Facilitating Absorption Spectroscopy of Strongly Absorbing Fluids: A High-Throughput Approach.

Measuring absorption spectra of strongly absorbing solutions is usually only possible by diluting the solution. However, the absorption spectra can be heavily influenced by concentration-dependent interactions, so dilution leads to misleading results. To enable reliable absorption measurements of concentrated solutions, we introduce in this work thinning fluid film spectroscopy (TFFS), a simple and highly automatable method.

Ultrafast Proton Conduction in an Aqueous Electrolyte Confined in Adamantane-like Micropores of a Sulfonated, Aromatic Framework.

Sulfonated, cross-linked porous polymers are promising frameworks for aqueous high-performance electrolyte-host systems for electrochemical energy storage and conversion. The systems offer high proton conductivities, excellent chemical and mechanical stabilities, and straightforward water management. However, little is known about mass transport mechanisms in such nanostructured hosts.

Effects of the Grazing Incidence Geometry on X-ray Photon Correlation Spectroscopy Measurements.

X-ray photon correlation spectroscopy (XPCS) is a versatile tool to measure dynamics on the nanometer to micrometer scale in bulk samples. XPCS has also been applied in grazing incidence (GI) geometry to examine the dynamics of surface layers. However, considering GI scattering experiments more universally, the GI geometry leads to a superposition of signals due to reflection and refraction effects, also known from the distorted-wave Born approximation (DWBA).

Spark Discharge Doping-Achieving Unprecedented Control over Aggregate Fraction and Backbone Ordering in Poly(3-hexylthiophene) Solutions.

The properties of semiconducting polymers are strongly influenced by their aggregation behavior, that is, their aggregate fraction and backbone planarity. However, tuning these properties, particularly the backbone planarity, is challenging. This work introduces a novel solution treatment to precisely control the aggregation of semiconducting polymers, namely current-induced doping (CID).

Effects of the diphenyl ether additive in halogen-free processed non-fullerene acceptor organic solar cells.

The development of an environmentally friendly fabrication process for non-fullerene acceptor organic solar cells is an essential condition for their commercialization. However, devices fabricated by processing the active layer with green solvents still struggle to reach, in terms of efficiency, the same performance as those fabricated with halogenated solvents. The reason behind this is the non-optimal nanostructure of the active layer obtained with green solvents.

Traps and transport resistance are the next frontiers for stable non-fullerene acceptor solar cells.

Stability is one of the most important challenges facing material research for organic solar cells (OSC) on their path to further commercialization. In the high-performance material system PM6:Y6 studied here, we investigate degradation mechanisms of inverted photovoltaic devices. We have identified two distinct degradation pathways: one requires the presence of both illumination and oxygen and features a short-circuit current reduction, the other one is induced thermally and marked by severe losses of open-circuit voltage and fill factor.

Degradation of low-density polyethylene to nanoplastic particles by accelerated weathering.

When plastics enter the environment, they are exposed to abiotic and biotic impacts, resulting in degradation and the formation of micro- and nanoplastic. Microplastic is ubiquitous in every environmental compartment. Nevertheless, the underlying degradation processes are not yet fully understood.

The Impact of Solvent Vapor on the Film Morphology and Crystallization Kinetics of Lead Halide Perovskites during Annealing.

One of the key factors for the remarkable improvements of halide perovskite solar cells over the last few years is the increased control over perovskite crystallinity and its thin film morphology. Among various processing methods, solvent vapor-assisted annealing (SVAA) has proven to be promising in achieving high-quality perovskite films. However, a comprehensive understanding of the perovskite crystallization process during SVAA is still lacking.

Ionic-Liquid Doping Enables High Transconductance, Fast Response Time, and High Ion Sensitivity in Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) are highly attractive for applications ranging from circuit elements and neuromorphic devices to transducers for biological sensing, and the archetypal channel material is poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), PEDOT:PSS. The operation of OECTs involves the doping and dedoping of a conjugated polymer due to ion intercalation under the application of a gate voltage. However, the challenge is the trade-off in morphology for mixed conduction since good electronic charge transport requires a high degree of ordering among PEDOT chains, while efficient ion uptake and volumetric doping necessitates open and loose packing of the polymer chains.

Directing the Aggregation of Native Polythiophene during in Situ Polymerization.

The performance of semiconducting polymers strongly depends on their intra- and intermolecular electronic interactions. Therefore, the morphology and particularly crystallinity and crystal structure play a crucial role in enabling a sufficient overlap between the orbitals of neighboring polymers. A new solution-based in situ polymerization for the fabrication of native polythiophene thin films is presented, which exploits the film formation process to influence the polymer crystal structure in the resulting thin films.

Resonant Grazing-Incidence Small-Angle X-ray Scattering at the Sulfur K-Edge for Material-Specific Investigation of Thin-Film Nanostructures.

Scattering techniques are a powerful tool for probing thin-film nanomorphologies but often require additional characterization by other methods. We applied the well-established grazing-incidence small-angle X-ray scattering (GISAXS) technique for a selection of energies around the absorption edge of sulfur to exploit the resonance effect (grazing incidence resonant tender X-ray scattering, GIR-TeXS) of the sulfur atoms within a poly(3-hexylthiophene-2,5-diyl):phenyl-C61-butyric acid methyl ester (P3HT:PC61BM) sample to gain information about the composition of the film morphology. With this approach, it is possible not only to identify structures within the investigated thin film but also to link them to a particular material combination.

