Microscopic Determination of Carrier Density and Mobility in Working Organic Electrochemical Transistors

A comprehensive understanding of electrochemical and physical phenomena originating the response of electrolyte‐gated transistors is crucial for improved handling and design of these devices. However, the lack of suitable tools for direct investigation of microscale effects has hindered the possibility to bridge the gap between experiments and theoretical models. In this contribution, a scanning probe setup is used to explore the operation mechanisms of organic electrochemical transistors by probing the local electrochemical potential of the organic film composing the device channel. Moreover, an interpretative model is developed in order to highlight the meaning of electrochemical doping and to show how the experimental data can give direct access to fundamental device parameters, such as local charge carrier concentration and mobility. This approach is versatile and provides insight into the organic semiconductor/electrolyte interface and useful information for materials characterization, device scaling, and sensing optimization.     

High‐Performance Vertical Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are promising transducers for biointerfacing due to their high transconductance, biocompatibility, and availability in a variety of form factors. Most OECTs reported to date, however, utilize rather large channels, limiting the transistor performance and resulting in a low transistor density. This is typically a consequence of limitations associated with traditional fabrication methods and with 2D substrates. Here, the fabrication and characterization of OECTs with vertically stacked contacts, which overcome these limitations, is reported. The resulting vertical transistors exhibit a reduced footprint, increased intrinsic transconductance of up to 57 mS, and a geometry‐normalized transconductance of 814 S m^?1. The fabrication process is straightforward and compatible with sensitive organic materials, and allows exceptional control over the transistor channel length. This novel 3D fabrication method is particularly suited for applications where high density is needed, such as in implantable devices.     

Fabric Organic Electrochemical Transistors for Biosensors

Flexible fabric biosensors can find promising applications in wearable electronics. However, high‐performance fabric biosensors have been rarely reported due to many special requirements in device fabrication. Here, the preparation of organic electrochemical transistors (OECTs) on Nylon fibers is reported. By introducing metal/conductive polymer multilayer electrodes on the fibers, the OECTs show very stable performance during bending tests. The devices with functionalized gates are successfully used as various biosensors with high sensitivity and selectivity. The fiber‐based OECTs are woven together with cotton yarns successfully by using a conventional weaving machine, resulting in flexible and stretchable fabric biosensors with high performance. The fabric sensors show much more stable signals in the analysis of moving aqueous solutions than planar devices due to a capillary effect in fabrics. The fabric devices are integrated in a diaper and remotely operated by using a mobile phone, offering a unique platform for convenient wearable healthcare monitoring.     

Highly Stable Conjugated Polyelectrolytes for Water‐Based Hybrid Mode Electrochemical Transistors

Hydrophobic, self‐doped conjugated polyelectrolytes (CPEs) are introduced as highly stable active materials for organic electrochemical transistors (OECTs). The hydrophobicity of CPEs renders films very stable in aqueous solutions. The devices operate at gate voltages around zero and show no signs of degradation when operated for 10⁴ cycles under ambient conditions. These properties make the produced OECTs ideal devices for applications in bioelectronics.     

A Microfluidic Ion Pump for In Vivo Drug Delivery

Implantable devices offer an alternative to systemic delivery of drugs for the treatment of neurological disorders. A microfluidic ion pump (µFIP), capable of delivering a drug without the solvent through electrophoresis, is developed. The device is characterized in vitro by delivering γ‐amino butyric acid to a target solution, and demonstrates low‐voltage operation, high drug‐delivery capacity, and high ON/OFF ratio. It is also demonstrated that the device is suitable for cortical delivery in vivo by manipulating the local ion concentration in an animal model and altering neural behavior. These results show that µFIPs represent a significant step forward toward the development of implantable drug‐delivery systems.     

Highly Sensitive Detection of Protein Biomarkers with Organic Electrochemical Transistors

The analysis of protein biomarkers is of great importance in the diagnosis of diseases. Although many convenient and low‐cost electrochemical approaches have been extensively investigated, they are not sensitive enough in the detection of protein biomarkers with low concentrations in physiological environments. Here, this study reports a novel organic‐electrochemical‐transistor‐based biosensor that can successfully detect cancer protein biomarkers with ultrahigh sensitivity. The devices are operated by detecting electrochemical activity on gate electrodes, which is dependent on the concentrations of proteins labeled with catalytic nanoprobes. The protein sensors can specifically detect a cancer biomarker, human epidermal growth factor receptor 2, down to the concentration of 10^?14 g mL^?1, which is several orders of magnitude lower than the detection limits of previously reported electrochemical approaches. Moreover, the devices can successfully differentiate breast cancer cells from normal cells at various concentrations. The ultrahigh sensitivity of the protein sensors is attributed to the inherent amplification function of the organic electrochemical transistors. This work paves a way for developing highly sensitive and low‐cost biosensors for the detection of various protein biomarkers in clinical analysis in the future.     

Dynamic and Tunable Threshold Voltage in Organic Electrochemical Transistors

In recent years, organic electrochemical transistors (OECTs) have found applications in chemical and biological sensing and interfacing, neuromorphic computing, digital logic, and printed electronics. However, the incorporation of OECTs in practical electronic circuits is limited by the relative lack of control over their threshold voltage, which is important for controlling the power consumption and noise margin in complementary and unipolar circuits. Here, the threshold voltage of OECTs is precisely tuned over a range of more than 1 V by chemically controlling the electrochemical potential at the gate electrode. This threshold voltage tunability is exploited to prepare inverters and amplifiers with improved noise margin and gain, respectively. By coupling the gate electrode with an electrochemical oscillator, single‐transistor oscillators based on OECTs with dynamic time‐varying threshold voltages are prepared. This work highlights the importance of electrochemistry at the gate electrode in determining the electrical properties of OECTs, and opens a path toward the system‐level design of low‐power OECT‐based electronics.     

Ion Exchange Gels Allow Organic Electrochemical Transistor Operation with Hydrophobic Polymers in Aqueous Solution

Conjugated-polymer-based organic electrochemical transistors (OECTs) are being studied for applications ranging from biochemical sensing to neural interfaces. While new polymers that interface digital electronics with the aqueous chemistry of life are being developed, the majority of high-performance organic transistor materials are poor at transporting biologically relevant ions. Here, the operating mode of an organic transistor is changed from that of an electrolyte-gated organic field-effect transistor (EGOFET) to that of an OECT by incorporating an ion exchange gel between the active layer and the aqueous electrolyte. This device works by taking up biologically relevant ions from solution and injecting more hydrophobic ions into the active layer. Using poly[2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene] as the active layer and a blend of an ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, and poly(vinylidene fluoride-co-hexafluoropropylene) as the ion exchange gel, four orders of magnitude improvement in device transconductance and a 100-fold increase in kinetics are demonstrated. The ability of the ion-exchange-gel OECT to record biological signals by measuring the action potentials of a Venus flytrap is demonstrated. These results show the possibility of using interface engineering to open up a wider palette of organic semiconductors as OECTs that can be gated by aqueous solutions.