Stretchable Tissue-Like Gold Nanowire Composites with Long-Term Stability for Neural Interfaces.

Soft and stretchable nanocomposites can match the mechanical properties of neural tissue, thereby minimizing foreign body reactions to provide optimal stimulation and recording specificity. Soft materials for neural interfaces should simultaneously fulfill a wide range of requirements, including low Young's modulus (<<1 MPa), stretchability (≥30%), high conductivity (>> 1000 S cm-1), biocompatibility, and chronic stability (>> 1 year). Current nanocomposites do not fulfill the above requirements, in particular not the combination of softness and high conductivity. Here, this challenge is addressed by developing a scalable and robust synthesis route based on polymeric reducing agents for smooth, high-aspect ratio gold nanowires (AuNWs) of controllable dimensions with excellent biocompatibility. AuNW-silicone composites show outstanding performance with nerve-like softness (250 kPa), high conductivity (16 000 S cm-1), and reversible stretchability. Soft multielectrode cuffs based on the composite achieve selective functional stimulation, recordings of sensory stimuli in rat sciatic nerves, and show an accelerated lifetime stability of >3 years. The scalable synthesis method provides a chemically stable alternative to the widely used AgNWs, thereby enabling new applications within electronics, biomedical devices, and electrochemistry.

In Vivo Organic Bioelectronics for Neuromodulation.

The nervous system poses a grand challenge for integration with modern electronics and the subsequent advances in neurobiology, neuroprosthetics, and therapy which would become possible upon such integration. Due to its extreme complexity, multifaceted signaling pathways, and ∼1 kHz operating frequency, modern complementary metal oxide semiconductor (CMOS) based electronics appear to be the only technology platform at hand for such integration. However, conventional CMOS-based electronics rely exclusively on electronic signaling and therefore require an additional technology platform to translate electronic signals into the language of neurobiology. Organic electronics are just such a technology platform, capable of converting electronic addressing into a variety of signals matching the endogenous signaling of the nervous system while simultaneously possessing favorable material similarities with nervous tissue. In this review, we introduce a variety of organic material platforms and signaling modalities specifically designed for this role as "translator", focusing especially on recent implementation in in vivo neuromodulation. We hope that this review serves both as an informational resource and as an encouragement and challenge to the field.

Exploiting mixed conducting polymers in organic and bioelectronic devices.

Efficient transport of both ionic and electronic charges in conjugated polymers (CPs) has enabled a wide range of novel electrochemical devices spanning applications from energy storage to bioelectronic devices. In this Perspective, we provide an overview of the fundamental physical processes which underlie the operation of mixed conducting polymer (MCP) devices. While charge injection and transport have been studied extensively in both ionic and electronic conductors, translating these principles to mixed conducting systems proves challenging due to the complex relationships among the individual materials properties. We break down the process of electrochemical (de)doping, the basic feature exploited in mixed conducting devices, into its key steps, highlighting recent advances in the study of these physical processes in the context of MCPs. Furthermore, we identify remaining challenges in further extending fundamental understanding of MCP-based device operation. Ultimately, a deeper understanding of the elementary processes governing operation in MCPs will drive the advancement in both materials design and device performance.

Organic mixed ionic-electronic conductors.

Materials that efficiently transport and couple ionic and electronic charge are key to advancing a host of technological developments for next-generation bioelectronic, optoelectronic and energy storage devices. Here we highlight key progress in the design and study of organic mixed ionic-electronic conductors (OMIECs), a diverse family of soft synthetically tunable mixed conductors. Across applications, the same interrelated fundamental physical processes dictate OMIEC properties and determine device performance. Owing to ionic and electronic interactions and coupled transport properties, OMIECs demand special understanding beyond knowledge derived from the study of organic thin films and membranes meant to support either electronic or ionic processes only. We address seemingly conflicting views and terminology regarding charging processes in these materials, and highlight recent approaches that extend fundamental understanding and contribute to the advancement of materials. Further progress is predicated on multimodal and multi-scale approaches to overcome lingering barriers to OMIEC design and implementation.

Implantable Organic Electronic Ion Pump Enables ABA Hormone Delivery for Control of Stomata in an Intact Tobacco Plant.

