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The versatile synthetic side chain toolbox assists in tuning the OECT parameters by controlling material properties of organic mixed conductors. In this review we critically summarise and evaluate various side chains used throughout OECT materials.
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We investigate the mechanism of ion-dependent charge compensation during electrochemical oxidation (doping) of the model mixed ionic/electronic transporting polythiophene derivative poly(3-{[2-(2-methoxyethoxy)ethoxy]methyl}thiophene-2,5-diyl) (P3MEEMT). Using a combination of electrochemical quartz microbalance gravimetry and glow discharge optical emission spectroscopy, we show that charge compensation during polymer redox processes proceeds via a cation-dependent mechanism. For p-type polymer oxidation in certain electrolytes, charge compensation is achieved by both eventual injection of anions into the film, as well as initial expulsion of cations from the film. We compare doping mechanisms for a variety of electrolyte salts including potassium chloride, tetrabutylammonium chloride, potassium hexafluorophosphate (KPF6), and tetrabutylammonium hexafluorophosphate. For the electrolyte KPF6, both the cations and anions coexist in the water-swelled polymer even prior to application of electrical bias. Our data indicate that electrochemical doping (hole injection into the polymer and ionic charge compensation) proceeds via the following mechanism: (1) hydration of the neutral film by electrolyte (water, cations, anions), (2) cation (K+) expulsion from the film upon initial application of an oxidative bias, and (3) anion injection into the film at higher oxidation/doping levels (>~2 × 1020/cm3). Understanding the mechanism of charge compensation during the doping process should allow for the design of improved mixed ionic/electronic conductors for use in applications ranging from organic supercapacitors and redox flow batteries to bioelectronic sensors, thermoelectrics, and devices for neuromorphic computing.
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Amide/imide-based conjugated polymers have been utilized as n-type OECT materials and have demonstrated promising device performance. However, their performance remains insufficient in terms of both efficiency and stability, which limits their practical applications. The development of conjugated polymers based on amide and imide groups represents a promising approach to address this issue. Here, in this study, we introduced dithieno[3,2-c:3′,2′-h][2,6]naphthyridine-4,9(5H,10H)-dione (TVTDA) into the design of the OECT materials for the first time. By copolymerizing it with (E)-2,2′-(ethene-1,2-diyl)bis(thiophene-3-carbonitrile), we prepared two polymers, TVTDA-2CNTVT-ST and TVTDA-2CNTVT-BR, which contain linear or branched ethylene glycol side chains, respectively. OECT devices based on these polymers demonstrate n-type charge transport characteristics, achieving promising μC* values of 7.17 and 26.5 F cm –1 V –1 s –1 for TVTDA-2CNTVT-ST and TVTDA-2CNTVT-BR, respectively. The higher electron mobility and μC* of TVTDA-2CNTVT-BR can be attributed to its mixed edge-on and face-on stacking mode, larger crystalline coherence length, and larger domain size in the thin film. To our delight, the OECT devices based on both polymers exhibit good operational stability after operating in an aqueous solution for 2000 s, with current retention rates exceeding 93%, representing the high level among the OECT devices based on amide/imide-conjugated polymers. Our study demonstrates that the TVTDA unit holds great potential for constructing high-performance n-type OECT materials.
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Organic electrochemical transistors (OECTs) enable the transduction of ionic signals into electronic outputs, positioning them as ideal candidates for next-generation sensing and (bio)signal processing applications. Recent years have witnessed the development of various OECT channel materials, affording insights into structural fine-tuning to achieve optimal performance and/or stability. However, homocouplings, commonly present in alternating conjugated polymers, have largely been overlooked. This study investigates the effect of homocoupling on OECT materials by employing two synthesis methods – standard Stille polymerization and an alternative symmetric approach – to create the p-type enhancement-mode benchmark polymer pgBTTT. The impact of homocoupling, and its absence, is studied by comparing the bulk properties of the two polymers and evaluating their respective OECT metrics. The new, homocoupling-free polymer exhibits a notably improved OECT performance ( μC *), mainly due to an average 3-fold increase in electronic mobility (μ).
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Abstract Extracellular electron transfer (EET) denotes the process of microbial respiration with electron transfer to extracellular acceptors and has been exploited in a range of microbial electrochemical systems (MESs). To further understand EET and to optimize the performance of MESs, a better understanding of the dynamics at the microscale is needed. However, the real‐time monitoring of EET at high spatiotemporal resolution would require sophisticated signal amplification. To amplify local EET signals, a miniaturized bioelectronic device, the so‐called organic microbial electrochemical transistor (OMECT), is developed, which includes Shewanella oneidensis MR‐1 integrated onto organic electrochemical transistors comprising poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) combined with poly(vinyl alcohol) (PVA). Bacteria are attached to the gate of the transistor by a chronoamperometric method and the successful attachment is confirmed by fluorescence microscopy. Monitoring EET with the OMECT configuration is achieved due to the inherent amplification of the transistor, revealing fast time‐responses to lactate. The limits of detection when using microfabricated gates as charge collectors are also investigated. The work is a first step toward understanding and monitoring EET in highly confined spaces via microfabricated organic electronic devices, and it can be of importance to study exoelectrogens in microenvironments, such as those of the human microbiome.
