View All Items

Title: INVESTIGATIONS ON MORPHOLOGY, SPECTROSCOPY AND NEAR-INFRARED PHOTORESPONSE SENSITIZATION OF CONJUGATED POLYMERS IN ORGANIC PHOTOVOLTAICS.
Creator: Hu, Zhongjian, Gesquiere, Andre, University of Central Florida
Abstract / Description: Conjugated polymer architecture and morphology are two of the key factors that determine corresponding opto-electronic device performance. It is well-known that conjugated polymers display a variety of conformations and exhibit aggregation in their materials and even for individual polymer chains. The intrinsic structural heterogeneity of conjugated polymers strongly complicates the active layer morphology and phase separation, which are crucial for photoinduced charge generation and...
Show moreConjugated polymer architecture and morphology are two of the key factors that determine corresponding opto-electronic device performance. It is well-known that conjugated polymers display a variety of conformations and exhibit aggregation in their materials and even for individual polymer chains. The intrinsic structural heterogeneity of conjugated polymers strongly complicates the active layer morphology and phase separation, which are crucial for photoinduced charge generation and transport in polymer based bulk heterojunction-organic photovoltaics device (BHJ-OPVs). Aiming to probe the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties, single molecule spectroscopy (SMS) and single particle spectroscopy (SPS) were employed. The molecular level folding properties of conjugated polymers were studied and correlated to the chemical architecture and rigidness of the polymer backbones by means of SMS and single molecule polarization anisotropy imaging. First, a block copolymer consisting of poly(3-hexylthiophene) (P3HT) and fullerene (C60) was investigated due to its potential for forming active layers in OPV devices that exhibit long-term phase stability and efficient exciton dissociation into free charge carriers. It was demonstrated that the grafting of the C60-containing block does not significantly affect the conformation of the backbone of the P3HT block. Next, a series of thiophene based polymers showing different macroscale crystallization behavior were investigated. The rigidness of the conjugated polymer backbones was found to be correlated with the chemical architecture of the molecules. However, even the polymers that show no folding in their respective crystals and are thus expected to be the most rigid, still exhibit folding at the single molecule level. From this work it is clear that besides chemical architecture, intermolecular interactions in the crystal structure also need to be considered. For conjugated polymer materials, in this dissertation specifically the blends of conjugated polymers with fullerenes as found in the active layer of OPVs, the investigation of the molecular level correlations between conjugated polymer architecture, morphology and optoelectronic properties can be prohibitively complex due to the presence of a large number of molecules. Furthermore, in the research presented herein, as well as in the literature, it has been clearly shown that the polymer molecules themselves exhibit severe heterogeneity in their properties (chain morphology, aggregation, optical and electronic properties). Therefore, in order to simplify the structure-property investigations concerning nanodomains in BHJ-OPVs, we developed P3HT/PC60BM (PC60BM: -phenyl-C61-butyric acid methyl ester) composite nanoparticles (NPs). The size of the nanoparticles corresponds with a few polymer and fullerene domains when considering a similarly sized volume in the active layer of OPVs. Single particle spectroscopy combined with this unique nanoparticle material system reveals variations in molecular conformation and aggregation of the conjugated polymer chains upon doping with different weight percentages of fullerene. These newly developed NPs were embedded in a hole-injection device to study the exciton-hole polaron interactions and the charge transfer processes at the interface between a hole-transporting layer and the NPs. Pronounced charge trapping was observed for donor-acceptor blend NPs due to the large amount of photogenerated free charge carriers. Besides fundamental studies on morphology-property relations for thiophene based conjugated polymers, fabrication of BHJ-OPVs based on P3HT and PC60BM was also completed. Low band gap polymer PTB-7 (polybenzo dithiophene-2,6-diyl]thieno thiophenediyl]]) and a near-infrared (NIR) small dye molecule were incorporated into active layers of these P3HT/PC60BM BHJ-OPVs to expand the photoresponse of the devices. The effects of doping the P3HT/PC60BM BHJ-OPVs with PTB-7 and NIR dye on the device performance and film morphology were investigated. The doping of PTB-7 can efficiently extend the photoresponse of the resultant devices into the NIR regime and improve the device performance with respect to the reference (undoped) devices, demonstrating an elegant and pragmatic approach in improving light-harvesting efficiency in BHJ-OPVs.
