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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Reducing the Barrier Height in Organic Transistors

Abstract Reducing the Schottky barrier height and Fermi level de‐pinning in metal‐organic semiconductor contacts are crucial for enhancing the performance of organic transistors. The reduction of the Schottky barrier height in bottom‐contact top‐gate organic transistors is demonstrated by adding 1 nm thick atomic layer deposited Al 2 O 3 on the source and drain contacts. By using two different donor‐acceptor copolymers, both p‐ and n‐ type transistors are investigated. Temperature‐dependent current–voltage measurements from non‐treated, self‐assembled monolayer treated, and Al 2 O 3 treated Au source‐drain contact field‐effect transistors with varying channel lengths are carried out. The drain current versus drain voltage near zero gate voltage, which may be described by the thermionic emission model at temperatures above 150 K, allows the estimation of the Schottky barrier height ( φ B ). The Al 2 O 3 contact‐treated transistors show more than 40% lower φ B compared with the non‐treated contacts in the p ‐type transistor. Similarly, an isoindigo‐based transistor, with n ‐type transport, shows a reduction in φ B with Al 2 O 3 treated contacts suggesting that such ultrathin oxide layers provide a universal method for reducing the barrier height.

Ghobadi, Arash↗

The effect of residual palladium on the performance of organic electrochemical transistors

Organic electrochemical transistors are a promising technology for bioelectronic devices, with applications in neuromorphic computing and healthcare. The active component enabling an organic electrochemical transistor is the organic mixed ionic-electronic conductor whose optimization is critical for realizing high-performing devices. In this study, the influence of purity and molecular weight is examined for a p-type polythiophene and an n-type naphthalene diimide-based polymer in improving the performance and safety of organic electrochemical transistors. Our preparative GPC purification reduced the Pd content in the polymers and improved their organic electrochemical transistor mobility by ~60% and 80% for the p- and n-type materials, respectively. These findings demonstrate the paramount importance of removing residual Pd, which was concluded to be more critical than optimization of a polymer’s molecular weight, to improve organic electrochemical transistor performance and that there is readily available improvement in performance and stability of many of the reported organic mixed ionic-electronic conductors.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radical Polymer-Based Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are an emerging platform for bioelectronic applications. Significant effort has been placed in designing advanced polymers that simultaneously transport both charge and ions (i.e., macromolecules that are mixed conductors). Furthermore, the considerations for mixed organic conductors are often different from the established principles that are well-known in the solid-state organic electronics field; thus, the discovery of new OECT macromolecular systems is highly desired. Here, we demonstrate a new materials system by blending a radical polymer (i.e., a macromolecule with a nonconjugated backbone and with stable open-shell sites at its pendant group) with a frequently used conjugated polymer. Specifically, poly(4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl) (PTEO) was blended with poly(3-hexylthiophene) (P 3 HT) to create thin films with distinct closed-shell and open-shell domains. Importantly, the sharp and unique oxidation–reduction (redox) potential associated with the radical moieties of the PTEO chain provided a distinct actuation feature to the blended films that modulated the ionic transport of the OECT devices. In turn, this led to controlled regulation of the doping of the P 3 HT phase in the composite film. By decoupling the ionic and electronic transport into two distinct phases and by using an ion transport phase with well-controlled redox activity, never-before-seen performance for a P3HT-based OECT was observed. That is, at loadings as low as 5% PTEO (by weight) OECTs achieved figure-of-merit (i.e., μC*) values >150 F V –1 cm –1 s –1 , which place the performance on the same order as state-of-the-art conjugated polymers despite the relatively common conjugated macromolecular moiety implemented. As such, this effort presents a design platform by which to readily create a tailored OECT response through strategic macromolecular selection and polymer processing.

