Electrochemical Transistors Research Articles

Real-time and multiplexed detection of sodium and potassium ions using PEDOT:PSS OECT microarrays integrated with ion-selective membranes

In recent years, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT: PSS)-based organic electrochemical transistors (OECTs) have been intensively studied, and various applications have been explored, such as neural interfaces, cell electrophysiological recording and wearable electronics. Furthermore, PEDOT: PSS OECTs have gained attention for monitoring ion concentrations, such as sodium (Na+) and potassium (K+), across various fields, including environmental monitoring, clinical diagnostics, food quality control and even sweat monitoring. However, multiplexed sensing of such ions with high sensitivity and selectivity is still challenging. Therefore, this work presents a multiplexed sensing of ions with high sensitivity and selectivity utilizing PEDOT: PSS OECTs integrated with ion-selective membranes (ISMs). First, a microscale fabrication method for manufacturing OECT arrays based on PEDOT: PSS is described, and then the integration of Na+ and K+ISMs on OECT microarrays using the spin coating technique is introduced. A microfluidic cell was integrated with the OECTs for real-time measurement of Na+ and K+ ion concentrations in a controlled flow-through manner. Following this, the influence of the membrane composition and thickness on the sensing performance of the OECTs was statistically investigated. The OECTs displayed a consistent linear response towards the detected ion type in a concentration range from 1 to 100 mM, while exhibiting notable selectivity against the undesired ions. Our results indicate that a reduction in membrane composition and thickness leads to an increase in sensitivity, with the drawback of a decrease in selectivity for ion concentration detection. We optimized the ISMs for both ion types and utilized them on one and the same array for multiplexed monitoring of Na+ and K+ ion concentrations.

Performance of Organic Electrochemical Transistors with Ionic Liquid Crystal Elastomers as Solid Electrolytes.

Organic electrochemical transistors (OECTs) have emerged as attractive devices for bioelectronics, wearable electronics, soft robotics, and energy storage devices. The electrolyte, being a fundamental component of OECTs, plays a crucial role in their performance. Recently, it has been demonstrated that ionic liquid crystal elastomers (iLCEs) can be used as a solid electrolyte for OECTs. Their capabilities, however, have only been shown for relatively large size substrate-free OECTs. Here, we study the influence of the different alignments of iLCEs on steady state and transient behavior of OECTs using a lateral geometry with source, drain, and gate in the same plane. We achieve excellent electrical response with an ON/OFF switching ratio of >105 and minimal leakage current. The normalized maximum transconductance gm/w of the most sensitive iLCE was found to be 33 S m-1, which is one of the highest among all solid-state-based OECTs reported so far. Additionally, iLCEs show high stability and can be removed and reattached multiple times to the same OECT device without decreasing performance.

High‐Performance, Single‐Component Ambipolar Organic Electrochemical Transistors with Balanced n/p‐Type Properties for Inverter and Biosensor Applications

AbstractAmbipolar organic electrochemical transistors (OECTs) with a single organic mixed ionic‐electronic conductor (OMIEC) have unique advantages by reducing fabrication complexity and cost in complementary logic circuit and bioelectronic applications. However, the design and synthesis of high‐performance ambipolar OMIECs for efficient transport and coupling both cation/anion and electron/hole remain challenging. Herein, a donor–acceptor (D–A)‐typed ambipolar OMIEC polymer (DHF‐gTT) is presented, whose superior ambipolarity stems from the concurrent oligoethyleneglycol‐functionalized D/A units that facilitates cation/anion injection and transport. Additionally, the fluorination of acceptor unit improves both hole/electron transports due to the fully‐locked backbone and promotes electron injection by down‐shifting molecular energy levels. Consequently, DHF‐gTT‐based OECTs achieve balanced figure‐of‐merit (µC*) for both p‐type and n‐type operations (12.4–14.6 F cm−1 V−1 s−1), setting new benchmarks for ambipolar OECTs, in terms of n‐type µC* and electron/hole mobilities. Such ambipolar OECTs enable the inverter to achieve a record‐high gain (102 V/V) and associated n‐type and p‐type molecular detectors to offer real‐time and highly sensitive detection of histamine and hydrogen peroxide detection, respectively. These results indicate the effectiveness of judicious molecular design on achieving high‐performance ambipolar OMIECs, allowing the state‐of‐the‐art single‐component ambipolar OECTs for both highly integrated logic circuit and bioelectronic applications.