Electronic control of biological processes with bioelectronic devices holds promise for sophisticated regulation of physiology, for gaining fundamental understanding of biological systems, providing new therapeutic solutions, and digitally mediating adaptations of organisms to external factors. The organic electronic ion pump (OEIP) provides a unique means for electronically-controlled, flow-free delivery of ions, and biomolecules at cellular scale. Here, a miniaturized OEIP device based on glass capillary fibers (c-OEIP) is implanted in a biological organism. The capillary form factor at the sub-100 µm scale of the device enables it to be implanted in soft tissue, while its hyperbranched polyelectrolyte channel and addressing protocol allows efficient delivery of a large aromatic molecule. In the first example of an implantable bioelectronic device in plants, the c-OEIP readily penetrates the leaf of an intact tobacco plant with no significant wound response (evaluated up to 24 h) and effectively delivers the hormone abscisic acid (ABA) into the leaf apoplast. OEIP-mediated delivery of ABA, the phytohormone that regulates plant's tolerance to stress, induces closure of stomata, the microscopic pores in leaf's epidermis that play a vital role in photosynthesis and transpiration. Efficient and localized ABA delivery reveals previously unreported kinetics of ABA-induced signal propagation.

Layer-by-Layer Assembly of High-Performance Electroactive Composites Using a Multiple Charged Small Molecule.

Layer-by-layer (LbL) assembly is a versatile tool for fabricating multilayers with tailorable nanostructures. LbL, however, generally relies on polyelectrolytes, which are mostly insulating and induce large interlayer distances. We demonstrate a method in which we replace polyelectrolytes with the smallest unit capable of LbL self-assembly: a molecule with multiple positive charges, tris(3-aminopropyl)amine (TAPA), to fabricate LbL films with negatively charged single-walled carbon nanotubes (CNTs). TAPA introduces less defects during the LbL build-up and results in more efficient assembly of films with denser micromorphology. Twenty bilayers of TAPA/CNT showed a low sheet resistance of 11 kΩ, a high transparency of 91% at 500 nm, and a high electronic conductivity of 1100 S/m on planar substrates. We also fabricated LbL films on porous foams with a conductivity of 69 mS/m and used them as electrodes for supercapacitors with a high specific capacitance of 43 F/g at a discharging current density of 1 A/g.

Organic Bioelectronics: Bridging the Signaling Gap between Biology and Technology.

The electronics surrounding us in our daily lives rely almost exclusively on electrons as the dominant charge carrier. In stark contrast, biological systems rarely use electrons but rather use ions and molecules of varying size. Due to the unique combination of both electronic and ionic/molecular conductivity in conducting and semiconducting organic polymers and small molecules, these materials have emerged in recent decades as excellent tools for translating signals between these two realms and, therefore, providing a means to effectively interface biology with conventional electronics-thus, the field of organic bioelectronics. Today, organic bioelectronics defines a generic platform with unprecedented biological recording and regulation tools and is maturing toward applications ranging from life sciences to the clinic. In this Review, we introduce the field, from its early breakthroughs to its current results and future challenges.

Thermoelectric materials and applications for energy harvesting power generation.

Thermoelectrics, in particular solid-state conversion of heat to electricity, is expected to be a key energy harvesting technology to power ubiquitous sensors and wearable devices in the future. A comprehensive review is given on the principles and advances in the development of thermoelectric materials suitable for energy harvesting power generation, ranging from organic and hybrid organic-inorganic to inorganic materials. Examples of design and applications are also presented.

Fast and Efficient Fabrication of Intrinsically Stretchable Multilayer Circuit Boards by Wax Pattern Assisted Filtration.

Intrinsically stretchable multilayer circuit boards are fabricated with a fast and material efficient method based on filtration. Silver nanowire conductor patterns of outstanding performance are defined by filtration through wax printed membranes and the circuit board is assembled by subsequent transfers of the nanowires onto the elastomer substrate. The method is used to fabricate a bright stretchable light emitting diode matrix display.

Modeling of charge transport in ion bipolar junction transistors.

Spatiotemporal control of the complex chemical microenvironment is of great importance to many fields within life science. One way to facilitate such control is to construct delivery circuits, comprising arrays of dispensing outlets, for ions and charged biomolecules based on ionic transistors. This allows for addressability of ionic signals, which opens up for spatiotemporally controlled delivery in a highly complex manner. One class of ionic transistors, the ion bipolar junction transistors (IBJTs), is especially attractive for these applications because these transistors are functional at physiological conditions and have been employed to modulate the delivery of neurotransmitters to regulate signaling in neuronal cells. Further, the first integrated complementary ionic circuits were recently developed on the basis of these ionic transistors. However, a detailed understanding of the device physics of these transistors is still lacking and hampers further development of components and circuits. Here, we report on the modeling of IBJTs using Poisson's and Nernst-Planck equations and the finite element method. A two-dimensional model of the device is employed that successfully reproduces the main characteristics of the measurement data. On the basis of the detailed concentration and potential profiles provided by the model, the different modes of operation of the transistor are analyzed as well as the transitions between the different modes. The model correctly predicts the measured threshold voltage, which is explained in terms of membrane potentials. All in all, the results provide the basis for a detailed understanding of IBJT operation. This new knowledge is employed to discuss potential improvements of ion bipolar junction transistors in terms of miniaturization and device parameters.

