Since the first demonstration of femtosecond laser written waveguides in 1996, femtosecond laser direct writing (FLDW) has been providing a versatile means to fabricate embedded 3-D microstructures in transparent materials. The key mechanisms are nonlinear absorption processes that occur when a laser beam is tightly focused into a material and the intensity of the focused beam reaches the range creating enough free electrons to induce structural modification. One of the most useful features that can be exploited in fabricating photonic structures is the refractive index change which results from the localized energy deposition. The laser processing system for FLDW can be realized as a compact, desktop station, implemented by a laser source, a 3-D stage and focusing optics. Thus, FLDW can be readily adopted for the fabrication of the photonic devices. For instance, it has been widely employed in various areas of photonic device fabrication such as active and passive waveguides, couplers, gratings, opto-fluidics and similar applications. This dissertation describes the use of FLDW towards the fabrication of custom designed diffractive optical elements (DOE’s). These are important micro-optical elements that are building blocks in integrated optical devices including on-chip sensors and systems. The fabrication and characterization of laser direct written DOEs in different glass materials is investigated. The design and performance of a range of DOE’s is described, especially, laser-written embedded Fresnel zone plates and linear gratings. Their diffractive efficiency as a function of the fabrication parameters is discussed and an optimized fabrication process is realized. The potential of the micro-DOEs and their integration shown in this dissertation will impact on the fabrication of future on-chip devices involving customized iv DOEs that will serve great flexibility and multi-functional capability on sensing, imaging and beam shaping.

Conjugated polymer based electronics, a type of flexible electronic devices, can be produced from solution by traditional printing and coating processes in a roll-to-roll format such as papers and graphic films. This shows great promise for the emerging energy generation and conversion. The device performance of polymer electronics is largely dependent of crystalline structures and morphology of photoactive layers. However, the solution crystallization kinetics of conjugated polymers in the presence of electron acceptor nanoparticles has not been fully understood yet. In this study, solution crystallization kinetics of poly (3-hexylthiophene) in the presence of carbon nanotubes and graphene oxide has been investigated by using UV-visible absorption spectroscopy and transmission electron microscope. Various kinetics parameters such as crystallization temperature, polymer solution concentration and nanoparticle loading will be discussed. The crystallization rate law and fold surface free energy will be addressed by using polymer crystallization theory of heterogeneous nucleation. This fundamental study will provide a foundation of fabricating high efficiency polymer based electronics.

CONSTRUCTING AND OPTIMIZING A SINGLE WAFER SOLAR CELL ARRAY IN THE MICROFABRICATION LAB AT CALIFORNIA POLYTECHNIC STATE UNIVERSITY AT SAN LUIS OBISPO Solar cells are more and more becoming a significant source of energy in the world today. They are used to power entire buildings as well as small devices and everything in between, and are utilized all around the world. Smaller solar devices, such as hearing aid battery chargers, cost a lot of money relative to the monetary wealth in third-world countries. For this purpose, a less expensive, more efficient solar cell array should be developed. This study contains research that details all aspects of how solar cells work. It also details three years’ worth of studies at California Polytechnic State University (Cal Poly) that attempt to fabricate a solar cell array on a single wafer. Two tests were carried out that will help determine the optimal attributes of the solar cells. The first compared a solar cell made on a 10 µm thick silicon on insulator (SOI) wafer to solar cells made with the exact same masks on a 500 µm thick wafer. The thicker solar cell had 2.5 times the maximum power as the SOI solar cell. Aspects of the solar cell that would need to be improved are: increase thickness to between 70-100 µm from the SOI thickness, texture the front surface, add a passivation layer on the front surface, decrease the contact resistance for the metal electrodes, and add in a rear reflector. The next test was all about analyzing the metal contacts and interconnects. Ten gold-silver filled epoxy-gold bonds were constructed and measured ten times each, giving a grand mean between 10 and 11 Ω. Another short test was run with a commercial solar cell to characterize the change in power based on the series resistance. It was discovered that the both the epoxy and the gold add too much to the resistance. To fix this, a silver solder-like paste and a thicker contact metal should be used. There is also a derivation that details the design of a top contact layer that optimizes the finger spacing and finger width based on other solar cell factors. With the materials available at Cal Poly, a solar cell array can be fabricated on a single wafer. When accounting for the materials and processes available to the scientific community as a whole, a very effective and efficient solar cell can be fabricated.

