An efficient nanoscale semiconducting optoelectronic system is reported, which is optimized for neuronal stimulation: the organic electrolytic photocapacitor. The devices comprise a thin (80 nm) trilayer of metal and p-n semiconducting organic nanocrystals. When illuminated in physiological solution, these metal-semiconductor devices charge up, transducing light pulses into localized displacement currents that are strong enough to electrically stimulate neurons with safe light intensities. The devices are freestanding, requiring no wiring or external bias, and are stable in physiological conditions. The semiconductor layers are made using ubiquitous and nontoxic commercial pigments via simple and scalable deposition techniques. It is described how, in physiological media, photovoltage and charging behavior depend on device geometry. To test cell viability and capability of neural stimulation, photostimulation of primary neurons cultured for three weeks on photocapacitor films is shown. Finally, the efficacy of the device is demonstrated by achieving direct optoelectronic stimulation of light-insensitive retinas, proving the potential of this device platform for retinal implant technologies and for stimulation of electrogenic tissues in general. These results substantiate the conclusion that these devices are the first non-Si optoelectronic platform capable of sufficiently large photovoltages and displacement currents to enable true capacitive stimulation of excitable cells.

Optical control of the electrophysiology of single cells can be a powerful tool for biomedical research and technology. Here, we report organic electrolytic photocapacitors (OEPCs), devices that function as extracellular capacitive electrodes for stimulating cells. OEPCs consist of transparent conductor layers covered with a donor-acceptor bilayer of organic photoconductors. This device produces an open-circuit voltage in a physiological solution of 330 mV upon illumination using light in a tissue transparency window of 630 to 660 nm. We have performed electrophysiological recordings on Xenopus laevis oocytes, finding rapid (time constants, 50 μs to 5 ms) photoinduced transient changes in the range of 20 to 110 mV. We measure photoinduced opening of potassium channels, conclusively proving that the OEPC effectively depolarizes the cell membrane. Our results demonstrate that the OEPC can be a versatile nongenetic technique for optical manipulation of electrophysiology and currently represents one of the simplest and most stable and efficient optical stimulation solutions.

Implantable devices for the wireless modulation of neural tissue need to be designed for reliability, safety and reduced invasiveness. Here we report chronic electrical stimulation of the sciatic nerve in rats by an implanted organic electrolytic photocapacitor that transduces deep-red light into electrical signals. The photocapacitor relies on commercially available semiconducting non-toxic pigments and is integrated in a conformable 0.1-mm3 thin-film cuff. In freely moving rats, fixation of the cuff around the sciatic nerve, 10 mm below the surface of the skin, allowed stimulation (via 50-1,000-μs pulses of deep-red light at wavelengths of 638 nm or 660 nm) of the nerve for over 100 days. The robustness, biocompatibility, low volume and high-performance characteristics of organic electrolytic photocapacitors may facilitate the wireless chronic stimulation of peripheral nerves. Introduction Implantable neural interfaces are at the heart of bioelectronic medicine, a growing field which aims to provide electrical solutions to medical problems 1-3 . Direct electrical actuation of the nervous system is utilized clinically in deep brain stimulation 4 , prosthetic retina implants 5 , vagus nerve stimulation for treatment of epilepsy 6 and other disorders 7,8 , as well as in numerous other applications. Meanwhile, the list of emerging technologies at a preclinical phase is constantly growing 9,10 . Several fundamental engineering hurdles need to be overcome to facilitate widespread implementation of bioelectronic devices and ensure optimal clinical outcomes 11,12 . A key challenge is to improve long-term powering and miniaturization of implantable devices, motivating exploration of methods to wirelessly actuate and control implants from outside of the body. The most common approaches involve radio frequency (RF) power transmission or electromagnetic induction 13 . Although

