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Abstract: Optical spacer layers based on titaniumalkoxide precursor solutions were prepared by spin-coating on top of bulk heterojunction layers based on poly-3-hexylthiophene (P3HT) and phenyl-C61-butyric acid methylester (PCBM). Models and experiment have shown that the performance of polymer solar cells can improve upon application of an optical spacer by shifting the maximum of the electrical field vector of the incident light into the active layer. This avoids the so called “dead zone” close to the reflective electrode. We demonstrate a simple linear model that can be used to predict the intensity variations of the electrical field vector of the incident light through a multilayer structure. Central to our study is the thickness of the optical layer and we find that it is critical to control the optical spacer thickness on the actual active layer employed. X-ray reflectometry allows for the simultaneous determination of the active layer thickness and of the optical spacer layer. [Copyright &y& Elsevier]

Computationally efficient simulations of grazing-incidence X-ray diffraction (GIXD) are discussed, with particular attention given to textured thin polycrystalline films on supporting substrates. A computer program has been developed for simulating scattering from thin films exhibiting varying degrees of preferred orientation. One emphasized common case is that of a `fibre' symmetry axis perpendicular to the sample plane, resulting from crystallites having one well defined crystal facet towards the substrate, but no preferred in- plane orientation. Peak splitting caused by additional scattering from the totally substrate-reflected beam (two-beam approximation) and refraction effects are also included in the program, together with the geometrical intensity corrections associated with GIXD measurements. To achieve `user friendliness' for scientists less familiar with diffraction, the mathematically simplest possible descriptions are sought whenever feasible. The practical use of the program is demonstrated for a selected thin-film example, perylene, which is of relevance for organic electronics. [ABSTRACT FROM AUTHOR]

Spin-coated poly(9,9-di-n-octylfluorene-alt-benzothiacliazole) (F8BT) films of different molecular weights (Mn = 9—255 kg/mol), both in the pristine and annealed state, were studied in an effort to elucidate changes in the polymer packing structure and the effects this structure has on the optoelectronic and charge transport properties of these films. A model based on quantum chemical calculations, wide-angle X-ray scattering, atomic force microscopy, Raman spectroscopy, photoluminescence, and electron mobility measurements was developed to describe the restructuring of the polymer film as a function of polymer chain length and annealing. In pristine high molecular weight films, the polymer chains exhibit a significant torsion angle between the F8 and BT units, and the BI units in neighboring chains are close to one another. Annealing films to sufficiently high transition temperatures allows the polymers to adopt a lower energy configuration in which the BT units in one polymer chain are adjacent to F8 units in a neighboring chain ("alternating structure"), and the torsion angle between F8 and BT units is reduced. This restructuring, dictated by the strong dipole on the BT unit, subsequently affects the efficiencies of interchain electron transfer and exciton migration. Films exhibiting the alternating structure show significantly lower electron mobilities than those of the pristine high molecular weight films, due to a decrease in the efficiency of interchain electron transport in this structure. In addition, interchain exciton migration to low energy weakly emissive states is also reduced for these alternating structure films, as observed in their photoluminescence spectra and efficiencies. [ABSTRACT FROM AUTHOR]

ABSTRACT Owing to changes in their chemistry and structure, polymers can be fabricated to demonstrate vastly different electrical conductivities over many orders of magnitude. At the high end of conductivity is the class of conducting polymers, which are ideal candidates for many applications in low-cost electronics. Here, we report the influence of the nature of the doping anion at high doping levels within the semi-metallic conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) on its electronic transport properties. Hall effect measurements on a variety of PEDOT samples show that the choice of doping anion can lead to an order of magnitude enhancement in the charge carrier mobility > 3 cm2/Vs at conductivities approaching 3000 S/cm under ambient conditions. Grazing Incidence Wide Angle X-ray Scattering, Density Functional Theory calculations, and Molecular Dynamics simulations indicate that the chosen doping anion modifies the way PEDOT chains stack together. This link between structure and specific anion doping at high doping levels has ramifications for the fabrication of conducting polymer-based devices. © 2017 The Authors. Journal of Polymer Science Part B: Polymer Physics Published by Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 97-104 [ABSTRACT FROM AUTHOR]

