Multi-phase semicrystalline microstructures drive exciton dissociation in neat plastic semiconductors

The optoelectronic properties of macromolecular semiconductors depend fundamentally on their solid-state microstructure. For example, the molecular-weight distribution influences polymeric- semiconductor properties via diverse microstructures; polymers of low weight-average molecular weight (Mw) form unconnected, extended-chain crystals, usually of a paraffinic structure. Because of the non-entangled nature of the relatively short-chain macromolecules, this leads to a polycrystalline, one-phase morphology. In contrast, with high-Mw materials, where average chain lengths are longer than the length between entanglements, two-phase morphologies, comprised of crystalline moieties embedded in largely unordered (amorphous) regions, are obtained. We investigate charge photogeneration processes in neat regioregular poly(3-hexylthiophene) (P3HT) of varying Mw by means of time-resolved photoluminescence (PL) spectroscopy. At 10 K, PL originating from recombination of long-lived charge pairs decays over microsecond timescales. Both the amplitude and decay rate distribution depend strongly on Mw. In films with dominant one-phase chain-extended microstructures, the delayed PL is suppressed as a result of a diminished yield of photoinduced charges, and its decay is significantly faster than in two-phase microstructures. However, independent of Mw, charge recombination regenerates singlet excitons in torsionally disordered chains forming more strongly coupled photophysical aggregates than those in the steady-state ensemble, with delayed PL lineshape reminiscent of that in paraffinic morphologies at steady state. We conclude that highly delocalized excitons in disordered regions between crystalline and amorphous phases dissociate extrinsically with yield and spatial distribution that depend intimately upon microstructure.Comment: 19 pages, 4 figure

Benchmarking organic mixed conductors for transistors.

Organic mixed conductors have garnered significant attention in applications from bioelectronics to energy storage/generation. Their implementation in organic transistors has led to enhanced biosensing, neuromorphic function, and specialized circuits. While a narrow class of conducting polymers continues to excel in these new applications, materials design efforts have accelerated as researchers target new functionality, processability, and improved performance/stability. Materials for organic electrochemical transistors (OECTs) require both efficient electronic transport and facile ion injection in order to sustain high capacity. In this work, we show that the product of the electronic mobility and volumetric charge storage capacity (µC*) is the materials/system figure of merit; we use this framework to benchmark and compare the steady-state OECT performance of ten previously reported materials. This product can be independently verified and decoupled to guide materials design and processing. OECTs can therefore be used as a tool for understanding and designing new organic mixed conductors

Voltage Amplifier Based on Organic Electrochemical Transistor.

Organic electrochemical transistors (OECTs) are receiving a great deal of attention as amplifying transducers for electrophysiology. A key limitation of this type of transistors, however, lies in the fact that their output is a current, while most electrophysiology equipment requires a voltage input. A simple circuit is built and modeled that uses a drain resistor to produce a voltage output. It is shown that operating the OECT in the saturation regime provides increased sensitivity while maintaining a linear signal transduction. It is demonstrated that this circuit provides high quality recordings of the human heart using readily available electrophysiology equipment, paving the way for the use of OECTs in the clinic

Organic Electrochemical Transistors

Organic electrochemical transistors (OECTs) leverage ion injection from an electrolyte into an organic semiconductor film to yield compelling advances in biological interfacing, printed logic circuitry and neuromorphic devices. Their defining characteristic is the coupling between electronic and ionic charges within the volume of an organic film. In this review we discuss the mechanism of operation and the materials that are being used, overview the various form factors, fabrication technologies and proposed applications, and take a critical look at the future of OECT research and development

Combined optical and electronic sensing of epithelial cells using planar organic transistors.

A planar, conducting-polymer-based transistor for combined optical and electronic monitoring of live cells provides a unique platform for monitoring the health of cells in vitro. Monitoring of MDCK-I epithelial cells over several days is shown, along with a demonstration of the device for toxicology studies, of use in future drug discovery or diagnostics applications

Using white noise to gate organic transistors for dynamic monitoring of cultured cell layers.

