High-Performance Bioelectronic Circuits Integrated on Biodegradable and Compostable Substrates with Fully Printed Mask-Less Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) rely on volumetric ion-modulation of the electronic current to provide low-voltage operation, large signal amplification, enhanced sensing capabilities, and seamless integration with biology. The majority of current OECT technologies require multistep photolithographic microfabrication methods on glass or plastic substrates, which do not provide an ideal path toward ultralow cost ubiquitous and sustainable electronics and bioelectronics. At the same time, the development of advanced bioelectronic circuits combining bio-detection, amplification, and local processing functionalities urgently demand for OECT technology platforms with a monolithic integration of high-performance iontronic circuits and sensors. Here, fully printed mask-less OECTs fabricated on thin-film biodegradable and compostable substrates are proposed. The dispensing and capillary printing methods are used for depositing both high- and low-viscosity OECT materials. Fully printed OECT unipolar inverter circuits with a gain normalized to the supply voltage as high as 136.6 V-1 , and current-driven sensors for ion detection and real-time monitoring with a sensitivity of up to 506 mV dec-1 , are integrated on biodegradable and compostable substrates. These universal building blocks with the top-performance ever reported demonstrate the effectiveness of the proposed approach and can open opportunities for next-generation high-performance sustainable bioelectronics.

Design of a Portable Microfluidic Platform for EGOT-Based in Liquid Biosensing.

In biosensing applications, the exploitation of organic transistors gated via a liquid electrolyte has increased in the last years thanks to their enormous advantages in terms of sensitivity, low cost and power consumption. However, a practical aspect limiting the use of these devices in real applications is the contamination of the organic material, which represents an obstacle for the realization of a portable sensing platform based on electrolyte-gated organic transistors (EGOTs). In this work, a novel contamination-free microfluidic platform allowing differential measurements is presented and validated through finite element modeling simulations. The proposed design allows the exposure of the sensing electrode without contaminating the EGOT device during the whole sensing tests protocol. Furthermore, the platform is exploited to perform the detection of bovine serum albumin (BSA) as a validation test for the introduced differential protocol, demonstrating the capability to detect BSA at 1 pM concentration. The lack of contamination and the differential measurements provided in this work can be the first steps towards the realization of a reliable EGOT-based portable sensing instrument.

Organic Electrochemical Transistors (OECTs) Toward Flexible and Wearable Bioelectronics.

Organic electronics have emerged as a fascinating area of research and technology in the past two decades and are anticipated to replace classic inorganic semiconductors in many applications. Research on organic light-emitting diodes, organic photovoltaics, and organic thin-film transistors is already in an advanced stage, and the derived devices are commercially available. A more recent case is the organic electrochemical transistors (OECTs), whose core component is a conductive polymer in contact with ions and solvent molecules of an electrolyte, thus allowing it to simultaneously regulate electron and ion transport. OECTs are very effective in ion-to-electron transduction and sensor signal amplification. The use of synthetically tunable, biocompatible, and depositable organic materials in OECTs makes them specially interesting for biological applications and printable devices. In this review, we provide an overview of the history of OECTs, their physical characterization, and their operation mechanism. We analyze OECT performance improvements obtained by geometry design and active material selection (i.e., conductive polymers and small molecules) and conclude with their broad range of applications from biological sensors to wearable devices.

Scaling Organic Electrochemical Transistors Down to Nanosized Channels.

The perspective of downscaling organic electrochemical transistors (OECTs) in the nanorange is approached by depositing poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) on electrodes with a nanogap designed and fabricated by electromigration induced break junction (EIBJ) technique. The electrical response of the fabricated devices is obtained by acquiring transfer characteristics in order to clarify the specific main characteristics of OECTs with sub-micrometer-sized active channels (nanogap-OECTs). On the basis of their electrical response to different scan times, the nanogap-OECT shows a maximum transconductance unaffected upon changing scan times in the time window from 1 s to 100 µs, meaning that fast varying signals can be easily acquired with unchanged amplifying performance. Hence, the scaling down of the channel size to the nanometer scale leads to a geometrical paradigm that minimizes effects on device response due to the cationic diffusion into the polymeric channel. A comprehensive study of these features is carried out by an electrochemical impedance spectroscopy (EIS) study, complemented by a quantitative analysis made by equivalent circuits. The propagation of a redox front into the polymer bulk due to ionic diffusion also known as the "intercalation pseudocapacitance" is identified as a limiting factor for the transduction dynamics.