Experimentally verified organic electrochemical transistor model

The Bernards–Malliaras model, published in 2007, is the primary reference for the operation of organic electrochemical transistors (OECTs). It assumes that, as in most transistors, the electronic transport is drift only. However, in other electrochemical devices, such as batteries, the charge neutrality is accompanied by diffusion-only transport. Using detailed 2D device simulations of the entire structure while accounting for ionic and electronic conduction, we show that high ion density (>1019 cm−3) results in Debye screening of the drain–source bias at the electrodes’ interface. Hence, unlike the drift-only current in standard FETs or low ion density OECTs, the current in high ion density OECTs is diffusion only. Also, we show that since in OECTs, the volumetric capacitor and the semiconductor are one, the threshold voltage has a different meaning than that in FETs, where the semiconductor and the gate-oxide capacitor are distinct entities. We use the above insights to derive a new model useful to experimentalists. Lastly, we fabricated PEDOT:PSS fiber-OECTs and used the results to verify the model.

Small-Molecule Mixed Ionic-Electronic Conductors for Efficient N-Type Electrochemical Transistors: Structure-Function Correlations.

The fundamental challenge in electron-transporting organic mixed ionic-electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6-type/U-shaped non-fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1g to 3g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U-shaped/planar core, close π-π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion-electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high normalized transconductance of 25.29 S cm-1, an on/off current ratio of ~106, and a turn-on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY-based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long-range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small-molecule-based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small-molecule OMIECs.

Small‐Molecule Mixed Ionic‐Electronic Conductors for Efficient N‐Type Electrochemical Transistors: Structure‐Function Correlations

The fundamental challenge in electron‐transporting organic mixed ionic‐electronic conductors (OMIECs) is simultaneous optimization of electron and ion transport. Beginning from Y6‐type/U‐shaped non‐fullerene solar cell acceptors, we systematically synthesize and characterize molecular structures that address the aforementioned challenge, progressively introducing increasing numbers of oligoethyleneglycol (OEG; g) sidechains from 1g to 3g, affording OMIECs 1gY, 2gY, and 3gY, respectively. The crystal structure of 1gY preserves key structural features of the Yn series: a U‐shaped/planar core, close π‐π molecular stacking, and interlocked acceptor groups. Versus inactive Y6 and Y11, all of the new glycolated compounds exhibit mixed ion‐electron transport in both conventional organic electrochemical transistor (cOECT) and vertical OECT (vOECT) architectures. Notably, 3gY with the highest OEG density achieves a high normalized transconductance of 25.29 S cm‐1, an on/off current ratio of ~106, and a turn‐on/off response time of 94.7/5.7 ms in vOECTs. Systematic optoelectronic, electrochemical, architectural, and crystallographic analysis explains the superior 3gY‐based OECT performance in terms of denser ngY OEG content, increased crystallite dimensions with decreased long‐range crystalline order, and enhanced film hydrophilicity which facilitates ion transport and efficient redox processes. Finally, we demonstrate an efficient small‐molecule‐based complementary inverter using 3gY vOECTs, showcasing the bioelectronic applicability of these new small‐molecule OMIECs.

