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Incorporating large organic cations to form 2D and mixed 2D/3D structures significantly increases the stability of perovskite solar cells. However, due to their low electron mobility, aligning the organic sheets to ensure unimpeded charge transport is critical to rival the high performances of pure 3D systems. While additives such as methylammonium chloride (MACl) can enable this preferential orientation, so far, no complete description exists explaining how they influence the nucleation process to grow highly aligned crystals. Here, by investigating the initial stages of the crystallization, as well as partially and fully formed perovskites grown using MACl, the origins underlying this favorable alignment are inferred. This mechanism is studied by employing 3-fluorobenzylammonium in quasi-2D perovskite solar cells. Upon assisting the crystallization with MACl, films with a degree of preferential orientation of 94%, capable of withstanding moisture levels of 97% relative humidity for 10 h without significant changes in the crystal structure are achieved. Finally, by combining macroscopic, microscopic, and spectroscopic studies, the nucleation process leading to highly oriented perovskite films is elucidated. Understanding this mechanism will aid in the rational design of future additives to achieve more defect tolerant and stable perovskite optoelectronics. Version of record

When studying electrochemical oxygen reduction reactions in homogeneous media, special attention must be given to the significant background activity present with conventional electrode materials. The intrinsic electrocatalytic activity of different materials can be investigated using complementary methods, such as the rotating ring-disc electrode (RRDE) technique and chronoamperometric electrolysis with product quantification. This report presents a detailed investigation of the electrocatalytic ability of hydroxy anthraquinone derivatives and riboflavin towards hydrogen peroxide (H2O2) production via a novel RRDE subtraction method together with chronoamperometric electrolysis. Qualitative trends linking the two methods were obtained, such as a higher excess current correlating with both higher productivity and selectivity. As such, a valuable tool is provided to increase the understanding of the electrocatalytic ability of homogeneous solutions toward improving the oxygen reduction reaction. Version of record

N,N′-Substituted quinacridones are a novel class of commercially available quinacridones for organic electronics which are reported here. In this study, we performed in-depth investigations of the material properties of these molecules i.e. their optical and charge transport properties, infrared-active vibrations (FTIR), electrochemical reduction and oxidation properties, thin film forming and processability, and finally performance in organic field effect transistor devices. We show that substitution plays a critical role in the charge transport properties, with methyl substituted amine being the most favorable, followed by di-phenyl and finally di-butyl. Osterreichische Forschungsforderungsgesellschaft 888408 Version of record

Strategies for production and use of nanomaterials have rapidly moved towards safety and sustainability. Beyond these requirements, the novel routes must prove to be able to preserve and even improve the performance of the resulting nanomaterials. Increasing demand of high-performance nanomaterials is mostly related to electronic components, solar energy harvesting devices, pharmaceutical industries, biosensors, and photocatalysis. Among nanomaterials, Zinc oxide (ZnO) is of special interest, mainly due to its environmental compatibility and vast myriad of possibilities related to the tuning and the enhancement of ZnO properties. Doping plays a crucial role in this scenario. In this work we report and discuss the properties of undoped ZnO as well as lanthanide (Eu, Tb, and La)-doped ZnO nanoparticles obtained by using whey, a by-product of milk processing, as a chelating agent, without using citrate nor any other chelators. The route showed to be very effective and feasible for the affordable large-scale production of both pristine and doped ZnO nanoparticles in powder form. Version of record

Homogeneous, aqueous solutions of the natural compound riboflavin were investigated for their electrocatalytic oxygen to hydrogen peroxide (H2O2) reduction performance using cyclic voltammetry and electrolysis. In addition to pH dependencies, interestingly the choice of carbon-based electrode material had a strong impact on the electrocatalytic performance. Therefore, the three electrode materials, glassy carbon, carbon paper (CP), and carbon felt were electrochemically compared and afterwards investigated with scanning electron microscopy. Attributed to the deprotonation of riboflavin, pH = 13 was identified as the best performing condition. Using CP at pH = 13, the addition of riboflavin enhanced the H2O2 production by a factor of 14 up to 355 μmol after 6 h at an average faradaic efficiency of around 80%. Fonds zur Förderung der Wissenschaftlichen Forschung Z222-N19 Version of record

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. Version of record

Natural dielectrics are emerging nowadays as a niche selection of materials for applications targeting biocompatibility and biodegradability for electronics and sensors within the overall effort of scientific community to achieve sustainable development and to build environmental consciousness. The two natural resins analyzed in this study, silver fir and Rocky mountain fir demonstrate robust dielectric properties and excellent film forming capabilities, while being trap free dielectrics in high-performance organic field effect transistors (OFETs) operating at voltages as low as 1 V. Immense research possibilities are demonstrated through the avenue of inorganic nanofillers insertions in the natural resins film, that opens the door for fabrication of very low voltage OFETs with high dielectric constant insulating layers. Osterreichische Forschungsforderungsgesellschaft 863530 867266 Fonds zur Förderung der Wissenschaftlichen Forschung (DE-588)2054142-9 I4323-N36 Y1298-N I1788 N20 M2323 N36 19-52-14006 Version of record

Stable radicals in organic conjugated molecules are of great interest due to their magnetic signals and broad optical absorptions. In this paper, we report on naphthalene, benzoperylene, perylene, terrylene, and quaterrylene carboximides, reduced under controlled conditions, where stable metal-free solid salts of radical anions could be obtained forming darkly colored solutions with line-rich UV/Vis/NIR spectra and exhibiting special magnetic properties. The most bathochromic shift of the absorption maxima extend from 760 until 1700 nm. Persistent paramagnetic properties of the solids were observed and temperature-dependent susceptibilities are measured. Graphical abstract

Important parameters of an organic semiconductor material are the electronic band gap (Eg) and the position of highest occupied and lowest unoccupied bands versus vacuum. These bands are called valence and conduction band for inorganic semiconductors. For organic semiconductors the bands defining the band gap are often called highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). One advantage of semiconducting polymers is the ability to tune the band gap and the position of HOMO and LUMO levels by molecular chemical design. The organic photovoltaic solar cells need absorbers with a smaller bandgap to maximize the power conversion efficiency of these devices. There are several chemical strategies to synthesize low band gap polymers for optoelectronic applications. In this manuscript, an updated overview on the current status of these low band gap conjugated polymers will be given. The design principles of low band gap polymers, the properties of the resulting materials, and important applications and devices realized with this material class will be briefly discussed. Version of record

The majority of energy storage devices like batteries, fuel cells or electrolyzers require heterogeneous electrodes. Immobilization of redox-active organic molecules by a polymeric approach seems to be a promising route towards organic electrodes for electrocatalytic energy storage or in batteries. Although numerous reports on synthesis and application of new poly-anthraquinones exist, a universal guideline or tool for selection of the best polymer, concerning several energy storage applications, is still underdeveloped. Moving into the direction of developing such a tool, we have selected and synthesized three poly(anthraquinones). NMR, FTIR, UV-Vis, TGA, contact angle measurement and SEM revealed certain structure-property trends, which can be correlated with the performance in the electrochemical investigation. The insights gained within this work demonstrate correlations between the FTIR frequencies and the electrochemical reduction potential, as well as between the polymer hydrophobicity and the electrochemical performance. Fonds zur Förderung der Wissenschaftlichen Forschung Z222-N19 Version of record