Show less
Date Issued: 2011
Identifier: CFE0004042, ucf:49167
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004042

Title: IMAGING AND SPECTROSCOPY OF CONDUCTING POLYMER-FULLERENE COMPOSITE MATERIALS.
Creator: Tenery, Daeri, Gesquiere, Andre, University of Central Florida
Abstract / Description: Since the development and optical study of conjugated (conducting) polymers it has become apparent that chain conformation and aggregation at the molecular scale result in complex heterogeneous nanostructured bulk materials for which a detailed insight into morphological, spectroscopic as well as optoelectronic properties and mechanisms is overwhelmingly difficult to obtain. Nanoparticles composed of the conjugated polymer poly (MEH-PPV) and nanocomposite nanoparticles consisting of MEH-PPV...
Show moreSince the development and optical study of conjugated (conducting) polymers it has become apparent that chain conformation and aggregation at the molecular scale result in complex heterogeneous nanostructured bulk materials for which a detailed insight into morphological, spectroscopic as well as optoelectronic properties and mechanisms is overwhelmingly difficult to obtain. Nanoparticles composed of the conjugated polymer poly (MEH-PPV) and nanocomposite nanoparticles consisting of MEH-PPV doped with 1-(3-methoxycarbonylpropyl)-1-phenyl-C61 (PCBM) were prepared as model systems to study these materials at the length scale of one to a few domains. The MEH-PPV and PCBM doped nanoparticles were analyzed by single imaging/particle spectroscopy (SPS) and revealed molecular scale information on the structure-property relationships of these composite materials. The data obtained from SPS were investigated in terms of spectral difference between doped and undoped nanoparticles. The doped nanoparticles are blue shifted by approximately 5-10 nm, have an additional blue shoulder, and show different vibronic structure than the undoped nanoparticles. Specifically, relative intensity of the 0-1 transition is lower than for the undoped nanoparticles. These data are indicative of differences in molecular order between both nanoparticle systems, detected at the molecular scale. In addition, the effect of electrical fields present in devices on the interfacial charge transfer properties was evaluated. Furthermore, these nanoparticles were incorporated into the lipid nanotubes to study the diffusion process of the single MEH-PPV nanoparticles inside the lipid nanotubes. Our data shows a clear proof of concept that diffusion of nanoparticles inside the hollow lipid nanotubes can be studied on a single particle basis, which will allow us to study diffusion processes quantitatively and mechanistically within the framework of developing a biocompatible drug and gene delivery platform.
Show less
Date Issued: 2009
Identifier: CFE0002708, ucf:48155
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002708

Title: Photoactivatable Organic and Inorganic Nanoparticles in Cancer Therapeutics and Biosensing.
Creator: Mathew, Mona, Gesquiere, Andre, Hickman, James, Ye, Jingdong, Campiglia, Andres, Schoenfeld, Winston, University of Central Florida
Abstract / Description: In photodynamic therapy a photosensitizer drug is administered and is irradiated with light. Upon absorption of light the photosensitizer goes into its triplet state and transfers energy or an electron to oxygen to form reactive oxygen species (ROS). These ROS react with biomolecules in cells leading to cell damage and cell death. PDT has interested many researchers because of its non-invasiveness as compared to surgery, it leaves little to no scars, it is time and cost effective, it has...
