Understanding the Microstructure Formation of Polymer Films by Spontaneous Solution Spreading Coating with a High-Throughput Engineering Platform.

An important step of the great achievement of organic solar cells in power conversion efficiency is the development of low-band gap polymer donors, PBDB-T derivatives, which present interesting aggregation effects dominating the device performance. The aggregation of polymers can be manipulated by a series of variables from a materials design and processing conditions perspective; however, optimization of film quality is a time- and energy-consuming work. Here, we introduce a robot-based high-throughput platform (HTP) that is offering automated film preparation and optical spectroscopy thin-film characterization in combination with an analysis algorithm. PM6 films are prepared by the so-called spontaneous film spreading (SFS) process, where a polymer solution is coated on a water surface. Automated acquisition of UV/Vis and photoluminescence (PL) spectra and automated extraction of morphological features is coupled to Gaussian Process Regression to exploit available experimental evidence for morphology optimization but also for hypothesis formulation and testing with respect to the underlying physical principles. The integrated spectral modeling workflow yields quantitative microstructure information by distinguishing amorphous from ordered phases and assesses the extension of amorphous versus the ordered domains. This research provides an easy to use methodology to analyze the exciton coherence length in conjugated semiconductors and will allow to optimize exciton splitting in thin film organic semiconductor layers as a function of processing.

Discovery of temperature-induced stability reversal in perovskites using high-throughput robotic learning.

Stability of perovskite-based photovoltaics remains a topic requiring further attention. Cation engineering influences perovskite stability, with the present-day understanding of the impact of cations based on accelerated ageing tests at higher-than-operating temperatures (e.g. 140°C). By coupling high-throughput experimentation with machine learning, we discover a weak correlation between high/low-temperature stability with a stability-reversal behavior. At high ageing temperatures, increasing organic cation (e.g. methylammonium) or decreasing inorganic cation (e.g. cesium) in multi-cation perovskites has detrimental impact on photo/thermal-stability; but below 100°C, the impact is reversed. The underlying mechanism is revealed by calculating the kinetic activation energy in perovskite decomposition. We further identify that incorporating at least 10 mol.% MA and up to 5 mol.% Cs/Rb to maximize the device stability at device-operating temperature (<100°C). We close by demonstrating the methylammonium-containing perovskite solar cells showing negligible efficiency loss compared to its initial efficiency after 1800 hours of working under illumination at 30°C.

Beyond Ternary OPV: High-Throughput Experimentation and Self-Driving Laboratories Optimize Multicomponent Systems.

Fundamental advances to increase the efficiency as well as stability of organic photovoltaics (OPVs) are achieved by designing ternary blends, which represents a clear trend toward multicomponent active layer blends. The development of high-throughput and autonomous experimentation methods is reported for the effective optimization of multicomponent polymer blends for OPVs. A method for automated film formation enabling the fabrication of up to 6048 films per day is introduced. Equipping this automated experimentation platform with a Bayesian optimization, a self-driving laboratory is constructed that autonomously evaluates measurements to design and execute the next experiments. To demonstrate the potential of these methods, a 4D parameter space of quaternary OPV blends is mapped and optimized for photostability. While with conventional approaches, roughly 100 mg of material would be necessary, the robot-based platform can screen 2000 combinations with less than 10 mg, and machine-learning-enabled autonomous experimentation identifies stable compositions with less than 1 mg.

Fully Printed Infrared Photodetectors from PbS Nanocrystals with Perovskite Ligands.

Colloidal nanocrystals from PbS are successfully applied in highly sensitive infrared photodetectors with various device architectures. Here, we demonstrate all-printed devices with high detectivity (∼1012 cm Hz1/2/W) and a cut-off frequency of >3 kHz. The low material consumption (<0.3 mg per detector) and short processing time (14 s per detector) enabled by the automated printing promises extremely low device costs. To enable all-printed devices, an ink formulation was developed based on nanocrystals stabilized by perovskite-like methylammonium iodobismuthate ligands, which are dispersed in a ternary solvent. Fully inkjet printed devices based on this solvent were achieved with printed silver electrodes and a ZnO interlayer. Considerable improvements were obtained by the addition of small amounts of the polymer poly(vinylpyrrolidone) to the ink. The polymer improved the colloidal stability of the ink and its film-formation properties and thus enabled the scalable printing of single detectors and detector arrays. While photoconductors were shown here, the developed ink will certainly find application in a series of further electronic devices based on nanocrystals from a broad range of materials.

Time-Resolved Analysis of Dielectric Mirrors for Vapor Sensing.