Exploring the Elastomer Influence on the Electromechanical Performance of Stretchable Conductors.

Stretchable electronics has received major attention in recent years due to the prospects of integrating electronics onto and into the human body. While many studies investigate how different conductive fillers perform in stretchable composites, the effect of different elastomers on composite performance, and the related fundamental understanding of what is causing the performance differences, is poorly understood. Here, we perform a systematic investigation of the elastomer influence on the electromechanical performance of gold nanowire-based stretchable conductors based on five chemically different elastomers of similar Young's modulus. The choice of elastomer has a huge impact on the electromechanical performance of the conductors under cyclic strain, as some composites perform well, while others fail rapidly at 100% strain cycling. The lack of macroscopic crack formation in the failing composites indicates that the key aspect for good electromechanical performance is not homogeneous films on the macroscale but rather beneficial interactions on the nanoscale. Based on the comprehensive characterization, we propose a failure mechanism related to the mechanical properties of the elastomers. By improving our understanding of elastomer influence on the mechanisms of electrical failure, we can move toward rational material design, which could greatly benefit the field of stretchable electronics.

Stretchable and biodegradable plant-based redox-diffusion batteries.

The redox-diffusion (RD) battery concept introduces an environmentally friendly solution for stretchable batteries in autonomous wearable electronics. By utilising plant-based redox-active biomolecules and cellulose fibers for the electrode scaffold, separator membrane, and current collector, along with a biodegradable elastomer encapsulation, the battery design overcomes the reliance on unsustainable transition metal-based active materials and non-biodegradable elastomers used in existing stretchable batteries. Importantly, it addresses the drawback of limited attainable battery capacity, where increasing the active material loading often leads to thicker and stiffer electrodes with poor mechanical properties. The concept decouples the active material loading from the mechanical structure of the electrode, enabling high mass loadings, while retaining a skin-like young's modulus and stretchability. A stretchable ion-selective membrane facilitates the RD process, allowing two separate redox couples, while preventing crossovers. This results in a high-capacity battery cell that is both electrochemically and mechanically stable, engineered from sustainable plant-based materials. Notably, the battery components are biodegradable at the end of their life, addressing concerns of e-waste and resource depletion.

Ion bipolar junction transistors.

Dynamic control of chemical microenvironments is essential for continued development in numerous fields of life sciences. Such control could be achieved with active chemical circuits for delivery of ions and biomolecules. As the basis for such circuitry, we report a solid-state ion bipolar junction transistor (IBJT) based on conducting polymers and thin films of anion- and cation-selective membranes. The IBJT is the ionic analogue to the conventional semiconductor BJT and is manufactured using standard microfabrication techniques. Transistor characteristics along with a model describing the principle of operation, in which an anionic base current amplifies a cationic collector current, are presented. By employing the IBJT as a bioelectronic circuit element for delivery of the neurotransmitter acetylcholine, its efficacy in modulating neuronal cell signaling is demonstrated.

Screen-Printed Corrosion-Resistant and Long-Term Stable Stretchable Electronics Based on AgAu Microflake Conductors.

High-throughput production methods such as screen printing can bring stretchable electronics out of the lab into the market. Most stretchable conductor inks for screen printing are based on silver nanoparticles or flakes due to their favorable performance-to-cost ratio, but silver is prone to tarnishing and corrosion, thereby limiting the stability of such conductors. Here, we report on a cost-efficient and scalable approach to resolve this issue by developing screen printable inks based on silver flakes chemically coated by a thin layer of gold. The printed stretchable AgAu conductors reach a conductivity of 8500 S cm-1, remain conductive up to 250% strain, show excellent corrosion and tarnishing stability, and are used to demonstrate wearable LED and NFC circuits. The reported approach is attractive for smart clothing, as the long-term functionality of such devices is expected in a variety of environments.

Tuneable Anisotropic Plasmonics with Shape-Symmetric Conducting Polymer Nanoantennas.