Show moreIn photodynamic therapy a photosensitizer drug is administered and is irradiated with light. Upon absorption of light the photosensitizer goes into its triplet state and transfers energy or an electron to oxygen to form reactive oxygen species (ROS). These ROS react with biomolecules in cells leading to cell damage and cell death. PDT has interested many researchers because of its non-invasiveness as compared to surgery, it leaves little to no scars, it is time and cost effective, it has potential for targeted treatment, and can be repeated as needed. Different photosensitizers such as porphyrines, chlorophylls, and dyes have been used in PDT to treat various cancers, skin diseases, aging and sun-damaged skin. These second generation sensitizers have yielded reduced skin sensitivity and improved extinction coefficients (up to ~ 105 L mol-1 cm-1). While PDT based on small molecule photosensitizers has shown great promise, several problems remain unsolved. The main issues with current sensitizers are (i) hydrophobicity leading to aggregation in aqueous media resulting in reduced efficacy and potential toxicity, (ii) dark toxicity of photosensitizers, (iii) non-selectivity towards malignant tissue resulting in prolonged cutaneous photosensitivity and damage to healthy tissue, (iv) limited light absorption efficiency, and (v) a lack of understanding of where the photosensitizer ends up in the tissue. In this dissertation research program, these issues were addressed by the development of conducting polymer nanoparticles as a next generation of photosensitizers. This choice was motivated by the fact that conducting polymers have large extinction coefficients ((>) 107 L mol-1 cm-1), are able to undergo intersystem crossing to the triplet state, and have triplet energies that are close to that of oxygen. It was therefore hypothesized that such polymers could be effective at generating ROS due to the large excitation rate that can be generated. Conducting polymer nanoparticles (CPNPs) composed of the conducting polymer poly[2-methoxy-5-(2-ethylhexyl-oxy)-p-phenylenevinylene] (MEH-PPV) were fabricated and studied in-vitro for their potential in PDT application. Although not fully selective, the nanoparticles exhibited a strong bias to the cancer cells. The formation of ROS was proven in-vitro by staining of the cells with CellROX Green Reagent, after which PDT results were quantified by MTT assays. Cell mortality was observed to scale with nanoparticle dosage and light dosage. Based on these promising results the MEH-PPV nanoparticles were developed further to allow for surface functionalization, with the aim of targeting these NPs to cancer cell lines. For this work targeting of cancers that overexpress folate receptors (FR) were considered. The functionalized nanoparticles (FNPs) were studied in OVCAR3 (ovarian cancer cell line) as FR+, MIA PaCa2 (pancreatic cell line) as FR-, and A549 (lung cancer cell line) having marginal FR expression. Complete selectivity of the FNPs towards the FR+ cell line was found. Quantification of PDT results by MTS assays and flow cytometry show that PDT treatment was fully selective to the FR+ cell line (OVCAR3). No cell mortality was observed for the other cell lines studied here within experimental error. Finally, the issue of confirming and quantifying small molecule drug delivery to diseased tissue was tackled by developing quantum dot (Qdot) biosensors with the aim of achieving fluorescence reporting of intracellular small molecule/drug delivery. For fluorescence reporting prior expertise in control of the fluorescence state of Qdots was employed, where redox active ligands can place the Qdot in a quenched OFF state. Ligand attachment was accomplished by disulfide linker chemistry. This chemistry is reversible in the presence of sulfur reducing biomolecules, resulting in Qdots in a brightly fluorescent ON state. Glutathione (GSH) is such a biomolecule that is present in the intracellular environment. Experimental in-vitro data shows that this design was successfully implemented.
Show less
Date Issued: 2014
Identifier: CFE0005839, ucf:50923
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005839

Title: Size, Charge and Dose Dependent In-vitro Kinetics of Polystyrene Nanoparticles.
Creator: Abdellatif, Yasmine, Gesquiere, Andre, Kang, Hyeran, Rajaraman, Swaminathan, University of Central Florida
Abstract / Description: The aim of the study described herein is to quantify the in-vitro kinetics of internalization of polystyrene nanoparticles (PS NPs) by cells. We used different charges, sizes and doses of fluorescently labelled PS NPs. Nanoparticles were characterized with UV-Vis, Fluorescence emission Dynamic Light Scattering (DLS) and Zeta potential for knowing their absorption, fluorescence spectra, size, charge, respectively. Additionally, cell viability was tested to know the toxicity of PS NPs. The...
