In Vitro Cytotoxicity of D18 and Y6 as Potential Organic Photovoltaic Materials for Retinal Prostheses.

Millions of people worldwide are diagnosed with retinal dystrophies such as retinitis pigmentosa and age-related macular degeneration. A retinal prosthesis using organic photovoltaic (OPV) semiconductors is a promising therapeutic device to restore vision to patients at the late onset of the disease. However, an appropriate cytotoxicity approach has to be employed on the OPV materials before using them as retinal implants. In this study, we followed ISO standards to assess the cytotoxicity of D18, Y6, PFN-Br and PDIN individually, and as mixtures of D18/Y6, D18/Y6/PFN-Br and D18/Y6/PDIN. These materials were proven for their high performance as organic solar cells. Human RPE cells were put in direct and indirect contact with these materials to analyze their cytotoxicity by the MTT assay, apoptosis by flow cytometry, and measurements of cell morphology and proliferation by immunofluorescence. We also assessed electrophysiological recordings on mouse retinal explants via microelectrode arrays (MEAs) coated with D18/Y6. In contrast to PFN-Br and PDIN, all in vitro experiments show no cytotoxicity of D18 and Y6 alone or as a D18/Y6 mixture. We conclude that D18/Y6 is safe to be subsequently investigated as a retinal prosthesis.

Overcoming intra-molecular repulsions in PEDTT by sulphate counter-ion.

We set out to demonstrate the development of a highly conductive polymer based on poly-(3,4-ethylenedithia thiophene) (PEDTT), PEDOTs structural analogue historically notorious for structural disorder and limited conductivities. The caveat therein was previously described to lie in intra-molecular repulsions. We demonstrate how a tremendous >2600-fold improvement in conductivity and metallic features, such as magnetoconductivity can be achieved. This is achieved through a careful choice of the counter-ion (sulphate) and the use of oxidative chemical vapour deposition (oCVD). It is shown that high structural order on the molecular level was established and the formation of crystallites tens of nanometres in size was achieved. We infer that the sulphate ions therein intercalate between the polymer chains, thus forming densely packed crystals of planar molecules with extended π-systems. Consequently, room-temperature conductivities of above 1000 S cm-1 are achieved, challenging those of conventional PEDOT:PSS. The material is in the critical regime of the metal-insulator transition.

Localizing Binding Sites on Bioconjugated Hydrogen-Bonded Organic Semiconductors at the Nanoscale.

Hydrogen-bonded organic semiconductors are extraordinarily stable organic solids forming stable, large crystallites with the ability to preserve favorable electrical properties upon bioconjugation. Lately, tremendous efforts have been made to use these bioconjugated semiconductors as platforms for stable multifunctional bioelectronics devices, yet the detailed characterization of bio-active binding sites (orientation, density, etc.) at the nanoscale has not been achieved yet. The presented work investigates the bioconjugation of epindolidione and quinacridone, two representative semiconductors, with respect to their exposed amine-functionalities. Relying on the biotin-avidin lock-and-key system and applying the atomic force microscopy (AFM) derivative topography and recognition (TREC) imaging, we used activated biotin to flag crystal-faces with exposed amine functional groups. Contrary to previous studies, biotin bonds were found to be stable towards removal by autolysis. The resolution strength and clear recognition capability makes TREC-AFM a valuable tool in the investigation of bio-conjugated, hydrogen-bonded semiconductors.

Tunable Properties of Nature-Inspired N,N'-Alkylated Riboflavin Semiconductors.

A series of novel soluble nature-inspired flavin derivatives substituted with short butyl and bulky ethyl-adamantyl alkyl groups was prepared via simple and straightforward synthetic approach with moderate to good yields. The comprehensive characterization of the materials, to assess their application potential, has demonstrated that the modification of the conjugated flavin core enables delicate tuning of the absorption and emission properties, optical bandgap, frontier molecular orbital energies, melting points, and thermal stability. Moreover, the thin films prepared thereof exhibit smooth and homogeneous morphology with generally high stability over time.