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. Version of record

The state-of-the-art procedure for investigating homogenous and heterogeneous electrocatalysts is cyclic voltammetry (CV). However, this technique usually requires an inactive electrode material. One common problem arising e. g. in studying the oxygen reduction reaction (ORR) is the significant background contribution to the overall ORR current provided by many carbon-based and metal-based electrode materials. Furthermore, rotating ring-disc electrodes (RRDEs) made of common materials like glassy carbon/platinum (GC/Pt) can be affected by overlapping reduction potentials on the disc. Interference from overlapping reactions on the ring might also occur, particularly in connection with oxygen reduction and hydrogen peroxide oxidation in ORR studies. We present herein a novel subtraction method which allows a semi-quantitative description of homogeneous electrocatalysts and helps to overcome the overlapping problems described above using anthraquinone-2-sulfonate (AQS) as a “case study material” for the ORR. Fonds zur Förderung der Wissenschaftlichen Forschung Z222-N19 Version of record

The most active and efficient catalysts for the electrochemical hydrogen evolution reaction (HER) rely on platinum, a fact that increases the cost of producing hydrogen and thereby limits the widespread adoption of this fuel. Here, a metalfree organic electrocatalyst that mimics the platinum surface by implementing a high work function and incorporating hydrogenaffine hydrogen bonds is introduced. These motifs, inspired from enzymology, are deployed here as selective reaction centres. It is shown that the ketoamine hydrogenbond motif enhances the ratedetermining step in proton reduction to molecular hydrogen. The ketoaminefunctionalized polymers reported herein evolve hydrogen at an overpotential of 190 mV. They share certain key properties with platinum: a similar work function and excellent electrochemical stability and chemical robustness. These properties allow the demonstration of one week of continuous HER operation without notable degradation nor delamination from the carrier electrode. Scaled continuousflow electrolysis is reported and 1 L net molecular hydrogen is produced within less than 9 h using 2.3 mg of polymer electrocatalyst. (VLID)5634597 Version of record

Mechanically interlocking redox-active anthraquinone onto single-walled carbon nanotubes (AQ-MINT) gives a new and advanced example of a noncovalent architecture for an electrochemical platform. Electrochemical studies of AQ-MINT as an electrode reveal enhanced electrochemical stability in both aqueous and organic solvents compared to physisorbed AQ-based electrodes. While maintaining the electrochemical properties of the parent anthraquinone molecules, we observe a stable oxygen reduction reaction to hydrogen peroxide (H2O2). Using such AQ-MINT electrodes, 7 and 2 μmol of H2O2 are produced over 8 h under basic and neutral conditions, while the control system of SWCNTs produces 2.2 and 0.5 μmol, respectively. These results reveal the potential of this rotaxane-type immobilization approach for heterogenized electrocatalysis. Fonds zur Förderung der Wissenschaftlichen Forschung Z222-N19 Version of record

Xray detectors play a pivotal role in development and advancement of humankind, from farreaching impact in medicine to furthering the ability to observe distant objects in outer space. While other electronics show the ability to adapt to flexible and lightweight formats, stateoftheart Xray detectors rely on materials requiring bulky and fragile configurations, severely limiting their applications. Lead halide perovskites is one of the most rapidly advancing novel materials with success in the field of semiconductor devices. Here, an ultraflexible, lightweight, and highly conformable passively operated thin film perovskite Xray detector with a sensitivity as high as 9.3 0.5 C Gy1 cm2 at 0 V and a remarkably low limit of detection of 0.58 0.05 Gy s1 is presented. Various electron and hole transporting layers accessing their individual impact on the detector performance are evaluated. Moreover, it is shown that this ultrathin formfactor allows for fabrication of devices detecting Xrays equivalently from front and back side. (VLID)5744134 Version of record

Photon cooling via anti-Stokes photoluminescence (ASPL) is a promising approach to realize all-solid-state cryo-refrigeration by photoexcitation. Photoluminescence quantum yields close to 100% and a strong coupling between phonons and excited states are required to achieve net cooling. We have studied the anti-Stokes photoluminescence of thin films of methylammonium lead bromide nanoparticles. We found that the anti-Stokes photoluminescence is thermally activated with an activation energy of ∼80 meV. At room temperature the ASPL up-conversion efficiency is ∼60% and it depends linearly on the excitation intensity. Our results suggest that upon further optimization of their optical properties, the investigated particles could be promising candidates for the demonstration of photon cooling in thin solid films. Version of record