Poly(ethylene oxide) (PEO) thin films of different thicknesses (220, 450, and 1500 nm) and molecular masses (4000, 8000, and 20 000 g/mol) have been fabricated by spin-coating of methanol solutions onto glass substrates. All these samples have been recrystallized from the melt using a directional thermal gradient technique. Millimeter-size domains with crystallites uniformly oriented in the direction of the thermal gradient are observed. Futhermore, the crystallites size and orientation distribution are enhanced (e.g., increases and decreases, respectively) when film thickness is decreased, ultimately leading to a single-crystal-like behavior for 220 nm thick PEO films of mass 8000 g/mol. Interestingly, this fine microstructure is partially retained after melting and subsequent cooling back to ambient temperature for the highest molecular weight polymer allowing, in this particular case, to significantly decrease the distribution of crystal orientation obtained after crystallization using the thermal gradient technique. [ABSTRACT FROM AUTHOR]

Conjugated polymers and small molecules based on alternating electron-donating (D) and electron-accepting (A) building blocks have led to state-of-the-art organic solar cell materials governing efficiencies beyond 10%. Unfortunately, the connection of D and A building blocks via cross-coupling reactions does not always proceed as planned, which can result in the generation of side products containing D-D or A-A homocoupling motifs. Previous studies have reported a reduced performance in polymer and small molecule solar cells when such defect structures are present. A general consensus on the impact of homocouplings on device performance is, however, still lacking as is a profound understanding of the underlying causes of the device deterioration. For differentiating the combined effect of molecular weight and homocouplings in polymer solar cells, a systematic study on a small molecule system (DTS(FBBTh2)2) is presented. The impact of homocouplings on nanomorphology, thermal, and electro-optical properties is investigated. It is demonstrated that small quantities of homocouplings (<10%) already lead to suboptimal device performance, as this strongly impacts the molecular packing and electronic properties of the photoactive layer. These results highlight the importance of material purity and pinpoint homocoupling defects as one of the most probable reasons for batch-to-batch variations. [ABSTRACT FROM AUTHOR]

In an effort to understand recent results showing differences between the power conversion efficiencies of lead halide (CH3NH3PbI3−xClx) solar cells on glass versus flexible substrates, this study investigates the influence that substrate and processing methods have on morphological and crystallographic development. Using our in situ slot-die micro roll-to-roll coater setup, we measured small and wide angle X-ray scattering in grazing incidence while the material dried, enabling us to follow the crystallization from just after the deposition and up to 25 minutes later. The data showed differing crystallographic developments between the substrates, especially seen through the behaviour of a crystalline precursor which survived longer on the flexible substrates than on glass. Additionally, the common degradation product PbI2 was absent on the thickest flexible substrate. This leads us to conjecture that the flexible substrates absorb part of the solvent, thereby delaying evaporation and changing the solvent environment around the perovskite. As a further test, we produced solar cells with the same substrates and confirmed that the ones made on flexible substrates performed worse than those made on glass, but that when including an ITO layer in the stack it seemed to act as a buffer, whereby the solar cell performance was improved. [ABSTRACT FROM AUTHOR]

The realization of a complete tandem polymer solar cell under ambient conditions using only printing and coating methods on a flexible substrate results in a fully scalable process but also requires accurate control during layer formation to succeed. The serial process where the layers are added one after the other by wet processing leaves plenty of room for error and the process development calls for an analytical technique that enables 3D reconstruction of the layer stack with the possibility to probe thickness, density, and chemistry of the individual layers in the stack. The use of ptychography on a complete 12-layer solar cell stack is presented and it is shown that this technique provides the necessary insight to enable efficient development of inks and processes for the most critical layers in the tandem stack such as the recombination layer where solvent penetration in fully solution processed 12-layer stacks is critical in eleven of the steps. [ABSTRACT FROM AUTHOR]

Fiber-reinforced composites deliver lightweight but strong structures that are crucial in applications ranging from aerospace to the automotive industry. The advent of freeform injection molding has made the manufacturing of complex fiber-reinforced composites with full design freedom possible. Prediction of the mechanical properties, dictated by the local microfiber orientation, is essential for the performance characterization of fiber-reinforced composites. However, with conventional microtomography, the required microscale spatial resolution and the macroscopic field of view for full-size fiber-reinforced composite pieces cannot be effectively decoupled. X-ray scattering tensor tomography enables non-destructive macroscopic mapping of the local microfiber orientation as well as their degree of alignment. Recent advancements in X-ray optics have significantly increased the acquisition speed, making the tensor tomography attractive for industrial applications. Nonetheless, integration of the tensor tomography within production lines requires a flexible and robust implementation. In this work, we demonstrate the potential of X-ray scattering tensor tomography for industrial applications by characterizing the microstructure of a centimeter-sized industrially relevant freeform injection molding fiber-reinforced composite sample. We also show that the tensor tomography is compatible with robotic arms, which can position and orient objects in three dimensions with high flexibility and therefore are ideal sample manipulators for the tensor tomography in industrial settings. The results obtained with the robotic arm are compared to those obtained with the state-of-the-art 2-axis sample manipulation scheme. The retrieved information is highly consistent and shows agreement also with structure tensor analyses of conventional microtomography data taken at selected regions of the sample for additional validation. [ABSTRACT FROM AUTHOR]