Photoconductive Properties of Dibenzotetrathiafulvalene-Tetracyanoquinodimethane (DBTTF-TCNQ) Nanorods Prepared by the Reprecipitation Method.

Charge-transfer complex crystals have been extensively studied because of their metallic conductivity, photoconductivity, ambipolar charge transport, and high career mobility. Numerous studies of their applications for organic electric devices such as organic field effect transistors and solar cells have reported. However, bulky single crystals of charge-transfer complexes are difficult to handle, specifically to be made into a form of a thin film. Recently, nano/micro crystallization of charge-transfer crystal is attracted to realize thin film applications. In this paper, charge transfer complex nanorods composed of dibenzotetrathiafulvalene-tetracyanoquinodimethane (DBTTF-TCNQ) were prepared by the reprecipitation method. The as-formed nanorods possess a kinetically metastable crystal structure different from the thermodynamically stable bulk crystal prepared by slow evaporation of the solvent. From photoconductive measurement, nanorod stacks show a significant photosensitivity (354.57 µA/W) on par with bulk crystal (417.14 µA/W). These results suggest dibenzotetrathiafulvalene-tetracyanoquinodimethane (DBTTF-TCNQ) nanorods have a favorable crystal structure for carrier transport due to the difference of molecular stacking assembly.

Novel Riboflavin-Inspired Conjugated Bio-Organic Semiconductors.

Flavins are known to be extremely versatile, thus enabling routes to innumerable modifications in order to obtain desired properties. Thus, in the present paper, the group of bio-inspired conjugated materials based on the alloxazine core is synthetized using two efficient novel synthetic approaches providing relatively high reaction yields. The comprehensive characterization of the materials, in order to evaluate the properties and application potential, has shown that the modification of the initial alloxazine core with aromatic substituents allows fine tuning of the optical bandgap, position of electronic orbitals, absorption and emission properties. Interestingly, the compounds possess multichromophoric behavior, which is assumed to be the results of an intramolecular proton transfer.

Nature-Inspired Photocatalytic Hydrogen Production with a Flavin Photosensitizer.

Green hydrogen, by definition, must be produced with renewable energy sources without using fossil fuels. To transform the energy system, we need a fully sustainable production of green and renewable energy as well as the introduction of such "solar fuels" to tackle the chemical storage aspect of renewable energies. Conventional electrolysis of water splitting into oxygen and hydrogen gases is a clean and nonfossil method, but the use of massive noble-metal electrodes makes it expensive. Direct photocatalytic hydrogen evolution in water is an ideal approach, but an industrial scale is not available yet. In this paper, we intend to introduce flavins as metal-free organic photosensitizers for photoinduced reduction processes. Specifically, a flavin photosensitizer was employed for the photocatalytic evolution of hydrogen gas in aqueous media. The ratio of photosensitizer to cocatalyst concentration has been found to affect the efficiency of the hydrogen evolution reaction. Since flavins are nature-inspired molecules (like vitamin B2) with easily tunable properties through structure modification, this family of compounds opens the door for new possibilities in sustainable green hydrogen production.

3-Thiophenemalonic Acid Additive Enhanced Performance in Perovskite Solar Cells.

The development of ambient-air-processable organic-inorganic halide perovskite solar cells (OIHPSCs) is a challenge necessary for the transfer of laboratory-scale technology to large-scale and low-cost manufacturing of such devices. Different approaches like additives, antisolvents, composition engineering, and different deposition techniques have been employed to improve the morphology of the perovskite films. Additives that can form Lewis acid-base adducts are known to minimize extrinsic impacts that trigger defects in ambient air. In this work, we used the 3-thiophenemalonic acid (3-TMA) additive, which possesses thiol and carboxyl functional groups, to convert PbI2, PbCl2, and CH3NH3I to CH3NH3PbI3 completely. This strategy is effective in regulating the kinetics of crystallization and improving the crystallinity of the light-absorbing layer under high relative humidity (RH) conditions (30-50%). As a result, the 3-TMA additive increases the yield of the power conversion efficiency (PCE) from 14.9 to 16.5% and its stability under the maximum power point. Finally, we found that the results of this work are highly relevant and provide additional inputs to the ongoing research progress related to additive engineering as one of the efficient strategies to reduce parasitic recombination and enhance the stability of inverted OIHPSCs in ambient environment processing.

