Correlating Structure And Function In Small Molecule Organic Solar Cells By Means Of Scanning Probe And Electron Microscopy

In this work nanoscale properties in active layers of small molecule organic solar cells are studied regarding their impact on device performance. For this, the effect of variations in stack design and process conditions is examined both electrically and with high resolution imaging techniques. Two topics are addressed: (i) the visualization of charge extraction/injection properties of solar cell contacts and (ii) the tailoring of structural properties of co-evaporated material blends for bulk heterojunction (BHJ) organic solar cells. (i) We study the impact of controlled contact manipulation on the internal electric potential distribution of fluorinated zincphtalocyanine (F4ZnPc)/fullerene (C60) organic solar cells under operating conditions. In a detailed analytical study using photoelectron spectroscopy and in-operando scanning Kelvin probe microscopy it is demonstrated that the electric field distribution of organic solar cells at the maximum power point depends in an overproportional manner on contact properties and ranges from bulk to contact dominated even for solar cells with decent device performance. (ii) The morphology of co-evaporated active layer blends depends on both substrate and substrate temperature. Here we study the morphology of F4ZnPc:C60 blends with analytical transmission electron microscopy. For all substrates used is found that co-evaporation of the materials at elevated substrate temperature (100° Cel) induces a distinct phase segregation of F4ZnPc and C60. However, only when using a C60 underlayer, as in inverted devices, also the crystallinity of the segregated C60 phase increases. There is only a slight increase in crystallinity when F4ZnPc acts as an underlayer, as typically for non-inverted devices. Solar cell characterization reveals that the crystalline C60 domains are the main driving force for enhanced free charge carrier generation and higher power conversion efficiencies. With this we could provide a novel explanation why record efficiencies of small molecule organic solar cells are realized in inverted device architecture only.

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 elect

This book features reviews by leading experts on the methods and applications of modern forms of microscopy. The recent awards of Nobel Prizes awarded for super-resolution optical microscopy and cryo-electron microscopy have demonstrated the rich scientific opportunities for research in novel microscopies. Earlier Nobel Prizes for electron microscopy (the instrument itself and applications to biology), scanning probe microscopy and holography are a reminder of the central role of microscopy in modern science, from the study of nanostructures in materials science, physics and chemistry to structural biology. Separate chapters are devoted to confocal, fluorescent and related novel optical microscopies, coherent diffractive imaging, scanning probe microscopy, transmission electron microscopy in all its modes from aberration corrected and analytical to in-situ and time-resolved, low energy electron microscopy, photoelectron microscopy, cryo-electron microscopy in biology, and also ion microscopy. In addition to serving as an essential reference for researchers and teachers in the fields such as materials science, condensed matter physics, solid-state chemistry, structural biology and the molecular sciences generally, the Springer Handbook of Microscopy is a unified, coherent and pedagogically attractive text for advanced students who need an authoritative yet accessible guide to the science and practice of microscopy.

The great tunability of structure and electronic properties of ?-conjugated organic molecules/polymers combined with other advantages such as light weight and flexibility etc., have made organic-based electronics the focus of an exciting still-growing field of physics and chemistry for more than half a century. The application of organic electronics has led to the appearance of wide range of organic electronic devices mainly including organic light emitting diodes (OLED), organic field effect transistors (OFET) and organic solar cells (OSC). The application of the organic electronic devices mainly is limited by two dominant parameters, i.e., their performance and stability. Up to date, OLED has been successfully commercialized in the market while the OSC are still on the way to commercialization hindered by low efficiency and inferior stability. Understanding the energy levels of organic materials and energy level alignment of the devices is crucial to control the efficiency and stability of the OSC. In this thesis, energy levels measured by different methods are studied to explore their relationship with device properties, and the strategies on how to design efficient and stable OSC based on energy level diagrams are provided. Cyclic Voltammetry (CV) is a traditional and widely used method to probe the energy levels of organic materials, although there is little consensus on how to relate the oxidation/reduction potential ((Eox/Ered) to the vacuum level. Ultraviolet Photoelectron Spectroscopy (UPS) can be used to directly detect vertical ionization potential (IP) of organic materials. In this thesis, a linear relationship of IP and Eox was found, with a slope equal to unity. The relationship provides for easy conversion of values obtained by the two techniques, enabling complementarily use in designing and fabricating efficient and stable OSC. A popular rule of thumb is that the offset between the LUMO levels of donor and acceptor should be 0.3 eV, according to which a binary solar cell with the minimum voltage losses around 0.49 V was designed here. Introduction of the ternary blend as active layer is an efficient way to improve both efficiency and stability of the OSC. Based on our studied energy-level diagram within the integer charge transfer (ICT) model, we designed ternary solar cells with enhanced open circuit voltage for the first time and improved thermal stability compared to reference binary ones. The ternary solar cell with minimum voltage losses was developed by combining two donor materials with same ionization potential and positive ICT energy while featuring complementary optical absorption. Furthermore, the fullerene acceptor was chosen so that the energy of the positive ICT state of the two donor polymers is equal to the energy of negative ICT state of the fullerene, which can enhance dissociation of all polymer donor and fullerene acceptor excitons and suppress bimolecular and trap-assistant recombination. Rapid development of non-fullerene acceptors in the last two years affords more recipes of designing both efficient and stabile OSC. We show in this thesis how non-fullerene acceptors successfully can be used to design ternary solar cells with both enhanced efficiency and thermal stability. Besides improving the efficiency of the devices, understanding of the stability and degradation mechanism is another key issue. The degradation of conjugated molecules/polymers often follow many complicated pathways and at the same time many factors for degradation are coupled with each other. Therefore, the degradation of non-fullerene acceptors was investigated in darkness by photoelectron spectroscopy in this thesis with the in-situ method of controlling exposure of O2 and water vapor separately.