Highly Stable Flexible Organic Electrochemical Transistors with Natural Rubber Latex Additives.

Organic electrochemical transistors (OECTs) have attracted considerable interest in the context of wearable and implantable biosensors due to their remarkable signal amplification combined with seamless integration into biological systems. These properties underlie OECTs' potential utility across a range of bioelectronic applications. One of the main challenges to their practical applications is the mechanical limitation of PEDOT:PSS, the most typical conductive polymer used as a channel layer, when the OECTs are applied to implantable and stretchable bioelectronics. In this work, we address this critical issue by employing natural rubber latex (NRL) as an additive in PEDOT:PSS to improve flexibility and stretchability of the OECT channels. Although the inclusion of NRL leads to a decrease in transconductance, mainly due to a reduced carrier mobility from 0.3 to 0.1 cm2/V·s, the OECTs maintain satisfactory transconductance, exceeding 5 mS. Furthermore, it is demonstrated that the OECTs exhibit excellent mechanical stability while maintaining their performance even after 100 repetitive bending cycles. This work, therefore, suggests that the NRL/PEDOT:PSS composite film can be deployed for wearable/implantable applications, where high mechanical stability is needed. This finding opens up new avenues for practical use of OECTs in more robust and versatile wearable and implantable biosensors.

In Situ Functionalization of Polar Polythiophene-Based Organic Electrochemical Transistor to Interface In Vitro Models.

Organic mixed ionic-electronic conductors are promising materials for interfacing and monitoring biological systems, with the aim of overcoming current challenges based on the mismatch between biological materials and convectional inorganic conductors. The conjugated polymer/polyelectrolyte complex poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT/PSS) is, up to date, the most widely used polymer for in vitro or in vivo measurements in the field of organic bioelectronics. However, PEDOT/PSS organic electrochemical transistors (OECTs) are limited by depletion mode operation and lack chemical groups that enable synthetic modifications for biointerfacing. Recently introduced thiophene-based polymers with oligoether side chains can operate in accumulation mode, and their chemical structure can be tuned during synthesis, for example, by the introduction of hydroxylated side chains. Here, we introduce a new thiophene-based conjugated polymer, p(g42T-T)-8% OH, where 8% of the glycol side chains are functionalized with a hydroxyl group. We report for the first time the compatibility of conjugated polymers containing ethylene glycol side chains in direct contact with cells. The additional hydroxyl group allows covalent modification of the surface of polymer films, enabling fine-tuning of the surface interaction properties of p(g42T-T)-8% OH with biological materials, either hindering or promoting cell adhesion. We further use p(g42T-T)-8% OH to fabricate the OECTs and demonstrate for the first time the monitoring of epithelial barrier formation of Caco-2 cells in vitro using accumulation mode OECTs. The conjugated polymer p(g42T-T)-8% OH allows organic-electronic-based materials to be easily modified and optimized to interface and monitor biological systems.

Additive Blending Effects on PEDOT:PSS Composite Films for Wearable Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) employing conductive polymers (CPs) have gained remarkable prominence and have undergone extensive advancements in wearable and implantable bioelectronic applications in recent years. Among the diverse arrays of CPs, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) is a common choice for the active-layer channel in p-type OECTs, showing a remarkably high transconductance for the high amplification of signals in biosensing applications. This investigation focuses on the novel engineering of PEDOT:PSS composite materials by seamlessly integrating several additives, namely, dimethyl sulfoxide (DMSO), (3-glycidyloxypropyl)trimethoxysilane (GOPS), and a nonionic fluorosurfactant (NIFS), to fine-tune their electrical conductivity, self-healing capability, and stretchability. To elucidate the intricate influences of the DMSO, GOPS, and NIFS additives on the formation of PEDOT:PSS composite films, theoretical calculations were performed, encompassing the solubility parameters and surface energies of the constituent components of the NIFS, PEDOT, PSS, and PSS-GOPS polymers. Furthermore, we conducted a comprehensive array of material analyses, which reveal the intricacies of the phase separation phenomenon and its interaction with the materials' characteristics. Our research identified the optimal composition for the PEDOT:PSS composite films, characterized by outstanding self-healing and stretchable capabilities. This composition has proven to be highly effective for constructing an active-layer channel in the form of OECT-based biosensors fabricated onto polydimethylsiloxane substrates for detecting dopamine. Overall, these findings represent significant progress in the application of PEDOT:PSS composite films in wearable bioelectronics and pave the way for the development of state-of-the-art biosensing technologies.

