The details of dye sensitized solar cells was explained and phenothiazine and porphyrin based dyes were synthesized for use in DSSCs. DSSCs offer a unique and cost effective method of renewable energy. DSSCs are characterized through various tests, with the overall efficiency, η, bearing the greatest importance. Incident photon to current conversion efficiency, or IPCE, is also another important characterization of DSSCs. Effect of positioning of the cyanoacrylic acid anchoring group on ring periphery of phenothiazine dye on the performance of dye sensitized solar cells (DSSCs) is reported. The performances of the cells are found to be prominent for solar cells made out of Type-1 dyes compared to Type-2 dyes. This trend has been rationalized based on spectral, electrochemical, computational and electrochemical impedance spectroscopy results. Free-base and zinc porphyrins bearing a carboxyl anchoring group at the para, meta, or ortho positions of one of the meso-phenyl rings were synthesized for DSSCs. Photoelectrochemical studies were performed after immobilization of porphyrins onto nanocrystalline TiO2. The performance of DSSCs with the porphyrin anchoring at the para or meta position were found to greatly exceed those in the ortho position. Additionally, zinc porphyrin derivatives outperformed the free-base porphyrin analogs, including better dye regeneration efficiency for the zinc porphyrin derivatives and for the meta and para derivatives through electrochemical impedance spectroscopy studies. The overall structure-performance trends observed for the present porphyrin DSSCs have been rationalized based on spectral, electrochemical, electrochemical impedance spectroscopy and transient spectroscopy results.

The molecular design, synthesis and spectroscopic characterization of a series of ruthenium(II), metal-free and platinum(II) photosensitizers were discussed. The applications of some of these compounds in dye-sensitized solar were also outlined. To start with, a brief overview on the background of dye-sensitized solar cells (DSSCs) was presented in Chapter 1. In Chapter 2, a series of new thiocyanate-free ruthenium(II) cyclometalated complexes with different ligands were successfully synthesized and some of them were fully characterized by spectroscopic and computational methods. The nature of cyclometalating ligands effectively tunes the properties of the metal complexes and the resulting DSSC performance. In Chapter 3, new di-anchoring organic dyes have been synthesized and characterized. This molecular design strategy can significantly enhance the . value because this successfully inhibits the undesirable charge combination and prolongs the electron lifetime. The discoveries open up a new avenue to the evolution of organic sensitizers and the optimization of bridged di-anchoring dyes for highly efficient co-adsorbent-free DSSCs. In Chapter 4, a series of new thiophene-free platinum sensitizers for the application of DSSCs was developed. Four unsymmetrical platinum(II) di-acetylide complexes containing phenothiazine moiety with different donor units were designed and synthesized. These photosensitizers were fully characterized by spectroscopic as well as computational studies and also successfully employed in DSSC fabrication. These findings provided positive evidence that platinum-acetylide complexes have a great potential and prospect for the use as promising metal-based photosensitizers in DSSC applications. Finally, Chapters 5 and 6 present the concluding remarks and the experimental details of the work described in Chapters 2–4.

Singlet fission, the conversion of one photoexcited singlet exciton into two triplet excitons, is a promising mechanism to overcome theoretical efficiency limits in single-junction solar cells. Intramolecular singlet fission materials based on molecular dimers are a powerful platform to study singlet fission since triplet dynamics can be fine-tuned through chemical structure. This thesis describes the critical nature of the molecular bridge between singlet fission chromophores in determining the fate of the triplet pair. We demonstrate how bridge energetics, connectivity, length, and planarity are tunable handles for controlling rates of triplet pair generation and recombination. These rates can even be modulated independent of each other, furnishing materials with desirable properties such as fast triplet generation and long triplet lifetimes. This thesis establishes key design principles to provide greater control over triplet pair formation, dephasing, and decay in intramolecular singlet fission materials. Chapter 1 introduces the process of singlet fission and provides an overview of the progress and challenges in the field. In Chapters 2 and 3, we detail the significance of bridge frontier molecular orbital energies and connectivity patterns in mediating triplet pair formation in bridged pentacene and tetracene dimers. We highlight key observables in the linear absorption spectra to predict relative rates of triplet pair formation, and demonstrate how quantum interference graphical models from single-molecule electronics can successfully be applied to explain triplet pair formation behavior in singlet fission. In Chapter 4, we investigate triplet pair recombination in these materials and propose that electronic coupling alone does not dictate triplet pair dephasing and decay. In Chapter 5, we present a new singlet fission chromophore and identify important triplet population signatures distinguishing singlet fission from intersystem crossing in contiguous dimers. Lastly, in Chapter 6, we explore dendrimers as a controlled macromolecular architecture to study singlet fission.