Electrostatically actuated silicon membranes were designed, modeled, fabricated, and characterized. The intended application was for use in a microspeaker. Fabrication issues necessitated the use of thick diaphragms with a large gap between the electrodes. The devices did not function as speakers but did show actuation with a high DC voltage. Device dimensions were chosen by examining membrane mechanics, testing the processing steps required for device fabrication, and modeling with COMSOL. Several adhesives were researched to fabricate the device sidewalls, including BCB, PMMA, and TRA-Bond F112. A method for patterning PMMA through photolithography was found using a scanning electron microscope. Masks were designed in AutoCAD to create the electrostatically actuated devices and a microfabrication process was developed to produce diaphragms that could be characterized. Twenty micron thick diaphragms were fabricated by etching an SOI wafer in 25% TMAH and the etch depth was measured with a profilometer. Glass slides were coated with gold and patterned with positive photoresist to create counter-electrodes. The diaphragms were bonded to the glass slides using a forty micron thick layer of patterned SU-8 as sidewalls. Bonding was successful in the initial fabrication testing but not successful for the final devices. The final fabrication run resulted in eight devices that were partially bonded. Three devices were chosen to test the membrane actuation and the data analyzed for statistical significance. A DC voltage was applied to the electrodes with a MEMS driver and the change in force measured with a micro-force displacement system. Data analysis showed device actuation at high voltages (300V) for the medium and large devices.

Quantum dots are semiconductor nanocrystals that have tunable emission through changes in their size. Producing bright, efficient quantum dots with stable fluorescence is important for using them in applications in lighting, photovoltaics, and biological imaging. This study aimed to optimize the process for coating CdSe quantum dots (which are colloidally suspended in octadecene) with a ZnS shell through the pyrolysis of organometallic precursors to increase their fluorescence and stability. This process was optimized by determining the ZnS shell thickness between 0.53 and 5.47 monolayers and the Zn:S ratio in the precursor solution between 0.23:1 and 1.6:1 that maximized the relative photoluminescence quantum yield (PLQY) while maintaining a small size dispersion and minimizing the shift in the center wavelength (CWL) of the fluorescence curve. The process that was developed introduced a greater amount of control in the coating procedure than previously available at Cal Poly. Quantum yield was observed to increase with increasing shell thickness until 3 monolayers, after which quantum yield decreased and the likelihood of flocculation of the colloid increased. The quantum yield also increased with increasing Zn:S ratio, possibly indicating that zinc atoms may substitute for missing cadmium atoms at the CdSe surface. The full-width at half-maximum (FWHM) of the fluorescence spectrum did not change more than ±5 nm due to the coating process, indicating that a small size dispersion was maintained. The center wavelength (CWL) of the fluorescence spectrum red shifted less than 35 nm on average, with CWL shifts tending to decrease with increasing Zn:S ratio and larger CdSe particle size. The highest quantum yield was achieved by using a Zn:S ratio of 1.37:1 in the precursor solution and a ZnS shell thickness of approximately 3 monolayers, which had a red shift of less than 30 nm and a change in FWHM of ±3 nm. Photostability increased with ZnS coating as well. Intense UV irradiation over 12 hours caused dissolution of CdSe samples, while ZnS coated samples flocculated but remained fluorescent. Atomic absorption spectroscopy was investigated as a method for determining the thickness of the ZnS shell, and it was concluded that improved sample preparation techniques, such as further purification and complete removal of unreacted precursors, could make this testing method viable for obtaining quantitative results in conjunction with other methods. However, the ZnS coating process is subject to variations due to factors that were not controlled, such as slight variations in temperature, injection speed, and rate and degree of precursor decomposition, resulting in standard deviations in quantum yield of up to half of the mean and flocculation of some samples, indicating a need for as much process control as possible.