Microporous and macro-mesoporous silicon templates for surface-enhanced Raman scattering (SERS) substrates were produced by anodization of low doped p-type silicon wafers. By immersion plating in AgNO3, the templates were covered with silver metallic film consisting of different silver nanostructures. Scanning electron microscopy (SEM) micrographs of these SERS substrates showed diverse morphology with significant difference in an average size and size distribution of silver nanoparticles. Ultraviolet-visible-near-infrared (UV-Vis-NIR) reflection spectroscopy showed plasmonic absorption at 398 and 469 nm, which is in accordance with the SEM findings. The activity of the SERS substrates was tested using rhodamine 6G (R6G) dye molecules and 514.5 nm laser excitation. Contrary to the microporous silicon template, the SERS substrate prepared from macro-mesoporous silicon template showed significantly broader size distribution of irregular silver nanoparticles as well as localized surface plasmon resonance closer to excitation laser wavelength. Such silver morphology has high SERS sensitivity that enables ultralow concentration detection of R6G dye molecules up to 10(-15) M. To our knowledge, this is the lowest concentration detected of R6G dye molecules on porous silicon-based SERS substrates, which might even indicate possible single molecule detection.

Photoactive organic semiconductor substrates are envisioned as a novel class of bioelectronic devices that transduce light into stimulating biological signals with relevance for retinal implants or guided cellular differentiation. The direct interface between the semiconductor and the electrolyte gives rise to different competing optoelectronic transduction mechanisms. A detailed understanding of such faradaic or capacitive processes and the underlying material science is necessary to develop and optimize future devices. Here, the problem in organic photoelectrodes is addressed based on a planar p‐n junction containing phthalocyanine (H2Pc) and N,N′‐dimethyl perylenetetracarboxylic diimide (PTCDI). The detailed characterization of photoelectrochemical current transients is combined with spectroscopic measurements, impedance spectroscopy, and local photovoltage measurements to establish a model that predicts quantitatively faradaic or capacitive current transients. The decisive elements of the model are the energy levels present at the interface and the voltage building up in the photoelectrode. The result of the efforts is a comprehensive model of photocapacitive and photofaradaic effects that can be applied to developing wireless bioelectronic photostimulation devices.

We report that eumelanin, the ubiquitous natural pigment found in most living organisms, is a photocatalytic material. Though the photoconductivity of eumelanin and its photochemical reactions with oxygen have been known for some time, eumelanins have not been regarded as photofaradaic materials. We find that eumelanin shows photocathodic behavior for both the oxygen reduction reaction and the hydrogen evolution reaction. Eumelanin films irradiated in aqueous solutions at pH 2 or 7 with simulated solar light photochemically reduce oxygen to hydrogen peroxide with accompanying oxidation of sacrificial oxalate, formate, or phenol.

Light, as a versatile and non-invasive means to elicit a physiological response, offers solutions to problems in basic research as well as in biomedical technologies. The complexity and limitations of optogenetic methods motivate research and development of optoelectronic alternatives. A recently growing subset of approaches relies on organic semiconductors as the active light absorber. Organic semiconductors stand out due to their high optical absorbance coefficients, mechanical flexibility, ability to operate in a wet environment, and potential biocompatibility. They could enable ultrathin and minimally invasive form factors not accessible with traditional inorganic materials. Organic semiconductors, upon photoexcitation in an aqueous medium, can transduce light into (1) photothermal heating, (2) photochemical/photocatalytic redox reactions, (3) photocapacitive charging of electrolytic double layers, and (4) photofaradaic reactions. In realistic conditions, different effects may coexist, and understanding their role in observed physiological phenomena is an area of critical interest. This article serves to evaluate the emerging picture of photofaradaic vs. photocapacitive effects in the context of our group's research efforts and that of others over the past few years. We present simple experiments which can be used to benchmark organic optoelectronic stimulation devices.

Hydrogen peroxide is one of the most important industrial chemicals and there is great demand for the production of HO using more sustainable and environmentally benign methods. We show electrochemical production of HO by the reduction of O, enabled by an organic semiconductor catalyst, N,N'-dimethyl perylenetetracarboxylic diimide (PTCDI). We make PTCDI cathodes that are capable of stable and reusable operation in aqueous electrolytes in a pH range of 1-13 with a catalytic figure of merit as high as 26 kg HO per g catalyst per h. These performance and stability open new avenues for organic small molecule semiconductors as electrocatalysts.