X-ray based tools for the investigation of buried interfaces in organic electronic devices

X-ray reflectivity combined with grazing incidence diffraction is a valuable tool for investigating organic multilayer structures that can be used in devices. We focus on a bilayer stack consisting of two materials (poly-(3-hexylthiophene)) (P3HT) and poly-(4-styrenesulfonic acid) (PSSA) spin cast from orthogonal solvents (water in the case of PSSA and chloroform or toluene for P3HT). X-ray reflectivity is used to determine the thickness of all layers as well as the roughness of the organic–organic hetero-interface and the P3HT surface. The surface roughness is found to be consistent with the results of atomic force microscopy measurements. For the roughness of P3HT/PSSA interface, we observe a strong dependence on the solvent used for P3HT deposition. The solvent also strongly impacts the texturing of the P3HT crystallites as revealed by grazing incidence diffraction. When applying the various PSSA/P3HT multilayers in organic thin-film transistors, we find an excellent correlation between the determined interface morphology, structure and the device performance.     

Diindenoperylene derivatives: A model to investigate the path from molecular structure via morphology to solar cell performance

Efficient organic electronic devices require a detailed understanding of the relation between molecular structure, thin film growth, and device performance, which is only partially understood at present. Here, we show that small changes in molecular structure of a donor absorber material lead to significant changes in the intermolecular arrangement within organic solar cells. For this purpose, phenyl rings and propyl side chains are fused to the diindenoperylene (DIP) molecule. Grazing incidence X-ray diffraction and variable angle spectroscopic ellipsometry turned out to be a powerful combination to gain detailed information about the thin film growth. Planar and bulk heterojunction solar cells with C60 as acceptor and the DIP derivatives as donor are fabricated to investigate the influence of film morphology on the device performance. Due to its planar structure, DIP is found to be highly crystalline in pristine and DIP:C60 blend films while its derivatives grow liquid-like crystalline. This indicates that the molecular arrangement is strongly disturbed by the steric hindrance induced by the phenyl rings. The high fill factor (FF) of more than 75% in planar heterojunction solar cells of the DIP derivatives indicates excellent charge transport in the pristine liquid-like crystalline absorber layers. However, bulk heterojunctions of these materials surprisingly result in a low FF of only 54% caused by a weak phase separation and thus poor charge carrier percolation paths due to the lower ordered thin film growth. In contrast, crystalline DIP:C60 heterojunctions lead to high FF of up to 65% as the crystalline growth induces better percolation for the charge carriers. However, the major drawback of this crystalline growth mode is the nearly upright standing orientation of the DIP molecules in both pristine and blend films. This arrangement results in low absorption and thus a photocurrent which is significantly lower than in the DIP derivative devices, where the liquid-like crystalline growth leads to a more horizontal molecular alignment. Our results underline the complexity of the molecular structure-device performance relation in organic semiconductor devices.     

Flexible,Mechanically Stable,Porous Self-Standing Microfiber Network Membranes of Covalent Organic Frameworks: Preparation Method and Characterization

Covalent organic frameworks (COFs) show advantageous characteristics, such as an ordered pore structure and a large surface area for gas storage and separation, energy storage, catalysis, and molecular separation. However, COFs usually exist as difficult-to-process powders, and preparing continuous, robust, flexible, foldable, and rollable COF membranes is still a challenge. Herein, such COF membranes with fiber morphology for the first time prepared via a newly introduced template-assisted framework process are reported. This method uses electrospun porous polymer membranes as a sacrificial large dimension template for making self-standing COF membranes. The porous COF fiber membranes, besides having high crystallinity, also show a large surface area (1153 m² g⁻¹), good mechanical stability, excellent thermal stability, and flexibility. This study opens up the possibility of preparation of large dimension COF membranes and their derivatives in a simple way and hence shows promise in technical applications in separation, catalysis, and energy in the future.     

Engineering guide to assessment of creep crack initiation on components by Two-Criteria-Diagram

To assess creep crack initiation on components, it is necessary to consider the stresses at the crack tip as well as in the remaining ligament or farfield region. For that aim the Two-Criteria-Diagram was established. The method was proven by a large number of creep crack initiation results from small and large scale specimens as well as components. In this paper some practical aspects for using the Two-Criteria-Diagram are described. A code of practice for the use of Two-Criteria-Diagram for creep and creep fatigue loading is given. The extension to the latter and the limits of applicability are discussed. The determination of crack initiation in a cast steel containing defects is described as an example showing the advantages of the method for engineering applications.     

Soft Iron/Silicon Composite Tubes for Magnetic Peristaltic Pumping: Frequency‐Dependent Pressure and Volume Flow

The combination of force and flexibility enables controlled and soft movements. In sharp contrast, presently used machines are solid and mostly based on stiff driveshafts or cog wheels. Magnetic elastomers are realized through dispersion of small particles in polymer matrices and have attracted significant interest as soft actuators for controlled movement or conveying and are particularly attractive candidates for magnetic pump applications. At present, low magnetic particle loading and thus limited actuator strength have restricted the application of such materials. Here, the direct incorporation of metal microparticles into a very soft and flexible silicone and its application as an ultra‐flexible, yet strong magnetic tube, is described. Because metals have a far higher saturation magnetization and higher density than oxides, the resulting increased force/volume ratio afforded significantly stronger magnetic actuators with high mechanical stability, flexibility, and shape memory. Elliptical inner diameter shape of the tubing allowed a very efficient contraction of the tube by applying an external magnetic field. The combination of magnetic silicone tubes and a magnetic field generating device results in a magnetic peristaltic pump.     

Poly(3-hexylthiophene)/C60 heterojunction solar cells: Implication of morphology on performance and ambipolar charge collection

The performance of heterojunction organic solar cells is critically dependent on the morphology of the donor and acceptor components in the active film. We report results of photovoltaic devices consisting of bilayers and bulk heterojunctions using poly(3-hexylthiophene) (P3HT) and Buckminsterfullerene C₆₀. White light power efficiencies of η2.2% (bulk heterojunction) and 2.6% (bilayer) were measured after a thermal annealing step on completed devices. Optical and structural investigations on non-annealed bilayer thin films indicated a distinct porosity of the spin-coated polymer, which allows C₆₀ to penetrate the P3HT layer and to touch the anode. This resulted for these bilayer solar cells in the experimental observation that electrons were collected predominantly at the cathode after photo-excitation of P3HT, but predominantly at the anode after C₆₀ excitation. A morphological model to explain the ambipolar charge collection phenomenon is proposed.     

Predictive and Adaptive Resource Reservation (PARR) for Cellular Networks

In cellular networks, a higher priority can, out of Quality of Service reasons, be given to ongoing connections than new call attempts. This can be achieved by having capacity in each cell (guard channels) exclusively reserved for arriving handover calls. In this paper, an advanced guard channel scheme, called Predictive and Adaptive Resource Reservation (PARR), will be introduced. The PARR scheme determines the amount of guard channels to allocate in a cell through subscriber movement predictions. The novelty of PARR is that both positioning and history-based measurements are used as input for the predictions. To improve the prediction accuracy, different data sets are applied for calls with different mobility and latest visited cells. Simulations will be used to show that significant performance improvements are obtainable with PARR.     

Gallium gradients in Cu(In,Ga)Se2 thin‐film solar cells

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co‐evaporation processes, plays a key role in the device performance of CIGS thin‐film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X‐ray measurements. In addition, the gallium grading of a CIGS layer grown with an in‐line co‐evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth‐dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co‐evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi‐Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross‐sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper‐vacancy‐mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co‐evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd.