Organic Electrochemical Transistor Common-Source Amplifier for Electrophysiological Measurements

The portability of physiological monitoring has necessitated the biocompatibility of components used in circuitry local to biological environments. A key component in processing circuitry is the linear amplifier. Amplifier circuit topologies utilize transistors, and recent advances in bioelectronics have focused on organic electrochemical transistors (OECTs). OECTs have shown the capability to transduce physiological signals at high signal-to-noise ratios. In this study high-performance interdigitated electrode OECTs are implemented in a common source linear amplifier topology. Under the constraints of OECT operation, stable circuit component parameters are found, and OECT geometries are varied to determine the best amplifier performance. An equation is formulated which approximates transistor behavior in the linear, nonlinear, and saturation regimes. This equation is used to simulate the amplifier response of the circuits with the best performing OECT geometries. The amplifier figures of merit, including distortion characterizations, are then calculated using physical and simulation measurements. Based on the figures of merit, prerecorded electrophysiological signals from spreading depolarizations, electrocorticography, and electromyography fasciculations are inputted into an OECT linear amplifier. Using frequency filtering, the primary features of events in the bioelectric signals are resolved and amplified, demonstrating the capability of OECT amplifiers in bioelectronics.     

Unraveling the Electrochemical Electrode Coupling in Integrated Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) have gained enormous attention due to their potential for bioelectronics and neuromorphic computing. However, their implementation into real-world applications is still impeded by a lack of understanding of the complex operation of integrated OECTs. This study, for the first time, elaborates on a peculiar behavior that integrated OECTs exhibit due to their electrolytic environment—the electrochemical electrode coupling (EEC), which has severe implications on the device and circuit performance, causing a loss of output saturation and a threshold voltage roll-off. After developing a physical model to describe this effect, it is substantiated with experimental data, and the crucial role of the gate electrode is discussed. Furthermore, the impact of the electrode/channel overlap on the saturation in the output curve is evaluated. It is then investigated how its detrimental effect on circuit performance can be minimized, and the optimization of a simple logic gate is demonstrated. This study has fundamental implications for researchers exploring materials and device architectures for OECTs and for engineers designing integrated OECT-based circuits.     

Wearable Organic Electrochemical Transistor Array for Skin-Surface Electrocardiogram Mapping Above a Human Heart

Electrocardiogram (ECG) mapping can provide vital information in sports training and cardiac disease diagnosis. However, most electronic devices for monitoring ECG signals need to use multiple long wires, which limit their wearability and conformability in practical applications, while wearable ECG mapping based on integrated sensor arrays has been rarely reported. Herein, ultra-flexible organic electrochemical transistor (OECT) arrays used for wearable ECG mapping on the skin surface above a human heart are presented. QRS complexes of ECG signals at different recording distances and directions relative to the heart are obtained. Furthermore, the ECG signals are successfully analyzed by the devices before and after exercise, indicating potential applications in some sports training and fitness scenarios. The OECT arrays that can conveniently monitor spacial ECG signals in the heart region may find niche applications in wearable electronics and healthcare products in the future.     

All-Polymer Fiber Organic Electrochemical Transistor for Chronic Chemical Detection in the Brain

Continuous and precise monitoring of chemicals in the brain can assist in understanding the working mechanism of the brain and exploring therapeutics for nerve disorders. Organic electrochemical transistors (OECTs) are employed for this purpose due to their high sensitivity from the in situ amplification effect. However, the chronic and stable detection of chemicals in the brain is rarely reported for OECTs. It is possibly due to the chronic inflammation from mechanical mismatch between the device and soft brain tissue as well as the biofouling that hinder the diffusion of chemicals to decrease the sensitivity similar to other implanted devices. Therefore, an all-polymer fiber OECT (PF-OECT) is designed, composed solely of conductive polymers and fluorine rubber. The PF-OECT shows matching modulus with the soft brain tissue and good anti-biofouling performance. It also demonstrates both high sensitivity and electrochemical stability under dynamic deformations and in complex protein solutions. Finally, the PF-OECT is implanted into the mouse brain, achieving a stable 14-day ascorbic acid monitoring. The design strategy of PF-OECT presents a potential avenue for developing more biomedical devices.     

