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.
Organic electrochemical transistors are attracting significant attention due to their excellent ability to transduce ionic into electrical fluxes, thus rendering them ideal devices for communication across the abiotic–biotic interface. This review covers the research progress on the various organic semiconductors employed as the channel materials, providing insights into structure–property relationships of current materials and design guidelines for future ones.
Organic mixed conductors are increasingly employed in electrochemical devices operating in aqueous solutions that leverage simultaneous transport of ions and electrons. Indeed, their mode of ...operation relies on changing their doping (oxidation) state by the migration of ions to compensate for electronic charges. Nevertheless, the structural and morphological changes that organic mixed conductors experience when ions and water penetrate the material are not fully understood. Through a combination of electrochemical, gravimetric, and structural characterization, the effects of water and anions with a hydrophilic conjugated polymer are elucidated. Using a series of sodium‐ion aqueous salts of varying anion size, hydration shells, and acidity, the links between the nature of the anion and the transport and structural properties of the polymer are systematically studied. Upon doping, ions intercalate in the crystallites, permanently modifying the lattice spacings, and residual water swells the film. The polymer, however, maintains electrochemical reversibility. The performance of electrochemical transistors reveals that doping with larger, less hydrated, anions increases their transconductance but decreases switching speed. This study highlights the complexity of electrolyte‐mixed conductor interactions and advances materials design, emphasizing the coupled role of polymer and electrolyte (solvent and ion) in device performance.
Electrochemical, gravimetric, and X‐ray characterization of organic mixed conductors reveals that structure and transport properties depend on the nature of the electrolyte's ions. Morphological and microstructural changes in the polymer upon swelling and doping are investigated. Anions and water penetrate the bulk of the polymer and can intercalate in the crystallites. Smaller anions exhibit faster transistor switching but lower transconductance.
Electrolyte-gated organic transistors offer low bias operation facilitated by direct contact of the transistor channel with an electrolyte. Their operation mode is generally defined by the ...dimensionality of charge transport, where a field-effect transistor allows for electrostatic charge accumulation at the electrolyte/semiconductor interface, whereas an organic electrochemical transistor (OECT) facilitates penetration of ions into the bulk of the channel, considered a slow process, leading to volumetric doping and electronic transport. Conducting polymer OECTs allow for fast switching and high currents through incorporation of excess, hygroscopic ionic phases, but operate in depletion mode. Here, we show that the use of glycolated side chains on a thiophene backbone can result in accumulation mode OECTs with high currents, transconductance, and sharp subthreshold switching, while maintaining fast switching speeds. Compared with alkylated analogs of the same backbone, the triethylene glycol side chains shift the mode of operation of aqueous electrolyte-gated transistors from interfacial to bulk doping/transport and show complete and reversible electrochromism and high volumetric capacitance at low operating biases. We propose that the glycol side chains facilitate hydration and ion penetration, without compromising electronic mobility, and suggest that this synthetic approach can be used to guide the design of organic mixed conductors.
Organic electrochemical transistors (OECTs) composed of organic mixed conductors can operate in aqueous, biological media and translate low-magnitude ionic fluctuations of biological origin into ...measurable electrical signals. The growing technological interest in these biotransducers makes the fundamental understanding of ion-to-electron coupling extremely important for the design of new materials and devices. One crucial aspect in this process that has been so far disregarded is the water taken up by the film during device operation and its effects on device performance. Here, using a series of the same electrolyte with varying ion concentrations, we quantify the amount of water that is incorporated into a hydrophilic p-type organic semiconductor film alongside the dopant anions and investigate structural and morphological changes occurring in the film upon electrochemical doping. We show that infiltration of the hydrated dopant ions into the film irreversibly changes the polymer structure and negatively impacts the efficiency, reversibility, and speed of charge generation. When less water is injected into the channel, OECTs exhibit higher transconductance and faster switching speeds. Although swelling is commonly suggested to be a necessity for efficient ion-to-electron transduction, this work uncovers the negative impact of a swollen channel material on the performance of accumulation mode OECTs and lays the foundation for future materials design.
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.
Avoiding faradaic side reactions during the operation of electrochemical devices is important to enhance the device stability, to achieve low power consumption, and to prevent the formation of ...reactive side‐products. This is particularly important for bioelectronic devices, which are designed to operate in biological systems. While redox‐active materials based on conducting and semiconducting polymers represent an exciting class of materials for bioelectronic devices, they are susceptible to electrochemical side‐reactions with molecular oxygen during device operation. Here, electrochemical side reactions with molecular oxygen are shown to occur during organic electrochemical transistor (OECT) operation using high‐performance, state‐of‐the‐art OECT materials. Depending on the choice of the active material, such reactions yield hydrogen peroxide (H2O2), a reactive side‐product, which may be harmful to the local biological environment and may also accelerate device degradation. A design strategy is reported for the development of redox‐active organic semiconductors based on donor–acceptor copolymers that prevents the formation of H2O2 during device operation. This study elucidates the previously overlooked side‐reactions between redox‐active conjugated polymers and molecular oxygen in electrochemical devices for bioelectronics, which is critical for the operation of electrolyte‐gated devices in application‐relevant environments.
Faradaic side‐reactions of redox‐active materials, that can produce harmful side‐products, should be minimized when employed in bioelectronic devices for studying biological systems. This work sheds light on side‐reactions with oxygen in state‑of‑the‑art materials for electrochemical transistors, forming hydrogen peroxide (H2O2), and provides design rules toward high‐performance materials that prevent adverse reactions by tailoring the energy levels of the redox‐active material.
Organic electrochemical transistors (OECTs) are receiving significant attention due to their ability to efficiently transduce biological signals. A major limitation of this technology is that only ...p-type materials have been reported, which precludes the development of complementary circuits, and limits sensor technologies. Here, we report the first ever n-type OECT, with relatively balanced ambipolar charge transport characteristics based on a polymer that supports both hole and electron transport along its backbone when doped through an aqueous electrolyte and in the presence of oxygen. This new semiconducting polymer is designed specifically to facilitate ion transport and promote electrochemical doping. Stability measurements in water show no degradation when tested for 2 h under continuous cycling. This demonstration opens the possibility to develop complementary circuits based on OECTs and to improve the sophistication of bioelectronic devices.
N-doping of conjugated polymers either requires a high dopant fraction or yields a low electrical conductivity because of their poor compatibility with molecular dopants. We explore n-doping of the ...polar naphthalenediimide–bithiophene copolymer p(gNDI-gT2) that carries oligoethylene glycol-based side chains and show that the polymer displays superior miscibility with the benzimidazole–dimethylbenzenamine-based n-dopant N-DMBI. The good compatibility of p(gNDI-gT2) and N-DMBI results in a relatively high doping efficiency of 13% for n-dopants, which leads to a high electrical conductivity of more than 10–1 S cm–1 for a dopant concentration of only 10 mol % when measured in an inert atmosphere. We find that the doped polymer is able to maintain its electrical conductivity for about 20 min when exposed to air and recovers rapidly when returned to a nitrogen atmosphere. Overall, solution coprocessing of p(gNDI-gT2) and N-DMBI results in a larger thermoelectric power factor of up to 0.4 μW K–2 m–1 compared to other NDI-based polymers.
This paper presents the development of alkali metal ion selective small molecules and conjugated polymers for optical ion sensing. A crown ether bithiophene unit is chosen as the detecting unit, as ...both a small molecule and incorporated into a conjugated aromatic structure. The complex formation and the resulting backbone twist of the detector unit is investigated by UV–vis and NMR spectroscopy where a remarkable selectivity toward sodium or potassium ions is found. X‐ray diffraction analysis of single crystals with and without alkali metal ions is carried out and a difference of the dihedral angle of more than 70° is observed. In a conjugated polymer structure, the detector unit has a higher sensitivity for alkali metal ion detection than its small molecule analog. Ion selectivity is retained in polymers with solubility in polar solvents facilitated by the attachment of polar ethylene glycol side chains. This design concept is further evolved to develop a sodium‐salt solid state sensor based on blends of the detecting polymer with a polyvinyl alcohol matrix where the detection of sodium ions is achieved in aqueous salt solutions with concentrations similar to biologically important environments.
Let's twist: Ion selective small molecules and conjugated polymers undergo a backbone twist in sodium‐ or potassium‐salt solutions. The color change of the polymers is detectable by the human eye and conjugated polymers have a higher sensitivity for ion detection compared to their analogous small molecule. Solid state sensors based on these polymers can detect alkali metal ions in aqueous solutions.
Conjugated polymers exhibit electrically driven volume changes when included in electrochemical devices via the exchange of ions and solvent. So far, this volumetric change is limited to 40% and 100% ...for reversible and irreversible systems, respectively, thus restricting potential applications of this technology. A conjugated polymer that reversibly expands by about 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000–10 000%, depending on the voltage applied is reported. From experimental and theoretical studies, it is found that this large and reversible volumetric switching is due to reorganization of the polymer during swelling as it transforms between a solid‐state phase and a gel, while maintaining percolation for conductivity. The polymer is utilized as an electroactive cladding to reduce the void sizes of a porous carbon filter electrode by 85%.
Conjugated polymers exhibit electrically driven volume changes when electrochemically switched. Here, a thiophene‐based polymer reversibly expands by 300% upon addressing, relative to its previous contracted state, while the first irreversible actuation can achieve values ranging from 1000–10 000%, depending on the applied voltage. Molecular dynamics reveal that the polymer transforms between a solid state to gelled state.