Inter‐Ion Mutual Repulsion Control for Nonvolatile Artificial Synapse

AbstractOrganic electrochemical transistors (OECTs) are promising candidates for artificial synapses to achieve high‐performance synaptic characteristics. While most research has focused on modifying the properties of organic semiconductors for efficient ion doping, there is a lack of systematic investigation into the relationship between ion‐mediated mechanisms and synaptic performance. In this study, an effective strategy for enhancing electrochemical doping and de‐doping by utilizing different coulombic anions is proposed. The findings reveal that doped ions in the channel layer affect inter‐ion interactions, influencing the non‐volatile effects by improving the doping performance of the synaptic device. Moreover, electrochemical analysis indicates that ions in the channel layer are sequentially de‐doped, enabling high linearity and symmetry. The fabricated devices demonstrate high‐performance synaptic properties including a retention time of ≈102 s with ≈50% retention over peak current and near‐ideal long‐term potentiation/long‐term depression (LTP/LTD) through effective electrochemical doping and de‐doping. These results show that controlling both the properties of organic semiconductors and ion interactions in the electrolyte is crucial for OECTs, opening up various applications for neuromorphic computing.

A plant based electrochemical device with transistor like behavior

Since its invention, transistor has become the fundamental building block of virtually all of today’s integrated circuits which constitute the electronics technology. In the present letter, we report the vegetal version of a self-powered electrochemical transistor, i.e., a device with an inherent energy source which exhibits energy-converting and amplifying-modulating properties. Surprisingly, at the interface constituted by the surface of an n-type germanium sample and a vegetal slice it become apparent that the surface of the n-type germanium passing anodic current acts as a multiplying collector for holes. Experimental transconductance characteristics show well-defined the cut-off, active and saturation regions. Likewise, since the collector is itself part of an electrolytic cell, device incorporates its own power supply. Thereby, it is able to reproduce an analogical AC signal via the DC electrolytic cell voltage. Furthermore, one of the most outstanding properties of the transistors is their DC current gain (hFE), which for commercially available small-signal transistors typically ranges 50–350, and for medium power transistors 15–70. The proposed device presents an hFE of 70 and 40 for the potato and apple based transistors respectively. Genuinely, this approach opens an alternative route for the development of a novel green electronics based on self-powered vegetative devices. Genuinely, this approach opens an alternative route for the development of a novel green electronics based on self-powered vegetative devices which could works as sensing devices for monitoring living plants during sow and harvest.

The New Era of Organic Field-Effect Transistors: Hybrid OECTs, OLEFETs and OFEWs

Advancements in electronic device technology have led to an exponential growth in demand for more efficient and versatile transistors. In this context, organic field-effect transistors (OFETs) have emerged as a promising alternative due to their unique properties and potential for flexible and low-cost applications. However, to overcome some of the inherent limitations of OFETs, the integration of organic materials with other materials and technologies has been proposed, giving rise to a new generation of hybrid devices. In this article, we explore the development and advances of organic field-effect transistors and highlight the growing importance of hybrid devices in this area. In particular, we focus on three types of emerging hybrid devices: organic electrochemical transistors (OECTs), organic light-emitting field-effect transistors (OLEFETs) and organic field-effect waveguides (OFEWs). These devices combine the advantages of organic materials with the unique capabilities of other technologies, opening up new possibilities in fields such as flexible electronics, bioelectronics, or optoelectronics. This article provides an overview of recent advances in the development and applications of hybrid transistors, highlighting their crucial role in the next generation of electronic devices.

High Performance Organic Mixed Ionic‐electronic Polymeric Conductor with Stability to Autoclave Sterilization

We present a series of newly developed donor‐acceptor (D‐A) polymers designed specifically for organic electrochemical transistors (OECTs) synthesized by a straightforward route. All polymers exhibited accumulation mode behavior in OECT devices, and tuning of the donor comonomer resulted in a three‐order‐of‐magnitude increase in transconductance. The best polymer gFBT‐g2T, exhibited normalized peak transconductance (gm,norm) of 298±10.4 S cm‐1 with a corresponding product of charge‐carrier mobility and volumetric capacitance, μC*, of 847 F V‐1 cm‐1 s‐1 and a μ of 5.76 cm2 V‐1 s‐1, amongst the highest reported to date. Furthermore, gFBT‐g2T exhibited exceptional temperature stability, maintaining the outstanding electrochemical performance even after undergoing a standard (autoclave) high pressure steam sterilization procedure. Steam treatment was also found to promote film porosity, with the formation of circular 200 – 400 nm voids. These results demonstrate the potential of gFBT‐g2T in p‐type accumulation mode OECTs, and pave the way for the use in implantable bioelectronics for medical applications.

