High-Performance Organic Electrochemical Transistors Research Articles

Amphiphilic Interface-Mediated Ion Doping for High Performance Organic Electrochemical Transistors with Hydrophobic Polymers.

An organic electrochemical transistor (OECT) is one of the promising devices for bioelectronics due to its high transconductance, encompassing low operation voltage, and good compatibility with aqueous conditions. Despite these advantages, the challenge of balancing ion penetration and electron transport remains a significant issue in OECTs. Herein, we present an amphiphilic interface modification strategy to successfully prepare OECTs in aqueous conditions based on a high-mobility hydrophobic polypyrrole derivative. An amphiphilic interface mixed with an amphiphilic polymer and the active layer markedly promotes ion penetration and results in a significant improvement in performance, with the switch time reduced from several seconds to nearly 100 ms and the transconductance increased by an order of magnitude. The high-performance OECTs fabricated by this method show promising applications in high-performance neuromorphic devices and ECG recording in advancing the field of electrochemical transistors.

High-Performance Organic Electrochemical Transistors Achieved by Optimizing Structural and Energetic Ordering of Diketopyrrolopyrrole-Based Polymers.

For optimizing steady-state performance in organic electrochemical transistors (OECTs), both molecular design and structural alignment approaches must work in tandem to minimize energetic and microstructural disorders in polymeric mixed ionic-electronic conductor films. Herein, a series of poly(diketopyrrolopyrrole)s bearing various lengths of aliphatic-glycol hybrid side chains (PDPP-mEG; m = 2-5) is developed to achieve high-performance p-type OECTs. PDPP-4EG polymer with the optimized length of side chains exhibits excellent crystallinity owing to enhanced lamellar and backbone interactions. Furthermore, the improved structural ordering in PDPP-4EG films significantly decreases trap state density and energetic disorder. Consequently, PDPP-4EG-based OECT devices produce a mobility-volumetric capacitance product ([µC*]) of 702 F V-1 cm-1 s-1 and a hole mobility of 6.49 ± 0.60 cm2 V-1 s-1 . Finally, for achieving the optimal structural ordering along the OECT channel direction, a floating film transfer method is employed to reinforce the unidirectional orientation of polymer chains, leading to a substantially increased figure-of-merit [µC*] to over 800 F V-1 cm-1 s-1 . The research demonstrates the importance of side chain engineering of polymeric mixed ionic-electronic conductors in conjunction with their anisotropic microstructural optimization to maximize OECT characteristics.

Screen-Printed Piezoelectric Sensors on Tattoo Paper Combined with All-Printed High-Performance Organic Electrochemical Transistors for Electrophysiological Signal Monitoring.

This work demonstrates sensitive and low-cost piezoelectric sensors on skin-friendly, ultrathin, and conformable substrates combined with organic electrochemical transistors (OECTs) for the detection and amplification of alternating low-voltage input signals. The fully screen-printed (SP) piezoelectric sensors were manufactured on commercially available tattoo paper substrates, while the all-printed OECTs, relying on an extended gate electrode architecture, were manufactured either by solely using SP or by combining SP and aerosol jet printing (AJP) on PET substrates. Applying a low-voltage signal (±25 mV) to the gate electrode of the SP+AJP OECT results in approximately five times higher current modulation as compared to the fully SP reference OECT. The tattoo paper-based substrate enables transfer of the SP piezoelectric sensor to the skin, which in turn allows for radial pulse monitoring when combined with the SP+AJP OECT; this is possible due to the ability of the conformable sensor to convert mechanical vibrations into voltage signals along with the highly sensitive current modulation ability of the transistor device to further amplify the output signal. The results reported herein pave the way toward all-printed fully conformable wearable devices with high sensitivity to be further utilized for the real-time monitoring of electrophysiological signals.

Carboxyl-Alkyl Functionalized Conjugated Polyelectrolytes for High Performance Organic Electrochemical Transistors.