The amount of traditional energy sources are finite and the ecological impact of continuing to produce energy using fossil fuels will only exacerbate the carbon footprint. It is for these reasons that photovoltaic modules are becoming a larger and more necessary part the world's electricity production paradigm. Photovoltaic (PV) semiconductor modules are grouped into three categories. 'First generation' monocrystalline and polycrystalline silicon modules that consist of pn junctions created via the addition of impurities known as dopants. Almost 85% of solar cells produced at this time are `first generation' and it is the high production costs of silicon PV modules that motivated the search for new methods and materials to use as PV cells. 'Second generation' PV modules consist of semiconductor thin films. The 'second generation' PV modules in production at this time are copper indium gallium diselenide (CIGS), copper indium gallium (CIG), amorphous silicon (a-Si), and cadmium telluride (CdTe). The 'third generation' PV modules consist of dye-sensitized and organic materials. Thin films use less material, have less stringent production parameters and less waste, making thin films cost effective. In this investigation, solar cells were prepared using un-doped Group II-VI semiconductor thin films that exploit differences in bandoffsets to form effective p-n heterojunctions as a viable low cost alternative to doping. The thin films were deposited by thermal evaporation upon glass substrates coated with indium tin oxide (ITO). A layer of aluminum formed the back contact. Various configurations of the solar cells were produced including: ITO/CdS/CdSe/Al, ITO/ZnTe/CdSe/Al, ITO/CdTe/CdSe/Al, ITO/ZnTe/CdTe/CdS/Al. The solar cells produced have been characterized to determine thin film internal resistances, quantum and 'wall-plug' efficiencies, as well as I-V and spectral response. The open circuit voltage, short circuit current density, fill factor, and efficiency of our best devices were 0.26 V, 4.6 mA, 27.5 and 0.4% respectively. Additional device optimization should be possible and should improve these results. Solar cell design based on band-offset is an effective method for predetermining likely PV structures, while future investigation using Group II-VI semiconductor nanowires and nanorods and employing epitaxial films are likely to enhance the efficiency.

No description available.

Research in fluorescent solar concentrators (FSCs) commenced in mid-1970’s to lower the cost of solar cells through the reduction of the required solar cell active area, and by incorporating them in-to buildings, thereby offsetting installation costs. In FSCs, light penetrates the top surface of a waveguide, is absorbed by the fluorescent material (FM) and is emitted at a longer wavelength that is then internally reflected towards edge solar cells. In this project, the use of cerium doped yttrium aluminum garnet (Ce:YAG) was explored as an FM, from which the optical transport of fluorescence must be enhanced towards solar cell edges. Optical spectroscopic techniques were conducted to characterize a sample of Ce:YAG with a doping level of 0.180 mol%. An excitation and emission profile indicated a strong absorption at 476 nm and a strong radiation at 530 nm, where the fluorescence process lasted for only 62.3 ns, with a conversion efficiency of 80.0%. Meanwhile, x-ray analysis concluded that this material had a density of 4.56 g/cm3. An acrylic concentrator with local islands of Ce:YAG was successfully fabricated. A lens sheet was used to provide strong sunlight coupling to Ce:YAG. The concentrator was analysed using Optics Lab, Monte Carlo simulations (MCS) and through experimental flux measurements, the percentage of light that waveguided to the edges was determined. Optics Lab yielded 56.10%, MCS yielded 59.20% and flux measurements resulted in 58.22% (without lenses) and 57.14% with lenses. Also, an overall experimental optical efficiency was determined to be 32.45% without lenses and 53.53% with lenses. These results can be improved by modifying the fabrication techniques and using substrates with higher refractive indices. / Thesis / Master of Applied Science (MASc)

