intermediates. We demonstrate fast and reversible charging of solution processed electrodes for both the p- and n type polymers in aqueous electrolytes, without using additives or porous scaffolds and for films up to micrometers thick. We apply spectroelectrochemistry as an in operando technique to probe the state of charge of the electrodes. This reveals that thin films of the p-type polymer and zwitterion n-type polymer can be charged reversibly with up to two electronic charges per repeat unit (bipolaron formation). We combine thin films of these polymers in a two-electrode cell and demonstrate output voltages of up to 1.4 V with high redox stability. Our findings demonstrate the potential of functionalizing conjugated polymers with appropriate polar side chains to improve specific capacity, reversibility and rate capabilities of polymer electrodes in aqueous electrolytes., Main text 16 pages including 6 figures + 49 pages of supporting information. arXiv admin note: substantial text overlap with arXiv:1711.10457

Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium-ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte-mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.

The authors thank the Dionne lab for access to their UV–vis spectrometer and the Soft and Hybrid Materials Facility in the Stanford Nano Shared Facilities for access to the rheometer and profilometer. A.G. and A.S. acknowledge funding from the TomKat Center for Sustainable Energy at Stanford University. A.S. and M.T. gratefully acknowledge support from the National Science Foundation Award CBET #1 804 915. A.M. gratefully acknowledges support from the Knut and Alice Wallenberg Foundation (KAW 2016.0494) for Postdoctoral Research at Stanford University. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF), supported by the National Science Foundation under award ECCS–1542152.

The authors would like to thank Mahmood H. Akhtar for assistance in microfabrication and Long Chen for assistance in AFM measurements. Figure 5 and the TOC image were produced by Heno Hwang, scientific illustrator at King Abdullah University of Science and Technology (KAUST). Portions of this research were carried out at the Stanford Synchrotron Radiation Lightsource, a national user facility operated by Stanford University on behalf of the U.S. Department of Energy, Office of Basic Energy Sciences.

In article number https://doi.org/10.1002/advs.201901144, Eleni Stavrinidou, Magnus Berggren, and co‐workers present a conjugated polymer that exhibits unprecedented volume change when electrochemically addressed. The thiophene‐based polymer expands between 1000% and 10 000% irreversibly and 300% reversibly when oxidized. Molecular Dynamics reveal that the polymer transforms between a solid state to gelled state upon redox switching.

With a host of new materials being investigated as active layers in organic electrochemical transistors (OECTs), several advantageous characteristics can be utilized to improve transduction and circuit level performance for biosensing applications. Here, the subthreshold region of operation of one recently reported high performing OECT material, poly(2‐(3,3′‐bis(2‐(2‐(2‐methoxyethoxy)ethoxy)ethoxy)‐[2,2′‐bithiophen]‐5‐yl)thieno[3,2‐b]thiophene), p(g2T‐TT) is investigated. The material's high subthreshold slope (SS) is exploited for high voltage gain and low power consumption. An ≈5× improvement in voltage gain (A V) for devices engineered for equal output current and 370× lower power consumption in the subthreshold region, in comparison to operation in the higher transconductance (g m), superthreshold region usually reported in the literature, are reported. Electrophysiological sensing is demonstrated using the subthreshold regime of p(g2T‐TT) devices and it is suggested that operation in this regime enables low power, enhanced sensing for a broad range of bioelectronic applications. Finally, the accessibility of the subthreshold regime of p(g2T‐TT) is evaluated in comparison with the prototypical poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), and the role of material design in achieving favorable properties for subthreshold operation is discussed.

This is the first ever demonstration of an accumulation mode OECT for biosensing and n-type polymer in electrocatalysis., The inherent specificity and electrochemical reversibility of enzymes poise them as the biorecognition element of choice for a wide range of metabolites. To use enzymes efficiently in biosensors, the redox centers of the protein should have good electrical communication with the transducing electrode, which requires either the use of mediators or tedious biofunctionalization approaches. We report an all-polymer micrometer-scale transistor platform for the detection of lactate, a significant metabolite in cellular metabolic pathways associated with critical health care conditions. The device embodies a new concept in metabolite sensing where we take advantage of the ion-to-electron transducing qualities of an electron-transporting (n-type) organic semiconductor and the inherent amplification properties of an ion-to-electron converting device, the organic electrochemical transistor. The n-type polymer incorporates hydrophilic side chains to enhance ion transport/injection, as well as to facilitate enzyme conjugation. The material is capable of accepting electrons of the enzymatic reaction and acts as a series of redox centers capable of switching between the neutral and reduced state. The result is a fast, selective, and sensitive metabolite sensor. The advantage of this device compared to traditional amperometric sensors is the amplification of the input signal endowed by the electrochemical transistor circuit and the design simplicity obviating the need for a reference electrode. The combination of redox enzymes and electron-transporting polymers will open up an avenue not only for the field of biosensors but also for the development of enzyme-based electrocatalytic energy generation/storage devices.