Show moreThe aim of the study described herein is to quantify the in-vitro kinetics of internalization of polystyrene nanoparticles (PS NPs) by cells. We used different charges, sizes and doses of fluorescently labelled PS NPs. Nanoparticles were characterized with UV-Vis, Fluorescence emission Dynamic Light Scattering (DLS) and Zeta potential for knowing their absorption, fluorescence spectra, size, charge, respectively. Additionally, cell viability was tested to know the toxicity of PS NPs. The quantitative uptake, the kinetics profile and rate of uptake were studied by using a new in-vitro fluorescence assay. This was achieved quantitatively and qualitatively by fluorescent plate reader and confocal imaging, respectively. It was found that the amine PS NPs are higher in cytotoxicity than the carboxy PS NPs due to the proton sponge phenomenon. It was observed that the fraction uptake of PS NPs changes by changing the physiochemical properties as charge, size (&) dose. The fraction uptake of neutral and amine PS NPs was higher than that of carboxy PS NPs. For the neutral PS NPs, the uptake depends on the macropinocytosis. For the amine PS NPs, the uptake depends on the electrostatic interaction and the rapid regeneration of new binding sites. Regarding the dose of PS NPs, for the amine PS NPs, it was found that the concentrations lower and higher than 5nM had lower fraction uptake, because the 5nM achieved the balance between the available number of binding sites and the rapid regeneration of new binding sites. For the kinetics profile of the amine and carboxy PS NPs, by comparing both of them, it was observed that the rate of uptake of applied doses lower than 5nM was different, but higher than 5nM was similar. However, for the neutral Ps NPs, they exhibit a steady state of rate of uptake in between the amine and carboxy PS NPs. Also, it was confirmed by the confocal images that as the concentration of amine PS NPs increase, the stress on the cells increase, leading to the cell death. These results were aligned with the results obtained from the cytotoxicity test.
Show less
Date Issued: 2018
Identifier: CFE0007386, ucf:52744
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007386

Title: Nano-Biophysical Approaches for Assessing Nanoparticle Interactions with Biological Systems.
Creator: Untracht, Zachary, Kang, Ellen, Gesquiere, Andre, Santra, Swadeshmukul, University of Central Florida
Abstract / Description: Understanding interactions between nanoparticles and biological systems is fundamental for the development of emerging nano-biotechnology applications. In this thesis, I present an investigation of zinc oxide (ZnO) nanoparticles interactions with biomolecules in two separate studies. The first section of my thesis covers tracking and detection of ZnO nanoparticles using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). ZinkicideTM is a bactericidal ZnO nanoparticle which...
Show moreUnderstanding interactions between nanoparticles and biological systems is fundamental for the development of emerging nano-biotechnology applications. In this thesis, I present an investigation of zinc oxide (ZnO) nanoparticles interactions with biomolecules in two separate studies. The first section of my thesis covers tracking and detection of ZnO nanoparticles using sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE). ZinkicideTM is a bactericidal ZnO nanoparticle which has been developed for agriculture. The characterization of Zinkicide in biological media and in solution has been difficult due to its high dispersibility and ultra-small size. SDS-PAGE is considered a golden standard for protein qualitative interpretations. In this study, we have modified this typical protein assay and developed protocols for quantifying Zinkicide concentration, fluorescence intensity, and relative molecular weight changes in aqueous solutions. We found that SDS-PAGE is a novel and fundamental approach for assessing ZnO nanoparticles.The second part of my thesis is focused on investigating biological toxicity induced by nanoparticles. Recent studies have shown that nanoparticles have the capabilities to induce abnormalities on cellular networks including actin cytoskeleton. We have studied the effects of ZnO nanoparticles on filamentous actin assembly dynamics utilizing total internal reflection fluorescence (TIRF) microscopy imaging and biophysical analysis. The combination of these studies has provided pertinent information for the future development of nanoparticles designed for biological applications.
Show less
Date Issued: 2019
Identifier: CFE0007738, ucf:52423
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007738

Title: Prediction of Optical Properties of Pi-Conjugated Organic Materials for Technological Innovations.
Creator: Nayyar, Iffat, Masunov, Artem, Saha, Haripada, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
Abstract / Description: Organic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged ...
