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<p>The urgent need for new, sustainable energy source intrigues scientists to provide the solution by developing new technology. Polymer solar cell appears to be the most promising candidate for its low cost, flexibility, and massive producibility. Novel polymers have been constantly synthesized and investigated, while the use of PCBM as acceptor seems to be the universal choice. Here, we studied the use of four dierent fullerene derivatives - [60]PCBM, [70]PCBM, and their bisadduct analogues - as acceptor in APFO-3 solar cells. A series of investigations were performed to study how the processing parameters - blend ratio, spin speed, and choice of solvent - influence the device performance. Using bisadduct fullerenes results in an enhanced Voc, as predicted by the up-shift of energy levels, but a strongly reduced Jsc, hence a poor PCE. Photoluminescence study indicates that all APFO-3:fullerene devices are limited by the inefficient dissociation of fullerene excitations, while it becomes more influential when bisadduct fullerenes were used as acceptor. The best device in this study was fabricated by using [70]PCBM as acceptor and chlorobenzene as solvent, exhibits a PCE of 2.9%, for the strong absorption, ne morphology, and comparatively strong driving force.</p>

The urgent need for new, sustainable energy source intrigues scientists to provide the solution by developing new technology. Polymer solar cell appears to be the most promising candidate for its low cost, flexibility, and massive producibility. Novel polymers have been constantly synthesized and investigated, while the use of PCBM as acceptor seems to be the universal choice. Here, we studied the use of four dierent fullerene derivatives - [60]PCBM, [70]PCBM, and their bisadduct analogues - as acceptor in APFO-3 solar cells. A series of investigations were performed to study how the processing parameters - blend ratio, spin speed, and choice of solvent - influence the device performance. Using bisadduct fullerenes results in an enhanced Voc, as predicted by the up-shift of energy levels, but a strongly reduced Jsc, hence a poor PCE. Photoluminescence study indicates that all APFO-3:fullerene devices are limited by the inefficient dissociation of fullerene excitations, while it becomes more influential when bisadduct fullerenes were used as acceptor. The best device in this study was fabricated by using [70]PCBM as acceptor and chlorobenzene as solvent, exhibits a PCE of 2.9%, for the strong absorption, ne morphology, and comparatively strong driving force.

Developing a fundamental understanding of photocurrent generation processes at organic-inorganic interfaces is critical for improving hybrid solar cell efficiency and stability. This dissertation explores processes at these interfaces by combining data from photovoltaic device performance tests with characterization experiments conducted directly on the device. The dissertation initially focuses on exploring how morphologically and chemically modifying the organic-inorganic interface, between poly(3-hexylthiophene) (P3HT) as the electron donating light absorbing polymer and titanium dioxide (TiO₂) as the electron acceptor, can result in stable and efficient hybrid solar cells. Given the heterogeneity which exists within bulk heterojunction devices, stable interfacial prototypes with well-defined interfaces between bilayers of TiO₂ and P3HT were developed, which demonstrate tunable efficiencies ranging from 0.01 to 1.6 %. Stability of these devices was improved by using Cu-based hole collecting electrodes. Efficiency values were tailored by changing TiO₂ morphology and by introducing sulfide layers like antimony trisulfide (Sb₂S₃) at the P3HT-TiO₂ interface. The simple bilayer device design developed in this dissertation provides an opportunity to study the precise role played by nanostructured TiO₂ surfaces and interfacial modifiers using a host of characterization techniques directly on a working device. Examples introduced in this dissertation include X-ray photoelectron spectroscopy (XPS) depth profiling analysis of metal-P3HT and P3HT-TiO₂ interfaces and Raman analysis of bonding between interface modifiers like Sb₂S₃ and P3HT. The incompatibility of TiO₂ with P3HT was significantly reduced by using P3HT derivatives with -COOH moieties at the extremity of a polymer chain. The role of functional groups like -COOH in interfacial charge separation phenomena was studied by comparing the photovoltaic behavior of these devices with those based on pristine P3HT. Finally, for hybrid solar cells discussed in this dissertation to become commercially viable, high temperature processing steps of the inorganic TiO₂ layer must be avoided. Accordingly, this dissertation demonstrates the novel use of electromagnetic radiation in the form of microwaves to catalyze growth of anatase TiO₂ thin films at temperatures as low as 150 °C, which is significantly lower than that used in conventional techniques. This low temperature process can be adapted to a variety of substrates and can produce patterned films. Accordingly, the ability to fabricate TiO₂ thin films by the microwave process at low temperatures is anticipated to have a significant impact in processing devices based on plastics. / text

