Relating Nanoscale Structure to Electronic Function in Organic Semiconductors Using Time-resolved Spectroscopy

Book excerpt: Molecular packing arrangements at the nanoscale level significantly contribute to the ultimate photophysical properties of organic semiconducting materials used in solar energy conversion applications. Understanding their precise structure-function relationships will provide insights that can lead to chemical and structural design rules for the next generation of organic solar cell materials. In this work, two major classes of materials were investigated: Singlet fission sensitizers and semiconducting block-copolymers. By exploiting chemical design and film processing techniques, a variety of controllable nanoscale structures could be developed and related to their subsequent photophysical properties, including triplet and charge transport. Time-resolved optical spectroscopies, including both absorption and emission techniques, were used to measure the population dynamics of excited states and charge carriers following photoexcitation of the semiconducting materials. Singlet fission, an exciton multiplication reaction that promises to boost solar cell efficiency by overcoming thermalization loss, has been characterized in several organic molecules. If the energetics are such that the excited state singlet energy is at least twice the triplet energy, then a singlet exciton may split into two triplet excitons through an intermolecular energy-sharing process. The thin film structure of a model singlet fission compound was exploited by modulating its crystallinity and controlling polymorphism. A combination of visible, near-infrared, and mid-infrared transient absorption spectroscopies were used to investigate the precise singlet fission reaction mechanism. It was determined that the reaction intermediates consist of bound triplet pairs that must physically separate in order to complete the reaction, which results in multiplied, independent triplet excitations. Triplet transfer, which is modulated by molecular packing arrangements that control orbital overlap coupling, was found to determine the efficacy of triplet pair separation. Furthermore, the formation of these independent triplets was found to occur on longer (picosecond) timescales than previously believed, indicating that any kinetically competing relaxation processes, such as internal conversion, need to be controlled. Last, it was found that the diffusion of the multiplied triplet excitons, and thus their harvestability in devices, is highly influenced by the crystallinity of the material. In particular, the presence of even a small amount of contaminant amorphous phase was determined to be detrimental to the ultimate triplet diffusion length. Future research directions are outlined, which will be used to develop further chemical and structural design rules for the next generation of singlet fission chromophores. Semiconducting block-copolymers, because of their natural tendency to self-assemble into ordered nanoscale structures, offer an appealing strategy for controlling phase segregation between the hole and electron transport materials in organic solar cells. Such phase segregation is important for both ensuring efficient conversion of the photogenerated excitons into charge carriers, and for creating percolation pathways for efficient transport of the charges to the device electrodes. Time-resolved mid-infrared spectroscopy was developed for monitoring charge recombination kinetics in a series of block-copolymer and polymer blend films possessing distinct, controlled nanoscale morphologies. In addition to explaining previous work that correlated film structure to device efficiency, it was revealed how the covalent linkage in block-copolymers can be carefully designed to prevent rapid recombination losses. Furthermore, novel solution-phase systems of block-copolymer aggregates and nanoparticles were developed for future fundamental spectroscopic work. Future studies promise to explain precisely how polymer chain organization, including intrachain and interchain interactions, governs their ultimate charge photogeneration and transport properties in solar cells.