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.     

An Organic Electrochemical Transistor Integrated Photodetector for High Quality Photoplethysmogram Signal Acquisition

The organic photodiode (OPD) is a promising building block for solution-processable, flexible, lightweight, and miniaturized photodetectors, ideal for wearable applications. Despite the advances in materials used in OPDs, their photocurrent and light responsivity are limited, and alternative methods are required to boost the signal response. Herein, a miniaturized organic electrochemical transistor (OECT) is integrated with an OPD module to unlock the potential of OPDs to acquire physiological signals. In this integrated photodetector (IPD) system, the light intensity regulates the OPD voltage output that modulates the OECT channel current. The high transconductance of the OECT provides efficient voltage-to-current conversion, enhancing the signal-to-noise ratio on the sensing site. A microscale, p-type enhancement-mode OECT with high g_m and fast switching speed performs better in this application than depletion-mode OECT of the same geometry. The IPD achieves a photocurrent and responsivity 318 and 140 times higher than the standalone OPD, respectively. It is shown that with the IPD, the amplitude of the photoplethysmogram signals detected by the OPD is enhanced by a factor of 2.9 × 10³, highlighting its potential as a wearable biosensor and to detect weak, often uncaptured, light-based signals from living systems.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Synergistic Effect of Multi-Walled Carbon Nanotubes and Ladder-Type Conjugated Polymers on the Performance of N-Type Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) have the potential to revolutionize the field of organic bioelectronics. To date, most of the reported OECTs include p-type (semi-)conducting polymers as the channel material, while n-type OECTs are yet at an early stage of development, with the best performing electron-transporting materials still suffering from low transconductance, low electron mobility, and slow response time. Here, the high electrical conductivity of multi-walled carbon nanotubes (MWCNTs) and the large volumetric capacitance of the ladder-type π-conjugated redox polymer poly(benzimidazobenzophenanthroline) (BBL) are leveraged to develop n-type OECTs with record-high performance. It is demonstrated that the use of MWCNTs enhances the electron mobility by more than one order of magnitude, yielding fast transistor transient response (down to 15 ms) and high μC* (electron mobility × volumetric capacitance) of about 1 F cm^?1 V^?1 s^?1. This enables the development of complementary inverters with a voltage gain of >16 and a large worst-case noise margin at a supply voltage of <0.6 V, while consuming less than 1 µW of power.     

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.     

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.     

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.     

Balancing Ionic and Electronic Conduction for High‐Performance Organic Electrochemical Transistors

Conjugated polymers that support mixed (electronic and ionic) conduction are in demand for applications spanning from bioelectronics to energy harvesting and storage. To design polymer mixed conductors for high‐performance electrochemical devices, relationships between the chemical structure, charge transport, and morphology must be established. A polymer series bearing the same p‐type conjugated backbone with increasing percentage of hydrophilic, ethylene glycol side chains is synthesized, and their performance in aqueous electrolyte gated organic electrochemical transistors (OECTs) is studied. By using device physics principles and electrochemical analyses, a direct relationship is found between the OECT performance and the balanced mixed conduction. While hydrophilic side chains are required to facilitate ion transport—thus enabling OECT operation—swelling of the polymer is not de facto beneficial for balancing mixed conduction. It is shown that heterogeneous water uptake disrupts the electronic conductivity of the film, leading to OECTs with lower transconductance and slower response times. The combination of in situ electrochemical and structural techniques shown here contributes to the establishment of the structure–property relations necessary to improve the performance of polymer mixed conductors and subsequently of OECTs.     

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.     

