Organic photovoltaics (OPVs) is a promising low-cost and environmental-friendly technology currently achieving 12-14% power conversion efficiency. Despite the extensive focus of the research community over the last years, critical mechanisms defining the performance of OPVs are still topics of debate. While energetic disorder is known to be characteristic of organic semiconductors in general, its potential role in OPV has received surprisingly little attention. In this thesis we investigate some aspects of the relation between energetic disorder and several optoelectronic properties of OPV. Charge carrier mobility is a key parameter in characterizing the performance of organic semiconductors. Analyzing the temperature dependence of the mobility is also an oftenused method to obtain (estimates for) the energetic disorder in the HOMO and LUMO levels of an organic semiconductor material. Different formalisms to extract and analyze mobilities from space charge limited conductivity (SCLC) experiments are reviewed. Surprisingly, the Murgatroyd-Gill analytical model in combination with the Gaussian disorder model in the Boltzmann limit yields similar mobilities and energetic disorders as a more elaborate drift-diffusion model with parametrized mobility functionals. Common analysis and measurement errors are discussed. All the models are incorporated in an automated analysis freeware tool. The open circuit voltage (Voc) has attracted considerable interest as the large difference between Voc and the bandgap is the main loss mechanism in bulk heterojunction OPVs. Surprisingly, in ternary devices composed of two donors and one acceptor, the Voc is not pinned to the shallowest HOMO but demonstrates a continuous tunability between the binary extremities. We show that this phenomenon can be explained with an equilibrium model where Voc is defined as the splitting of the quasi-Fermi levels of the photo-created holes and electrons in a common density of states accounting for the stoichiometry, i.e. the ratio of the donor materials and the broadening by Gaussian disorder. Evaluating the PCE, it is found that ternary devices do not offer advantages over binary unless the fill factor (FF) is increased at intermediate compositions, as a result of improved transport/recombination upon material blending. Stressing the importance of material intermixing to improve the performance, we found that the presence of an acceptor may drastically alter the mobility and energetic disorder of the donor and vice versa. The effect of different acceptors was studied in a ternary onedonor- two-acceptors system, where the unpredictable variability with composition of the energetic disorder in the HOMO and the LUMO explained the almost linear tunability of Voc. Designing binary OPVs based on the design rule that the energetic disorder can be reduced upon material blending, as we observed, can yield a relative PCE improvement of at least 20%. CT states currently play a key role in evaluating the performance of OPVs and CTelectroluminescence (CT-EL) is assumed to stem from the recombination of thermalized electron-hole pairs. The varying width of the CT-EL peak for different material combinations is intuitively expected to reflect the energetic disorder of the effective HOMO and LUMO. We employ kinetic Monte Carlo (kMC) CT-EL simulations, using independently measured disorder parameters as input, to calculate the ground-to-ground state (0-0) transition spectrum. Including the vibronic broadening according to the Franck Condon principle, we reproduce the width and current dependence of the measured CT-EL peak for a large number of donor-acceptor combinations. The fitted dominant phonon modes compare well with the values measured using the spectral line narrowing technique. Importantly, the calculations show that CT-EL originates from a narrow, non-thermalized subset of all available CT states, which can be understood by considering the kinetic microscopic process with which electron-hole pairs meet and recombine. Despite electron-hole pairs being strongly bound in organic materials, the charge separation process following photo-excitation is found to be extremely efficient and independent of the excitation energy. However, at low photon energies where the charges are excited deep in the tail of the DOS, it is intuitively expected for the extraction yield to be quenched. Internal Quantum Efficiency (IQE) experiments for different material systems show both inefficient and efficient charge dissociation for excitation close to the CT energy. This finding is explained by kinetic Monte Carlo simulations accounting for a varying degree of e-h delocalization, where strongly bound localized CT pairs (< 2nm distance) are doomed to recombine at low excitation energies while extended delocalization over 3-5nm yields an increased and energy-independent IQE. Using a single material parameter set, the experimental CT electroluminescence and absorption spectra are reproduced by the same kMC model by accounting for the vibronic progression of the calculated 0-0 transition. In contrast to CT-EL, CT-absorption probes the complete CT manifold. Charge transport in organic solar cells is currently modelled as either an equilibrium or a non-equilibrium process. The former is described by drift-diffusion (DD) equations, which can be calculated quickly but assume local thermal equilibrium of the charge carriers with the lattice. The latter is described by kMC models, that are time-consuming but treat the charge carriers individually and can probe all relevant time and energy scales. A hybrid model that makes use of the multiple trap and release (MTR) concept in combination with the DD equations is shown to describe both steady-state space charge limited conductivity experiments and non-equilibrium time-resolved transport experiments using a single parameter set. For the investigated simulations, the DD-MTR model is in good agreement with kMC and ~10 times faster. Steady-state mobilities from DD equations have been argued to be exclusively relevant for operating OPVs while charge carrier thermalization and non-equilibrium time-dependent mobilities (although acknowledged) can be disregarded. This conclusion, based on transient photocurrent experiments with ?s time resolution, is not complete. We show that non-equilibrium kMC simulations can describe the extraction of charge carriers from subps to 100 ?s timescales with a single parameter set. The majority of the fast charge carriers, mostly non-thermalized electrons, are extracted at time scales below the resolution of the experiment. In other words, the experiment resolves only the slower fraction of the charges, predominantly holes.