<p>The energy diagram for organic photovoltaics (OPV), involving the bulk heterojunction (BHJ), on which the device analysis is usually based, has long been a subject of debate. The widely used Metal-insulator-Metal model and P-type Schottky Junction model, both of which are based on inappropriate assumptions, could be incorrect to explain the working principle of BHJ OPV.</p> <p>To further explore the controversy, we start the investigation from the opposite direction, to the usually asymmetrical OPV, involving electron and hole passages, by introducing a pair of symmetric electrodes to a BHJ, to form a completely symmetrical device structure, which, in theory, would produce zero output.</p> <p>Surprisingly, it is found that such a symmetrical device exhibits asymmetrical I-V curves. In particular, it produces a non-zero open-circuit voltage, and a finite short-circuit current. The cause of the output was the asymmetrical charge carrier distribution due to the asymmetrical illumination. To explain the operational mechanism of the symmetrical device, the equivalent circuit including a pair of inverse-parallel diodes and a new model for the BHJ energy diagram are introduced. Those findings would certainly improve the understanding of the device physics of OPV, especially the working principle for BHJ.</p> / Master of Materials Science and Engineering (MMatSE)

<p>Please email me at kdunn@celccocontrols.com to confirm receipt of my thesis.</p> <p>Thanks,</p> <p>Kayne</p> / <p>In current microelectronic interconnect technology, significant delay is incurred due to capacitances in the intermediate and global interconnect layers. To avoid capacitive effects optical interconnects can be used; however conventional technologies are expensive to manufacture. One method to address these issues is to make use of quantum confinement effects and states lying within the bandgap of the material to enhance luminescence in a CMOS compatible silicon based system. Thin SiCxNy films appear to be suitable to work as luminescent silicon based films due to their lower direct bandgap and chemical stability but have not yet been studied in great detail.</p> <p>This thesis is an exploratory work aiming to assess the suitability of SiCxNy films for the above applications and to identify future research areas. The films analyzed in this thesis were manufactured on the inductively coupled plasma-chemical vapour deposition reactor (ICP-CVD) at McMaster University. The ICP-CVD produces films of high uniformity by using a remote RF plasma and an arrangement of high vacuum pumps to attain a vacuum on the order of 10-7Torr.</p> <p>Several experimental techniques have been used to analyse the films. The complex index of refraction has been determined through the use of ellipsometry giving results typical of that of a-SiNx:H. The photoluminescence spectroscopy results show a large broad emission peak with at least one shoulder at higher energies. The precise luminescence mechanism(s) could not be identified though a strong relationship with the bonding state of nitrogen has been found. The composition and structure of the films, as determined through ion beam measurements, infrared absorption measurements, and transmission electron microscopy measurements demonstrate the formation of a two phase structure consisting of carbon rich clusters surrounded by a mostly silicon nitride matrix. These carbon rich regions have some graphitic character and act to dampen the luminescence.</p> / Master of Applied Science (MASc)

