Matching Items (155)
Description
Thin film solar cells are based on polycrystalline materials that contain a high concentration of intrinsic and extrinsic defects. Improving the device efficiency in such systems relies on understanding the nature of defects - whether they are positive, negative, or neutral in their influence - and their sources in order to engineer optimized absorbers. Oftentimes, these are studied individually, as characterization techniques are limited in their ability to directly relate material properties in individual layers to their impact on the actual device performance. Expanding the tools available for increased understanding of materials and devices has been critical for reducing the translation time of laboratory-scale research to changes in commercial module manufacturing lines. The use of synchrotron X-ray fluorescence (XRF) paired with X-ray beam induced current and voltage (XBIC, XBIV respectively) has proven to be an effective technique for understanding the impact of material composition and inhomogeneity on solar cell device functioning. The combination of large penetration depth, small spot size, and high flux allows for the measurement of entire solar cell stacks with high spatial resolution and chemical sensitivity. In this work, I combine correlative XRF/XBIC/XBIV with other characterization approaches across varying length scales, such as micro-Raman spectroscopy and photoluminescence, to understand how composition influences device performance in thin films. The work described here is broken into three sections. Firstly, understanding the influence of KF post-deposition treatment (PDT) and the use of Ag-alloying to reduce defect density in the Ga-free material system, CuInSe2 (CIS). Next, applying a similar characterization workflow to industrially relevant Ga-containing Cu(In1-xGax)Se2 (CIGS) modules with Ag and KF-PDT. The influence of light soaking and dark heat exposure on the modules are also studied in detail. Results show that Ag used with KF-PDT in CIS causes undesirable cation ordering at the CdS interface and affects the device through increased potential fluctuations. The results also demonstrate the importance of tuning the concentration of KF-PDT used when intended to be used in Ag-alloyed devices. Commercially-processed modules with optimized Ag and KF concentrations are shown to have the device performance instead be dominated by variations in the CIGS composition itself. In particular, changes in Cu and Se concentrations are found to be most influential on the device response to accelerated stressors such as dark heat exposure and light soaking. In the final chapter, simulations of nano-scale XBIC and XBIV are done to contribute to the understanding of these measurements.
ContributorsNietzold, Tara (Author) / Bertoni, Mariana I. (Thesis advisor) / Holt, Martin (Committee member) / Shafarman, William N. (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2021
Description
Exposure of liquid biospecimens like plasma and serum (P/S) to improper handling and storage can impact the integrity of biomolecules, potentially leading to apparent quantitative changes of important clinical proteins. An accurate and quick estimate of the quality of biospecimens employed in biomarker discovery and validation studies is essential to facilitating accurate conclusions. ΔS-Cys-Albumin is a marker of blood P/S exposure to thawed conditions that can quantitatively track the exposure of P/S to temperatures greater than their freezing point of -30 C. Reported here are studies carried out to evaluate the potential of ΔS-Cys-Albumin to track the stability of clinically important analytes present in P/S upon their exposure to thawed conditions. P/S samples obtained from both cancer-free donors and cancer patients were exposed to 23 C (room temperature), 4 C and -20 C degrees, and the degree to which the apparent concentrations of clinically relevant biomolecules present in P/S were impacted during the time it took ΔS-Cys-Albumin to reach zero was measured. Analyte concentrations measured by molecular interaction-based assays were significantly impacted when samples were exposed to the point where average ΔS-Cys-Albumin fell below 12% at each temperature. Furthermore, the percentage of proteins that became unstable with time under thawed conditions exhibited a strong inverse linear relationship to ΔS-Cys-Albumin, indicating that ΔS-Cys-Albumin can serve as an effective surrogate marker to track the stability of other clinically relevant proteins in plasma as well as to estimate the fraction of proteins that have been destabilized by exposure to thawed conditions, regardless of what the exposure temperature(s) may have been. These results indicated that P/S exposure to thawed conditions disrupts epitopes required for clinical protein quantification via molecular interaction-based assays. In continuation of this theme, a spurious binding event between two clinically important proteins, Apolipoprotein E (ApoE) and Interferon- (IFN) present in human plasma under in vitro experimental conditions is also reported. The interaction was confirmed to be evident only when ApoE was expressed in vitro with a Glutathione-S-Transferase (GST) fusion tag. Future steps required to find the exact manner in which the GST fusion tag facilitated the association between ApoE and IFNγ are discussed with emphasis on the possible pitfalls associated with using fusion proteins for studying novel protein-protein interactions.
