In this work, we employ a simple two-step growth technique to deposit impurity doped heteroepitaxial thin films of (0001) ZnO onto (111) MgAl2O4 spinel substrates through a combination of atomic layer deposition (ALD) and hydrothermal growth. The hydrothermal layer is doped with Al, Ga, and In through the addition of their respective nitrate salts. We evaluated the effect that varying the concentrations of these dopants has on both the structural and optical properties of these films. It was found that the epitaxial ALD layer created a ⟨111⟩MgAl2O4∥⟨0001⟩ZnO out-of-plane orientation and a ⟨1¯1¯2⟩MgAl2O4∥∥⟨011¯0⟩ZnO in-plane orientation between the film and substrate. The rocking curve line widths ranged between 0.75° and 1.80° depending on dopant concentration. The optical bandgap determined through the Tauc method was between 3.28 eV and 3.39 eV and showed a Burstein-Moss shift with increasing dopant concentration.

The film thickness of one of the most crystalline and highest performing polymer semiconductors, poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b] thiophene) (PBTTT), is varied in order to determine the effects of interfaces and confinement on the microstructure and performance in organic field effect transistors (OFETs). Crystalline texture and overall film crystallinity are found to depend strongly on film thickness and thermal processing. The angular distribution of crystallites narrows upon both a decrease in film thickness and thermal annealing. These changes in the film microstructure are paired with thin-film transistor characterization and shown to be directly correlated with variations in charge carrier mobility. Charge transport is shown to be governed by film crystallinity in films below 20 nm and by crystalline orientation for thicker films. An optimal thickness is found for PBTTT at which the mobility is maximized in unannealed films and where mobility reaches a plateau at its highest value for annealed films. The effects of confinement on the morphology and charge transport properties of poly(2,5-bis(3-tetradecylthiophen-2-yl) thieno[3,2-b]thiophene) (PBTTT) are studied using quantitative X-ray diffraction and field-effect transistor measurements. Polymer crystallinity is found to limit charge transport in the thinnest films while crystalline texture and intergrain connectivity modulate carrier mobility in thicker films. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

© 2014 Cambridge University Press. A pinned or free-floating rigid plate lying on the free surface of a thin film of viscous fluid, which itself lies on top of a horizontal substrate that is moving to the right at a constant speed is considered. The focus of the present work is to describe how the competing effects of the speed of the substrate, surface tension, viscosity, and, in the case of a pinned plate, the prescribed pressure in the reservoir of fluid at its upstream end, determine the possible equilibrium positions of the plate, the free surface, and the flow within the film. The present problems are of interest both in their own right as paradigms for a range of fluid-structure interaction problems in which viscosity and surface tension both play an important role, and as a first step towards the study of elastic effects.

© 2014 American Chemical Society. We investigate the role of molecular weight (MW) of the photoactive polymer poly(3-hexylthiophene) (P3HT) on the temperature-dependent decohesion kinetics of bulk heterojunction (BHJ) organic solar cells (OSCs). The MW of P3HT has been directly correlated to its carrier field effect mobilities and the ambient temperature also affects OSC in-service performance and P3HT arrangement within the BHJ layer. Under inert conditions, time-dependent decohesion readily occurs within the BHJ layer at loads well below its fracture resistance. We observe that by increasing the MW of P3HT, greater resistance to decohesion is achieved. However, failure consistently occurs within the BHJ layer representing the weakest layer within the device stack. Additionally, it was found that at temperatures below the glass transition temperature (∼41-45 °C), decohesion was characterized by brittle failure via molecular bond rupture. Above the glass transition temperature, decohesion growth occurred by a viscoelastic process in the BHJ layer, leading to a significant degree of viscoelastic deformation. We develop a viscoelastic model based on molecular relaxation to describe the resulting behavior. The study has implications for OSC long-term reliability and device performance, which are important for OSC production and implementation.

© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Nanoionics has become an increasingly promising field for the future development of advanced energy conversion and storage devices, such as batteries, fuel cells, and supercapacitors. Particularly, nanostructured materials offer unique properties or combinations of properties as electrodes and electrolytes in a range of energy devices. However, the enhancement of the mass transport properties at the nanoscale has often been found to be difficult to implement in nanostructures. Here, an artificial mixed ionic electronic conducting oxide is fabricated by grain boundary (GB) engineering thin films of La0.8Sr0.2MnO3+δ. This electronic conductor is converted into a good mixed ionic electronic conductor by synthesizing a nanostructure with high density of vertically aligned GBs with high concentration of strain-induced defects. Since this type of GBs present a remarkable enhancement of their oxide-ion mass transport properties (of up to six orders of magnitude at 773 K), it is possible to tailor the electrical nature of the whole material by nanoengineering, especially at low temperatures. The presented results lead to fundamental insights into oxygen diffusion along GBs and to the application of these engineered nanomaterials in new advanced solid state ionics devices such are micro-solid oxide fuel cells or resistive switching memories. An electronic conductor such as La0.8Sr0.2MnO3+δ is converted into a good mixed ionic electronic conductor by synthesizing a nanostructure with excellent electronic and oxygen mass transport properties. Oxygen diffusion highways are created by promoting a high concentration of strain-induced defects in the grain boundary region. This novel strategy opens the way for synthesizing new families of artificial mixed ionic-electronic conductors by design.