High-Gain Chemically Gated Organic Electrochemical Transistor

Organic electrochemical transistors (OECTs) have exhibited promising performance as transducers and amplifiers of low potentials due to their exceptional transconductance, enabled by the volumetric charging of organic mixed ionic/electronic conductors (OMIECs) employed as the channel material. OECT performance in aqueous electrolytes as well as the OMIECs’ redox activity has spurred a myriad of studies employing OECTs as chemical transducers. However, the OECT's large (potentiometrically derived) transconductance is not fully leveraged in common approaches that directly conduct chemical reactions amperometrically within the OECT electrolyte with direct charge transfer between the analyte and the OMIEC, which results in sub-unity transduction of gate to drain current. Hence, amperometric OECTs do not truly display current gains in the traditional sense, falling short of the expected transistor performance. This study demonstrates an alternative device architecture that separates chemical transduction and amplification processes on two different electrochemical cells. This approach fully utilizes the OECT's large transconductance to achieve current gains of 10³ and current modulations of four orders of magnitude. This transduction mechanism represents a general approach enabling high-gain chemical OECT transducers.     

Highly Sensitive Glucose Biosensors Based on Organic Electrochemical Transistors Using Platinum Gate Electrodes Modified with Enzyme and Nanomaterials

Organic electrochemical transistors with glucose oxidase‐modified Pt gate electrodes are successfully used as highly sensitive glucose sensors. The gate electrodes are modified with nanomaterials (multi‐wall carbon nanotubes or Pt nanoparticles) for the first time, which results in a dramatic improvement in the sensitivity of the devices. The detection limit of the device modified with Pt nanoparticles on the gate electrode is about 5 nM, which is three orders of magnitude better than a device without the nanoparticles. The improvement of the device performance can be attributed to the excellent electrocatalytic properties of the nanomaterials and more effective immobilization of enzyme on the gate electrodes. Based on the same principle, many other types of enzyme sensors with high sensitivity and low cost are expected to be realized by modifying the gate electrodes of organic electrochemical transistors with specific enzymes and nanomaterials.     

Toward Stable p-Type Thiophene-Based Organic Electrochemical Transistors

Operational stability is essential for the success of organic electrochemical transistors (OECTs) in bioelectronics. The oxygen reduction reaction (ORR) is a common electrochemical side reaction that can compromise the stability of OECTs, but the relationship between ORR and materials degradation is poorly understood. In this study, the impact of ORR on the stability and degradation mechanisms of thiophene-based OECTs is investigated. The findings show that an increase in pH during ORR leads to the degradation of the polymer backbone. By using a protective polymer glue layer between the semiconductor channel and the aqueous electrolyte, ORR is effectively suppressed and the stability of the OECTs is significantly improved, resulting in current retention of nearly 90% for ≈2 h cycling in the saturation regime.     

Highly Stable Ladder-Type Conjugated Polymer Based Organic Electrochemical Transistors for Low Power and Signal Processing-Free Surface Electromyogram Triggered Robotic Hand Control

Organic electrochemical transistors (OECTs) based complementary inverters have been considered as promising candidates in electrophysiological amplification, owing to their low power consumption, and high gain. To create complementary inverters, it is important to use highly stable p-type and n-type polymers with well-balanced current. In this study, the electrochemical stability of p-type ladder-conjugated polymer-based OECT is improved through an annealing process that maintains its doped-state drain current from 76% to 105% after 4,500 cycles in ambient environment. Next an OECT-based complementary inverter made from p-type and n-type ladder-conjugated polymers (PBBTL and BBL) that possess ultra-low power consumption (≈170 nW), high gain (67 V/V), and high noise margin (92%) with full rail-to-rail swing, is presented. Furthermore, its potential for amplifying the envelope of surface electromyography (EMG) for robotic hand control is demonstrated. The high variation in the output (0.35 V) allows the amplified EMG signals to be directly captured by a commercial analog-to-digital converter, which in turn controls the robot hand to grasp different objects with low delay and low noise. These results demonstrate the capability of OECT inverter-based amplifier in future signal processing-free human-machine interface, particularly useful for prosthetic control and gesture control applications.     

