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(2022)ThesisTime series models are used to model, simulate, and forecast the behaviour of a phenomenon over time based on data recorded over consistent intervals. The digital era has resulted in data being captured and archived in unprecedented amounts, such that vast amounts of information are available for analysis. Feature-rich time-series datasets are one of the data sets that have become available due to the expanding trend of data collection technologies worldwide. With the application of time series analysis to support financial and managerial decision-making, the development and advancement of time series models in the transportation domain are unavoidable. As a result, this thesis redefines time series models for transportation planning use with the following three aims: (1) To combine parametric and bootstrapping techniques within time series models; (2) to develop a time series model capable of modelling both temporal and spatial dependencies in time-series data; and (3) to leverage the hierarchical Bayesian modelling paradigm to accommodate flexible representations of heterogeneity in data. The first main chapter introduces an ensemble of ARIMA models. It compares its performance against conventional ARIMA (a parametric method) and LSTM models (a non-parametric method) for short-term traffic volume prediction. The second main chapter introduces a copula time series model that describes correlations between variables through time and space. Temporal correlations are modelled by an ARMA-GARCH model which enables a modeller to describe heteroscedastic data. The copula model has a flexible correlation structure and is used to model spatial correlations with the ability to model nonlinear, tailed and asymmetric correlations. The third main chapter provides a Bayesian modelling framework to raise awareness about using hierarchical Bayesian approaches for transport time series data. In addition, this chapter presents a Bayesian copula model. The combination of the two models provides a fully Bayesian approach to modelling both temporal and spatial correlations. Compared with frequentist models, the proposed modelling structures can incorporate prior knowledge. In the fourth main chapter, the fully Bayesian model is used to investigate mobility patterns before, during and after the COVID-19 pandemic using social media data. A more focused analysis is conducted on the mobility patterns of Twitter users from different zones and land use types.
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(2022)ThesisSinglet fission is a photo-physical process that generates two triplet excitons from one singlet exciton and can potentially enhance efficiency in photovoltaic systems. The combination of photovoltaics and singlet fission is a novel field for solar energy conversion when there is much interest in renewable, non-destructive, and continuously available energy sources. Singlet fission can also overcome thermalization losses in photovoltaics, which happens in traditional cells when the incident photon energy is higher than the silicon bandgap energy, using a carrier multiplication mechanism. This thesis will design, construct, and characterize photovoltaic devices incorporating singlet fission materials to study singlet fission in practical application. The research focuses on materials characterization, spin dynamics, and electron transfers between acene and the semiconductor layer in Au/TiO2 ballistic cells, and the incorporation of singlet fission layers on silicon-based cell structures. In detail, a set of investigations was developed and summarized by implementing singlet fission materials into a state-of-the-art ballistic photovoltaic device and silicon-based solar cell. The studies demonstrate proof of concept and rationally explain the process. The first part of the thesis investigates thin films of pentacene, TIPS-pentacene, and tetracene via crystallinity, morphology, absorption, and thickness characterization. Additionally, Au and TiO2 layers in Schottky device structures were optimized to achieve the best performance for energy transfer from an applied dye layer (merbromin). The drop-casted dye layer influences the device performance by increasing short-circuit current and open-circuit voltage, demonstrating the ability of charge transfer between the device and the applied film. This device structure provides a test bed for studying charge and energy transfer from singlet fission films. The latter part of the thesis describes several investigations to understand singlet fission in a thin film using this architecture. Magneto-photoconductivity measurements were primarily used to observe the spin dynamics via photoconductivity under an external magnetic field. Control experiments with bare Au/TiO2 devices showed no observable magneto-photoconductivity signal. In contrast, devices with pentacene and tetracene singlet fission layers showed a strong magnetoconductivity effect caused by ballistic electron transfer from the singlet fission layer into the TiO2 n-type semiconductor through an ultra-thin gold layer inserted between the layers. A qualitatively different behavior is seen between the pentacene and tetracene, which reveals that the energy alignment plays a crucial part in the charge transfer between the singlet fission layer and the device. The last section investigates the application of pentacene and tetracene evaporated thin-films as sensitizer layers to a silicon-based solar cell. The optimized Si cell structure with the annealing treatment improved the cell's performance by increasing short-circuit current and open-circuit voltage. The deposition of pentacene and tetracene as sensitizer layers into the device showed some results but posed several challenges that need to be addressed. As the current-voltage and external quantum efficiency measurements were taken, it was observed that material interfaces need to be designed to fully achieve the singlet fission of the acene layer into the Si devices.