We investigate and compare the boundary conditions that are to be applied to free-surface problems involving inlet and outlets of Newtonian fluid, typically found in coating processes. The flux of fluid is a priori known at an inlet, but unknown at an outlet, where it is governed by the local behaviour near the film-forming meniscus. In the limit of vanishing capillary number Ca it is well known that the flux scales with Ca 2/3, but this classical result is non-uniform as the contact angle approaches π. By examining this limit we find a solution that is uniformly valid for all contact angles. Furthermore, by considering the far-field behaviour of the free surface we show that there exists a critical capillary number above which the problem at an inlet becomes over-determined. The implications of this result for the modelling of coating flows are discussed. © 2012 Cambridge University Press.

Grazing incidence X-ray scattering (GIXS) is used to characterize the morphology of poly(3-hexylthiophene) (P3HT)-phenyl-C61-butyric acid methyl ester (PCBM) thin film bulk heterojunction (BHJ) blends as a function of thermal annealing temperature, from room temperature to 220 °C. A custom-built heating chamber for in situ GIXS studies allows for the morphological characterization of thin films at elevated temperatures. Films annealed with a thermal gradient allow for the rapid investigation of the morphology over a range of temperatures that corroborate the results of the in situ experiments. Using these techniques the following are observed: the melting points of each component; an increase in the P3HT coherence length with annealing below the P3HT melting temperature; the formation of well-oriented P3HT crystallites with the (100) plane parallel to the substrate, when cooled from the melt; and the cold crystallization of PCBM associated with the PCBM glass transition temperature. The incorporation of these materials into BHJ blends affects the nature of these transitions as a function of blend ratio. These results provide a deeper understanding of the physics of how thermal annealing affects the morphology of polymer-fullerene BHJ blends and provides tools to manipulate the blend morphology in order to develop high-performance organic solar cell devices. © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

We show here that treatment of thin films of conjugated polymers by illumination with light leads to an increase of the intensity of their photoluminescence by up to 42%. The corresponding enhancement of absorbance was much less pronounced. We explain this significant enhancement of photoluminescence by a planarization of the conjugated polymer chains induced by photoexcitations even below the glass transition temperature, possibly due to an increased conjugation length. Interestingly, the photoluminescence remains at the enhanced level for more than 71 h after treatment of the films by illumination with light, likely due to the fact that below the glass transition temperature no restoring force could return the conjugated chains into their initial conformational state. © 2014 American Chemical Society.

The microstructure of neat conjugated polymers is crucial in determining the ultimate morphology and photovoltaic performance of polymer/fullerene blends, yet until recently, little work has focused on controlling the former. Here, we demonstrate that both the long-range order along the (100)-direction and the lamellar crystal thickness along the (001)-direction in neat poly(3-hexylthiophene) (P3HT) and poly[(3,3″-didecyl[2,2′:5′, 2″-terthiophene]-5,5″-diyl)] (PTTT-10) thin films can be manipulated by varying crystallization temperature. Changes in crystalline domain size impact the yield and dynamics of photogenerated charge carriers. Time-resolved microwave conductivity measurements show that neat polymer films composed of larger crystalline domains have longer photoconductance lifetimes and charge carrier yield decreases with increasing crystallite size for P3HT. Our results suggest that the classical polymer science description of temperature-dependent crystallization of polymers from solution can be used to understand thin-film formation in neat conjugated polymers, and hence, should be considered when discussing the structural evolution of organic bulk heterojunctions. © 2014 Wiley Periodicals, Inc.

The steady three-dimensional flow of a thin, slowly varying ring of Newtonian fluid on either the outside or the inside of a uniformly rotating large horizontal cylinder is investigated. Specifically, we study 'full-ring' solutions, corresponding to a ring of continuous, finite and non-zero thickness that extends all of the way around the cylinder. In particular, it is found that there is a critical solution corresponding to either a critical load above which no full-ring solution exists (if the rotation speed is prescribed) or a critical rotation speed below which no full-ring solution exists (if the load is prescribed). We describe the behaviour of the critical solution and, in particular, show that the critical flux, the critical load, the critical semi-width and the critical ring profile are all increasing functions of the rotation speed. In the limit of small rotation speed, the critical flux is small and the critical ring is narrow and thin, leading to a small critical load. In the limit of large rotation speed, the critical flux is large and the critical ring is wide on the upper half of the cylinder and thick on the lower half of the cylinder, leading to a large critical load. We also describe the behaviour of the non-critical full-ring solution and, in particular, show that the semi-width and the ring profile are increasing functions of the load but, in general, non-monotonic functions of the rotation speed. In the limit of large rotation speed, the ring approaches a limiting non-uniform shape, whereas in the limit of small load, the ring is narrow and thin with a uniform parabolic profile. Finally, we show that, while for most values of the rotation speed and the load the azimuthal velocity is in the same direction as the rotation of the cylinder, there is a region of parameter space close to the critical solution for sufficiently small rotation speed in which backflow occurs in a small region on the upward-moving side of the cylinder. © 2013 Cambridge University Press.