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Abstract 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. 

Abstract Highly crystalline thin films in organic semiconductors are important for applications in high‐performance organic optoelectronics. Here, the effect of grain boundaries on the Hall effect and charge transport properties of organic transistors based on two exemplary benchmark systems is elucidated: (1) solution‐processed blends of 2,7‐dioctyl[1]benzothieno[3,2‐b][1]benzothiophene (C₈‐BTBT) small molecule and indacenodithiophene‐benzothiadiazole (C₁₆IDT‐BT) conjugated polymer, and (2) large‐area vacuum evaporated polycrystalline thin films of rubrene (C₄₂H₂₈). It is discovered that, despite the high field‐effect mobilities of up to 6 cm²V⁻¹s⁻¹and the evidence of a delocalized band‐like charge transport, the Hall effect in polycrystalline organic transistors is systematically and significantly underdeveloped, with the carrier coherence factor α < 1 (i.e., yields an underestimated Hall mobility and an overestimated carrier density). A model based on capacitively charged grain boundaries explaining this unusual behavior is described. This work significantly advances the understanding of magneto‐transport properties of organic semiconductor thin films. 

Abstract Organic electrochemical transistors (OECTs) exhibit strong potential for various applications in bioelectronics, especially as miniaturized, point‐of‐care biosensors, because of their efficient transducing ability. To date, however, the majority of reported OECTs have relied on p‐type (hole transporting) polymer mixed conductors, due to the limited number of n‐type (electron transporting) materials suitable for operation in aqueous electrolytes, and the low performance of those which exist. It is shown that a simple solvent‐engineering approach boosts the performance of OECTs comprising an n‐type, naphthalenediimide‐based copolymer in the channel. The addition of acetone, a rather bad solvent for the copolymer, in the chloroform‐based polymer solution leads to a three‐fold increase in OECT transconductance, as a result of the simultaneous increase in volumetric capacitance and electron mobility in the channel. The enhanced electrochemical activity of the polymer film allows high‐performance glucose sensors with a detection limit of 10 × 10⁻⁶mof glucose and a dynamic range of more than eight orders of magnitude. The approach proposed introduces a new tool for concurrently improving the conduction of ionic and electronic charge carriers in polymer mixed conductors, which can be utilized for a number of bioelectronic applications relying on efficient OECT operation.