Polymer solar cells are promising in that they are inexpensive to produce, and due to their mechanical flexibility have the potential for use in applications not possible for more traditional types of solar cells. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime of polymer solar cells has become at least as important as improving the efficiency.   In this thesis, the relation between morphology and solar cell performance is studied, and the material stability for blend films of the thiophene-quinoxaline copolymer TQ1 and the fullerene derivatives PCBM and PC70BM. Atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) are used to investigate the lateral morphology, secondary ion mass spectrometry (SIMS) to measure the vertical morphology and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed TQ1 surface enrichment does not affect the performance. Changes to the unoccupied molecular orbitals as a result of illumination in ambient air are observed by NEXAFS spectroscopy for PCBM, but not for TQ1. The NEXAFS spectrum of PCBM in a blend with TQ1 changes more than that of pristine PCBM. Solar cells in which the active layer has been illuminated in air prior to the deposition of the top electrode exhibit greatly reduced electrical performance. The valence band and absorption spectrum of TQ1 is affected by illumination in air, but the effects are not large enough to account for losses in solar cell performance, which are mainly attributed to PCBM degradation at the active layer surface. / The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime has become at least as important as improving the efficiency for polymer solar cells to become a viable technology.   In this work, the relation between morphology and solar cell performance is studied as well as the material stability for polymer:fullerene blend films. A combination of microscopic and spectroscopic methods is used to investigate the lateral and vertical morphology as well as the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed surface enrichment of polymer does not affect the performance. Changes to the unoccupied molecular states as a result of illumination in ambient air are observed for the fullerene, but not for the polymer, and fullerenes in a blend change more than pristine fullerenes. Solar cells in which the active layer has been illuminated exhibit greatly reduced electrical performance, mainly attributed to fullerene degradation at the active layer surface. / <p>Paper 2 ingick som manuskript i avhandlingen. Nu publicerad. </p>

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23223号 / 工博第4867号 / 新制||工||1760(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大北 英生, 教授 辻井 敬亘, 教授 田中 一生 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18291号 / 工博第3883号 / 新制||工||1596(附属図書館) / 31149 / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 伊藤 紳三郎, 教授 木村 俊作, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20406号 / 工博第4343号 / 新制||工||1673(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 大北 英生, 教授 辻井 敬亘, 教授 竹中 幹人 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Polymer solar cells form a promising technology for converting sunlight into electricity, and have reached record efficiencies over 10% and lifetimes of several years. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor materials in the active layer. To achieve longer lifetimes, degradation processes in the materials have to be understood. In this thesis, a set of complementary spectroscopy and microscopy techniques, among which soft X-ray techniques have been used to determine the morphology of polymer:fullerene based active layers. We have found that the morphology of TQ1:PC70BM films is strongly influenced by the processing solvent and the use of solvent additives. We have also found, by using soft X-ray techniques, that not only the light-absorbing polymer TQ1, but also the fullerene is susceptible to photo-degradation in air. Moreover, the fullerene degradation is accelerated in the presence of the polymer. Additionally, this thesis addresses the role of the interfacial layers for device performance and stability. The commonly used hole transport material PEDOT:PSS has the advantage of being solution processable at room temperature, but this layer is also known to contribute to the device degradation. We have found that low-temperature processed NiOx is a promising alternative to PEDOT:PSS, leading to improved device performance. Even for encapsulated polymer solar cells, some photo-induced degradation of the electrical performance is observed and is found to depend on the nature of the hole transport material. We found a better initial stability for solar cells with MoO3 hole transport layers than with PEDOT:PSS. In the pursuit of understanding the initial decrease in electrical performance of PEDOT:PSS-based devices, simulations were performed, from which a number of degradation sources could be excluded. / With the increasing global demand for energy, solar cells provide a clean method for converting the abundant sunlight to electricity. Polymer solar cells can be made from a large variety of light-harvesting and electrically conducting molecules and are inexpensive to produce. They have additional advantages, like their mechanical flexibility and low weight, which opens opportunities for novel applications. In order for polymer solar cells to be more competitive, however, both the power conversion efficiencies and lifetimes need to further improve. One way to achieve this is to optimize the morphology of the active layer. The active layer of a polymer solar cell consists of electron donating and electron accepting molecules whose distribution in the bulk of the film is a major factor that determines the solar cell performance. This thesis presents the use of complementary spectroscopy and microscopy methods to probe the local composition in the active layer of polymer solar cells. The stability of the active layer is studied and the interplay between the photo-degradation of the donor and acceptor molecules is investigated. Additionally, this thesis addresses how the interfacial layers between the active layer and the electrodes can influence device performance and stability. / <p>I publikationen felaktigt ISBN 978-91-7063-739-1</p>