Contemporary design principles for organic mixed ionic electronic conductors (OMIECs) are mostly based on the ethylene glycol moiety, which may not be representative of the OMIEC class as a whole. Furthermore, glycolated polymers can be difficult to synthesize and process effectively. As an emerging alternative, we present a series of polythiophenes functionalized with a hybrid carboxyl-alkyl side chain. By variation of the alkyl spacer length, a comprehensive evaluation of both the impact of carboxylic acid functionalization and alkyl spacer length was conducted. COOH-functionalization endows the polymer with preferential intrinsic low-swelling behavior and water processability to yield solvent-resistant conjugated polyelectrolytes while retaining substantial electroactivity in aqueous environments. Advanced in situ techniques, including time-resolved spectroelectrochemistry and Raman spectroscopy, are used to interrogate the materials' microstructure, ionic-electronic coupling, and operational stability in devices. To compare these materials' performance to state-of-the-art technology for the design of OMIECs, we benchmarked the materials and demonstrated significant application potential in both planar and interdigitated organic electrochemical transistors (OECTs). The polythiophene bearing carboxyl-butyl side chains exhibits greater electrochemical performance and faster doping kinetics within the polymer series, with a record-high OECT performance among conjugated polyelectrolytes ([μC*]pOECT = 107 ± 4 F cm-1 V-1 s-1). The results provide an enhanced understanding of structure-property relationships for conjugated polyelectrolytes operating in aqueous media and expand the materials options for future OMIEC development. Further, this work demonstrates the potential for conjugated polymers bearing alkyl-COOH side chains as a path toward robust OMIEC designs that may facilitate further facile (bio)chemical functionalization for a range of (bio)sensing applications.

High-performance organic electrochemical transistors gated with 3D-printed graphene oxide electrodes

High-performance organic electrochemical transistors gated with 3D-printed graphene oxide electrodes

Experimental design of stencil-printed high-performance organic electrochemical transistors

This study discusses a simple and cost-effective stencil-printing fabrication and optimization of high-performance organic electrochemical transistors through experimental design.

Proton-penetrable Nafion-induced phase separation in organic semiconductors for high-performance organic electrochemical transistors

By introducing proton-penetrable Nafion into the channel layer of OECTs, we realize a significant enhancement in transconductance and drop in response time, which are attributed to the promoted ion doping/de-doping of the channel induced by Nafion.

High Performance Organic Electrochemical Transistors and Logic Circuits Manufactured via a Combination of Screen and Aerosol Jet Printing Techniques

AbstractThis work demonstrates a novel fabrication approach based on the combination of screen and aerosol jet printing to manufacture fully printed organic electrochemical transistors (OECTs) and OECT‐based logic circuits on PET substrates with superior performances. The use of aerosol jet printing allows for a reduction of the channel width to ≈15 µm and the estimated volume by a factor of ≈40, compared to the fully screen printed OECTs. Hence, the OECT devices and OECT‐based logic circuits fabricated with the proposed approach emerge with a high ON/OFF ratio (103–104) and remarkably fast switching response, reaching an ON/OFF ratio of >103 in 4–8 ms, which is further demonstrated by a propagation delay time of just above 1 ms in OECT‐based logic inverter circuits operated at a frequency of 100 Hz. All‐printed monolithically integrated OECT‐based five‐stage ring oscillator circuits further validated the concept with a resulting self‐oscillation frequency of 60 Hz.

Stretchable Redox-Active Semiconducting Polymers for High-Performance Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) represent an emerging device platform for next-generation bioelectronics owing to the uniquely high amplification and sensitivity to biological signals. For achieving seamless tissue-electronics interfaces for accurate signal acquisition, skin-like softness and stretchability are essential requirements, but they have not yet been imparted onto high-performance OECTs, largely due to the lack of stretchable redox-active semiconducting polymers. Here, a stretchable semiconductor is reported for OECT devices, namely poly(2-(3,3'-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-[2,2'-bithiophen]-5)yl thiophene) (p(g2T-T)), which gives exceptional stretchability over 200% strain and 5000 repeated stretching cycles, together with OECT performance on par with the state-of-the-art. Validated by systematic characterizations and comparisons of different polymers, the key design features of this polymer that enable the combination of high stretchability and high OECT performance are a nonlinear backbone architecture, a moderate side-chain density, and a sufficiently high molecular weight. Using this highly stretchable polymer semiconductor, an intrinsically stretchable OECT is fabricated with high normalized transconductance (≈223 S cm-1 ) and biaxial stretchability up to 100% strain. Furthermore, on-skin electrocardiogram (ECG) recording is demonstrated, which combines built-in amplification and unprecedented skin conformability.

Highly stretchable organic electrochemical transistors with strain-resistant performance.

Realizing fully stretchable electronic materials is central to advancing new types of mechanically agile and skin-integrable optoelectronic device technologies. Here we demonstrate a materials design concept combining an organic semiconductor film with a honeycomb porous structure with biaxially prestretched platform that enables high-performance organic electrochemical transistors with a charge transport stability over 30-140% tensional strain, limited only by metal contact fatigue. The prestretched honeycomb semiconductor channel of donor-acceptor polymer poly(2,5-bis(2-octyldodecyl)-3,6-di(thiophen-2-yl)-2,5-diketo-pyrrolopyrrole-alt-2,5-bis(3-triethyleneglycoloxy-thiophen-2-yl) exhibits high ion uptake and completely stable electrochemical and mechanical properties over 1,500 redox cycles with 104 stretching cycles under 30% strain. Invariant electrocardiogram recording cycles and synapse responses under varying strains, along with mechanical finite element analysis, underscore that the present stretchable organic electrochemical transistor design strategy is suitable for diverse applications requiring stable signal output under deformation with low power dissipation and mechanical robustness.

