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Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result

Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Recent advancements in the field of light wavefront engineering rely on complex 3D metasurfaces composed of sub-wavelength structures which, for the near infrared range, are challenging to manufacture using contemporary scalable micro- and nanomachining solutions. To address this demand, a novel parallel micromachining method, called metal-assisted electrochemical nanoimprinting (Mac-Imprint) was

Recent advancements in the field of light wavefront engineering rely on complex 3D metasurfaces composed of sub-wavelength structures which, for the near infrared range, are challenging to manufacture using contemporary scalable micro- and nanomachining solutions. To address this demand, a novel parallel micromachining method, called metal-assisted electrochemical nanoimprinting (Mac-Imprint) was developed. Mac-Imprint relies on the catalysis of silicon wet etching by a gold-coated stamp enabled by mass-transport of the reactants to achieve high pattern transfer fidelity. This was realized by (i) using nanoporous catalysts to promote etching solution diffusion and (ii) semiconductor substrate pre-patterning with millimeter-scale pillars to provide etching solution storage. However, both of these approaches obstruct scaling of the process in terms of (i) surface roughness and resolution, and (ii) areal footprint of the fabricated structures. To address the first limitation, this dissertation explores fundamental mechanisms underlying the resolution limit of Mac-Imprint and correlates it to the Debye length (~0.9 nm). By synthesizing nanoporous catalytic stamps with pore size less than 10 nm, the sidewall roughness of Mac-Imprinted patterns is reduced to levels comparable to plasma-based micromachining. This improvement allows for the implementation of Mac-Imprint to fabricate Si rib waveguides with limited levels of light scattering on its sidewall. To address the second limitation, this dissertation focuses on the management of the etching solution storage by developing engineered stamps composed of highly porous polymers coated in gold. In a plate-to-plate configuration, such stamps allow for the uniform patterning of chip-scale Si substrates with hierarchical 3D antireflective and antifouling patterns. The development of a Mac-Imprint system capable of conformal patterning onto non-flat substrates becomes possible due to the flexible and stretchable nature of gold-coated porous polymer stamps. Understanding of their mechanical behavior during conformal contact allows for the first implementation of Mac-Imprint to directly micromachine 3D hierarchical patterns onto plano-convex Si lenses, paving the way towards scalable fabrication of multifunctional 3D metasurfaces for applications in advanced optics.
ContributorsSharstniou, Aliaksandr (Author) / Azeredo, Bruno (Thesis advisor) / Chan, Candace (Committee member) / Rykaczewski, Konrad (Committee member) / Petuskey, William (Committee member) / Chen, Xiangfan (Committee member) / Arizona State University (Publisher)
Created2022
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Description
This work correlates microscopic material changes to short- and long-term performance in modern, Cu-doped, CdTe-based solar cells. Past research on short- and long-term performance emphasized the device-scale impact of Cu, but neglected the microscopic impact of the other chemical species in the system (e.g., Se, Cl, Cu), their distributions, their

This work correlates microscopic material changes to short- and long-term performance in modern, Cu-doped, CdTe-based solar cells. Past research on short- and long-term performance emphasized the device-scale impact of Cu, but neglected the microscopic impact of the other chemical species in the system (e.g., Se, Cl, Cu), their distributions, their local atomic environments, or their interactions/reactions. Additionally, technological limitations precluded nanoscale measurements of the Cu distributions in the cell, and microscale measurements of the material properties (i.e. composition, microstructure, charge transport) as the cell operates. This research aims to answer (1) what is the spatial distribution of Cu in the cell, (2) how does its distribution and local environment correlate with cell performance, and (3) how do local material properties change as the cell operates? This work employs a multi-scale, multi-modal, correlative-measurement approach to elucidate microscopic mechanisms. Several analytical techniques are used – including and especially correlative synchrotron X-ray microscopy – and a unique state-of-the-art instrument was developed to access the dynamics of microscopic mechanisms as they proceed. The work shows Cu segregates around CdTe grain boundaries, and Cu-related acceptor penetration into the CdTe layer is crucial for well-performing cells. After long-term operation, the work presents strong evidence of Se migration into the CdTe layer. This redistribution correlates with microstructural changes in the CdTe layer and limited charge transport around the metal-CdTe interface. Finally, the work correlates changes in microstructure, Cu atomic environment, and charge collection as a cell operates. The results suggest that, as the cell ages, a change to Cu local environment limits charge transport through the metal-CdTe interface, and this change could be influenced by Se migration into the CdTe layer of the cell.
ContributorsWalker, Trumann (Author) / Bertoni, Mariana I (Thesis advisor) / Holman, Zachary (Committee member) / Chan, Candace (Committee member) / Colegrove, Eric (Committee member) / Arizona State University (Publisher)
Created2022
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Description
The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one