Ultrathin Organic Electrochemical Transistor with Nonvolatile and Thin Gel Electrolyte for Long‐Term Electrophysiological Monitoring

Skin‐based electrical‐signal monitoring is one of the basic and noninvasive diagnostic methods for observing vital signals that contain valuable information about the dynamic status of the inner body. Soft bioelectronic devices are developed for the acquisition of high‐quality biosignals by taking advantage of their inherent thin and soft bodies. Among these devices, the organic electrochemical transistor (OECT) is a promising local transducing amplifier because of its key advantages, such as low operating voltage, high transconductance, and biocompatibility. However, the transistor's direct electrolyte‐gated operation limits its ability to measure biosignals only when the electrolyte exists. Here, an ultrathin OECT‐based wearable electrophysiological sensor based on a thin (≈6 µm) and nonvolatile gel electrolyte is reported, which can operate on dry biological surfaces. This sensor can measure biopotentials with a high mechanical stability and high signal‐to‐noise ratio (24 dB) even from dry surfaces of the human body and also shows stable performance during long‐term continuous monitoring and multiple reuse in a test that lasted more than a week.     

Flexible,Conformal Organic Synaptic Transistors on Elastomer for Biomedical Applications

Bioelectronics in synaptic transistors for future biomedical applications, such as implanted treatments and human–machine interfaces, must be flexible with good mechanical compatibility with biological tissues. The rigid nature and high deposition temperature in conventional inorganic synaptic transistors restrict the development of flexible, conformal synaptic devices. Here, the dinaphtho[2,3‐b:2′,3′‐f]thieno[3,2‐b]‐thiophene organic synaptic transistor on elastic polydimethylsiloxane is demonstrated to avoid these limitations. The unique advantages of organic materials in low Young's modulus and low temperature process enable seamless adherence of organic synaptic transistors on arbitrary‐shaped objects. On 3D curved surfaces, the essential synaptic functions, such as potentiation/depression, short/long‐term synaptic plasticity, and spike voltage–dependent plasticity, are successfully realized. The time‐dependent surface potential characterization reveals the slow polarization of dipoles in the dielectric is responsible for hysteresis and synaptic behaviors. This work represents that organic materials offer a potential platform to realize the flexible, conformal synaptic transistors for the development of wearable and implantable artificial neuromorphic systems.     

A Large Bandgap Organic Salt Dopant for Sn-Based Perovskite Thin-Film Transistor

Metal halide perovskite optoelectronic devices have made significant progress over the past few years, but precise control of charge carrier density through doping is essential for optimizing these devices. In this study, the potential of using an organic salt, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, as a dopant for Sn-based perovskite devices, is explored. Under optimized conditions, the thin film transistors based on the doped 2D/3D perovskite PEAFASnI₃ demonstrate remarkable improvement in hole mobility, reaching 7.45 cm²V⁻¹s⁻¹ with a low subthreshold swing and the smallest sweep hysteresis (ΔV_hysteresis = 2.27 V) and exceptional bias stability with the lowest contact resistance (2.2 kΩ cm). The bulky chemical structure of the dopant prevents it from penetrating the perovskite lattice and also surface passivation against Sn oxidation due to its hydrophobic nature surface. This improvement is attributed to the bifunctional effect of the dopant, which simultaneously passivates defects and improves crystal orientation. These findings provide new insights into potential molecular dopants that can be used in metal halide perovskite devices.     

Materials in Organic Electrochemical Transistors for Bioelectronic Applications: Past,Present, and Future

Organic electrochemical transistors are bioelectronic devices that exploit the coupled nature of ionic and electronic fluxes to achieve superior transducing abilities compared to conventional organic field effect transistors. In particular, the operation of organic electrochemical transistors relies on a channel material capable of conducting both ionic and electronic charge carriers to ensure bulk electrochemical doping. This review explores the various types of organic semiconductors that are employed as channel materials, with a particular focus on the past 5 years, during which the transducing abilities of organic electrochemical transistors have witnessed an almost tenfold increase. Specifically, the structure–property relationships of the various channel materials employed are investigated, highlighting how device performance can be related to functionality at the molecular level. Finally, an outlook on the field is provided, in particular toward the design guidelines of future materials and the challenges ahead in the field.