A wide range of nanophotonic applications rely on polarization-dependent plasmonic resonances, which usually requires metallic nanostructures that have anisotropic shape. This work demonstrates polarization-dependent plasmonic resonances instead by breaking symmetry via material permittivity. The study shows that molecular alignment of a conducting polymer can lead to a material with polarization-dependent plasma frequency and corresponding in-plane hyperbolic permittivity region. This result is not expected based only on anisotropic charge mobility but implies that also the effective mass of the charge carriers becomes anisotropic upon polymer alignment. This unique feature is used to demonstrate circularly symmetric nanoantennas that provide different plasmonic resonances parallel and perpendicular to the alignment direction. The nanoantennas are further tuneable via the redox state of the polymer. Importantly, polymer alignment could blueshift the plasma wavelength and resonances by several hundreds of nanometers, forming a novel approach toward reaching the ultimate goal of redox-tunable conducting polymer nanoantennas for visible light.

Soft Electromagnetic Vibrotactile Actuators with Integrated Vibration Amplitude Sensing.

Soft vibrotactile devices have the potential to expand the functionality of emerging electronic skin technologies. However, those devices often lack the necessary overall performance, sensing-actuation feedback and control, and mechanical compliance for seamless integration on the skin. Here, we present soft haptic electromagnetic actuators that consist of intrinsically stretchable conductors, pressure-sensitive conductive foams, and soft magnetic composites. To minimize joule heating, high-performance stretchable composite conductors are developed based on in situ-grown silver nanoparticles formed within the silver flake framework. The conductors are laser-patterned to form soft and densely packed coils to further minimize heating. Soft pressure-sensitive conducting polymer-cellulose foams are developed and integrated to tune the resonance frequency and to provide internal resonator amplitude sensing in the resonators. The above components together with a soft magnet are assembled into soft vibrotactile devices providing high-performance actuation combined with amplitude sensing. We believe that soft haptic devices will be an essential component in future developments of multifunctional electronic skin for future human-computer and human-robotic interfaces.

Flexible Organic Electronic Ion Pump Fabricated Using Inkjet Printing and Microfabrication for Precision In Vitro Delivery of Bupivacaine.

The organic electronic ion pump (OEIP) is an on-demand electrophoretic drug delivery device, that via electronic to ionic signal conversion enables drug delivery without additional pressure or volume changes. The fundamental component of OEIPs is their polyelectrolyte membranes which are shaped into ionic channels that conduct and deliver ionic drugs, with high spatiotemporal resolution. The patterning of these membranes is essential in OEIP devices and is typically achieved using laborious microprocessing techniques. Here, the development of an inkjet printable formulation of polyelectrolyte is reported, based on a custom anionically functionalized hyperbranched polyglycerol (i-AHPG). This polyelectrolyte ink greatly simplifies the fabrication process and is used in the production of free-standing OEIPs on flexible polyimide (PI) substrates. Both i-AHPG and the OEIP devices are characterized, exhibiting favorable iontronic characteristics of charge selectivity and the ability to transport aromatic compounds. Further, the applicability of these technologies is demonstrated by the transport and delivery of the pharmaceutical compound bupivacaine to dorsal root ganglion cells with high spatial precision and effective nerve blocking, highlighting the applicability of these technologies for biomedical scenarios.

Flexible Organic Electronic Ion Pump for Flow-Free Phytohormone Delivery into Vasculature of Intact Plants.

Plant vasculature transports molecules that play a crucial role in plant signaling including systemic responses and acclimation to diverse environmental conditions. Targeted controlled delivery of molecules to the vascular tissue can be a biomimetic way to induce long distance responses, providing a new tool for the fundamental studies and engineering of stress-tolerant plants. Here, a flexible organic electronic ion pump, an electrophoretic delivery device, for controlled delivery of phytohormones directly in plant vascular tissue is developed. The c-OEIP is based on polyimide-coated glass capillaries that significantly enhance the mechanical robustness of these microscale devices while being minimally disruptive for the plant. The polyelectrolyte channel is based on low-cost and commercially available precursors that can be photocured with blue light, establishing much cheaper and safer system than the state-of-the-art. To trigger OEIP-induced plant response, the phytohormone abscisic acid (ABA) in the petiole of intact Arabidopsis plants is delivered. ABA is one of the main phytohormones involved in plant stress responses and induces stomata closure under drought conditions to reduce water loss and prevent wilting. The OEIP-mediated ABA delivery triggered fast and long-lasting stomata closure far away from the delivery point demonstrating systemic vascular transport of the delivered ABA, verified delivering deuterium-labeled ABA.