Imaging nanoparticles under relevant reaction conditions of high temperature and gas pressure is difficult because conventional imaging techniques, like transmission electron microscopy, cannot be used. Here we demonstrate that the coherent diffractive imaging technique of X-ray ptychography can be used for in situ phase contrast imaging in structure studies at atmospheric pressure and elevated temperatures. Lithium zirconate, a candidate CO2 capture material, was studied at a pressure of one atmosphere in air and in CO2, at temperatures exceeding 600 °C. Images with a spatial resolution better than 200 nm were retrieved, and possibilities for improving the experiment are described. [ABSTRACT FROM AUTHOR]

Polymers are lightweight, flexible, solution-processable materials that are promising for low-cost printed electronics as well as for mass-produced and large-area applications. Previous studies demonstrated that they can possess insulating, semiconducting or metallic properties; here we report that polymers can also be semi-metallic. Semi-metals, exemplified by bismuth, graphite and telluride alloys, have no energy bandgap and a very low density of states at the Fermi level. Furthermore, they typically have a higher Seebeck coefficient and lower thermal conductivities compared with metals, thus being suitable for thermoelectric applications. We measure the thermoelectric properties of various poly(3,4-ethylenedioxythiophene) samples, and observe a marked increase in the Seebeck coefficient when the electrical conductivity is enhanced through molecular organization. This initiates the transition from a Fermi glass to a semi-metal. The high Seebeck value, the metallic conductivity at room temperature and the absence of unpaired electron spins makes polymer semi-metals attractive for thermoelectrics and spintronics. [ABSTRACT FROM AUTHOR]

• 3D X-ray diffraction yields per-grain strain, texture, twin relations and structure. • Applicable to a broad scope of functional polycrystalline materials. • Demonstrated by application to a kesterite (CZTS) thin film solar cell. • CZTS is a technologically interesting case with complex phase composition. • 3DXRD may detect and characterize secondary phases not otherwise distinguishable. [Display omitted] The non-destructive structural characterization of individual grains in thin-films photovoltaics based on polycrystalline materials is a powerful tool for revealing important details of the microstructure of solar cell absorbers. Here, we use three-dimensional X-ray diffraction (3DXRD) to obtain statistics on the phase, size, orientation and strain tensors of the grains, as well as their twin relations in Cu 2 ZnSnS 4 (CZTS) absorbers. Moreover, this powerful approach allows the non-ambiguous determination of phases with distinct optical and electrical properties but similar lattice parameters, such as CZTS and ZnS. Our analysis over cumulative statistics of nearly 600 grains in polycrystalline CZTS reveals that a fraction of 2.5% corresponds to the ZnS secondary phase. Statistics of the strain distribution in the polycrystalline CZTS layer indicate an average tensile stress in the plane of the film of ~70 MPa and a compressive stress along the normal to the film of ~145 MPa. We found that 41% of the total number of grains in CZTS absorbers are Σ3 twins. We calculate the frequency of the six types of Σ3 boundaries, revealing that the 180° rotation along the axis<221>is the most frequent. Accessing the microstructure opens the possibility to study its influence on the properties of the film, such as bandgap variations due to strain or the role of twin boundaries in the charge transport mechanisms. [ABSTRACT FROM AUTHOR]

Studying noninvasively the internal nanoporous structureof a singleTussah silk fiber under different humidity conditions, we demonstratefor the first time the feasibility of in-situ ptychographic tomography.The resulting 3D images of the silk fiber interior, obtained at bothdry and humid conditions, yield quantitative information about thespatial density variations in the form of detailed maps of the size,shape, and orientation distributions of the nanopores inside the silkfiber, revealing that the fiber swells anisotropically in humid conditions,with the expansion taking place solely normal to the fiber axis. Exploitingquantitative information on the fiber’s electron density, hydrationwas found to proceed through interaction with the silk protein ratherthan filling of pores. [ABSTRACT FROM AUTHOR]

