ASU Electronic Theses and Dissertations
This collection includes most of the ASU Theses and Dissertations from 2011 to present. ASU Theses and Dissertations are available in downloadable PDF format; however, a small percentage of items are under embargo. Information about the dissertations/theses includes degree information, committee members, an abstract, supporting data or media.
In addition to the electronic theses found in the ASU Digital Repository, ASU Theses and Dissertations can be found in the ASU Library Catalog.
Dissertations and Theses granted by Arizona State University are archived and made available through a joint effort of the ASU Graduate College and the ASU Libraries. For more information or questions about this collection contact or visit the Digital Repository ETD Library Guide or contact the ASU Graduate College at gradformat@asu.edu.
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- All Subjects: Optical Coatings
Description
In this dissertation, far UV spectroscopy is applied to investigate the optical properties of dielectric thin films grown by atomic layer deposition. The far UV (120 – 200 nm) reflectance for several dielectric oxides and fluorides, including AlF3, Al2O3, Ga2O3, HfO2, and SiO2, was measured at variable angles and thicknesses. Multiple optical calculation methods were developed for the accurate determination of the optical constants from the reflectance. The deduced optical constants were used for optical designs, such as high-reflectivity coatings, and Fabry-Perot bandpass interference filters. Three filters were designed for use at 157 nm, 212 nm, and 248 nm wavelengths, based on multilayer structures consisting of SiO2, Al2O3, HfO2, and AlF3. A thorough error analysis was made to quantify the non-idealities of the optical performance for the designed filters. Far UV spectroscopy was also applied to analyze material mixtures, such as AlF3/Al and h-BN/c-BN mixtures. Using far UV spectroscopy, different phases in the composite can be distinguished, and the volume concentration of each constituent can be determined. A middle UV reflective coating based on A2O3 and AlF3 was fabricated and characterized. The reflective coating has a smooth surface (?? < 1 nm), and a peak reflectance of 25 – 30 % at a wavelength of 196 nm. The peak reflectance deviated from the design, and an analysis of the AlF3 layer prepared by plasma-enhanced atomic layer deposition (PEALD) indicated the presence of Al-rich clusters, which were associated with the UV absorption. Complementary techniques, such as spectroscopic ellipsometry, and X-ray photoelectron spectroscopy, were used to verify the results from far UV spectroscopy. In conclusion, this Dissertation demonstrated the use of in-situ far UV spectroscopy to investigate the optical properties of thin films at short wavelengths. This work extends the application of far UV spectroscopy to ultrawide bandgap semiconductors and insulators. This work supports a path forward for far UV optical filters and devices. Various errors have been discussed with solutions proposed for future research of methods and materials for UV optics.
ContributorsHuang, Zhiyu (Author) / Nemanich, Robert (Thesis advisor) / Ponce, Fernando (Committee member) / Menéndez, Jose (Committee member) / Holman, Zachary (Committee member) / Arizona State University (Publisher)
Created2021
Description
The absorption spectra of metal-centered phthalocyanines (MPc's) have been investigated since the early 1960's. With improved experimental techniques to characterize this class of molecules the band assignments have advanced. The characterization remains difficult with historic disagreements. A new push for characterization came with a wave of interest in using these molecules for absorption/donor molecules in organic photovoltaics. The use of zinc phthalocyanine (ZnPc) became of particular interest, in addition to novel research being done for azaporphyrin analogs of ZnPc.
A theoretical approach is taken to research the excited states of these molecules using time-dependent density functional theory (TDDFT). Most theoretical results for the first excited state in ZnPc are in only limited agreement with experiment (errors near 0.1 eV or higher). This research investigates ZnPc and 10 additional porphyrin analogs. Excited-state properties are predicted for 8 of these molecules using ab initio computational methods and symmetry breaking for accurate time- dependent self-consistent optimization. Franck-Condon analysis is used to predict the Q-band absorption spectra for all 8 of these molecules. This is the first time that Franck-Condon analysis has been reported in absolute units for any of these molecules. The first excited-state energy for ZnPc is found to be the closest to experiment thus far using a range-separated meta-GGA hybrid functional. The theoretical results are used to find a trend in the novel design of new porphyrin analog molecules.
A theoretical approach is taken to research the excited states of these molecules using time-dependent density functional theory (TDDFT). Most theoretical results for the first excited state in ZnPc are in only limited agreement with experiment (errors near 0.1 eV or higher). This research investigates ZnPc and 10 additional porphyrin analogs. Excited-state properties are predicted for 8 of these molecules using ab initio computational methods and symmetry breaking for accurate time- dependent self-consistent optimization. Franck-Condon analysis is used to predict the Q-band absorption spectra for all 8 of these molecules. This is the first time that Franck-Condon analysis has been reported in absolute units for any of these molecules. The first excited-state energy for ZnPc is found to be the closest to experiment thus far using a range-separated meta-GGA hybrid functional. The theoretical results are used to find a trend in the novel design of new porphyrin analog molecules.
ContributorsTheisen, Rebekah (Author) / Adams, James B (Thesis advisor) / Li, Jian (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2014