Dielectric mirrors based on bilayers of polystyrene- block-poly(ethylene- ran-butylene)- block-polystyrene (SEBS) and poly(vinyl alcohol) (PVA)-zirconium dioxide (ZrO2) nanocomposites are fabricated for vapor sensing. When exposed to specific solvent vapor, the layers of dielectric mirrors can gradually swell and cause a red-shift of the reflection band. Because PVA solely responds to water and SEBS is sensitive to several different types of organic solvents, the mirrors can respond to a large variety of solvents. The dual-functional hydrophilic ZrO2 nanoparticles are introduced to not only enlarge the refractive index contrast but also increase the permeability. Time-resolved measurements show that mirrors with nanoparticles have a significantly faster response than those without nanoparticles. Moreover, the dependence on relative humidity is studied for representative solvents, and several types of solvents are selected to show the dependence on the solvent-polymer interaction parameters at typical relative humidity, which allows one to predict the responsivity and selectivity of the sensors.

Robot-Based High-Throughput Engineering of Alcoholic Polymer: Fullerene Nanoparticle Inks for an Eco-Friendly Processing of Organic Solar Cells.

Development of high-quality organic nanoparticle inks is a significant scientific challenge for the industrial production of solution-processed organic photovoltaics (OPVs) with eco-friendly processing methods. In this work, we demonstrate a novel, robot-based, high-throughput procedure performing automatic poly(3-hexylthio-phene-2,5-diyl) and indene-C60 bisadduct nanoparticle ink synthesis in nontoxic alcohols. A novel methodology to prepare particle dispersions for fully functional OPVs by manipulating the particle size and solvent system was studied in detail. The ethanol dispersion with a particle diameter of around 80-100 nm exhibits reduced degradation, yielding a power conversion efficiency of 4.52%, which is the highest performance reported so far for water/alcohol-processed OPV devices. By successfully deploying the high-throughput robot-based approach for an organic nanoparticle ink preparation, we believe that the findings demonstrated in this work will trigger more research interest and effort on eco-friendly industrial production of OPVs.

Suppression of Thermally Induced Fullerene Aggregation in Polyfullerene-Based Multiacceptor Organic Solar Cells.

A novel main-chain polyfullerene, poly[fullerene-alt-2,5-bis(octyloxy)terephthalaldehyde] (PPC4), is investigated for its hypothesized superior morphological stability as an electron-accepting material in organic photovoltaics relative to the widely used fullerene phenyl-C61-butyric acid methyl ester (PCBM). When mixed with poly(3-hexylthiophene-2,5-diyl) (P3HT), PPC4 affords low-charge-generation yields because of poor intermixing within the blend. The adoption of a multiacceptor system, by introducing PCBM into the P3HT:polyfullerene blend, was found to lead to a 3-fold enhancement in charge generation, affording power conversion efficiencies very close to that of the prototypical P3HT:PCBM binary control. Upon thermal stressing and in contrast to the P3HT:PCBM binary, photovoltaic devices based on the multiacceptor system demonstrated significantly improved stability, outperforming the control because of suppression of the PCBM migration and aggregation processes responsible for rapid device failure. We rationalize the influence of the fullerene miscibility and its implications on the device performance in terms of a thermodynamic model based on Flory-Huggins solution theory. Finally, the potential universal applicability of this approach for thermal stabilization of organic solar cells is demonstrated, utilizing an alternative low-band-gap polymer-donor system.

Abnormal strong burn-in degradation of highly efficient polymer solar cells caused by spinodal donor-acceptor demixing.

The performance of organic solar cells is determined by the delicate, meticulously optimized bulk-heterojunction microstructure, which consists of finely mixed and relatively separated donor/acceptor regions. Here we demonstrate an abnormal strong burn-in degradation in highly efficient polymer solar cells caused by spinodal demixing of the donor and acceptor phases, which dramatically reduces charge generation and can be attributed to the inherently low miscibility of both materials. Even though the microstructure can be kinetically tuned for achieving high-performance, the inherently low miscibility of donor and acceptor leads to spontaneous phase separation in the solid state, even at room temperature and in the dark. A theoretical calculation of the molecular parameters and construction of the spinodal phase diagrams highlight molecular incompatibilities between the donor and acceptor as a dominant mechanism for burn-in degradation, which is to date the major short-time loss reducing the performance and stability of organic solar cells.

Combined Computational Approach Based on Density Functional Theory and Artificial Neural Networks for Predicting The Solubility Parameters of Fullerenes.

