Tremendous progress in the development of thin film solar cell techniques has been made over the last decade. The field of organic solar cells is constantly developing, new material classes like Perowskite solar cells are emerging and different types of hybrid organic/inorganic material combinations are being investigated for their physical properties and their applicability in thin film electronics. Besides typical single-junction architectures for solar cells, multi-junction concepts are also being investigated as they enable the overcoming of theoretical limitations of a single-junction. In multi-junction devices each sub-cell operates in different wavelength regimes and should exhibit optimized band-gap energies. It is exactly this tunability of the band-gap energy that renders organic solar cell materials interesting candidates for multi-junction applications. Nevertheless, only few attempts have been made to combine inorganic and organic solar cells in series connected multi-junction architectures. Even though a great diversity...

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 covers in a textbook-like fashion the basics or organic solar cells, addressing the limits of photovoltaic energy conversion and giving a well-illustrated introduction to molecular electronics with focus on the working principle and characterization of organic solar cells. Further chapters based on the author’s dissertation focus on the electrical processes in organic solar cells by presenting a detailed drift-diffusion approach to describe exciton separation and charge-carrier transport and extraction. The results, although elaborated on small-molecule solar cells and with focus on the zinc phthalocyanine: C60 material system, are of general nature. They propose and demonstrate experimental approaches for getting a deeper understanding of the dominating processes in amorphous thin-film based solar cells in general. The main focus is on the interpretation of the current-voltage characteristics (J-V curve). This very standard measurement technique for a solar cell reflects the electrical processes in the device. Comparing experimental to simulation data, the author discusses the reasons for S-Shaped J-V curves, the role of charge carrier mobilities and energy barriers at interfaces, the dominating recombination mechanisms, the charge carrier generation profile, and other efficiency-limiting processes in organic solar cells. The book concludes with an illustrative guideline on how to identify reasons for changes in the J-V curve. This book is a suitable introduction for students in engineering, physics, material science, and chemistry starting in the field of organic or hybrid thin-film photovoltaics. It is just as valuable for professionals and experimentalists who analyze solar cell devices.

Organic solar cells are photovoltaic devices that use semiconducting plastics as the active layer rather than traditional inorganic materials such as Silicon. Like any solar cell, their efficiency at producing electricity from sunlight is characterized by three parameters: their short-circuit current (Jsc), open-circuit voltage (Voc) and fill factor (FF). While the factors that determine each of these parameters are well-understood for established solar technologies, this is not the case for organic solar cells. The short-circuit current is much higher than we would expect given the strong attraction between electrons and holes in organic semiconductors that should lead to fast recombination, preventing the carriers from being collected as current. In contrast, the open-circuit voltage is much lower than we would expect based on the traditional relationship between optical absorption and voltage in inorganic semiconductors. Finally, the fill factor is highly variable from device to device and typically gets much worse as the cells are made thicker. In this work we develop a novel and general framework for understanding the short-circuit current, open-circuit voltage and fill factor of organic solar cells. The concept that turns out to unify all three aspects of device operation is the idea that electrons and holes move rapidly enough relative to their lifetimes to equilibrate with each other in the statistical mechanics sense before recombining. Previously, it had been thought that such equilibration was impossible because of the low macroscopic mobilities of charge carriers in organic solar cells. We first show using Kinetic Monte Carlo simulations that the charge carrier mobility is 3-5 orders of magnitude higher on short length scales and immediately after light absorption by comparing simulated results to experimental terahertz spectroscopy data. Combining this high mobility with experimental lifetime data fully rationalizes high charge carrier generation efficiency and also explains how carriers can live long enough to be affected by strong inhomogeneities in the energetic landscape of the solar cell, which also improves charge generation. Turning to Voc, we use the same concept of fast carrier motion relative to the recombination rate to show that recombination proceeds from an equilibrated population of Charge Transfer states. This simplification permits us to develop an analytical understanding of the open-circuit voltage and explain numerous puzzling Voc trends that have been observed over the years. Finally, we generalize our equilibrium result from open-circuit to explain the entire IV curve and use it to show how the low fill-factor of organic solar cells is not caused, as is often thought, by a voltage dependent carrier generation process but instead by low macroscopic charge carrier mobilities and the presence of dark charge carriers injected during device fabrication. Taken together, these results represent the first complete theory of organic solar cell operation.

This book focuses on the essential scientific ideas and breakthroughs in the last three decades for organic solar cells that have realized practical applications. The motivation for publishing this book is to explain how those essential ideas have arisen and to provide a foundation for future progress by target readers—students, novices in the field, and scientists with expertise. The main topics covered in the book include the fundamental principles and history of organic solar cells, blended junction, nanostructure control, photocurrent generation, photovoltage generation, doping, practical organic solar cells, and possible ideas for the future. The editors enthusiastically anticipate the vigorous development of the field of organic solar cells by young scientists of the next generation.

Perovskite Photovoltaics and Optoelectronics Discover a one-of-a-kind treatment of perovskite photovoltaics In less than a decade, the photovoltaics of organic-inorganic halide perovskite materials has surpassed the efficiency of semiconductor compounds like CdTe and CIGS in solar cells. In Perovskite Photovoltaics and Optoelectronics: From Fundamentals to Advanced Applications, distinguished engineer Dr. Tsutomu Miyasaka delivers a comprehensive exploration of foundational and advanced topics regarding halide perovskites. It summarizes the latest information and discussion in the field, from fundamental theory and materials to critical device applications. With contributions by top scientists working in the perovskite community, the accomplished editor has compiled a resource of central importance for researchers working on perovskite related materials and devices. This edited volume includes coverage of new materials and their commercial and market potential in areas like perovskite solar cells, perovskite light-emitting diodes (LEDs), and perovskite-based photodetectors. It also includes: A thorough introduction to halide perovskite materials, their synthesis, and dimension control Comprehensive explorations of the photovoltaics of halide perovskites and their historical background Practical discussions of solid-state photophysics and carrier transfer mechanisms in halide perovskite semiconductors In-depth examinations of multi-cation anion-based high efficiency perovskite solar cells Perfect for materials scientists, crystallization physicists, surface chemists, and solid-state physicists, Perovskite Photovoltaics and Optoelectronics: From Fundamentals to Advanced Applications is also an indispensable resource for solid state chemists and device/electronics engineers.