Organic Junction Field‐Effect Transistor

The realization and performance of a novel organic field‐effect transistor—the organic junction field‐effect transistor (JFET)—is discussed. The transistors are based on the modulation of the thickness of a depletion layer in an organic pin junction with varying gate potential. Based on numerical modeling, suitable layer thicknesses and doping concentrations are identified. Experimentally, organic JFETs are realized and it is shown that the devices clearly exhibit amplification. Changes in the electrical characteristics due to a variation of the intrinsic and the p‐doped layer thickness are rationalized by the numerical model, giving further proof to the proposed operational mechanism.     

Ultimately Sensitive Organic Bioelectronic Transistor Sensors by Materials and Device Structure Design

Organic bioelectronic sensors are gaining momentum as they can combine high‐performance sensing level with flexible large‐area processable materials. This opens to potentially highly powerful sensing systems for point‐of‐care health monitoring and diagnostics at low cost. Prominent to detect biochemical recognition events, are electrolyte‐gated organic field‐effect transistors (EGOFETs) and organic electrochemical transistors (OECTs) as they are easily fabricated and operated. EGOFETs are recently shown to be capable of label‐free single‐molecule detections, even in serum. This progress report aims to provide a critical perspective through a selected overview of the literature on both EGOFET and OECT biosensors. Attention is paid to correctly attribute them to the potentiometric and amperometric biosensor categories, which is important to set the right conditions for quantification purposes. Moreover, to deepen the understanding of the sensing mechanisms, with the support of unpublished data, focus is put on two among the most critical aspects, namely, the capacitance interplay and the role of Faradaic currents. The final aim is to provide a rationale of the functional mechanisms encompassing both EGOFET and OECT sensors, to improve materials and devices' designs taking advantage of the processes that enhance the sensing response enabling the extremely high‐performance level resulting in ultimate sensitivity, selectivity, and fast response.     

Organic Light-Emitting Transistors in a Smart-Integrated System for Plasmonic-Based Sensing

The smart integration of multiple devices in a single functional unit is boosting the advent of compact optical sensors for on-site analysis. Nevertheless, the development of miniaturized and cost-effective plasmonic sensors is hampered by the strict angular constraints of the detection scheme, which are fulfilled through bulky optical components. Here, an ultracompact system for plasmonic-sensing is demonstrated by the smart integration of an organic light-emitting transistor (OLET), an organic photodiode (OPD), and a nanostructured plasmonic grating (NPG). The potential of OLETs, as planar multielectrode devices with inherent micrometer-wide emission areas, offers the pioneer incorporation of an OPD onto the source electrode to obtain a monolithic photonic module endowed with light-emitting and light-detection characteristics at unprecedented lateral proximity of them. This approach enables the exploitation of the angle-dependent sensing of the NPG in a miniaturized system based on low-cost components, in which a reflective detection is enabled by the elegant fabrication of the NPG onto the encapsulation glass of the photonic module. The most effective layout of integration is unraveled by an advanced simulation tool, which allows obtaining an optics-less plasmonic system able to perform a quantitative detection up to 10⁻² RIU at a sensor size as low as 0.1 cm³.     