Abstract: Intrinsic polymer parameters such as regio-regularity, molecular weight, and crystallinity play an important role when studying polymer stability. 18 different batches of poly-3-hexyl-thiophene (P3HT) were degraded in a solar simulator (AM1.5G, 1000 W/m2) and the degradation kinetics were monitored. The results suggest that the radical reaction responsible for the photodegradation takes place at terminal thiophene rings exposed at points were the conjugation is broken. This proposed mechanism is supported by the fact that stability scales with regio-regularity following the ratio of head-to-tail connected thiophene units. Annealing was found to relax the P3HT films and increase conjugation length and, in turn, increase stability observed as a delayed spectral blueshift caused by photochemical degradation. Crystallinity was found to play a minor role in terms of stability. Oxygen diffusion and light shielding effects were shown to have a negligible effect on the photochemical degradation rate. The results obtained in this work advance the understanding of polymer stability and will help improve the design of materials used for polymer solar cells resulting in longer lifetimes, which will push the technology closer to large-scale applications. [Copyright &y& Elsevier]

Abstract: Large area polymer tandem solar cells completely processed using roll-to-roll (R2R) coating and printing techniques are demonstrated. A stable tandem structure was achieved by the use of orthogonal ink solvents for the coating of all layers, including both active layers. Processing solvents included water, alcohols and chlorobenzene. Open-circuit voltages close to the expected sum of sub cell voltages were achieved, while the overall efficiency of the tandem cells was found to be limited by the low yielding back cell, which was processed from water based ink. Many of the challenges associated with upscaling the multilayer tandem cells were identified giving valuable information for future experiments and development. [Copyright &y& Elsevier]

Abstract: Double slot-die coating using aqueous inks was employed for the simultaneous coating of the active layer and the hole transport layer (HTL) in fully roll-to-roll (R2R) processed polymer solar cells. The double layer film was coated directly onto an electron transport layer (ETL) comprising doped zinc oxide that was processed by single slot-die coating from water. The active layer comprised poly-3-hexylthiophene:Phenyl-C61-butyric acid methyl ester (P3HT:PCBM) as a dispersion of nanoparticles with a radius of 46nm in water characterized using small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and atomic force microscopy (AFM). The HTL was a dispersion of poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) in water. The films were analyzed using time-of-flight secondary ion mass spectrometry (TOF-SIMS) as chemical probe and X-ray reflectometry as physical probe, confirming the identity of the layered structure. The devices were completed with a back electrode of either Cu tape or evaporated Ag. Under standard solar spectrum irradiation (AM1.5G), current–voltage characterization (J–V) yielded an open-circuit voltage (V oc ), short-circuit current (J sc ), fill factor (FF), and power conversion efficiency (PCE) of 0.24V, 0.5mAcm−2, 25%, and 0.03%, respectively, for the best double slot-die coated cell. A single slot-die coated cell using the same aqueous inks and device architecture yielded a V oc , J sc , FF, and PCE of 0.45V, 1.95mAcm−2, 33.1%, and 0.29%, respectively. [Copyright &y& Elsevier]

The use of hydrated vanadium(V)oxide as a replacement of the commonly employed hole transporting material PEDOT:PSS was explored in this work. Polymer solar cells were prepared by spin coating on glass. Polymer solar cells and modules comprising 16 serially connected cells were prepared using full roll-to-roll (R2R) processing of all layers. The devices were prepared on flexible polyethyleneterphthalate (PET) and had the structure PET/ITO/ZnO/P3HT:PCBM/V2O5∙(H2O)n/Ag. The ITO and silver electrodes were processed and patterned by use of screen printing. The zinc oxide, P3HT:PCBM and vanadium(V)oxide layers were processed by slot-die coating. The hydrated vanadium(V)oxide layer was slot-die coated using an isopropanol solution of vanadyl-triisopropoxide (VTIP). Coating experiments were carried out to establish the critical thickness of the hydrated vanadium(V)oxide layer by varying the concentration of the VTIP precursor over two orders of magnitude. Hydrated vanadium(V)oxide layers were characterized by profilometry, scanning electron microscopy, energy dispersive X-ray spectroscopy, and grazing incidence wide angle X-ray scattering. The power conversion efficiency (PCE) for completed modules was up to 0.18%, in contrast to single cells where efficiencies of 0.4% were achieved. Stability tests under indoor and outdoor conditions were accomplished over three weeks on a solar tracker. [ABSTRACT FROM AUTHOR]