Printed Thin Magnetic Films Based on Diblock Copolymer and Magnetic Nanoparticles.

Printing techniques have been well established for large-scale production and have developed to be effective in controlling the morphology and thickness of the film. In this work, printing is employed to fabricate magnetic thin films composed of polystyrene coated maghemite nanoparticles (γ-FeO NPs) and polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer. By applying an external magnetic field during the print coating step, oriented structures with a high content of nanoscale magnetic particles are created.

Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films.

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale.

Codependence between Crystalline and Photovoltage Evolutions in P3HT:PCBM Solar Cells Probed with in-Operando GIWAXS.

We address the correlation between the crystalline state of photoactive materials in a model organic solar cell based on poly(3-hexylthiophene-2,5-diyl):phenyl-C-butyric acid methyl ester (P3HT:PCBM) and the photovoltage in an in-operando investigation. I-V curves are simultaneously measured together with grazing incidence wide-angle X-ray scattering probing the crystalline state of the device active layer as a function of the operation time. The results show a high degree of correlation between open-circuit voltage V and the crystalline state of P3HT.

Solvent-Morphology-Property Relationship of PTB7:PCBM Polymer Solar Cells.

The influence of three different solvents and a solvent additive on the morphology and photovoltaic performance of bulk heterojunction films made of the copolymer based on thieno[3,4-b]thiophene-alt-benzodithiophene unit PTB7-F40 blended with [6,6]-phenyl-C71-butyric acid methyl ester (PCBM) is investigated. Optical microscopy and atomic force microscopy are combined with X-ray reflectivity and grazing incidence small and wide-angle X-ray scattering (GISAXS and GIWAXS, respectively), enabling the characterization of the morphology of the whole photoactive film. The detailed study reveals that different length scales of PCBM clusters are observed using different solvents, while adding a solvent additive results in the PCBM clusters being selectively dissolved.

Substituted Septithiophenes with End Groups of Different Size: Packing and Frustration in Bulk and Thin Films.

We report on three different liquid crystalline compounds with a central septithiophene core and alkylated end groups of strongly increasing bulkiness. In principle, the thiophene cores prefer to pack parallel to optimize their π-π interactions, which becomes sterically impossible for the bulkier end groups. Using X-ray diffraction, we find that the way out of this packing dilemma is toward liquid-crystal phases of higher dimensionality in the order smectic → columnar ↔ bicontinuous cubic.

Effect of Methanol Addition on the Resistivity and Morphology of PEDOT:PSS Layers on Top of Carbon Nanotubes for Use as Flexible Electrodes.

Unlabelled: Overcoating carbon nanotube (CNT) films on flexible poly(ethylene terephthalate) (PET) foils with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (

Pedot: PSS) layers reduces the surface roughness, which is interesting for use in organic electronics. Adding methanol to the

Pedot: PSS aqueous solution used for spin coating of the

Pedot: PSS layer improves the wetting behavior of the CNT/PET surface. Samples with different volume fractions of methanol (0, 33, 50, 67, and 75 vol %) are compared with respect to the transmission, horizontal, and vertical resistivity.

Monolayer properties of asymmetrically substituted sexithiophene.

We present a structural comparison of monolayers on a SiO2 substrate of two asymmetrically substituted sexithiophenes (6T). Molecule 1 consists of 6T with a branched alkyl chain at one end only and shows a crystalline structure. In molecule 2, the bifunctional 6T has in addition at the other end a linear alkyl chain.

Influence of solvent and solvent additive on the morphology of PTB7 films probed via X-ray scattering.

Films of the semiconducting polymer poly[[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl]] with 40% fluorinated monomers, denoted PTB7-F40, are spin coated out of different solvents onto PEDOT:PSS films. The influence of the used solvents chlorobenzene, 1,2-dichlorobenzene, and 1,2,4-trichlorobenzene as well as the influence of the additive 1,8-diiodooctane (DIO) is probed with grazing incidence small- and wide-angle X-ray scattering (GISAXS and GIWAXS). As seen with GISAXS, without DIO, the films are homogeneous and show roughness correlation with the PEDOT:PSS film surface.

Custom-made morphologies of ZnO nanostructured films templated by a poly(styrene-block-ethylene oxide) diblock copolymer obtained by a sol-gel technique.

Zinc oxide (ZnO) nanostructured films are synthesized on silicon substrates to form different morphologies that consist of foamlike structures, wormlike aggregates, circular vesicles, and spherical granules. The synthesis involves a sol-gel mechanism coupled with an amphiphilic diblock copolymer poly(styrene-block-ethylene oxide), P(S-b-EO), which acts as a structure-directing template. The ZnO precursor zinc acetate dihydrate (ZAD) is incorporated into the poly(ethylene oxide) block.

Low-temperature sol-gel synthesis of nanostructured polymer/titania hybrid films based on custom-made poly(3-alkoxy thiophene).

A low-temperature route to directly obtain polymer/titania hybrid films is presented. For this, a custom-made poly(3-alkoxy thiophene) was synthesized and used in a sol-gel process together with an ethylene-glycol-modified titanate (EGMT) as a suitable titania precursor. The poly(3-alkoxy thiophene) was designed to act as the structure-directing agent for titanium dioxide through selective incorporation of the titania precursor.