36 MATERIALS SCIENCE↗

Salts as Additives: A Route to Improve Performance and Stability of n-Type Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) are becoming increasingly ubiquitous in various applications at the interface with biological systems. However, their widespread use is hampered by the scarcity of electron-conducting (n-type) backbones and the poor performance and stability of the existing n-OECTs. Here, we introduce organic salts as a solution additive to improve the transduction capability, shelf life, and operational stability of n-OECTs. We demonstrate that the salt-cast devices present a 10-fold increase in transconductance and achieve at least one year-long stability, while the pristine devices degrade within four months of storage. The salt-added films show improved backbone planarity and greater charge delocalization, leading to higher electronic charge carrier mobility. These films show a distinctly porous morphology where the interconnectivity is affected by the salt type, responsible for OECT speed. The salt-based films display limited changes in morphology and show lower water uptake upon electrochemical doping, a possible reason for the improved device cycling stability. Our work provides a new and easy route to improve n-type OECT performance and stability, which can be adapted for other electrochemical devices with n-type films operating at the aqueous electrolyte interface.

36 MATERIALS SCIENCE↗

New Chemical Dopant and Counterion Mechanism for Organic Electrochemical Transistors and Organic Mixed Ionic–Electronic Conductors

Abstract Organic mixed ionic–electronic conductors (OMIECs) have varied performance requirements across a diverse application space. Chemically doping the OMIEC can be a simple, low‐cost approach for adapting performance metrics. However, complex challenges, such as identifying new dopant materials and elucidating design rules, inhibit its realization. Here, these challenges are approached by introducing a new n‐dopant, tetrabutylammonium hydroxide (TBA‐OH), and identifying a new design consideration underpinning its success. TBA‐OH behaves as both a chemical n‐dopant and morphology additive in donor acceptor co‐polymer naphthodithiophene diimide‐based polymer, which serves as an electron transporting material in organic electrochemical transistors (OECTs). The combined effects enhance OECT transconductance, charge carrier mobility, and volumetric capacitance, representative of the key metrics underpinning all OMIEC applications. Additionally, when the TBA + counterion adopts an “edge‐on” location relative to the polymer backbone, Coulombic interaction between the counterion and polaron is reduced, and polaron delocalization increases. This is the first time such mechanisms are identified in doped‐OECTs and doped‐OMIECs. The work herein therefore takes the first steps toward developing the design guidelines needed to realize chemical doping as a generic strategy for tailoring performance metrics in OECTs and OMIECs.

36 MATERIALS SCIENCE↗

Flexible carbon-based ohmic contacts for organic transistors

The present invention relates to a system and method of organic thin-film transistors (OTFTs). More specifically, the present invention relates to employing a flexible, conductive particle-polymer composite material for ohmic contacts (i.e. drain and source).

Brandon, Erik↗

Flexible, Carbon-Based Ohmic Contacts for Organic Transistors

A low-temperature process for fabricating flexible, ohmic contacts for use in organic thin-film transistors (OTFTs) has been developed. Typical drainsource contact materials used previously for OTFTs include (1) vacuum-deposited noble-metal contacts and (2) solution-deposited intrinsically conducting molecular or polymeric contacts. Both of these approaches, however, have serious drawbacks.

Brandon, Erik↗

Stretchable Redox‐Active Semiconducting Polymers for High‐Performance Organic Electrochemical Transistors

Abstract 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.

36 MATERIALS SCIENCE↗

A Semiconducting Two‐Dimensional Polymer as an Organic Electrochemical Transistor Active Layer