The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one of the most promising candidates to enable Li metal batteries due to its high ionic conductivity, chemical stability, and wide electrochemical stability window against Li metal. However, synthesis and processing of c-LLZO through conventional solid-sate reaction methods requires long periods of calcination (> 6 h) at high reaction temperatures (> 1000 °C). The need for high reaction temperature results to attain cubic-LLZO phase results in large aggerated LLZO particles and causes Li-loss from the garnet structure, making them unfavorable to process further as bulk pellets or thin films. To overcome processing challenges with solid-state reaction method, two novel facile synthesis approaches molten salt (flux growth method), and solution combustion are employed to produce submicron-sized LLZO powders at low reaction temperatures (< 1000 °C) in a short time. In the first case, molten salt synthesis method with LiCl-KCl eutectic mixture is employed to produce sub-micron sized Ta-doped LLZO (LLZTO) powders at low temperatures (900 °C, 4 h). In addition, a detailed investigation on effect of sintering medium and sintering additives on the structural, microstructural, chemical, and Li-ion transport behavior of the LLZTO pellets are investigated. Sintered LLZTO pellets prepared using molten salt synthesis route exhibited high Li-ion conductivity up to 0.6 mS cm-1 and high relative density (> 95 %) using Pt-crucible. In the second case, a facile solution-combustion technique using an amide-based fuel source CH6N4O is utilized to produce submicron-sized Al-doped LLZO (Al-LLZO) powders at low reaction temperatures 600-800 °C in a short duration of 4 h. In addition, effect of fuel to oxidizer ratio on phase purity, particle growth size, and formation mechanism of conductive Al-LLZO are reported and discussed. The Al-LLZO pellets sintered at 1100 °C/ 6 h exhibited high Li-ion conductivity up to 0.45 mS cm-1 with relative densities (> 90 %).
ContributorsBadami, Pavan Pramod (Author) / Kannan, Arunachalandar Mada (Thesis advisor) / Chan, Candace (Thesis advisor) / Song, Kenan (Committee member) / Arizona State University (Publisher)
Created2021
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Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and

Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021
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Description
The metallization and interconnection of Si photovoltaic (PV) devices are among some of the most critically important aspects to ensure the PV cells and modules are cost-effective, highly-efficient, and robust through environmental stresses. The aim of this work is to contribute to the development of these innovations to move them

The metallization and interconnection of Si photovoltaic (PV) devices are among some of the most critically important aspects to ensure the PV cells and modules are cost-effective, highly-efficient, and robust through environmental stresses. The aim of this work is to contribute to the development of these innovations to move them closer to commercialization.Shingled PV modules and laser-welded foil-interconnected modules present an alternative to traditional soldered ribbons that can improve module power densities in a cost-effective manner. These two interconnection methods present new technical challenges for the PV industry. This work presents x-ray imaging methods to aid in the process-optimization of the application and curing of the adhesive material used in shingled modules. Further, detailed characterization of laser welds, their adhesion, and their effect on module performances is conducted. A strong correlation is found between the laser-weld adhesion and the modules’ durability through thermocycling. A minimum laser weld adhesion of 0.8 mJ is recommended to ensure a robust interconnection is formed. Detailed characterization and modelling are demonstrated on a 21% efficient double-sided tunnel-oxide passivating contact (DS-TOPCon) cell. This technology uses a novel approach that uses the front-metal grid to etch-away the parasitically-absorbing poly-Si material everywhere except for underneath the grid fingers. The modelling yielded a match to the experimental device within 0.06% absolute of its efficiency. This DS-TOPCon device could be improved to a 23.45%-efficient device by improving the optical performance, n-type contact resistivity, and grid finger aspect ratio. Finally, a modelling approach is explored for simulating Si thermophotovoltaic (TPV) devices. Experimentally fabricated diffused-junction devices are used to validate the optical and electrical aspects of the model. A peak TPV efficiency of 6.8% is predicted for the fabricated devices, but a pathway to 32.5% is explained by reducing the parasitic absorption of the contacts and reducing the wafer thickness. Additionally, the DS-TOPCon technology shows the potential for a 33.7% efficient TPV device.
ContributorsHartweg, Barry (Author) / Holman, Zachary (Thesis advisor) / Chan, Candace (Committee member) / Bertoni, Mariana (Committee member) / Yu, Zhengshan (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Electrochemical technologies emerge as a feasible solution to monitor and treat pollutants. Although electrochemical technologies have garnered widespread attention, their commercial applications are still constrained by the use of expensive electrocatalysts, and the bulky and rigid plate design of electrodes that restricts electrochemical reactor design to systems with poor electrode