Interfacial Stabilization of Organic Electrochemical Transistors Conferred Using Polythiophene-Based Conjugated Block Copolymers with a Hydrophobic Coil Design.

The recent interest in developing low-cost, biocompatible, and lightweight bioelectronic devices has focused on organic electrochemical transistors (OECTs), which have the potential to fulfill these requirements. In this study, three types of poly(3-hexylthiophene) (P3HT)-based block copolymers (BCPs) incorporating different insulating blocks (poly(nbutyl acrylate) (PBA), polystyrene, and poly(ethylene oxide) (PEO)) were synthesized for application in OECTs. The morphological, crystallographic, and electrochemical properties of these BCPs are systematically investigated. Accordingly, P3HT-b-PBA demonstrates superior performance in the KCl-based aqueous electrolyte, with a higher product of mobility and capacitance (μC*) at 170 F s-1 cm-1 V-1 than that of the P3HT homopolymer at 58 F s-1 cm-1 V-1. P3HT-b-PBA exhibits better stability over 50 ON/OFF switching cycles than do other BCPs and P3HT homopolymers. With regard to the performance in the KPF6-based aqueous electrolyte, P3HT-b-PBA outperforms with a higher μC* of 9.2 F s-1 cm-1 V-1 than that of 8.6 F s-1 cm-1 V-1 observed from P3HT. Notably, both polymers exhibited almost no decay in device performance over 110 ON/OFF switching cycles. The strongly different performance of polymers in these two electrolytes is due to the side chain's hydrophobicity and interdigitated lamellar structures, thereby retarding the doping kinetics of the highly hydrated Cl- ions compared with the slightly hydrated PF6- ions. Concerning the improved performance of P3HT-b-PBA, this is attributed to its soft and hydrophobic backbone. Our morphological and crystallographic analyses reveal that P3HT-b-PBA experiences minimal structural disorder when swelled by the electrolyte, maintaining its original structure better than the P3HT homopolymer and the hydrophilic BCP of P3HT-b-PEO. The hydrophobic nature of P3HT-b-PBA contributes to the stability of its backbone structure, ensuring enhanced capacitance during the operation of the OECT operation. These findings provide reassurance about the stability and performance of P3HT-b-PBA in the field of OECT applications. In summary, this study represents the first exploration of P3HT-based BCPs for OECT applications and investigates their structure-performance relationships in mixed ionic-electronic conductors.

Non-invasive Healthcare Analytical Platform Based on Organic Electrochemical Transistors

Non-invasive Healthcare Analytical Platform Based on Organic Electrochemical Transistors

Ultrathin Indium Tin Oxide Accumulation Mode Electrolyte‐Gated Transistors for Bioelectronics

AbstractElectrolyte‐gated field effect transistors and electrochemical transistors have emerged as powerful components for bioelectronic sensors and biopotential recording devices. A set of parameters must be considered when developing devices to amplify weak electrophysiological signals. These include maximum transconductance values, cut‐off frequencies, and large on/off current ratios. Organic polymer‐based devices have recently dominated the field, especially when considering flexibility as a key factor. Oxide semiconductors may also offer these features, as well as advantages like higher mobility. Herein, flexible, ultrathin, indium tin oxide (ITO) electrolyte‐gated transistors are reported. These accumulation‐mode devices combine n‐type operation with µe = 9.5 cm2 Vs−1, high transconductance (gm = 44 mS), and on/off ratios (105) as well as optically transparent layouts. While oxides are normally considered brittle, mechanically flexible ITO layers are obtained by room temperature deposition of amorphous layers onto parylene C. This process results in low strain, producing devices that survive bending. ITO electrochemically degrades, however, with cycling. To overcome this, the surface is passivated with high dielectric constant inert capping layers of Ta2O5 or Ta2O5/AlN. This greatly improves stability while preserving low gate voltages. Based on their overall performance, ITO‐based EGFETs are promising for bioelectronics.

