Organic mixed ionic-electronic conductors (OMIECs), which can be used to build organic electrochemical transistors (OECTs), are of potential use in flexible, large-area and bioelectronic systems. Although hole-transporting p-type OMIECs are susceptible to oxidation, and oxygen leads to OECT instability, it is unclear whether oxygen also behaves as an uncontrolled p-dopant. We show that oxygen dissolved in a solvent can act as a p-dopant in OMIECs and OECTs by filling traps to enable effective electrochemical doping. To address the fact that the presence of oxygen simultaneously jeopardizes OECT stability, we develop a two-step strategy in which we first degas the solvent, and then dope the OMIEC in a controlled manner using a chemical dopant. Our approach improves the stability of both p-type and n-type OECTs, while increasing the on-off ratio, tuning the threshold voltage and enhancing the transconductance, charge carrier mobility, and the mu C* product-that is, the product of mobility and the volumetric capacitance.

n essential part of developing organic mixed ionic–electronic conducting materials and organic electrochemical transistors is consistent and standardized reporting of the product of charge carrier mobility and volumetric capacitance, the μC * product. This Comment argues that unexpected changes in transistor channel resistance can overestimate this figure of merit, leading to a confusion of comparisons in the literature.

Although p-type organic mixed ionic electronic conductors (OMIECs) are susceptible to oxidation, it has not yet been considered as to whether oxygen could behave as an uncontrolled p-dopant. Here, oxygen dissolved in solvents is shown to be behave as a p-dopant, that fills traps to enable more effective electrochemical doping in OMIECs and organic electrochemical transistors (OECTs). Yet the presence of oxygen also jeopardizes OECT stability. A two-step strategy is introduced to solve this contradictory problem, where first the solvent is degassed, and second the OMIEC is doped in a controlled manner using a chemical p-dopant. This strategy has a remarkable impact on OECT stability in air and water, while simultaneously increasing on-off ratio, tuning the threshold voltage, and enhancing the transconductance, mobility and the µC* product. This simple solution-processing technique is easily implemented, low-cost, highly effective in air and water, and effective in materials systems with different polymers, solvent and dopants. Overall, the data herein suggests that combining chemical doping with solvent degassing could be a broadly applicable technique to improve essential criteria needed to realize organic bioelectronics and more complex OMIEC circuitry.

Abstract Four glycolated polythiophene‐based organic mixed ionic‐electronic conductors (OMIECs), PE2gTT, PE2gT, PT2gTT, and PT2gT are prepared by atom‐efficient direct arylation polymerization, avoiding the need for toxic organometallic precursors. PE2gT, PT2gTT, and PT2gT are operable in p‐type accumulation mode organic electrochemical transistors (OECTs), with PT2gT displaying the best device performance with a µC* product figure‐of‐merit of 290 F cm−1 V−1 s−1. A record volumetric capacitance among p‐type glycolated polythiophene OMIECs of 313 F cm−3 is observed for PE2gT, ascribed to the high proportionality of polar components in its materials design. The good OECT performance of PE2gT with µC* = 84.2 F cm−1 V−1 s−1, comparable with state‐of‐the‐art poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) devices, coupled with its synthetic accessibility and favorable accumulation mode operation makes PE2gT an ideal glycolated alternative to PEDOT:PSS in bioelectronics. PE2gT with the least negative threshold voltage also displays the best OECT operational cycling stability, linked to better resistance of its oxidized state against parasitic redox side reactions . Shelf life stability of OECTs stored (without bias) is observed to be better for materials with a more negative threshold voltage and higher average molecular weight (PT2gT), that are less susceptible to ambient auto‐oxidation and film delamination.

Organic mixed ionic-electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low-cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n-dopant, tetrabutylammonium hydroxide (TBA-OH), and identifying a new design consideration underpinning its success. TBA-OH behaves as both a chemical n-dopant and morphology additive in donor acceptor co-polymer naphthodithiophene diimide-based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA+ counterion adopts an "edge-on" location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped-OECTs and doped-OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.

The latest developments in fiber design and materials science are paving the way for fibers to evolve from parts in passive components to functional parts in active fabrics. Designing conformable, organic electrochemical transistor (OECT) structures using poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) fibers has excellent potential for low-cost wearable bioelectronics, bio-hybrid devices, and adaptive neuromorphic technologies. However, to achieve high-performance, stable devices from PEDOT:PSS fibers, approaches are required to form electrodes on fibers with small diameters and poor wettability, that leads to irregular coatings. Additionally, PEDOT:PSS-fiber fabrication needs to move away from small batch processing to roll-to-roll or continuous processing. Here, it is shown that synergistic effects from a superior electrode/organic interface, and exceptional fiber alignment from continuous processing, enable PEDOT:PSS fiber-OECTs with stable contacts, high µC* product (1570.5 F cm-1 V-1 s-1 ), and high hole mobility over 45 cm2 V-1 s-1 . Fiber-electrochemical neuromorphic organic devices (fiber-ENODes) are developed to demonstrate that the high mobility fibers are promising building blocks for future bio-hybrid technologies. The fiber-ENODes demonstrate synaptic weight update in response to dopamine, as well as a form factor closely matching the neuronal axon terminal.

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 electro-chemical 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.