We report a design strategy that allows the preparation of solution processable n type materials from low boiling point solvents for organic electrochemical transistors (OECTs). The polymer backbone is based on NDI-T2 copolymers where a branched alkyl side chain is gradually exchanged for a linear ethylene glycol based side chain. A series of random copolymers are prepared with glycol side chain percentages of 0, 10, 25, 50, 75, 90 and 100 with respect to the alkyl side chains. These are characterized in order to study the influence of the polar side chains on interaction with aqueous electrolytes, their electrochemical redox reactions and performance in OECTs when operated in aqueous electrolytes. We observe that glycol side chain percentages of >50 % are required to achieve volumetric charging while lower glycol chain percentages show a mixed operation with high required voltages to allow for bulk charging of the organic semiconductor. A strong dependence of the electron mobility on the fraction of glycol chains was found for copolymers based on NDI-T2, with a significant drop as alkyl side chains are replaced by glycol side chains.

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 mu W K-2 m(-1) compared to other NDI-based polymers.

A novel dibenzoylmethane-fullerene e,e,e-tris adduct was synthesized by the application of a variation of the Bingel–Hirsch conditions and characterized among others by X-ray crystallography. In addition, the corresponding hexakis adduct was detected by MALDI-TOF-MS analysis. Its existence was supported by density-functional-theory (DFT) computations. Furthermore a new synthesis of bis(benzoyl)methanofullerene was established, and its molecular structure was elucidated by X-ray crystallography. DFT computations reproduced the experimentally determined conformation and predict a low energy barrier for the rotation of the two benzoyl moieties.

Electrolyte-gated organic transistors offer low bias operation facilitated by direct contact of the transistor channel with an electrolyte. Their operation mode is generally defined by the dimensionality of charge transport, where a field-effect transistor allows for electrostatic charge accumulation at the electrolyte/semiconductor interface, whereas an organic electrochemical transistor (OECT) facilitates penetration of ions into the bulk of the channel, considered a slow process, leading to volumetric doping and electronic transport. Conducting polymer OECTs allow for fast switching and high currents through incorporation of excess, hygroscopic ionic phases, but operate in depletion mode. Here, we show that the use of glycolated side chains on a thiophene backbone can result in accumulation mode OECTs with high currents, transconductance, and sharp subthreshold switching, while maintaining fast switching speeds. Compared with alkylated analogs of the same backbone, the triethylene glycol side chains shift the mode of operation of aqueous electrolyte-gated transistors from interfacial to bulk doping/transport and show complete and reversible electrochromism and high volumetric capacitance at low operating biases. We propose that the glycol side chains facilitate hydration and ion penetration, without compromising electronic mobility, and suggest that this synthetic approach can be used to guide the design of organic mixed conductors.

The authors acknowledge funding from KAUST and thank Engineering and Physical Sciences Research Council Projects EP/G037515/1, EP M−005143/1, ECFP7 Project SC2 (610115), EP/N509486/1 for the financial support. M.M. gratefully thanks the Imperial College Schrodinger Scholarship for financial support.

Organic electrochemical transistors (OECTs) are receiving significant attention due to their ability to efficiently transduce biological signals. A major limitation of this technology is that only p-type materials have been reported, which precludes the development of complementary circuits, and limits sensor technologies. Here, we report the first ever n-type OECT, with relatively balanced ambipolar charge transport characteristics based on a polymer that supports both hole and electron transport along its backbone when doped through an aqueous electrolyte and in the presence of oxygen. This new semiconducting polymer is designed specifically to facilitate ion transport and promote electrochemical doping. Stability measurements in water show no degradation when tested for 2 h under continuous cycling. This demonstration opens the possibility to develop complementary circuits based on OECTs and to improve the sophistication of bioelectronic devices., Organic electrochemical transistors transduce ionic to electronic signals in aqueous solutions, holding promise for biological sensing applications. Here, Giovannitti et al. report an ambipolar organic electrochemical transistor, based on a conjugated copolymer, which has a high stability in water.