Tactile sensory synapse based on organic electrochemical transistors with ionogel triboelectric layer

Recent advancements in artificial tactile sensory systems have significantly improved their ability to replicate the sensory functions of biological systems by integrating various sensory and synaptic components, yet these configurations often lack the efficiency and seamless integration seen in nature. To address these limitations, we introduce a monolithic artificial mechanoreceptor that combines an organic electrochemical transistor with an ionogel (IG), serving as both a mechano-responsive triboelectric sensing layer and a gate electrolyte. Triboelectrification upon mechanical stimulation using different materials produces an output voltage of the triboelectric generator which drives the movement of ions within the tribo-negative IG based on 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquid and poly(vinylidene fluoride-co-hexafluoropropylene), modulating de-doping of the poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) channel. This enhances synaptic functionalities such as spike number-dependent plasticity (SNDP) and spike duration-dependent plasticity (SDDP) during mechanical stimulation, allowing the device to mimic biological mechanoreceptors by sensing and converting external mechanical signals, including the number, force, and duration of touches, into synaptic plasticity. Furthermore, the device shows potential for material recognition using machine learning techniques, marking a significant advancement towards efficient artificial tactile systems.

Dynamic monitoring of a 3D-printed airway tissue model using an organic electrochemical transistor

Assessing the transepithelial resistance to ion flow in the presence of an electric field enables the evaluation of the integrity of the epithelial cell layer. In this study, we introduce an organic electrochemical transistor (OECT) interfaced with a 3D living tissue, designed to monitor the electrical resistance of cellular barriers in real-time. We have developed a non-invasive, tissue-sensing platform by integrating an inkjet-printed large-area OECT with a 3D-bioprinted multilayered airway tissue. This unique configuration enables the evaluation of epithelial barrier integrity through the dynamic response capabilities of the OECT. Our system effectively tracks the formation and integrity of 3D-printed airway tissues in both liquid-liquid and air-liquid interface culture environments. Furthermore, we successfully quantified the degradation of barrier function due to influenza A (H1N1) viral infection and the dose-dependent efficacy of oseltamivir (Tamiflu®) in mitigating this degradation. The tissue-electronic platform offers a non-invasive and label-free method for real-time monitoring of 3D artificial tissue barriers, without disturbing the cellular biology. It holds the potential for further applications in monitoring the structures and functions of 3D tissues and organs, significantly contributing to the advancement of personalized medicine.

The Effect of Organic Semiconductor Electron Affinity on Preventing Parasitic Oxidation Reactions Limiting Performance of n-Type Organic Electrochemical Transistors.

A key challenge in the development of organic mixed ionic-electronic conducting materials (OMIEC) for high performance electrochemical transistors is their stable performance in ambient. When operating in aqueous electrolyte, potential reactions of the electrochemically injected electrons with air and water could hinder their persistence, leading to a reduction in charge transport. Here, the impact of deepening the LUMO energy level of a series of electron-transporting semiconducting polymers is evaluated, and subsequently rendering the most common oxidation processes of electron polarons thermodynamically unfavorable, on organic electrochemical transistors (OECTs) performance. Employing time resolved spectroelectrochemistry with three analogous polymers having varying electron affinities (EA), it is found that an EA below the thermodynamic threshold for oxidation of its electron polarons by oxygen significantly improves electron transport and lifetime in air. A polymer with a sufficiently large EA and subsequent thermodynamically unfavorable oxidation of electron polarons is reported, which is used as the semiconducting layer in an OECT, in its neutral and N-DMBI doped form, resulting in an excellent and air-stable OECT performance. These results show a general design methodology to avoid detrimental parasitic reactions under ambient conditions, and the benefits that arise in electrical performance.