This book focuses on organic semiconductors with particular attention paid to their use as photovoltaic devices. It addresses a fundamental and hitherto overlooked concept in the field of organic optoelectronics, namely the role that sub-gap states play in the performance of organic semiconducting devices. From a technological point of view, organic semiconductor-based devices are of significant interest due to their lightweight, ease of processability, conformal flexibility, and potentially low cost and low embodied energy production. Motivated by these rather unique selling points, the performance of organic semiconductors has been a subject of multidisciplinary study for more than 60 years with steady progress in applications such as solar cells, transistors, light emitting diodes, and various sensors. The book begins with a review of the main electro-optical phenomena in organic solar cells and presents a new method for measuring exciton diffusion lengths based on a low-quencher-content device structure. Furthermore, the book reveals how mid-gap trap states are a universal feature in organic semiconductor donor–acceptor blends, unexpectedly contributing to charge generation and recombination, and having profound impact on the thermodynamic limit of organic photovoltaic devices. Featuring cutting-edge experimental observations supported with robust and novel theoretical arguments, this book delivers important new insight as to the underlying dynamics of exciton generation and diffusion, charge transfer state dissociation, and indeed the ultimate fate of photogenerated free carriers.

This volume presents the results of a multi-year research programme funded by the Deutsche Forschungsgemeinschaft (German Research Council), which explains how organic solar cells work. In this new promising photovoltaic technology, carbon-based materials are deposited by low-cost methods onto flexible substrates, thus allowing devices which open completely new applications like transparent coatings for building, solar cells integrated into clothing or packages, and many more. The investigation of organic solar cells is an interdisciplinary topic, covering physics, chemistry and engineering. The different chapters address topics ranging from the synthesis of new organic materials, to the characterization of the elementary processes such as exciton transport and separation, and the principles of highly efficient device design. /div

With power conversion efficiencies on the rise, organic photovoltaics (OPVs) hold promise as a next-generation thin-film solar technology. However, both device performance and stability are inextricably linked to local film structure. Methods capable of probing nanoscale electronic properties as a function of film structure are thus a crucial component of the rational design of efficient and robust devices. This dissertation describes the use of three scanning probe methods for studying local charge generation and photodegradation in polymer/fullerene solar cells. First, we show that time-resolved electrostatic force microscopy (trEFM) is capable of resolving local photocurrent from sub-bandgap excitation down to attoampere level currents, a result unattainable by traditional contact-mode methods. We find that the local charging rates measured with trEFM are proportional to external quantum efficiency (EQE) measurements made on completed devices, making trEFM images equivalent to local EQE maps across the entire solar spectrum. For both phase-segregated and well-mixed MDMO-PPV:PCBM film morphologies, we show that the local distribution of photocurrent is invariant to excitation wavelength, providing local evidence for the controversial result that the probability of generating separated charge carriers does not depend on whether excitons are formed at the singlet state or charge transfer state. Next, we describe how local dissipation imaging can be performed with commercially-available frequency-modulated electrostatic force microscopy (FM-EFM) and show that dissipation maps are highly sensitive to photo-oxidative effects in organic semiconductors. We show that photo-oxidation induced changes in cantilever energy dissipation are proportional to device performance losses. We further develop dissipation imaging by implementing ringdown imaging, which directly measures the quality factor of the cantilever, enabling quantitative dissipation mapping. Using organic photovoltaic materials as a testbed, we study macroscopic device degradation as a function of photooxidation for three different film morphologies. According to EQE measurements, we find that the stability of the macroscopic devices is very sensitive to processing conditions, with films processed with the solvent additive 1,8-diiodooctane being the most stable. At the microscopic level, we compare the evolution of cantilever power dissipation as a function of photochemical degradation for three different polymer/fullerene blend morphologies, and show that the evolution of local power dissipation correlates with device stability. Lastly, we show that cantilever power dissipation increases more rapidly over large fullerene aggregates than in well-mixed polymer/fullerene regions, suggesting that local photochemistry on the fullerene contributes strongly to the dissipation signal.

Organic photovoltaic (OPV) cells have the potential to make a significant contribution to the increasing energy needs of the future. In this book, 15 chapters written by selected experts explore the required characteristics of components present in an OPV device, such as transparent electrodes, electron- and hole-conducting layers, as well as electron donor and acceptor materials. Design, preparation, and evaluation of these materials targeting highest performance are discussed. This includes contributions on modeling down to the molecular level to device-level electrical and optical testing and modeling, as well as layer morphology control and characterization. The integration of the different components in device architectures suitable for mass production is described. Finally, the technical feasibility and economic viability of large-scale manufacturing using fast inexpensive roll-to-roll deposition technologies is assessed.

Undoubtedly the applications of polymers are rapidly evolving. Technology is continually changing and quickly advancing as polymers are needed to solve a variety of day-to-day challenges leading to improvements in quality of life. The Encyclopedia of Polymer Applications presents state-of-the-art research and development on the applications of polymers. This groundbreaking work provides important overviews to help stimulate further advancements in all areas of polymers. This comprehensive multi-volume reference includes articles contributed from a diverse and global team of renowned researchers. It offers a broad-based perspective on a multitude of topics in a variety of applications, as well as detailed research information, figures, tables, illustrations, and references. The encyclopedia provides introductions, classifications, properties, selection, types, technologies, shelf-life, recycling, testing and applications for each of the entries where applicable. It features critical content for both novices and experts including, engineers, scientists (polymer scientists, materials scientists, biomedical engineers, macromolecular chemists), researchers, and students, as well as interested readers in academia, industry, and research institutions.