<p>The world’s dependence on oil cannot continue indefinitely. As reserves dwindle and demand continues to increase, prices will soar to new highs and fundamentally change the way society deals with energy generation and consumption. Use of oil and other carbon-based fuels also have detrimental effects on human health, as pollution that arises from the combustion of these fuels necessitates treating respiratory problems in millions of people annually. Moreover, evidence that climate change is anthropogenic has become undeniable and has been proven to be direct related to dependence on carbon-based fuels.</p> <p>Renewable energy offers clean and dependable alternatives for electricity, heating and transport. In particular, solar energy looks to be the most promising owing to its sheer abundance and ubiquity. The main obstacle hindering the adoption of solar cell technology en masse is cost. One of the ways to reduce cost is to fabricate thinner solar cells, but this compromises efficiency due to lower optical absorption that results, especially in silicon. In order to become a serious competitor in the energy market, highly absorptive solar cells must be developed at reduced material costs, which is the essence of light-trapping.</p> <p>In this study, two of the most common ways to trap light by reducing reflection were investigated: the application of anti-reflection coatings and surface texturing in silicon. Analytic models were created to optimize optical design in both single-junction and multi-junction solar cells. The single-junction silicon models accounted for non-normal incidence, which allowed angle-averaged calculations to be made for planar and textured surfaces. Single-junction GaAs models included a GaInP window layer whose optical effects were considered in anti-reflection coating optimization. The multi-junction GaAs-on-silicon (GaAs/Si) and AlGaAs-on-silicon (AlGaAs/Si) models that were created clearly demonstrated the need to adjust individual subcell thicknesses in order to optimize optical design.</p> / Master of Applied Science (MASc)

<p>The pore-size dependence of liquid diffusivity in mesopores has been a controversial topic. It is especially meaningful in dye-sensitized solar cells (DSSCs) because the triiodide ion diffusivity is closely related to the cell performance. By applying electrochemical measurements, the pore-size dependence of ion diffusivity in DSSCs was investigated based on TiO₂ thin films of variable pore diameters. The alternation of pore-size was achieved by the epitaxial growth of TiO₂ after TiCl₄ post-treatments. From the trend of normalized diffusivities, the respective valid regimes of pore-size dependent and independent diffusion were determined, which were separated by the transition point located at 5-7 nm. In addition, my results have showed that the DSSC fabrication processes, e.g., dye loading, TiCl₄ post-treatment will not lead to the transition of diffusion behaviors. Furthermore, the unexpected drop of diffusivity after one TiCl₄ treatment is attributed to the involvement of surface diffusion in untreated TiO₂ matrix.</p> / Master of Applied Science (MASc)

The contributions of nonlinear absorption processes to laser-induced damage of three selected groups of transparent dielectrics were investigated. The studied materials were irradiated and non-irradiated fused silica, doped and undoped fluorozirconate glass and cubic zirconia stabilized with yttria. The laser-induced damage thresholds, prebreakdown transmission, and nonlinear absorption processes were studied for several specimens of each group. Experimental measurements were performed at wavelengths of 1064 nm and 532 nm using nanosecond and picosecond Nd:YAG laser pulses. In the irradiated fused silica and fluorozirconate glasses, we found that there is a correlation between the damage thresholds at wavelength λ and the linear absorption of the studied specimens at λ/2. In other words, the laser-induced breakdown is related to the probability of all possible two-photon transitions. The results are found to be in excellent agreement with a proposed two-photon-initiated electron avalanche breakdown model. In this model, the initial "seed" electrons for the formation of an avalanche are produced by two-photon excitations of E' centers and metallic impurity levels which are located within the bandgaps of irradiated Si02 and fluorozirconate glasses, respectively. Once the initial electrons are liberated in the conduction band, a highly absorbing plasma is formed by avalanche impact ionization. The resultant heating causes optical damage. In cubic zirconia, we present direct experimental evidence that significant energy is deposited in the samples at wavelength 532 nm prior to electron avalanche formation. The mechanism is found to be due to formation of color centers (F+ or F° centers) by the two-photon absorption process. The presence of these centers was directly shown by transmission measurements. The two-photon absorption (2PA) process was independently investigated and 2PA coefficients obtained. The accumulated effects of the induced centers on the nonlinear absorption measurements were also considered and the 2PA coefficients were measured using short pulses where this effect is negligible. At room temperature, the color centers slowly diffuse out of the irradiated region. The density of these centers was monitored as a function of time. The initial distribution of the centers was assumed to have a Gaussian profile. For this model the diffusion equation was solved exactly and the diffusion constant obtained.