Efficient Fabrication of Organic Electrochemical Transistors via Wet Chemical Processing.

A wet processing method to fabricate high-performance organic electrochemical transistors (OECTs) is reported. Wet chemical processing enables a simple and reliable patterning step, substituting several complex and expensive cleanroom procedures in the fabrication of OECTs. We fabricate depletion-mode OECTs based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and enhancement-mode OECTs based on a conjugated polyelectrolyte PCPDTBT-SO3K on rigid and flexible substrates using this wet processing method. We show that the wet chemical processing step can also serve as a chemical treatment to enhance the electrical properties of the active material in OECTs. To highlight the potential of the fabrication process in applications, a transistor-based chemical sensor is demonstrated, capable of detecting methylene blue, a popular redox reporter in biodetection and immunoassays, with good detectivity. Given the tremendous potential of OECTs in emerging technologies such as biosensing and neuromorphic computing, this simple fabrication process established herein will render the OECT platform more accessible for research and applications.

Designing Donor-Acceptor Copolymers for Stable and High-Performance Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are oft-used for bioelectronic applications, and a variety of OECT channel materials have been developed in recent years. However, the majority of these materials are still limited by long-term performance and stability challenges. To resolve these issues, we implemented a next-generation design of polymers for OECTs. Specifically, diketopyrrolopyrrole (DPP) building blocks were copolymerized with propylene dioxythiophene-based (Pro-based) monomers to create a donor-acceptor-type conjugated polymer (PProDOT-DPP). These PProDOT-DPP macromolecules were synthesized using a straightforward direct arylation polymerization synthetic route. The PProDOT-DPP polymer thin film exhibited excellent electrochemical response, low oxidation potential, and high crystallinity, as evidenced by spectroelectrochemical measurements and grazing incidence wide-angle X-ray scattering measurements. Thus, the resultant polymer thin films had high charge mobility and volumetric capacitance values (i.e., μC* as high as 310 F cm-1 V-1 s-1) when they were used as the active layer materials in OECT devices, which places PProDOT-DPP among the highest performing accumulation-mode OECT polymers reported to date. The performance of the PProDOT-DPP thin films was also retained for 100 cycles and over 2000 s of ON-OFF cycling, indicating the robust stability of the materials. Therefore, this effort provides a clear roadmap for the design of electrochemically active macromolecules for accumulation-mode OECTs, where crystalline acceptor cores are incorporated into an all-donor polymer. We anticipate that this will ultimately inspire future polymer designs to enable OECTs with both high electrical performance and operational stability.

Ultrahigh-Gain Organic Electrochemical Transistor Chemosensors Based on Self-Curled Nanomembranes.

Organic electrochemical transistors (OECTs) are technologically relevant devices presenting high susceptibility to physical stimulus, chemical functionalization, and shape changes-jointly to versatility and low production costs. The OECT capability of liquid-gating addresses both electrochemical sensing and signal amplification within a single integrated device unit. However, given the organic semiconductor time-consuming doping process and their usual low field-effect mobility, OECTs are frequently considered low-end category devices. Toward high-performance OECTs, microtubular electrochemical devices based on strain-engineering are presented here by taking advantage of the exclusive shape features of self-curled nanomembranes. Such novel OECTs outperform the state-of-the-art organic liquid-gated transistors, reaching lower operating voltage, improved ion doping, and a signal amplification with a >104 intrinsic gain. The multipurpose OECT concept is validated with different electrolytes and distinct nanometer-thick molecular films, namely, phthalocyanine and thiophene derivatives. The OECTs are also applied as transducers to detect a biomarker related to neurological diseases, the neurotransmitter dopamine. The self-curled OECTs update the premises of electrochemical energy conversion in liquid-gated transistors, yielding a substantial performance improvement and new chemical sensing capabilities within picoliter sampling volumes.

Strain-Engineering Induced Anisotropic Crystallite Orientation and Maximized Carrier Mobility for High-Performance Microfiber-Based Organic Bioelectronic Devices.