Abstract Organic electrochemical transistors (OECTs) are devices with broad potential in bioelectronic sensing, circuits, and neuromorphic hardware. Their unique properties arise from the use of organic mixed ionic/electronic conductors (OMIECs) as the active channel. Typical OMIECs are linear polymers, where defined and controlled microstructure/morphology, and reliable characterization of transport and charging can be elusive. Semiconducting two‐dimensional polymers (2DPs) present a new avenue in OMIEC materials development, enabling electronic transport along with precise control of well‐defined channels ideal for ion transport/intercalation. To this end, a recently reported 2DP, TIIP, is synthesized and patterned at 10 µm resolution as the channel of a transistor. The TIIP films demonstrate textured microstructure and show semiconducting properties with accessible oxidation states. Operating in an aqueous electrolyte, the 2DP‐OECT exhibits a device‐scale hole mobility of 0.05 cm 2 V –1 s –1 and a µ C * figure of merit of 1.75 F cm –1 V –1 s –1 . 2DP OMIECs thus offer new synthetic degrees of freedom to control OECT performance and may enable additional opportunities such as ion selectivity or improved stability through reduced morphological modulation during device operation.

2D-polymer↗

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.

Bischak, Connor G.↗

Vertical organic electrochemical transistors for complementary circuits

Abstract Organic electrochemical transistors (OECTs) and OECT-based circuitry offer great potential in bioelectronics, wearable electronics and artificial neuromorphic electronics because of their exceptionally low driving voltages (<1 V), low power consumption (<1 µW), high transconductances (>10 mS) and biocompatibility 1–5 . However, the successful realization of critical complementary logic OECTs is currently limited by temporal and/or operational instability, slow redox processes and/or switching, incompatibility with high-density monolithic integration and inferior n-type OECT performance 6–8 . Here we demonstrate p- and n-type vertical OECTs with balanced and ultra-high performance by blending redox-active semiconducting polymers with a redox-inactive photocurable and/or photopatternable polymer to form an ion-permeable semiconducting channel, implemented in a simple, scalable vertical architecture that has a dense, impermeable top contact. Footprint current densities exceeding 1 kA cm −2 at less than ±0.7 V, transconductances of 0.2–0.4 S, short transient times of less than 1 ms and ultra-stable switching (>50,000 cycles) are achieved in, to our knowledge, the first vertically stacked complementary vertical OECT logic circuits. This architecture opens many possibilities for fundamental studies of organic semiconductor redox chemistry and physics in nanoscopically confined spaces, without macroscopic electrolyte contact, as well as wearable and implantable device applications.

Science & Technology - Other Topics↗

Engineering donor–acceptor conjugated polymers for high-performance and fast-response organic electrochemical transistors

To date, high-performance organic electrochemical transistors (OECTs) have mostly been based on polythiophene systems. Donor–acceptor (D–A) conjugated polymers are expected to be promising materials for OECTs owing to their high mobility and comparatively low crystallinity (good for ion diffusion). However, the OECT performance of D–A polymers lags far behind that of the polythiophenes. Here we synergistically engineered the backbone and side chain of a series of diketopyrrolopyrrole (DPP)-based D–A polymers and found that redox potential, molecular weight, solution processability, and film microstructures all have a severe impact on their performance. After systematic engineering, P(bgDPP-MeOT2) exhibited the best figure-of-merit (μC*) of 225 F cm -1 V -1 s -1 , amongst the highest performance of the reported D–A polymers. Besides, the DPP polymers exhibited high hole mobility of over 1.6 cm 2 V -1 s -1 , leading to fast response OECTs with a record low turn-off response time of 30 μs. The polymer also exhibited good operation stability with a current retention of 98.8% over 700 electrochemical switching cycles. This work reveals the complexity and systematicness in the development of D–A polymer based high-performance OECTs.

36 MATERIALS SCIENCE↗

Improved Organic Electrochemical Transistors via Directed Crystallizable Small Molecule Templating