Optical and electrical properties of electrochemically doped organic field effect transistors.

Mixed ionic/electronic conduction in conducting polymers introduces new physics/chemistry and an additional functionality in organic optoelectronic devices. The incorporation of an ionic species in a conjugated polymer matrix results in the increase in electrical conductivity associated with the electrochemical doping of the material. In recent years polymer light emitting electrochemical cells (LECs) have been demonstrated. In such electrochemical optoelectronic devices, mobile ions facilitate the efficient injection of electronic charge carriers creating "in situ" doping regions near the electrodes and lead to efficient electroluminescence light emission. Here, we introduce the same concept of an LEC in the organic field effect transistors (OFETs). The presence of both electronic and ionic charge carriers in the active layers of OFETs brings high charge carrier mobility and light emission even using symmetric source and drain metal electrodes.

Amplifying the dielectric constant of shellac by incorporating natural clays for organic field effect transistors (OFETs).

We demonstrate in this work the practical use of uniform mixtures of a bioresin shellac and four natural clays, i.e. montmorillonite, sepiolite, halloysite and vermiculate as dielectrics in organic field effect transistors (OFETs). We present a thorough characterization of their processability and film forming characteristic, surface characterization, elaborate dielectric investigation and the fabrication of field effect transistors with two classic organic semiconductors, i.e. pentacene and fullerene C60. We show that low operating voltage of approximately 4 V is possible for all the OFETs using several combinations of clays and shellac. The capacitance measurements show an improvement of the dielectric constant of shellac by a factor of 2, to values in excess of 7 in the uniform mixtures of sepiolite and montmorillonite with this bioresin.

Pinaceae Pine Resins (Black Pine, Shore Pine, Rosin, and Baltic Amber) as Natural Dielectrics for Low Operating Voltage, Hysteresis-Free, Organic Field Effect Transistors.

Four pinaceae pine resins analyzed in this study: black pine, shore pine, Baltic amber, and rosin demonstrate excellent dielectric properties, outstanding film forming, and ease of processability from ethyl alcohol solutions. Their trap-free nature allows fabrication of virtually hysteresis-free organic field effect transistors operating in a low voltage window with excellent stability under bias stress. Such green constituents represent an excellent choice of materials for applications targeting biocompatibility and biodegradability of electronics and sensors, within the overall effort of sustainable electronics development and environmental friendliness.

Single-Component Organic Solar Cells Based on Intramolecular Charge Transfer Photoabsorption.

Conjugated donor-acceptor molecules with intramolecular charge transfer absorption are employed for single-component organic solar cells. Among the five types of donor-acceptor molecules, the strong push-pull structure of DTDCPB resulted in solar cells with high JSC, an internal quantum efficiency exceeding 20%, and high VOC exceeding 1 V with little photon energy loss around 0.7 eV. The exciton binding energy (EBE), which is a key factor in enhancing the photocurrent in the single-component device, was determined by quantum chemical calculation. The relationship between the photoexcited state and the device performance suggests that the strong internal charge transfer is effective for reducing the EBE. Furthermore, molecular packing in the film is shown to influence photogeneration in the film bulk.

Synthesis conditions influencing formation of MAPbBr3 perovskite nanoparticles prepared by the ligand-assisted precipitation method.