Despite the importance of carrier mobility, recent research efforts have been mainly focused on the improvement of volumetric capacitance in order to maximize the figure-of-merit, μC* (product of carrier mobility and volumetric capacitance), for high-performance organic electrochemical transistors. Herein, high-performance microfiber-based organic electrochemical transistors with unprecedentedly large μC* using highly ordered crystalline poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) microfibers with very high carrier mobilities are reported. The strain engineering via uniaxial tension is employed in combination with solvent-mediated crystallization in the course of drying coagulated fibers, resulting in the permanent preferential alignment of crystalline PEDOT:PSS domains along the fiber direction, which is verified by atomic force microscopy and transmission wide-angle X-ray scattering. The resultant strain-engineered microfibers exhibit very high carrier mobility (12.9 cm2 V-1 s-1 ) without the trade-off in volumetric capacitance (122Fcm-3 ) and hole density (5.8×1020 cm-3 ). Such advantageous electrical and electrochemical characteristics offer the benchmark parameter of μC* over ≈1500Fcm-1 V-1 s-1 , which is the highest metric ever reported in the literature and can be beneficial for realizing a new class of substrate-free fibrillar and/or textile bioelectronics in the configuration of electrochemical transistors and/or electrochemical ion pumps.

Ethylenedioxythiophene incorporated diketopyrrolopyrrole conjugated polymers for high-performance organic electrochemical transistors

Diketopyrrolopyrrole-based conjugated polymers with ethylenedioxythiophene and glycolated side chains are used in organic electrochemical transistors, which demonstrate low threshold voltage, a high on/off ratio, high stability and fast response.

High-Performance Organic Electrochemical Transistors with Nanoscale Channel Length and Their Application to Artificial Synapse.

Organic electrochemical transistors (OECTs) have attracted considerable interests for various applications ranging from biosensors to digital logic circuits and artificial synapses. However, the majority of reported OECTs utilize large channel length up to several or several tens of micrometers, which limits the device performance and leads to low transistor densities. Here, we demonstrate a new design of vertical OECT architecture with a nanoscale channel length down to ∼100 nm. The devices exhibit a high on-state current of over 20 mA under a low bias voltage of 0.5 V, a fast transient response of less than 300 μs, and an extraordinary transconductance up to 68.88 mS, representing a record-high value for OECTs. The excellent electrical performance is attributed to the novel structure with a nanoscale channel length defined by the channel material thickness, which is intrinsically different from that of conventional OECTs with the channel length limited by the lithography resolution. Owing to the low thermal budget, we fabricate flexible devices on a flexible substrate, which exhibit unprecedented endurance characteristics and mechanical robustness after 1000 blending cycles. Furthermore, the proposed device is capable of mimicking biological inhibitory synapses for application in intelligent artificial neural networks. Our work not only pushes the performance limit of OECTs but also opens up a new design of OECTs for high-performance biosensors, digital logic, and neuromorphic devices.

High-Performance Organic Electrochemical Transistors Based on Conjugated Polyelectrolyte Copolymers

A new generation of polythiophene-based polyelectrolytes is reported to address fundamental issues in organic electrochemical transistors (OECTs). In such devices, the semiconductor must be able to transport and store ions and possess simultaneously a very high electronic mobility. For this, the ion-conducting 6-(thiophen-3-yl) hexane-1-sulfonate tetramethylammonium monomer (THS–TMA+) is copolymerized with the hole-conducting 3-hexylthiophene (3HT) to obtain copolymers, PTHS–TMA+-co-P3HT 1–3 with a gradient architecture. The copolymers having up to 50 mol % 3HT content are easily oxidizable and are crystalline. Consequently, for the copolymers, a higher stability in water is achieved, thus reducing the amount of cross-linker needed to stabilize the film. Furthermore, OECTs using copolymers with 75 and 50 mol % of PTHS–TMA+ content exhibit 2–3 orders of magnitude higher ON/OFF ratio and an extremely lower threshold voltage (−0.15 V) compared to PTHS–TMA+. Additionally, high volumetric capacitance (C* > 100...

Molecular Design of Semiconducting Polymers for High-Performance Organic Electrochemical Transistors.

The organic electrochemical transistor (OECT), capable of transducing small ionic fluxes into electronic signals in an aqueous environment, is an ideal device to utilize in bioelectronic applications. Currently, most OECTs are fabricated with commercially available conducting poly(3,4-ethylenedioxythiophene) (PEDOT)-based suspensions and are therefore operated in depletion mode. Here, we present a series of semiconducting polymers designed to elucidate important structure–property guidelines required for accumulation mode OECT operation. We discuss key aspects relating to OECT performance such as ion and hole transport, electrochromic properties, operational voltage, and stability. The demonstration of our molecular design strategy is the fabrication of accumulation mode OECTs that clearly outperform state-of-the-art PEDOT-based devices, and show stability under aqueous operation without the need for formulation additives and cross-linkers.