ContributorsKapuruge, Erandi Prasadini (Author) / Borges, Chad R (Thesis advisor) / LaBaer, Joshua (Committee member) / Van Horn, Wade (Committee member) / Arizona State University (Publisher)
Created2021
Description
Osteocalcin (Oc) is the most abundant non-collagen protein found in the bone, but its precise function is still not completely understood. Three glutamic acid (Glu) residues within its sequence are sites for vitamin K-dependent post-translational modification, replacing a hydrogen with a carboxylate located at the γ-carbon position, converting these to γ-carboxyglutamic acid (Gla) residues. This modification confers increased binding of Oc to Ca2+ and hydroxyapatite matrix. Presented here, novel metal binding partners Mn2+, Fe3+, and Cr3+ of human Oc were determined, while the previously identified binders to (generally) non-human Oc, Ca2+, Mg2+, Pb2+ and Al3+ were validated as binders to human Oc by direct infusion mass spectrometry with all metals binding with higher affinity to the post-translationally modified form (Gla-Oc) compared to the unmodified form (Glu-Oc). Oc was also found to form pentamer (Gla-Oc) and pentamer and tetramer (Glu-Oc) homomeric self-assemblies in the absence of NaCl, which disassembled to monomers in the presence of near physiological Na+ concentrations. Additionally, Oc was found to form filamentous structures in vitro by negative stain TEM in the presence of increased Ca2+ titrations in a Gla- and pH-dependent manner. Finally, by combining circular dichroism spectroscopy to determine the fraction of Gla-Oc bound, and inductively-coupled plasma mass spectrometry to quantify total Al concentrations, the data were fit to a single-site binding model and the equilibrium dissociation constant for Al3+ binding to human Gla-Oc was determined (Kd = 1.0 ± 0.12 nM). Including citrate, a known competitive binder of Al3+, maintained Al in solution and enabled calculation of free Al3+ concentrations using a Matlab script to solve the complex set of linear equations. To further improve Al solubility limits, the pH of the system was lowered to 4.5, the pH during bone resorption. Complementary binding experiments with Glu-Oc were not possible due to the observed precipitation of Glu-Oc at pH 4.5, although qualitatively if Glu-Oc binds Al3+, it is with much lower affinity compared to Gla-Oc. Taken together, the results presented here further support the importance of post-translational modification, and thus adequate nutritional intake of vitamin K, on the binding and self-assembly properties of human Oc.
ContributorsThibert, Stephanie (Author) / Borges, Chad R (Thesis advisor) / LaBaer, Joshua (Committee member) / Chiu, Po-Lin (Committee member) / Arizona State University (Publisher)
Created2021
Description
The 5-year survival rate for late-stage metastatic melanoma is only ~30%. A major reason for this low survival rate is that one of the most commonly mutated genes in melanoma, NRAS, has no FDA-approved targeted therapies. Because the RAS protein does not have any targeted therapies, patients with RAS mutant tumors have an ongoing need for treatments that indirectly target RAS. This thesis project aims to identify expression and phosphorylation levels of proteins downstream of RAS in melanoma cell lines with the most common driver mutations. By analyzing the protein-level differences between these genetic mutants, we hope to identify additional indirect RAS protein targets for the treatment of NRAS mutant melanoma. RAS has several downstream effector proteins involved in oncogenic signaling pathways including FAK, Paxillin, AKT, and ERK. 5 melanoma cell lines (2 BRAF mutant, 2 NRAS mutant, and 1 designated wildtype) were analyzed using western bloting for FAK, Paxillin, AKT, and ERK phosphorylation and total expression levels. The results of western blot analysis showed that NRAS mutant cell lines had increased expression of phosphorylated Paxillin. Increased Paxillin phosphorylation corresponds to increased Paxillin binding at the FAT domain of FAK. Therefore, cell lines with increased FAK FAT – Paxillin interaction would be more sensitive to FAK FAT domain inhibition. The data presented provide an an explanation for the reduction in cell viability in NRAS mutant cell lines infected with Ad-FRNK. This information also has significant clinical relevance as researchers work to develop synthetic FAK FAT domain inhibitors, such as cyclic peptides. Additionally, cell lines with high levels of phosphorylated AKT showed a significant reduction in the amount of phosphorylated ERK. The identification of this inverse relationship may help to explain why BRAF and NRAS mutations are mutually exclusive. To conclude, NRAS mutant cell lines have increased expression of phosphorylated Paxillin and AKT which may explain why NRAS mutant cell lines are more sensitive to FAK FAT domain inhibition.