Organic electrochemical transistors (OECTs) are of great interest as biosensors and for flexible electronics applications. Historically, processing techniques have been widely used to improve the performance of polymers in organic electronics but have been underutilized in the field of OECTs. Here, in this work, we study the effects of a crystallizable small molecule template for improving the performance of poly(3-hexylthiophene-2,5-diyl) (P3HT)-based OECTs. We utilize 1,3,5-trichlorobenzene (TCB) as a crystallizable additive to induce directional crystallization during blade coating. This procedure results in an aligned, highly ordered, and moderately porous layer of the semiconducting polymer. We find that compared to neat P3HT solutions, films cast with TCB additive show a greater than 8× improvement in the steady state figure of merit for OECTs. Additionally, the optimum TCB loading produces anisotropic OECTs where the polymer chain aligned parallel to the current outperforms the perpendicular alignment by more than a factor of 10. We investigated the mechanism of this improvement and found that polymer alignment, polymer ordering, and film porosity all play a role in improving the device performance. Overall, these results demonstrate the importance of processing on the optimization of polymers for OECTs and suggest a route to greatly improve the performance of commercially available hydrophobic polymers.

36 MATERIALS SCIENCE↗

Biomaterial–Based Solid–Electrolyte Organic Electrochemical Transistors for Electronic and Neuromorphic Applications

In this work a systematic study of biomaterial–based solid–state organic electrochemical transistors (OECTs) is presented in which biogels consisting of gelatin and glycerol, two food–grade materials, are chosen as the model solid electrolyte. Such gels are fundamentally attractive for bioelectronics and wearable applications due to their superior and tunable electrical and mechanical properties, which allow one to fabricate solid–state organic transistors with high ON/OFF ratio and transconductance, possible millisecond–switching speed, and 6–month stability in ambient air. Next, the authors show a good control of the state–retention property of biogel OECTs, demonstrated herein by employing them as artificial synapses with various synaptic functions, such as frequency–based short–term plasticity. This study herein paves the way for the development of biomaterial–based electronics by providing guiding principles for future works that employ biomaterials in OECTs.

36 MATERIALS SCIENCE↗

Tuning Organic Electrochemical Transistor Threshold Voltage using Chemically Doped Polymer Gates

Organic electrochemical transistors (OECTs) have shown promise as transducers and amplifiers of minute electronic potentials due to their large transconductances. Tuning the OECT threshold voltage is important to achieve low-powered devices with amplification properties within the desired operational voltage range. However, traditional design approaches have struggled to decouple channel and materials properties from threshold voltage, thereby compromising on several other OECT performance metrics, such as electrochemical stability, transconductance, and dynamic range. In this work, simple solution-processing methods are utilized to chemically dope polymer gate electrodes, thereby controlling their work function, which in turn tunes the operation voltage range of the OECTs without perturbing their channel properties. Chemical doping of initially air-sensitive polymer electrodes further improves their electrochemical stability in ambient conditions. Thus, OECTs that are simultaneously low-powered and electrochemically resistant to oxidative side reactions under ambient conditions are demonstrated. Furthermore, this approach shows that threshold voltage, which is once interwoven with other OECT properties, can in fact be an independent design parameter, expanding the design space of OECTs.

chemical doping↗

Additive-Induced Morphology Change of Polymer Film Enables Enhanced Charge Mobility and Faster Organic Electrochemical Transistor Switching

Conjugated polymers (CPs) play an important role in organic electrochemical transistors (OECTs) for bioelectronics and related applications, where they serve as channel materials. Currently, most successful polymers for CPs are re-engineered from traditional CPs by replacing hydrophobic alkyl side chains with hydrophilic ethylene glycol or ionic groups. Frustratingly, the enhanced ion transport often compromises the charge mobility of the original CP. In this work, we present an additive-mediated method to construct a modified poly(3-hexylthiophene) (P3HT) film to enable efficient ion migration. The additive is designed with a cleavable diazo group that releases nitrogen and 2-methoxyethanol, a volatile compound, to alter the P3HT film morphology. OECTs based on the film exhibit improved response times. Interestingly, the process also enhances the crystallinity of P3HT, leading to higher hole mobility compared with pristine P3HT. This study proposes an in situ strategy to achieve the functionality of the OMIEC via morphological regulation, offering a promising route to simultaneously enhance both ion accessibility and charge mobility.

Organic polymers↗