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. Refereed/Peer-reviewed Fonds zur Forderung der Wissenschaftlichen Forschung P 25357-B20 Z222-N19 Osterreichische Forschungsforderungsgesellschaft P13540004 3D-OFET Version of record

In this report, we present results on the electrocatalytic activity of conducting polymers [polyaniline (PANI) and polypyrrole (PPy)] toward the electrochemical oxygen reduction reaction (ORR) to hydrogen peroxide (H2O2). The electropolymerization of the polymers and electrolysis conditions were optimized for H2O2 production. On flat glassy carbon (GC) electrodes, the faradaic efficiency (FE) for H2O2 production was significantly improved by the polymers. Rotating disc electrode (RDE) studies revealed that this is mainly a result of blocking further H2O2 to the water reduction pathway by the polymers. PPy on carbon paper (CP) significantly increased the molar production of H2O2 by over 250% at an average FE of above 95% compared to bare CP with a FE of 25%. Thus, the polymers are acting as catalysts on the electrode for the ORR, although their catalytic mechanisms differ from other electrocatalysts. Version of record

In this work, the preparation of conducting polymerbased composites using a biological anionic polymer based on salmon deoxyribonucleic acid (DNA) is presented. The most commonly used polymers poly(3,4ethylenedioxythiophene) (PEDOT), as well as polypyrrole, are polymerized in the presence of DNA. Since conjugated polymers are in the polycationic state in their electrically conducting form, the role of the counterion is now fulfilled by the low cost biomolecule DNA as an alternative material, which is also a polyanion thanks to its phosphate chain. The resulting synthesized material is a conducting polymerDNA biocomposite. Such materials are highly attractive for the rising field of bioelectronics and biosensors, especially in organic electrochemical transistors (OECTs) and ion pumps. OECTs made of these conducting polymer biocomposites are fabricated and their electrochemical device operation is compared to the most widely used PEDOT:polystyrenesulfonate. (VLID)4844471 Version of record

Using enzymes as bioelectrocatalysts is an important step toward the next level of biotechnology for energy production. In such biocatalysts, a sacrificial cofactor as an electron and proton source is needed. This is a great obstacle for upscaling, due to cofactor instability and product separation issues, which increase the costs. Here, we report a cofactor-free electroreduction of CO2 to a high energy density chemical (methanol) catalyzed by enzyme–graphene hybrids. The biocatalyst consists of dehydrogenases covalently bound on a well-defined carboxyl graphene derivative, serving the role of a conductive nanoplatform. This nanobiocatalyst achieves reduction of CO2 to methanol at high current densities, which remain unchanged for at least 20 h of operation, without production of other soluble byproducts. It is thus shown that critical improvements on the stability and rate of methanol production at a high Faradaic efficiency of 12% are possible, due to the effective electrochemical process from the electrode to the enzymes via the graphene platform.

We report on a self‐assembled system comprising a molecular copper‐porphyrin photoelectrocatalyst, 5‐(4‐carboxy‐phenyl)‐10,15,20‐triphenylporphyrinatocopper(II) (CuTPP‐COOH), covalently bound to self‐organized, anodic titania nanotube arrays (TiO2 NTs) for photoelectrochemical reduction of oxygen. Visible light irradiation of the porphyrin‐covered TiO2 NTs under cathodic polarization up to −0.3 V vs. Normal hydrogen electrode (NHE) photocatalytically produces H2O2 in pH neutral electrolyte, at room temperature and without need of sacrificial electron donors. The formation of H2O2 upon irradiation is proven and quantified by direct colorimetric detection using 4‐nitrophenyl boronic acid (p‐NPBA) as a reactant. This simple approach for the attachment of a small molecular catalyst to TiO2 NTs may ultimately allow for the preparation of a low‐cost H2O2 evolving cathode for efficient photoelectrochemical energy storage under ambient conditions.