ContributorsSherwood, Nicole (Author) / Gould, Ian (Thesis director) / LaBaer, Joshua (Committee member) / Marlowe, Timothy (Committee member) / Barrett, The Honors College (Contributor) / School of Life Sciences (Contributor)
Created2022-05
Description
The application of silicon thin films in solar cells has evolved from their use in amorphous silicon solar cells to their use as passivating and carrier-selective contacts in crystalline silicon solar cells. Their use as carrier-selective contacts has enabled crystalline silicon solar cell efficiencies above 26%, just 3% shy of the theoretical efficiency limit. The two cell architectures that have exceeded 26% are the silicon heterojunction and tunnel oxide passivating contact cell. These two cell architectures use two different forms of silicon thin films. In the case of the silicon heterojunction, the crystalline wafer is sandwiched between layers of intrinsic amorphous silicon, which acts as the passivation layer, and doped amorphous silicon, which acts as the carrier-selective layer. On the other hand, the tunnel oxide passivating contact cell uses a thin silicon oxide passivation layer and a doped polycrystalline silicon layer as the carrier-selective layer. Both cell structures have their distinct advantages and disadvantages when it comes to production. The processing of the silicon heterojunction relies on a low thermal budget and leads to high open-circuit voltages, but the cost of high-vacuum processing equipment presents a major hurdle for industrial scale production while the tunnel oxide passivating contact can be easily integrated into current industrial lines, yet it requires a higher thermal budgets and does not produce as high of an open-circuit voltage as the silicon heterojunction. This work focuses on using both forms of silicon thin films applied as passivating and carrier-selective contacts to crystalline silicon thin films.First, a thorough analysis of the series resistivity in silicon heterojunction solar cells is conducted. In particular, variations in the thickness and doping of the individual
ii
contact layers are performed to reveal their effect on the contact resistivity and in turn the total series resistivity of the cell. Second, a tunnel oxide passivated contact is created using a novel deposition method for the silicon oxide layer. A 21% efficient proof-of-concept device is presented demonstrating the potential of this deposition method. Finally, recommendations to further improve the efficiency of these cells is presented.
ContributorsWeigand, William (Author) / Holman, Zachary (Thesis advisor) / Yu, Zhengshan (Committee member) / Bertoni, Mariana (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023
Description
Emerging pathogens present several challenges to medical diagnostics. Primarily, the exponential spread of a novel pathogen through naïve populations require a rapid and overwhelming diagnostic response at the site of outbreak. While point-of-care (PoC) platforms have been developed for detection of antigens, serologic responses, and pathogenic genomes, only nucleic acid diagnostics currently have the potential to be developed and manufactured within weeks of an outbreak owing to the speed of next-generation sequencing and custom DNA synthesis. Among nucleic acid diagnostics, isothermal amplification strategies are uniquely suited for PoC implementation due to their simple instrumentation and lack of thermocycling requirement. Unfortunately, isothermal strategies are currently prone to spurious nonspecific amplification, hindering their specificity and necessitating extensive empirical design pipelines that are both time and resource intensive. In this work, isothermal amplification strategies are extensively compared for their feasibility of implementation in outbreak response scenarios. One such technology, Loop-mediated Amplification (LAMP), is identified as having high-potential for rapid development and PoC deployment. Various approaches to abrogating nonspecific amplification are described including a novel in silico design tool based on coarse-grained simulation of interactions between thermophilic DNA polymerase and DNA strands in isothermal reaction conditions. Nonspecific amplification is shown to be due to stabilization of primer secondary structures by high concentrations of Bst DNA polymerase and a mechanism of micro-complement-mediated cross-priming is demonstrated as causal via nanopore sequencing of nonspecific reaction products. The resulting computational model predicts primer set background in 64% of 67 test assays and its usefulness is illustrated further by determining problematic primers in a West Nile Virus-specific LAMP primer set and optimizing primer 3’ nucleotides to eliminate micro-complements within the reaction, resulting in inhibition of background accumulation. Finally, the emergence of Orthopox monkeypox (MPXV) as a recurring threat is discussed and SimCycle is utilized to develop a novel technique for clade-specific discrimination of MPXV based on bridging viral genomic rearrangements (Bridging LAMP). Bridging LAMP is implemented in a 4-plex microfluidic format and demonstrates 100% sensitivity in detection of 100 copies of viral lysates and 45 crude MPXV-positive patient samples collected during the 2022 Clade IIb outbreak.
ContributorsKnappenberger, Mark Daniel (Author) / Anderson, Karen S (Thesis advisor) / LaBaer, Joshua (Committee member) / Roberson, Robert (Committee member) / Lindsay, Stuart (Committee member) / Arizona State University (Publisher)
Created2023
Description
MicroRNAs (miRNAs) are 17-22 nucleotide non-coding RNAs that regulate gene expression by targeting non-complementary elements in the 3’ untranslated regions (3’UTRs) of mRNAs. miRNAs, which form complex networks of interaction that differ by tissue and developmental stage, display conservation in their function across metazoan species. Yet much remains unknown regarding their biogenesis, localization, strand selection, and their absolute abundance due to the difficulty of detecting and amplifying such small molecules. Here, I used an updated HT qPCR-based methodology to follow miRNA expression of 5p and 3p strands for all 190 C. elegans miRNAs described in miRBase throughout all six developmental stages in triplicates (total of 9,708 experiments), and studied their expression levels, tissue localization, and the rules underlying miRNA strand selection. My study validated previous findings and identified novel, conserved patterns of miRNA strand expression throughout C. elegans development, which at times correlate with previously observed developmental phenotypes. Additionally, my results highlighted novel structural principles underlying strand selection, which can be applied to higher metazoans.