J-Type Self-Assembled Supramolecular Polymers for High-Performance and Fast-Response n-Type Organic Electrochemical Transistors

To date, high-performance organic electrochemical transistors (OECTs) are almost all based on conjugated polymers. Small molecules can be synthesized with high purity without batch-to-batch variations. However, small molecules require highly crystalline films and good molecular packings to achieve high charge carrier mobilities. Such features make their films unsuitable for ion diffusion or make their molecular packing distorted due to ion diffusion, resulting in poor ion/charge carrier transport properties and slow response speed. Herein, it is proposed to construct small-molecule-based supramolecular polymers to address these issues. A molecule, namely TDPP-RD-G7 is designed, which exhibits J-type self-assembling behaviors and can form supramolecular polymers in solution and conjugated-polymer-like networks in solid state. More importantly, the porous supramolecular polymer networks allow fast ion diffusion and greatly increase the device response speeds. As a result, the TDPP-RD-G7 exhibits record fast response speeds (τ_on/τ_off) of 10.5/0.32 ms with high figure-of-merit (µC*) of 5.88 F cm⁻¹ V⁻¹ s⁻¹ in small-molecule OECTs. This work reveals the possible reasons that hinder the response speeds in small-molecule OECTs and demonstrates a new “supramolecular polymer” approach to high-performance and fast-response small-molecule-based OECTs.     

Tuning the Transconductance of Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) operate at very low voltages, transduce ions into electronic signals, and reach extremely large transconductance values, making them ideally suited for bio-sensing applications. However, despite their promising performance, the dependence of their maximum transconductance on device geometry and applied voltages are not correctly captured by current capacitive device models. Here, current scaling laws are revised in the light of a recently developed 2D device model that adequately accounts for drift and diffusion of ions inside the polymer channel. It is shown that the maximum transconductance of the devices is found at the transition between the depletion and accumulation region of the transistors, which as well provides an explanation for the observed shift of the transconductance peak with geometric dimensions and the drain potential. Overall, the results provide a better understanding of the working mechanisms of OECTs, and facilitate design rules to optimize OECT performance further.     

An Iontronic Multiplexer Based on Spatiotemporal Dynamics of Multiterminal Organic Electrochemical Transistors

The seamless integration of electronics with biology requires new bio-inspired approaches that, analogously to nature, rely on the presence of electrolytes for signal multiplexing. On the contrary, conventional multiplexing schemes mostly rely on electronic carriers and require peripheral circuitry for their implementation, which imposes severe limitations toward their adoption in bio-applications. Here, a bio-inspired iontronic multiplexer based on spatiotemporal dynamics of organic electrochemical transistors (OECTs), with an electrolyte as the shared medium of communication, is shown. The iontronic system discriminates locally random-access events with no need of peripheral circuitry or address assignment, thus deceasing significantly the integration complexity. The form factors of OECTs that allow for intimate biointerfacing as well as the electrochemical nature of the communication medium, open new avenues for unconventional multiplexing in the emerging fields of bioelectronics, wearables, and neuromorphic computing or sensing.     

High-Speed Operation of Electrochemical Logic Circuits Depending on 3D Construction of Transistor Architectures

The emergence of organic electrochemical transistors (OECTs) has opened a new era of printable electronics and bioelectronics, due to their unique advantages including innately superior transconductance and biocompatibility. Despite the foreseeable advancements available from their further implementations in fundamental logic circuitry, however, insufficient operation speeds and short compatibilities to scaling-down have so far hindered advanced integrations other than biosensing and biosignal amplifications. Here, a 3D-construction-dependent operational analysis of OECTs is reported, with which an all-vertical architectural design enabled unprecedentedly high operating speed and a facile expansion to large-area and high-density 3D crossbar arrays. A simple vertical channel architecture completed with solid-state Ag/AgCl top-gate electrodes enables an ultrafast redistribution of ions within channels, yielding a state-of-the-art operation frequency reaching 12 MHz V⁻¹. Various printed logic circuit arrays, including NOT, NAND, and NOR gates, with high stability and reproducibility.     

Single-Component CMOS-Like Logic using Diketopyrrolopyrrole-Based Ambipolar Organic Electrochemical Transistors

Complementary circuits based on organic electrochemical transistors (OECTs) are attractive for the development of inexpensive and disposable point-of-care bioelectronic devices. Ambipolar OECTs, which employ a single channel material, could decrease the fabrication complexity and manufacturing costs of such circuits. An ideal channel material for ambipolar OECTs should be electrochemically stable in aqueous environments, afford facile ion insertion for both cations and anions, and also facilitate high and balanced electron and hole transport. In this study, triethylene glycol functionalized diketopyrrolopyrrole (DPP)-based polymer is proposed for the development of ambipolar OECTs. It is shown that DPP-based OECTs have a high and comparable figure of merit for both n- and p-type operations. Logic NOT, NAND, and NOR operations with corresponding complementary circuits constructed from identical DPP-based OECT devices are demonstrated. This study is an important step toward the development of sophisticated complementary metal–oxide–semiconductor-like logic circuits using single-component OECTs.     