Passivating-contact technologies fabricated from polycrystalline-silicon (poly-Si) are increasingly considered by the crystalline silicon (c-S) PV industry to be key enablers towards record performance. This is largely thanks to their ability to provide excellent carrier collection and surface passivation, while being compatible with industrial scale production. Poly-Si based passivating contacts consist of a stack of an ultrathin silicon oxide (SiOx) film on the surface of crystalline silicon (c-Si), covered by a doped silicon film. Thin films of SiOx can be grown by several different methods: chemically, thermally, or via UV-ozone exposure. However, each of these methods presents challenges towards industrial implementation. Here, we report an alternative method to grow SiOx films using an in-situ plasma process, where we subsequently deposit the doped poly-Si layer in the same process chamber by plasma enhanced chemical vapor deposition (PECVD). This process presents several advantages, such as ease of fabrication, inherently single-side oxide growth and poly-Si deposition, and the combined deposition in one chamber, lowering capital expenditure. Subsequently, we studied the structure of the SiOx films and the doped poly-Si(p+) capping layers using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) in order to determine the films’ elemental composition, and the band alignment at the semiconductor/oxide interfaces. A less p-type polysilicon was observed grown on top of a wet SiOx/c-Si with the origin tentatively attributed to depletion of the boron dopant via pin holes evidenced by AFM. A surface photo-voltage (SPV) was observed by XPS under in-situ light bias (AM 1.5) and a representation of the band alignment of the c-Si/SiOx/p-polysilicon under illumination is derived. The SPV was attributed to the photo accumulation of holes at the p-polysilicon and a splitting of quasi-fermi levels with its magnitude correlated to the device measured iVoc . Finally, a valuable application for this contact technology is the integration of silicon with perovskite solar cells, in the so-called monolithic tandem configuration. This approach is very promising to develop a new generation of PV with unmatched performances. Here, poly-Si contacts offer a variety of advantages, thanks to their broader material selection and to the stability at high processing temperature.

Lead halide perovskite solar cells (PSCs) are considered the next generation of photovoltaic technology, reaching an outstanding certified power conversion efficiency of 25.7% in just 20 years. The best-performing PSCs are based on polycrystalline films, where the presence of grain boundaries and a tremendous number of defects limit stability and efficiency and thus further industrial development. Compared to their polycrystalline counterparts, single crystals of lead halide perovskites have been shown to possess much lower trap-state densities, long diffusion lengths, high stability, and near-IR absorption. This thesis describes the use of a confined space and inverse temperature method to grow perovskite single crystals of MAPbI3 directly on PTAA (poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine]) films. This method allowed the fabrication of p-i-n inverted solar cells with the structure ITO/PTAA/perovskite single-crystal thin film/C60 (fullerene)/BCP (bathocuproine)/Cu (copper). A key requirement in achieving high photoconversion efficiency (PCE) is avoiding iodine oxidation, which forms triiodide impurities that function as defects in perovskites and that can seriously hinder the performance of perovskites. By suppressing the formation of triiodide, high-quality perovskite photodetectors and solar cells can be realized. For single crystals, orientation has a strong effect on device performance. Here, (100)- and (001)-facet single-crystal thin films were fabricated into solar cells. Unlike traditional (100)-facet films, which exhibit high PCE in a glovebox environment, (001)-facet single-crystal thin films show high stability under ambient conditions.

GaSb is a semiconductor material having a narrow band gap in the infrared spectrum of 0.72 eV. This research is intended to investigate the low cost growth and properties of GaSb and to propose this material as a candidate for a cost effective method of developing a GaSb /silicon tandem solar cell. This work investigated the sputtering of GaSb films onto a glass substrate from a GaSb/Sb split-sputtering target. A GaSb compound was formed by placing Ga and Sb elements inside a vacuum sealed ampule. The ampule was placed inside a box furnace and heated at 800 0 C successfully forming a GaSb compound. Both GaSb and Sb were molded into a semicircular shape in a quartz container. X-ray diffraction (XRD) was conducted on sputtered films in order to confirm their structure. XRD peaks of the film were compared with reference peaks found on the Inorganic Crystal Structure Database (ICSD). GaSb peaks were apparent at specific sputtering chamber conditions of substrate temperature and source-to-substrate distance. Sputtered GaSb films were then further characterized with the Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR) and Hall Effect measurements. A theoretical thickness of the films was calculated using FTIR measurements to be about 1 μm and 0.35 μm for the films grown on a substrate heated with heater powers of 280 watts and 250 watts respectively. SEM confirmed the sample thicknesses with 20% error. Hall Effect measurements resulted in a high carrier concentration and low free carrier activation energy; 7.545 x1019 cm-3 and 0.1017 eV respectively. These values are attributed to the possible existence of anti-site defects. / Thesis / Master of Applied Science (MASc)

<p> Solar cells were made by diffusing impurities into the rough or backside of commercially available silicon wafers to form a junction. The properties of these solar cells were compared to solar cells made by diffusing impurities into the polished surface of similar silicon wafers. The processing steps involved in preparing each type of solar cell were identical. </p> / Thesis / Master of Engineering (MEngr)