Semiconducting polymers are promising materials for next-generation, flexible electronics devices. Over the last decades, various types of polymers have been developed and applied to devices such as light-emitting diodes (OLEDs), photovoltaics (OPVs), and field-effect transistors (OFETs). Conductivity is one of the most important parameters for the device performance since it directly affects charge carrier collection, injection, and transport. Besides, not only bulk conductivity but also interfacial energy barrier is critical for multilayer devices, especially an energy alignment of layers is essential to collect/inject charge carriers smoothly. Therefore reliable systems for both p- and n-type doping are sought after. Chemical doping (molecular doping) is a promising technique to achieve both, to enhance the conductivity in polymers and to shift energy levels by generating charge carriers (holes or electrons) in polymer films. The method enables to transport charge carriers in thin films or between neighboring layers effectively. This thesis investigates the chemical doping from the nanostructure level, particularly two types of devices where doping plays a crucial role: 1) pressure sensor based on p-doped semiconducting polymer nanopillars, 2) novel n-type doping system for a technologically advantageous thick interlayer in organic solar cells. In the first part, an application of nanostructured p-doped polymer was explored in a new type of device. While p-type doping is relatively common, especially for P3HT or PEDOT:PSS, in OPVs or OFETs, the potential of semiconducting polymer material, especially its mechanical flexibility and high electrical conductivity, is not fully utilized in these types of devices. Therefore new electronic device, a pressure sensor, is fabricated based on nanopillar structures made of p-doped P3HT by a templating method. The highly flexible and conductive nanostructure was obtained by combining templating and chemical doping. Through utilizing the buckling behavior of nanopillars, the pressure sensor was constructed and used for the detection of finger movement and touch sensing with a robotic gripper. Besides, the templating process can be tuned by annealing conditions, that enable adjusting the length of nanopillars and thus sensing properties. Finally, the sensing mechanism was investigated by finite element modeling and Euler buckling theory. In the second part, n-type doping in novel polymers was investigated. Generally, n-type doping has relatively limited reports since the n-doped state of commonly used polymers is readily oxidized by oxygen or water in air. A newly synthesized series of naphthalene diimide (NDI)-based conjugated polyelectrolytes (CPEs) contains cations in side chains, which stabilize the generated charge carriers. The stability of conductivity, spectroscopic characteristics, morphology, and the application of CPEs to interlayers in polymer solar cells (PSCs) were investigated. The polymer film showed air-stable high conductivity by introducing self-compensation doping and anion doping methods. The LUMO level of CPEs has a strong correlation with the conductivity in air and long-term stability. Moreover, the work function of the ITO cathode can be shifted by CPEs and the chemical doping, enabling a highly conductive, thick cathode interlayer, applicable to scalable film deposition methods, e.g., the blade-coating method. For the outlook, various new applications can be realized by combining these techniques and materials for p-/n-doping systems. This research expands the utilization of semiconducting polymer as a nano-structurable, flexible, highly conductive, and air-stable component for future flexible electronics devices.