Switching Response in Organic Electrochemical Transistors by Ionic Diffusion and Electronic Transport.

The switching response in organic electrochemical transistors (OECT) is a basic effect in which a transient current occurs in response to a voltage perturbation. This phenomenon has an important impact on different aspects of the application of OECT, such as the equilibration times, the hysteresis dependence on scan rates, and the synaptic properties for neuromorphic applications. Here we establish a model that unites vertical ion diffusion and horizontal electronic transport for the analysis of the time-dependent current response of OECTs. We use a combination of tools consisting of a physical analytical model; advanced 2D drift-diffusion simulation; and the experimental measurement of a poly(3-hexylthiophene) (P3HT) OECT. We show the reduction of the general model to simple time-dependent equations for the average ionic/hole concentration inside the organic film, which produces a Bernards-Malliaras conservation equation coupled with a diffusion equation. We provide a basic classification of the transient response to a voltage pulse, and the correspondent hysteresis effects of the transfer curves. The shape of transients is basically related to the main control phenomenon, either the vertical diffusion of ions during doping and dedoping, or the equilibration of electronic current along the channel length.

A Universal Biocompatible and Multifunctional Solid Electrolyte in p-Type and n-Type Organic Electrochemical Transistors for Complementary Circuits and Bioelectronic Interfaces.

The development of soft and flexible devices for collection of bioelectrical signals is gaining momentum for wearable and implantable applications. Among these devices, organic electrochemical transistors (OECTs) stand out due to their low operating voltage and large signal amplification capable of transducing weak biological signals. While liquid electrolytes have demonstrated efficacy in OECTs, they limit its operating temperature and pose challenges for electronic packaging due to potential leakage. Conversely, solid electrolytes offer advantages such as mechanical flexibility, robustness against environmental factors, and ability to bridge the interface between rigid dry electronics systems and soft wet biological tissues. However, few systems have demonstrated generality and compatibility with a wide range of state-of-the-art organic mixed ionic-electronic conductors (OMIECs). This paper introduces a highly stretchable, flexible, biocompatible, self-healable gelatin-based solid-state electrolyte, compatible with both p- and n-type OMIEC channels while maintaining high performance and excellent stability. Furthermore, this nonvolatile electrolyte is stable up to 120°C and exhibits high ionic conductivity even in dry environment. Additionally, an OECT-based complementary inverter with a record-high normalized-gain of 228 V-1 and a corresponding ultralow static power consumption of 1 nW is demonstrated. These advancements pave the way for versatile applications ranging from bioelectronics to power-efficient implants.

Small signal analysis for the characterization of organic electrochemical transistors

A method for the characterization of organic electrochemical transistors (OECTs) based on small signal analysis is presented that allows to determine the electronic mobility as a function of continuous gate potential using a standard two-channel AC potentiostat. Vector analysis in the frequency domain allows to exclude parasitic components in both ionic and electronic conduction regardless of film thickness, thus resulting in a standard deviation as low as 4%. Besides the electronic mobility, small signal analysis of OECTs also provides information about a wide range of other parameters including the conductance, transconductance, conductivity and volumetric capacitance through a single measurement. General applicability of small signal analysis is demonstrated by characterizing devices based on n-type, p-type, and ambipolar materials operating in accumulation or depletion modes. Accurate benchmarking of organic mixed ionic-electronic conductors through small signal analysis can be anticipated to guide both materials development and the design of bioelectronic devices.

Light‐Broadened Faradaic Regime of Organic Electrochemical Transistors for Accelerated Amperometric Biodetection

Light‐Broadened Faradaic Regime of Organic Electrochemical Transistors for Accelerated Amperometric Biodetection