Developing efficient methods for capture and controlled release of carbon dioxide is crucial to any carbon capture and utilization technology. Herein we present an approach using an organic semiconductor electrode to electrochemically capture dissolved CO2 in aqueous electrolytes. The process relies on electrochemical reduction of a thin film of a naphthalene bisimide derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically tailored to afford one-electron reversible and one-electron quasi-reversible reduction in aqueous conditions while not dissolving or degrading. The reduced NBIT reacts with CO2 to form a stable semicarbonate salt, which can be subsequently oxidized electrochemically to release CO2. The semicarbonate structure is confirmed by in situ IR spectroelectrochemistry. This process of capturing and releasing carbon dioxide can be realized in an oxygen-free environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g–1. This is on par with the best solution-phase amine chemical capture technologies available today.

Microbial electrosynthetic cells containing Methylobacterium extorquens were studied for the reduction of CO2 to formate by direct electron injection and redox mediator‐assisted approaches, with CO2 as the sole carbon source. The formation of a biofilm on a carbon felt (CF) electrode was achieved while applying a constant potential of −0.75 V versus Ag/AgCl under CO2‐saturated conditions. During the biofilm growth period, continuous H2 evolution was observed. The long‐term performance for CO2 reduction of the biofilm with and without neutral red as a redox mediator was studied by an applied potential of −0.75 V versus Ag/AgCl. The neutral red was introduced into the systems in two different ways: homogeneous (dissolved in solution) and heterogeneous (electropolymerized onto the working electrode). The heterogeneous approach was investigated in the microbial system, for the first time, where the CF working electrode was coated with poly(neutral red) by the oxidative electropolymerization thereof. The formation of poly(neutral red) was characterized by spectroscopic techniques. During long‐term electrolysis up to 17 weeks, the formation of formate was observed continuously with an average Faradaic efficiency of 4 %. With the contribution of neutral red, higher formate accumulation was observed. Moreover, the microbial electrosynthetic cell was characterized by means of electrochemical impedance spectroscopy to obtain more information on the CO2 reduction mechanism. Refereed/Peer-reviewed Version of record

Robust organic thin-film transistors (OTFTs) with high temperature stability allow device integration with mass production methods like thermoforming and injection molding, and enable operation in extreme environment applications. Herein we elaborate a series of materials to make suitable gate dielectric and active semiconductor layers for high temperature stable OTFTs. We employ an anodized aluminum oxide layer passivated with cross-linked low-density polyethylene (LD-PE) to form a temperature-stable gate capacitor. As the semiconductor, we use quinacridone, an industrial organic colorant pigment produced on a mass scale. Evaporated MoOx/Ag source and drain electrodes complete the devices. Here we evaluate the performance of the OTFTs healing them in air from 100 degrees C in 25 degrees C increments up to 225 degrees C, holding each temperature for a period of 30 minutes. We find large differences in stability between quinacridone and its dimethylated derivative, with the former showing the best performance with only a factor of 2 decline in mobility after healing at 225 degrees C, and unaffected on/off ratio and threshold voltage. The approach presented here shows how industriallys calable fabrication of thermally robust OTFTs can be rationalized.

Stable radicals in organic conjugated molecules are of great interest due to their magnetic signals and broad optical absorptions. In this paper, we report on naphthalene, benzoperylene, perylene, terrylene, and quaterrylene carboximides, reduced under controlled conditions, where stable metal-free solid salts of radical anions could be obtained forming darkly colored solutions with line-rich UV/Vis/NIR spectra and exhibiting special magnetic properties. The most bathochromic shift of the absorption maxima extend from 760 until 1700 nm. Persistent paramagnetic properties of the solids were observed and temperature-dependent susceptibilities are measured. Fonds zur Förderung der Wissenschaftlichen Forschung Z 222-N19 Version of record