Large Transconductance of Electrochemical Transistors Based on Fluorinated Donor-Acceptor Conjugated Polymers.

Organic electrochemical transistors (OECTs) have enormous potential for use in biosignal amplifiers, analyte sensors, and neuromorphic electronics owing to their exceptionally large transconductance. However, it is challenging to simultaneously achieve high charge carrier mobility and volumetric capacitance, the two most important figures of merit in OECTs. Herein, a method of achieving high-performance OECT with donor-acceptor conjugated copolymers by introducing fluorine units is proposed. A series of cyclopentadithiophene-benzothiadiazole (CDT-BT) copolymers for use in high-performance OECTs with enhanced charge carrier mobility (from 0.65 to 1.73 cm2·V-1·s-1) and extended volumetric capacitance (from 44.8 to 57.6 F·cm-3) by fluorine substitution is achieved. The increase in the volumetric capacitance of the fluorinated polymers is attributed to either an increase in the volume at which ions can enter the film or a decrease in the effective distance between the ions and polymer backbones. The fluorine substitution increases the backbone planarity of the CDT-BT copolymers, enabling more efficient charge carrier transport. The fluorination strategy of this work suggests the more versatile use of conjugated polymers for high-performance OECTs.

Recent Advances in Conjugated Polymer-Based Biosensors for Virus Detection.

Nowadays, virus pandemics have become a major burden seriously affecting human health and social and economic development. Thus, the design and fabrication of effective and low-cost techniques for early and accurate virus detection have been given priority for prevention and control of such pandemics. Biosensors and bioelectronic devices have been demonstrated as promising technology to resolve the major drawbacks and problems of the current detection methods. Discovering and applying advanced materials have offered opportunities to develop and commercialize biosensor devices for effectively controlling pandemics. Along with various well-known materials such as gold and silver nanoparticles, carbon-based materials, metal oxide-based materials, and graphene, conjugated polymer (CPs) have become one of the most promising candidates for preparation and construction of excellent biosensors with high sensitivity and specificity to different virus analytes owing to their unique π orbital structure and chain conformation alterations, solution processability, and flexibility. Therefore, CP-based biosensors have been regarded as innovative technologies attracting great interest from the community for early diagnosis of COVID-19 as well as other virus pandemics. For providing precious scientific evidence of CP-based biosensor technologies in virus detection, this review aims to give a critical overview of the recent research related to use of CPs in fabrication of virus biosensors. We emphasize structures and interesting characteristics of different CPs and discuss the state-of-the-art applications of CP-based biosensors as well. In addition, different types of biosensors such as optical biosensors, organic thin film transistors (OTFT), and conjugated polymer hydrogels (CPHs) based on CPs are also summarized and presented.

Organic Electrochemical Transistors for In Vivo Bioelectronics.

Organic electrochemical transistors (OECTs) are presently a focus of intense research and hold great potential in expanding the horizons of the bioelectronics industry. The notable characteristics of OECTs, including their electrolyte-gating, which offers intimate interfacing with biological environments, and aqueous stability, make them particularly suitable to be operated within a living organism (in vivo). Unlike the existing in vivo bioelectronic devices, mostly based on rigid metal electrodes, OECTs form a soft mechanical contact with the biological milieu and ensure a high signal-to-noise ratio because of their powerful amplification capability. Such features make OECTs particularly desirable for a wide range of in vivo applications, including electrophysiological recordings, neuron stimulation, and neurotransmitter detection, and regulation of plant processes in vivo. In this review, a systematic compilation of the in vivo applications is presented that are addressed by the OECT technology. First, the operating mechanisms, and the device design and materials design principles of OECTs are examined, and then multiple examples are provided from the literature while identifying the unique device properties that enable the application progress. Finally, one critically looks at the future of the OECT technology for in vivo bioelectronic applications.