Abstract: By mapping the small-angle X-ray scattering (SAXS) from a looped poly-(para-phenylene terephtalamide) (aramid, PPTA) filament using a synchrotron X-ray microbeam, we investigate the effects of axially compressive and tensile strain on internal fibrillar structures. Unique observations of oscillations in the highly anisotropic SAXS patterns indicate a regular internal structure. Upon increase of the applied compressive strain, a significant decrease in oscillation frequency is observed in the scattering pattern. With an increase in imposed tensile strain an increase in oscillation frequency in the scattering pattern is observed. One model capable of describing the intensity is a model of stacked cylinders. These cylinders could be part of the fibrillar structure present in the PPTA fibres, which consist of cylinder- to tape-like objects, the presence of which is supported by SEM images. One hypothetical physical interpretation presented here for the appearance of a regular internal structure is the occurrence of fibrillar separation in regions undergoing axially compressive strain, and the appearance of strain relief/slip planes between packs of fibrils in regions undergoing tensile strain. Compaction of these packs upon increase of tensile strain could increase the repetition distance in the structure as multiple packs combine to form a single pack. [Copyright &y& Elsevier]

Blends and other multicomponent systems are used in various polymer applications to meet multiple requirements that cannot be fulfilled by a single material. In polymer optoelectronic devices it is often desirable to combine the semiconducting properties of the conjugated species with the excellent mechanical properties of certain commodity polymers. Here we investigate bicomponent blends comprising semicrystalline regioregular poly(3-hexylthiophene) and selected semicrystalline commodity polymers, and show that, owing to a highly favourable, crystallization-induced phase segregation of the two components, during which the semiconductor is predominantly expelled to the surfaces of cast films, we can obtain vertically stratified structures in a one-step process. Incorporating these as active layers in polymer field-effect transistors, we find that the concentration of the semiconductor can be reduced to values as low as 3 wt% without any degradation in device performance. This is in stark contrast to blends containing an amorphous insulating polymer, for which significant reduction in electrical performance was reported. Crystalline–crystalline/semiconducting–insulating multicomponent systems offer expanded flexibility for realizing high-performance semiconducting architectures at drastically reduced materials cost with improved mechanical properties and environmental stability, without the need to design all performance requirements into the active semiconducting polymer itself. [ABSTRACT FROM AUTHOR]

Abstract: The dehydrogenation kinetics of pure and nickel (Ni)-doped (2w/w%) magnesium hydride have been investigated by in situ time-resolved powder X-ray diffraction (PXD). Deactivated samples, i.e. air exposed, are investigated in order to focus on the effect of magnesium oxide (MgO) surface layers, which might be unavoidable for magnesium (Mg)-based storage media for mobile applications. A curved position-sensitive detector covering in and a rotating anode X-ray source provide a time resolution of 45s and up to 90 powder patterns collected during an experiment under isothermal conditions. A quartz capillary cell allowed the in situ study of gas/solid reactions. Three phases were identified: Mg, and MgO and their phase fractions were extracted by Rietveld refinement or integration of selected reflections from each phase. Dehydrogenation curves were constructed and analysed by the Johnson–Mehl–Avrami formalism in order to derive rate constants at different temperatures. The apparent activation energies for dehydrogenation of pure and Ni-doped magnesium hydride were and , respectively. Differential scanning calorimetry gave, for dehydrogenation of the Ni-doped sample. The relatively high activation energies are due to MgO surface layers, retarding the diffusion of hydrogen out of . The observed difference in of ca. 50kJ/mol is likely due to the catalytic effect of Ni on the recombination of H atoms to molecules verified by theoretical considerations. [Copyright &y& Elsevier]

Determining the effects of stress on the internal structure of high-performance fibres may provide insight into their structure-property relationships. The deformation of voids inside a poly( p-phenylene terephthalamide) (PPTA) fibre upon application of stress is one such effect which may be observed using in situ small-angle X-ray scattering. For this purpose, a compact in-vacuum stretching device is described here, capable of applying a force of up to 500 N using specially designed fibre clamps. Furthermore, a small radiative heater is placed around the fibre at the measurement position, so that the effects of the application of heat during tensile load can also be determined. Initial results show a slight but significant effect of stress and heating on the internal void structure of PPTA fibres. The effects on the void structure of heating and stress appear to be markedly different. [ABSTRACT FROM AUTHOR]

Jens W. Andreasen and co‐workers identify and surmount the challenges of fast and scalable manufacture of polymer tandem solar cells as reported in article number 1400736. This is accomplished by combining in situ X‐ray scattering and the high resolution 3D X‐ray vision provided by coherent synchrotron radiation diffractive imaging. [ABSTRACT FROM AUTHOR]

A correction to the article "Semi-metallic polymers" that was published online in a previous issue is presented.