Covalent organic frameworks (COFs) are a promising class of crystalline polymer networks that are useful due to their high porosity, versatile functionality, and tunable architecture. Conventional solution-based methods of producing COFs are marred by slow reactions that produce powders that are difficult to process into adaptable form factors for functional applications, and there is a need for facile and fast synthesis techniques for making crystalline and ordered covalent organic framework (COF) thin films. In this work, we report a chemical vapor deposition (CVD) approach utilizing co-evaporation of two monomers onto a heated substrate to produce highly crystalline, defect-free COF films and coatings with hydrazone, imine, and ketoenamine COF linkages. Further, this all-in-one synthesis technique produces highly crystalline, 40 nm–1 μm-thick COF films on Si/SiO2 substrates in less than 30 min. Crystallinity and alignment were proven by using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and transmission electron microscopy (TEM), and successful conversion of the monomers to produce the target COF was supported by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and UV–vis measurements. Additionally, we used atomic force microscopy (AFM) to investigate the growth mechanisms of these films, showing the coalescence of triangular crystallites into a smooth film. To show the wide applicability and scope of the CVD process, we also prepared crystalline ordered COF films with imine and ketoenamine linkages. These films show potential as high-quality size exclusion membranes, catalytic platforms, and organic transistors.
Topics covered include: Laser System for Precise, Unambiguous Range Measurements; Flexible Cryogenic Temperature and Liquid-Level Probes; Precision Cryogenic Dilatometer; Stroboscopic Interferometer for Measuring Mirror Vibrations; Some Improvements in H-PDLCs; Multiple-Bit Differential Detection of OQPSK; Absolute Position Encoders With Vertical Image Binning; Flexible, Carbon-Based Ohmic Contacts for Organic Transistors; GaAs QWIP Array Containing More Than a Million Pixels; AutoChem; Virtual Machine Language; Two-Dimensional Ffowcs Williams/Hawkings Equation Solver; Full Multigrid Flow Solver; Doclet To Synthesize UML; Computing Thermal Effects of Cavitation in Cryogenic Liquids; GUI for Computational Simulation of a Propellant Mixer; Control Program for an Optical-Calibration Robot; SQL-RAMS; Distributing Data from Desktop to Hand-Held Computers; Best-Fit Conic Approximation of Spacecraft Trajectory; Improved Charge-Transfer Fluorescent Dyes; Stability-Augmentation Devices for Miniature Aircraft; Tool Measures Depths of Defects on a Case Tang Joint; Two Heat-Transfer Improvements for Gas Liquefiers; Controlling Force and Depth in Friction Stir Welding; Spill-Resistant Alkali-Metal-Vapor Dispenser; A Methodology for Quantifying Certain Design Requirements During the Design Phase; Measuring Two Key Parameters of H3 Color Centers in Diamond; Improved Compression of Wavelet-Transformed Images; NASA Interactive Forms Type Interface - NIFTI; Predicting Numbers of Problems in Development of Software; Hot-Electron Photon Counters for Detecting Terahertz Photons; Magnetic Variations Associated With Solar Flares; and Artificial Intelligence for Controlling Robotic Aircraft.
In this study, we demonstrated for the first time that a metal-containing semicrystalline polymer was used as an additive to mediate the thin film morphology of solution-grown, small-molecule organic semiconductors. By mixing polyferrocenylsilane (PFS) with an extensively-studied organic semiconductor 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene), PFS as a semicrystalline polymer independently forms nucleation and crystallization while simultaneously ameliorating diffusivity of the blend system and tuning the surface energies as a result of its partially amorphous property. We discovered that the resultant blend film exhibited a 6-fold reduction in crystal misorientation angle and a 3-fold enlargement in average grain width. Enhanced crystal orientation considerably reduces mobility variation, while minimized defects and trap centers located at grain boundaries lessen the adverse impact on the charge transport. Consequently, bottom-gate, top-contact organic thin film transistors (OTFTs) based on the TIPS pentacene/PFS mixture yielded a 40% increase in performance consistency (represented by the ratio of average mobility to the standard deviation of mobility). The PFS semicrystalline polymer-controlled crystallization can be used to regulate the thin film morphology of other high-performance organic semiconductors and shed light on applications in organic electronic devices.
Abstract Conjugated polymers (CPs) with polar side chains can conduct electronic and ionic charges simultaneously, making them promising for bioelectronics, electrocatalysis and energy storage. Recent work showed that adding alkyl spacers between CP backbones and polar side chains improved electronic charge carrier mobility, reduced swelling and enhanced stability, without compromising ion transport. However, how alkyl spacers impact polymer backbone conformation and, subsequently, electronic properties remain unclear. In this work, we design two oxy‐bithiophene‐based CP series, each featuring progressively extended alkyl spacer lengths and two distinct molecular weight (MW) distributions. Using operando characterisations, we evaluate the (spectro)electrochemical and swelling properties of the polymer thin films, and their performance in organic field‐effect transistors and organic electrochemical transistors. Surprisingly, alkyl spacers negatively impact the hole mobility of our polymers, with higher MW amplifying this effect. Using molecular dynamics simulations, we show that it is thermodynamically favourable for adjacent non‐polar alkyl spacers to aggregate in polar electrolytes, leading to backbone twisting. Further spectroscopic measurements corroborate this prediction. Our findings demonstrate the active interactions between side chain structure, MW and electrolyte/solvent polarity in influencing polymer performance, underscoring the importance of considering solvation environment effects on polymer conformation when designing new mixed conducting CPs for electrochemical applications.