Organic photovoltaic (OPV) devices based on semiconducting polymers and small molecules allow for a low cost alternative to inorganic solar cells. Recent developments show power conversion efficiencies as high as 10-12%, highlighting the potential of this technology. Nevertheless, further improvements are necessary to achieve commercialization. To a large extent the performance of these devices is dictated by their ability to extract the photo-generated charge, which is related to the charge carrier mobility. Various time-resolved and steady-state techniques are available to probe the charge carrier mobility in OPVs but often lead to different mobility values for one and the same system. Despite such conflicting observations it is generally assumed that charge transport in OPV devices can be described by well-defined charge carrier mobilities, typically obtained using a single steady-state technique. This thesis shows that the relevance of such well-defined mobilities for the charge separation and extraction processes is very limited. Although different transient techniques probe different time scales after photogeneration, they are mutually consistent as they probe the same physical mechanism governing charge motion – gradual thermalization of the photo-generated carriers in the disorder broadened density of states (DOS). The photo-generated carriers gradually lose their excess energy during transport to the extracting electrodes, but not immediately. Typically not all excess energy is dissipated as the photo-generated carriers tend to be extracted from the OPV device before reaching quasi-equilibrium. Carrier motion is governed by thermalization, leading to a time-dependent carrier mobility that is significantly higher than the steady-state mobility. This picture is confirmed by several transient techniques: Time-resolved Terahertz Spectroscopy (TRTS), Time-resolved Microwave Conductance (TRMC) combined with Transient Absorption (TA), electrical extraction of photo-induced charges (photo-CELIV). The connection between transient and steady-state mobility measurements (space-charge limited conductivity, SCLC) is described. Unification of transient opto-electric techniques to probe charge motion in OPVs is presented. Using transient experiments the distribution of extraction times of photo-generated charges in an operating OPV device has been determined and found to be strongly dispersive, spanning several decades in time. In view of the strong dispersion in extraction times the relevance of even a well-defined time-dependent mean mobility is limited. In OPVs a continuous ‘percolating’ donor network is often considered necessary for efficient hole extraction, whereas if the network is discontinuous, hole transport is thought to deteriorate significantly, limiting device performance. Here, it is shown that even highly diluted donor sites (5.7-10 %) in a buckminsterfullerene (C60) matrix enable reasonably efficient hole transport. Using transient measurements it is demonstrated that hole transport between isolated donor sites can occur by long-range hole tunneling (over distances of ~4 nm) through several C60 molecules – even a discontinuous donor network enables hole transport

This book contains detailed information on the types, structure, fabrication, and characterization of organic solar cells (OSCs). It discusses processes to improve efficiencies and the prevention of degradation in OSCs. It compares the cost-effectiveness of OSCs to those based on crystalline silicon and discusses ways to make OSCs more economical. This book provides a practical guide for the fabrication, processing, and characterization of OSCs and paves the way for further development in OSC technology.

The sun provides many times the energy we need, making it the most promising energy source. Conversion of sunlight to electrical energy is obtained in photovoltaic (PV) devices. Organic Solar Cells represent a new class of PV devices in which organic molecules serve as semiconductor materials. Although there has been huge progress in the performance of these devices, the physical fundamentals of charge transport still require a complete description. The author developed a powerful and novel method to investigate the cross section of electronic devices using in-situ focused ion beam preparation and scanning Kelvin probe microscopy. Using this method it was possible for the first time to spatially resolve the open circuit voltage in operating organic solar cells. Furthermore, charge transport loss mechanisms in bulk heterojunction solar cells and the origin of S-shaped current-voltage characteristics were revealed. This dissertation describes preparation techniques, challenges, and results in an unconcealed way complementing the publications "Imaging the electric potential within organic solar cells" and "Understanding S-shaped current-voltage characteristics of organic solar cells."