The solubility of organic semiconductors in environmentally benign solvents is an important prerequisite for the widespread adoption of organic electronic appliances. Solubility can be determined by considering the cohesive forces in a liquid via Hansen solubility parameters (HSP). We report a numerical approach to determine the HSP of fullerenes using a mathematical tool based on artificial neural networks (ANN). ANN transforms the molecular surface charge density distribution (σ-profile) as determined by density functional theory (DFT) calculations within the framework of a continuum solvation model into solubility parameters. We validate our model with experimentally determined HSP of the fullerenes C60, PC61BM, bisPC61BM, ICMA, ICBA, and PC71BM and through comparison with previously reported molecular dynamics calculations. Most excitingly, the ANN is able to correctly predict the dispersive contributions to the solubility parameters of the fullerenes although no explicit information on the van der Waals forces is present in the σ-profile. The presented theoretical DFT calculation in combination with the ANN mathematical tool can be easily extended to other π-conjugated, electronic material classes and offers a fast and reliable toolbox for future pathways that may include the design of green ink formulations for solution-processed optoelectronic devices.

High-performance semitransparent perovskite solar cells with solution-processed silver nanowires as top electrodes.

In this work, we report efficient semitransparent perovskite solar cells using solution-processed silver nanowires (AgNWs) as top electrodes. A thin layer of zinc oxide nanoparticles is introduced beneath the AgNWs, which fulfills two essential functionalities: it ensures ohmic contact between the PC60BM and the AgNWs and it serves as a physical foundation that enables the solution-deposition of AgNWs without causing damage to the underlying perovskite. The as-fabricated semitransparent perovskite cells show a high fill factor of 66.8%, Voc = 0.964 V, Jsc = 13.18 mA cm(-2), yielding an overall efficiency of 8.49% which corresponds to 80% of the reference devices with reflective opaque electrodes.

Classification of additives for organic photovoltaic devices.

The use of additives to improve the performance of organic photovoltaic cells has been intensely researched in recent years. However, so far, no system has been reported for the classification of additives and their functions. In this report, a system for classifying additives according to the fundamental mechanism by which they influence microstructure formation for P3HT:PCBM is suggested. The major parameters used for their classification are solubility and drying kinetics. Both are discussed in detail and their consequences on processing are analyzed. Furthermore, a general mechanism to classify the impact of additives on structure formation is suggested and discussed for different materials relevant to organic photovoltaic devices.

Posaconazole in the management of refractory invasive fungal infections.

The rising incidence of invasive fungal infections due to the expanding population of immunocompromised hosts and the increasing prevalence of fungal resistance has led to the need for novel antifungal agents. Posaconazole, a new member of the triazole class has demonstrated in vitro activity against a broad spectrum of fungi and clinical activity against various fungal pathogens, including Aspergillus spp., Candida spp., zygomycetes, and Fusarium spp. To date, posaconazole has been approved for prophylaxis of invasive fungal infections in stem cell transplant recipients with acute graft versus host disease (GVHD) and neutropenic patients receiving intensive induction chemotherapy for acute myelogenous leukemia and myelodys-plastic syndrome. In addition, it has been licensed for use in oropharyngeal candidiasis and for salvage therapy in invasive aspergillosis, fusariosis, coccidioidomycosis, chromoblastomycosis, and mycetoma. Posaconazole is the only azole with activity against zygomycetes and other difficult-to-treat fungi, representing a potential treatment option for refractory invasive mycosis. This article reviews available preclinical and clinical data of posaconazole, focusing on its role in the teatment of refractory invasive fungal infections.

Antifungal management in cancer patients.

Invasive fungal infections (IFI) are a major cause of morbidity and mortality in cancer patients receiving myelotoxic chemotherapy. Established risk factors are previous fungal infection, neutropenia exceeding 10 days, older age, active cancer, corticosteroid therapy, administration of broad spectrum antibiotics, allogeneic HSCT, central venous catheter and organ dysfunction. The strategies to manage IFI comprise chemoprophylaxis, preemptive, empirical and directed antifungal therapy. Benefit of antifungal prophylaxis has been proven for fluconazole (400 mg/d) in allogeneic transplant recipients, and for posaconazole (600 mg/d) in patients during AML/MDS induction chemotherapy as well as in patients with GvHD. Pre-emptive therapy based on sensitive diagnostic non-culture methods needs further validation in larger randomized studies before becoming a standard. Empirical antifungal therapy is well established and should consist of either liposomal amphotericin B, itraconazole, voriconazole, or caspofungin. In patients with documented invasive aspergillosis, therapy with voriconazole is the treatment of choice. Liposomal amphotericin B is a good alternative candidate and caspofungin is reserved for salvage treatment. Invasive candidiasis should be treated with caspofungin or one of the lipid based amphotericin B formulations. Since non-albicans species are increasingly observed, the use of fluconazole is reserved for "stable", non-neutropenic patients.