Membrane‐Free Detection of Metal Cations with an Organic Electrochemical Transistor

Alkali‐metal ions, particularly sodium (Na⁺) and potassium (K⁺), are the messengers of living cells, governing a cascade of physiological processes through the action of ion channels. Devices that can monitor, in real time, the concentrations of these cations in aqueous media are in demand not only for the study of cellular machinery, but also to detect conditions in the human body that lead to electrolyte imbalance. In this work, conducting polymers are developed that respond rapidly and selectively to varying concentrations of Na⁺ and K⁺ in aqueous media. These polymer films, bearing crown‐ether‐functionalized thiophene units specific to either Na⁺ or K⁺, generate an electrical output proportional to the cation type and concentration. Using electropolymerization, the ion‐selective polymers are integrated as the gate electrode of an organic electrochemical transistor (OECT). The OECT current changes with respect to the concentration of the ion to which the polymer electrode is selective. Designed as a single, miniaturized chip, the OECT enables the selective detection of the cations within a physiologically relevant range. These electrochemical ion sensors require neither ion‐selective membranes nor a reference electrode to operate and have the potential to surpass existing technologies for the detection of alkali‐metal ions in aqueous media.     

Measurement of Electrophysiological Signals In Vitro Using High-Performance Organic Electrochemical Transistors

Biological environments use ions in charge transport for information transmission. The properties of mixed electronic and ionic conductivity in organic materials make them ideal candidates to transduce physiological information into electronically processable signals. A device proven to be highly successful in measuring such information is the organic electrochemical transistor (OECT). Previous electrophysiological measurements performed using OECTs show superior signal-to-noise ratios than electrodes at low frequencies. Subsequent development has significantly improved critical performance parameters such as transconductance and response time. Here, interdigitated-electrode OECTs are fabricated on flexible substrates, with one such state-of-the-art device achieving a peak transconductance of 139 mS with a 138 µs response time. The devices are implemented into an array with interconnects suitable for micro-electrocorticographic application and eight architecture variations are compared. The two best-performing arrays are subject to the full electrophysiological spectrum using prerecorded signals. With frequency filtering, kHz-scale frequencies with 10 µV-scale voltages are resolved. This is supported by a novel quantification of the noise, which compares the gate voltage input and drain current output. These results demonstrate that high-performance OECTs can resolve the full electrophysiological spectrum and suggest that superior signal-to-noise ratios could be achieved in high frequency measurements of multiunit activity.     

Porous Organic Field‐Effect Transistors for Enhanced Chemical Sensing Performances

The thin‐film structures of chemical sensors based on conventional organic field‐effect transistors (OFETs) can limit the sensitivity of the devices toward chemical vapors, because charge carriers in OFETs are usually concentrated within a few molecular layers at the bottom of the organic semiconductor (OSC) film near the dielectric/semiconductor interface. Chemical vapor molecules have to diffuse through the OSC films before they can interact with charge carriers in the OFET conduction channel. It has been demonstrated that OFET ammonia sensors with porous OSC films can be fabricated by a simple vacuum freeze‐drying template method. The resulted devices can have ammonia sensitivity not only much higher than the pristine OFETs with thin‐film structure but also better than any previously reported OFET sensors, to the best of our knowledge. The porous OFETs show a relative sensitivity as high as 340% ppm^?1 upon exposure to 10 parts per billion (ppb) NH₃. In addition, the devices also exhibit decent selectivity and stability. This general and simple strategy can be applied to a wide range of OFET chemical sensors to improve the device sensitivity.