Impedance sensing of biological systems allows for monitoring of cell and tissue properties, including cell-substrate attachment, layer confluence, and the "tightness" of an epithelial tissue. These properties are critical for electrical detection of tissue health and viability in applications such as toxicological screening. Organic transistors based on conducting polymers offer a promising route to efficiently transduce ionic currents to attain high quality impedance spectra, but collection of complete impedance spectra can be time consuming (minutes). By applying uniform white noise at the gate of an organic electrochemical transistor (OECT), and measuring the resulting current noise, we are able to dynamically monitor the impedance and thus integrity of cultured epithelial monolayers. We show that noise sourcing can be used to track rapid monolayer disruption due to compounds which interfere with dynamic polymerization events crucial for maintaining cytoskeletal integrity, and to resolve sub-second alterations to the monolayer integrity

Conjugated Polymers in Bioelectronics.

The emerging field of organic bioelectronics bridges the electronic world of organic-semiconductor-based devices with the soft, predominantly ionic world of biology. This crosstalk can occur in both directions. For example, a biochemical reaction may change the doping state of an organic material, generating an electronic readout. Conversely, an electronic signal from a device may stimulate a biological event. Cutting-edge research in this field results in the development of a broad variety of meaningful applications, from biosensors and drug delivery systems to health monitoring devices and brain-machine interfaces. Conjugated polymers share similarities in chemical "nature" with biological molecules and can be engineered on various forms, including hydrogels that have Young's moduli similar to those of soft tissues and are ionically conducting. The structure of organic materials can be tuned through synthetic chemistry, and their biological properties can be controlled using a variety of functionalization strategies. Finally, organic electronic materials can be integrated with a variety of mechanical supports, giving rise to devices with form factors that enable integration with biological systems. While these developments are innovative and promising, it is important to note that the field is still in its infancy, with many unknowns and immense scope for exploration and highly collaborative research. The first part of this Account details the unique properties that render conjugated polymers excellent biointerfacing materials. We then offer an overview of the most common conjugated polymers that have been used as active layers in various organic bioelectronics devices, highlighting the importance of developing new materials. These materials are the most popular ethylenedioxythiophene derivatives as well as conjugated polyelectrolytes and ion-free organic semiconductors functionalized for the biological interface. We then discuss several applications and operation principles of state-of-the-art bioelectronics devices. These devices include electrodes applied to sense/trigger electrophysiological activity of cells as well as electrolyte-gated field-effect and electrochemical transistors used for sensing of biochemical markers. Another prime application example of conjugated polymers is cell actuators. External modulation of the redox state of the underlying conjugated polymer films controls the adhesion behavior and viability of cells. These smart surfaces can be also designed in the form of three-dimensional architectures because of the processability of conjugated polymers. As such, cell-loaded scaffolds based on electroactive polymers enable integrated sensing or stimulation within the engineered tissue itself. A last application example is organic neuromorphic devices, an alternative computing architecture that takes inspiration from biology and, in particular, from the way the brain works. Leveraging ion redistribution inside a conjugated polymer upon application of an electrical field and its coupling with electronic charges, conjugated polymers can be engineered to act as artificial neurons or synapses with complex, history-dependent behavior. We conclude this Account by highlighting main factors that need to be considered for the design of a conjugated polymer for applications in bioelectronics-although there can be various figures of merit given the broad range of applications, as emphasized in this Account

Sodium and Potassium Ion Selective Conjugated Polymers for Optical Ion Detection in Solution and Solid State

EPSRC. Grant Number: EP/G037515/1; EC FP7 Project SC2. Grant Number: 610115; EC FP7 Project ArtESun. Grant Number: 604397; EC FP7 POLYMED. Grant Number: 61253

Tattoo-Paper Transfer as a Versatile Platform for All-Printed Organic Edible Electronics

The use of natural or bioinspired materials to develop edible electronic devices is a potentially disruptive technology that can boost point-of-care testing. The technology exploits devices which can be safely ingested, along with pills or even food, and operated from within the gastrointestinal tract. Ingestible electronics could potentially target a significant number of biomedical applications, both as therapeutic and diagnostic tool, and this technology may also impact the food industry, by providing ingestible or food-compatible electronic tags that can smart track goods and monitor their quality along the distribution chain. We hereby propose temporary tattoo-paper as a simple and versatile platform for the integration of electronics onto food and pharmaceutical capsules. In particular, we demonstrate the fabrication of all-printed Organic Field-Effect Transistors (OFETs) on untreated commercial tattoo-paper, and their subsequent transfer and operation on edible substrates with a complex non-planar geometry