Electrochemical technologies emerge as a feasible solution to monitor and treat pollutants. Although electrochemical technologies have garnered widespread attention, their commercial applications are still constrained by the use of expensive electrocatalysts, and the bulky and rigid plate design of electrodes that restricts electrochemical reactor design to systems with poor electrode surface/ volume treated ratios. By making electrodes flexible, more compact designs that maximize electrode surface per volume treated might become a reality. This dissertation encompasses the successful fabrication of flexible nanocomposite electrodes for electrocatalysis and electroanalysis applications.First, nano boron-doped diamond electrodes (BDD) were prepared as an inexpensive alternative to commercial boron-doped diamond electrodes. Comparative detailed surface and electrochemical characterization was conducted. Empirical study showed that replacing commercial BDD electrodes with nano-BDD electrodes can result in a cost reduction of roughly 1000x while maintaining the same electrochemical performance. Next, self-standing electrodes were fabricated through the electropolymerization of conducing polymer, polypyrrole. Surface characterizations, such as SEM, FTIR and XPS proved the successful fabrication of these self-standing electrodes. High mechanical stability and bending flexibility demonstrated the ability to use these electrodes in different designs, such as roll-to-roll membranes. Electrochemical nitrite reduction was employed to demonstrate the viability of using self-standing nanocomposite electrodes for electrocatalytic applications reducing hazardous nitrogen oxyanions (i.e., nitrite) towards innocuous species such as nitrogen gas. A high faradaic efficiency of 78% was achieved, with high selectivity of 91% towards nitrogen gas. To further enhance the conductivity and charge transfer properties of self-standing polypyrrole electrodes, three different nanoparticles, including copper (Cu), gold (Au), and platinum (Pt), were incorporated in the polypyrrole matrix. Effect of nanoparticle wt% and interaction between metal nanoparticles and polypyrrole matrix was investigated for electroanalytical applications, specifically dopamine sensing. Flexible nanocomposite electrodes showed outstanding performance as electrochemical sensors with PPy-Cu 120s exhibiting a low limit of detection (LOD) of 1.19 µM and PPy-Au 120s exhibiting a high linear range of 5 µM - 300 µM. This dissertation outlines a method of fabricating self-standing electrodes and provides a pathway of using self-standing electrodes based on polypyrrole and polypyrrole-metal nanocomposites for various applications in wastewater treatment and electroanalytical sensing.
ContributorsBansal, Rishabh (Author) / Garcia-Segura, Sergio (Thesis advisor) / Westerhoff, Paul (Committee member) / Perreault, Francois (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the corresponding structure change during the reaction is very important. Local structural and chemical information on nanoparticle surfaces or interfaces can

Photocatalytic water splitting is a promising technique to produce H2 fuels from water using sustainable solar energy. To better design photocatalysts, the understanding of charge transfer at surfaces/interfaces and the corresponding structure change during the reaction is very important. Local structural and chemical information on nanoparticle surfaces or interfaces can be achieved through characterizations on transmission electron microscopy (TEM). Emphasis should be put on materials structure changes during the reactions in their “working conditions”. Environmental TEM with in situ light illumination system allows the photocatalysts to be studied under light irradiation when exposed to H2O vapor. A set of ex situ and in situ TEM characterizations are carried out on typical types of TiO2 based photocatalysts. The observed structure changes during the reaction are correlated with the H2 production rate for structure-property relationships.

A surface disordering was observed in situ when well-defined anatase TiO2 rhombohedral nanoparticles were exposed to 1 Torr H2O vapor and 10suns light inside the environmental TEM. The disordering is believed to be related to high density of hydroxyl groups formed on surface oxygen vacancies during water splitting reactions.

Pt co-catalyst on TiO2 is able to split pure water producing H2 and O2. The H2 production rate drops during the reaction. Particle size growth during reaction was discovered with Z-contrast images. The particle size growth is believed to be a photo-electro-chemical Ostwald ripening.

Characterizations were also carried out on a more complicated photocatalyst system: Ni/NiO core/shell co-catalyst on TiO2. A decrease of the H2 production rate resulting from photo-corrosion was observed. The Ni is believed to be oxidized to Ni2+ by OH• radicals which are intermediate products of H2O oxidation. The mechanism that the OH• radicals leak into the cores through cracks on NiO shells is more supported by experiments.