Though optimized for use in C. elegans, this method can be easily adapted to other eukaryotic systems, allowing for more scalable quantitative investigation of miRNA biology and/or miRNA diagnostics.
ContributorsMeadows, Dalton Alexander (Author) / Mangone, Marco (Thesis advisor) / LaBaer, Joshua (Committee member) / Murugan, Vel (Committee member) / Wilson-Rawls, Jeanne (Committee member) / Arizona State University (Publisher)
Created2023
Description
Metal-Oxide-Semiconductor (MOS) is essential to modern VLSI devices. In the past decades, a wealth of literature has been created to understand the impact of the radiation-induced charges on the devices, i.e., the creation of electron-hole pairs in the oxide layer which is the most sensitive part of MOS structure to the radiation effect. In this work, both MOS and MNOS devices were fabricated at ASU NanoFab to study the total ionizing dose effect using capacitance-voltage (C-V) electrical characterization by observing the direction and amounts of the shift in C-V curves and electron holography observation to directly image the charge buildup at the irradiated oxide film of the oxide-only MOS device.C-V measurements revealed the C-V curves shifted to the left after irradiation (with a positive bias applied) because of the net positive charges trapped at the oxide layer for the oxide-only sample. On the other hand, for nitride/oxide samples with positive biased during irradiation, the C-V curve shifted to the right due to the net negative charges trapped at the oxide layer. It was also observed that the C-V curve has less shift in voltage for MNOS than MOS devices after irradiation due to the less charge buildup after irradiation.
Off-axis electron holography was performed to map the charge distribution across the MOSCAP sample. Compared with both pre-and post-irradiated samples, a larger potential drop at the Si/SiO2 was noticed in post-irradiation samples, which indicates the presence of greater amounts of positive charges that buildup the Si/SiO2 interface after the TID exposure.
TCAD modeling was used to extract the density of charges accumulated near the SiO2/Si and SiO2/ Metal interface by matching the simulation results to the potential data from holography. The increase of near-interface positive charges in post-irradiated samples is consistent with the C-V results.
ContributorsChang, Ching Tao (Author) / Barnaby, Hugh (Thesis advisor) / Holbert, Keith (Committee member) / Tongay, Sefaattin (Committee member) / Arizona State University (Publisher)
Created2023
Description
My thesis, Design of Hierarchically Porous Materials Containing Covalent Organic Frameworks, focuses on testing the validity of incorporating nanoporous organic materials into macroporous scaffolding to improve the functionality of covalent organic frameworks as materials for filtration applications. The macroporous scaffold was based off of a material recently described in literature and the bulk of the experimentation was focused on the effects of the necessary processing for the creation of the macroporous material on the structure of the covalent organic frameworks. The property primarily investigated was the Brunauer-Emmett-Teller surface area, as the applicability of the frameworks is largely determined by their nanoporous surface area.
ContributorsRidenour, Brian (Author) / Jin, Kailong (Thesis director) / Tongay, Sefaattin (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2023-05
Description
The recent discoveries of 2D van der Waals (vdW) materials have led to the realization of 2D magnetic crystals. Previously debated and thought impossible, transition metal halides (TMH) have given rise to layer dependent magnetism. Using these TMH as a basis, an alloy composing of Fe1-xNixCl2 (where 0 ≤ x ≤ 1) was grown using chemical vapor transport. The intrigue for this alloy composition stems from the interest in spin canting and magnet moment behavior since NiCl2 has in-plane ferromagnetism whereas FeCl2 has out-of-plane ferromagnetism. While in its infancy, this project lays out a foundation to fully develop and characterize this TMH via cationic alloying. To study the magnetic properties of this alloy system, Vibrating Sample Magnetometry was employed extensively to measure the magnetism as a function of temperature as well as applied magnetic field. Future work with use a combination of X-Ray Diffraction, Raman, Scanning Electron Microscopy, and Energy-Dispersive X-Ray Spectroscopy Mapping to verify homogeneous alloying rather than phase separation. Additionally, ellipsometry will be used with Kramer-Kronig relations to extract the dielectric constant from Fe1-xNixCl2. This work lays the foundation for future, fruitful work to prepare this vdW cationic alloy for eventual device applications.
ContributorsPovilus, Blake (Author) / Tongay, Sefaattin (Thesis director) / Yang, Sui (Committee member) / Barrett, The Honors College (Contributor) / Materials Science and Engineering Program (Contributor)
Created2022-05