Organic Microbial Electrochemical Transistor Monitoring Extracellular Electron Transfer.

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.

All-Polymer Conducting Fibers and 3D Prints via Melt Processing and Templated Polymerization.

Because of their attractive mechanical properties, conducting polymers are widely perceived as materials of choice for wearable electronics and electronic textiles. However, most state-of-the-art conducting polymers contain harmful dopants and are only processable from solution but not in bulk, restricting the design possibilities for applications that require conducting micro-to-millimeter scale structures, such as textile fibers or thermoelectric modules. In this work, we present a strategy based on melt processing that enables the fabrication of nonhazardous, all-polymer conducting bulk structures composed of poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized within a Nafion template. Importantly, we employ classical polymer processing techniques including melt extrusion followed by fiber spinning or fused filament 3D printing, which cannot be implemented with the majority of doped polymers. To demonstrate the versatility of our approach, we fabricated melt-spun PEDOT:Nafion fibers, which are highly flexible, retain their conductivity of about 3 S cm-1 upon stretching to 100% elongation, and can be used to construct organic electrochemical transistors (OECTs). Furthermore, we demonstrate the precise 3D printing of complex conducting structures from OECTs to centimeter-sized PEDOT:Nafion figurines and millimeter-thick 100-leg thermoelectric modules on textile substrates. Thus, our strategy opens up new possibilities for the design of conducting, all-polymer bulk structures and the development of wearable electronics and electronic textiles.

Water-Based PEDOT:Nafion Dispersion for Organic Bioelectronics.

The water dispersion of the conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) is one of the most used material precursors in organic electronics also thanks to its industrial production. There is a growing interest for conductive polymers that could be alternative surrogates or replace PEDOT:PSS in some applications. A recent study by our group compared electrodeposited PEDOT:Nafion vs PEDOT:PSS in the use for neural recordings. Here, we introduce an easy and reproducible synthetic protocol to prepare a water dispersion of PEDOT:Nafion. The conductivity of the pristine material is on the order of 2 S cm-1 and was improved up to ≈6 S cm-1 upon treatment with ethylene glycol. Faster ion transfer was assessed by electrochemical impedance spectroscopy (EIS), and, interestingly, an improved adhesion was observed for coatings of the new PEDOT:Nafion dispersion on glass substrates, even without the addition of the silane cross-linker needed for PEDOT:PSS. As proof of concept, we demonstrate the use of this novel water dispersion of PEDOT:Nafion in three different organic electronic device architectures, namely, an organic electrochemical transistor (OECT), a memristor, and an artificial synapse.

Complementary Logic Circuits Based on High-Performance n-Type Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) have been the subject of intense research in recent years. To date, however, most of the reported OECTs rely entirely on p-type (hole transport) operation, while electron transporting (n-type) OECTs are rare. The combination of efficient and stable p-type and n-type OECTs would allow for the development of complementary circuits, dramatically advancing the sophistication of OECT-based technologies. Poor stability in air and aqueous electrolyte media, low electron mobility, and/or a lack of electrochemical reversibility, of available high-electron affinity conjugated polymers, has made the development of n-type OECTs troublesome. Here, it is shown that ladder-type polymers such as poly(benzimidazobenzophenanthroline) (BBL) can successfully work as stable and efficient n-channel material for OECTs. These devices can be easily fabricated by means of facile spray-coating techniques. BBL-based OECTs show high transconductance (up to 9.7 mS) and excellent stability in ambient and aqueous media. It is demonstrated that BBL-based n-type OECTs can be successfully integrated with p-type OECTs to form electrochemical complementary inverters. The latter show high gains and large worst-case noise margin at a supply voltage below 0.6 V.