Overall this research has done a comprehensive ex situ and in situ TEM characterizations following some typical TiO2 based photocatalysts during reactions. This research has shown the technique availability to study photocatalyst inside TEM in photocatalytic conditions. It also demonstrates the importance to follow structure changes of materials during reactions in understanding deactivation mechanisms.
ContributorsZhang, Liuxian (Author) / Crozier, Peter (Thesis advisor) / Smith, David (Committee member) / Chan, Candace (Committee member) / Liu, Jingyue (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Nanoscale semiconductors with their unique properties and potential applications have been a focus of extensive research in recent years. There are many ways in which semiconductors change the world with computers, cell phones, and solar panels, and nanoscale semiconductors having a promising potential to expand the efficiency, reduce the cost,

Nanoscale semiconductors with their unique properties and potential applications have been a focus of extensive research in recent years. There are many ways in which semiconductors change the world with computers, cell phones, and solar panels, and nanoscale semiconductors having a promising potential to expand the efficiency, reduce the cost, and improve the flexibility and durability of their design. In this study, theoretical quantum mechanical simulations were performed on several different nanoscale semiconductor materials, including graphene/phosphorene nanoribbons and group III-V nanowires. First principles density functional theory (DFT) was used to study the electronic and structural properties of these nanomaterials in their fully relaxed and strained states. The electronic band gap, effective masses of charge carriers, electronic orbitals, and density of states were most commonly examined with strain, both from intrinsic and external sources. For example, armchair graphene nanoribbons (AGNR) were found to have unprecedented band gap-strain dependence. Phosphorene nanoribbons (PNRs) demonstrate a different behavior, including a chemical scissors effect, and studies revealed a strong relationship between passivation species and band gap tunability. Unlike the super mechanical flexibility of AGNRs and PNRs which can sustain incredible strain, modest yet large strain was applied to group III-V nanowires such as GaAs/InAs. The calculations showed that a direct and indirect band gap transition occurs at some critical strains and the origination of these gap transitions were explored in detail. In addition to the pure nanowires, GaAs/InAs core/shell heterostructure nanowires were also studied. Due to the lattice mismatch between GaAs and InAs, the intrinsic strain in the core/shell nanowires demonstrates an interesting behavior on tuning the electronic properties. This interesting behavior suggests a mechanical way to exert compressive strain on nanowires experimentally, and can create a finite quantum confinement effect on the core.
ContributorsCopple, Andrew (Author) / Peng, Xihong (Thesis advisor) / Chan, Candace (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2016
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Description
LiNbO3 and ZnO have shown great potential for photochemical surface reactions and specific photocatalytic processes. However, the efficiency of LiNbO3 is limited due to recombination or back reactions and ZnO exhibits a chemical instability in a liquid cell. In this dissertation, both materials were coated with precise thickness of metal

LiNbO3 and ZnO have shown great potential for photochemical surface reactions and specific photocatalytic processes. However, the efficiency of LiNbO3 is limited due to recombination or back reactions and ZnO exhibits a chemical instability in a liquid cell. In this dissertation, both materials were coated with precise thickness of metal oxide layers to passivate the surfaces and to enhance their photocatalytic efficiency. LiNbO3 was coated with plasma enhanced atomic layer deposited (PEALD) ZnO and Al2O3, and molecular beam deposited TiO2 and VO2. On the other hand, PEALD ZnO and single crystal ZnO were passivated with PEALD SiO2 and Al2O3.

Metal oxide/LiNbO3 heterostructures were immersed in aqueous AgNO3 solutions and illuminated with ultraviolet (UV) light to form Ag nanoparticle patterns. Alternatively, Al2O3 and SiO2/ZnO heterostructures were immersed in K3PO4 buffer solutions and studied for photoelectrochemical reactions. A fundamental aspect of the heterostructures is the band alignment and band bending, which was deduced from in situ photoemission measurements.

This research has provided insight to three aspects of the heterostructures. First, the band alignment at the interface of metal oxides/LiNbO3, and Al2O3 or SiO2/ZnO were used to explain the possible charge transfer processes and the direction of carrier flow in the heterostructures. Second, the effect of metal oxide coatings on the LiNbO3 with different internal carrier concentrations was related to the surface photochemical reactions. Third is the surface passivation and degradation mechanism of Al2O3 and SiO2 on ZnO was established. The heterostructures were characterized after stability tests using atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross-section transmission electron microscopy (TEM).

The results indicate that limited thicknesses of ZnO or TiO2 on polarity patterned LiNbO3 (PPLN) enhances the Ag+ photoinduced reduction process. ZnO seems more efficient than TiO2 possibly due to a higher carrier mobility. However, an increase of the ZnO thickness (≥ 4 nm) reduced the effect of the PPLN substrate on the Ag nanoparticle pattern. For the case of Al2O3 and SiO2/ZnO heterostructures, SiO2 remains intact through 1 h stability tests. Unlike SiO2, Al2O3 shows surface degradation after a short stability test of a few minutes. Thus, SiO2 provides improved passivation over Al2O3. A detailed microscopy analysis indicates the underneath ZnO photocorrodes in the SiO2/ZnO samples, which is possibly due to transport of ions through the SiO2 protective layer.
ContributorsKaur, Manpuneet (Author) / Nemanich, Robert (Thesis advisor) / Dey, Sandwip (Committee member) / Crozier, Peter (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2016