This work reports on an optimized procedure to synthesize methylammonium bromide perovskite nanoparticles. The ligand-assisted precipitation synthetic pathway for preparing nanoparticles is a cost-effective and promising method due to its ease of scalability, affordable equipment requirements and convenient operational temperatures. Nevertheless, there are several parameters that influence the resulting optical properties of the final nanomaterials. Here, the influence of the choice of solvent system, capping agents, temperature during precipitation and ratios of precursor chemicals is described, among other factors. Moreover, the colloidal stability and stability of the precursor solution is studied. All of the above-mentioned parameters were observed to strongly affect the resulting optical properties of the colloidal solutions. Various solvents, dispersion media, and selection of capping agents affected the formation of the perovskite structure, and thus qualitative and quantitative optimization of the synthetic procedure conditions resulted in nanoparticles of different dimensions and optical properties. The emission maxima of the nanoparticles were in the 508-519 nm range due to quantum confinement, as confirmed by transmission electron microscopy. This detailed study allows the selection of the best optimal conditions when using the ligand-assisted precipitation method as a powerful tool to fine-tune nanostructured perovskite features targeted for specific applications.

Cyclic Peptide Stabilized Lead Halide Perovskite Nanoparticles.

Combining the unique properties of peptides as versatile tools for nano- and biotechnology with lead halide perovskite nanoparticles can bring exceptional opportunities for the development of optoelectronics, photonics, and bioelectronics. As a first step towards this challenge sub 10 nm methylammonium lead bromide perovskite colloidal nanoparticles have been synthetizes using commercial cyclic peptide Cyclo(RGDFK), containing 5 amino acids, as a surface stabilizer. Perovskite nanoparticles passivated with Cyclo(RGDFK) possess charge transfer from the perovskite core to the peptide shell, resulting in lower photoluminescence quantum yields, which however opens a path for the application where charge transfer is favorable.

Stability of Selected Hydrogen Bonded Semiconductors in Organic Electronic Devices.

The electronics era is flourishing and morphing itself into Internet of Everything, IoE. At the same time, questions arise on the issue of electronic materials employed: especially their natural availability and low-cost fabrication, their functional stability in devices, and finally their desired biodegradation at the end of their life cycle. Hydrogen bonded pigments and natural dyes like indigo, anthraquinone and acridone are not only biodegradable and of bio-origin but also have functionality robustness and offer versatility in designing electronics and sensors components. With this Perspective, we intend to coalesce all the scattered reports on the above-mentioned classes of hydrogen bonded semiconductors, spanning across several disciplines and many active research groups. The article will comprise both published and unpublished results, on stability during aging, upon electrical, chemical and thermal stress, and will finish with an outlook section related to biological degradation and biological stability of selected hydrogen bonded molecules employed as semiconductors in organic electronic devices. We demonstrate that when the purity, the long-range order and the strength of chemical bonds, are considered, then the Hydrogen bonded organic semiconductors are the privileged class of materials having the potential to compete with inorganic semiconductors. As an experimental historical study of stability, we fabricated and characterized organic transistors from a material batch synthesized in 1932 and compared the results to a fresh material batch.

Dielectric Function of Undoped and Doped Poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene] by Ellipsometry in a Wide Spectral Range.

Ellipsometric measurements in a wide spectral range (from 0.05 to 6.5 eV) have been carried out on the organic semiconducting polymer, poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene] (MDMO-PPV), in both undoped and doped states. The real and imaginary parts of the dielectric function and the refractive index are determined accurately, provided that the layer thickness is measured independently. After doping, the optical properties show the presence of new peaks, which could be well-resolved by spectroscopic ellipsometry. Also for the doped material, the complex refractive index, with respect to the dielectric function, has been determined. The broadening of the optical transitions is due to the delocalization of polarons at higher doping level. The detailed information about the dielectric function as well as refractive index function obtained by spectroscopic ellipsometry allows not only qualitative but also quantitative description of the optical properties of the undoped/doped polymer. For the direct characterization of the optical properties of MDMO-PPV, ellipsometry turns out to be advantageous compared to conventional reflection and transmission measurements.