Show moreOrganic ?-conjugated solids are promising candidates for new optoelectronic materials. The large body of evidence points at their advantageous properties such as high charge-carrier mobility, large nonlinear polarizability, mechanical flexibility, simple and low cost fabrication and superior luminescence. They can be used as nonlinear optical (NLO) materials with large two-photon absorption (2PA) and as electronic components capable of generating nonlinear neutral (excitonic) and charged (polaronic) excitations. In this work, we investigate the appropriate theoretical methods used for the (a) prediction of 2PA properties for rational design of organic materials with improved NLO properties, and (b) understanding of the essential electronic excitations controlling the energy-transfer and charge-transport properties in organic optoelectronics. Accurate prediction of these electro-optical properties is helpful for structure-activity relationships useful for technological innovations.In Chapter 1 we emphasize on the potential use of the organic materials for these two applications. The 2PA process is advantageous over one-photon absorption for deep-tissue fluorescence microscopy, photodynamic therapy, microfabrication and optical data storage owing to the three-dimensional spatial selectivity and improved penetration depth in the absorbing or scattering media. The design of the NLO materials with large 2PA cross-sections may reduce the optical damage due to the use of the high intensity laser beams for excitation. The organic molecules also possess self-localized excited states which can decay radiatively or nonradiatively to form excitonic states. This suggests the use of these materials in the electroluminescent devices such as light-emitting diodes and photovoltaic cells through the processes of exciton formation or dissociation, respectively. It is therefore necessary to understand ultrafast relaxation processes required in understanding the interplay between the efficient radiative transfer between the excited states and exciton dissociation into polarons for improving the efficiency of these devices. In Chapter 2, we provide the detailed description of the various theoretical methods applied for the prediction as well as the interpretation of the optical properties of a special class of substituted PPV [poly (p-phenylene vinylene)] oligomers. In Chapter 3, we report the accuracy of different second and third order time dependent density functional theory (TD-DFT) formalisms in prediction of the 2PA spectra compared to the experimental measurements for donor-acceptor PPV derivatives. We recommend a posteriori Tamm-Dancoff approximation method for both qualitative and quantitative analysis of 2PA properties. Whereas, Agren's quadratic response methods lack the double excitations and are not suitable for the qualitative analysis of the state-specific contributions distorting the overall quality of the 2PA predictions. We trace the reasons to the artifactual excited states above the ionization threshold. We also study the effect of the basis set, geometrical constraints and the orbital exchange fraction on the 2PA excitation energies and cross-sections. Higher exchange (BMK and M05-2X) and range-separated (CAM-B3LYP) hybrid functionals are found to yield inaccurate predictions both quantitatively and qualitatively. The failure of the exchange-correlation (XC) functionals with correct asymptotic is traced to the inaccurate transition dipoles between the valence states, where functionals with low HF exchange succeed. In Chapter 4, we test the performance of different semiempirical wavefunction theory methods for the prediction of 2PA properties compared to the DFT results for the same set of molecules. The spectroscopic parameterized (ZINDO/S) method is relatively better than the general purpose parameterized (PM6) method but the accuracy is trailing behind the DFT methods. The poor performances of PM6 and ZINDO/S methods are attributed to the incorrect description of excited-to-excited state transition and 2PA energies, respectively. The different semiempirical parameterizations can at best be used for quantitative analysis of the 2PA properties. The ZINDO/S method combined with different orders of multi-reference configuration interactions provide an improved description of 2PA properties. However, the results are observed to be highly dependent on the specific choice for the active space, order of excitation and reference configurations.In Chapter 5, we present a linear response TD-DFT study to benchmark the ability of existing functional models to describe the extent of self-trapped neutral and charged excitations in PPV and its derivative MEH-PPV considered in their trans-isomeric forms. The electronic excitations in question include the lowest singlet (S1) and triplet (T1†) excitons, positive (P+) and negative (P-) polarons and the lowest triplet (T1) states. Use of the long-range-corrected DFT functional, such as LC-wPBE, is found to be crucial in order to predict the physically correct spatial localization of all the electronic excitations in agreement with experiment. The inclusion of polarizable dielectric environment play an important role for the charged states. The particle-hole symmetry is preserved for both the polymers in trans geometries. These studies indicate two distinct origins leading to self-localization of electronic excitations. Firstly, distortion of molecular geometry may create a spatially localized potential energy well where the state wavefunction self-traps. Secondly, even in the absence of geometric and vibrational dynamics, the excitation may become spatially confined due to energy stabilization caused by polarization effects from surrounding dielectric medium.In Chapter 6, we aim to separate these two fundamental sources of spatial localization. We observe the electronic localization of P+ and P- is determined by the polarization effects of the surrounding media and the character of the DFT functional. In contrast, the self-trapping of the electronic wavefunctions of S1 and T1(T1†) mostly follows their lattice distortions. Geometry relaxation plays an important role in the localization of the S1 and T1† excitons owing to the non-variational construction of the excited state wavefunction. While, mean-field calculated P+, P- and T1 states are always spatially localized even in ground state S0 geometry. Polaron P+ and P- formation is signified by the presence of the localized states for the hole or the electron deep inside the HOMO-LUMO gap of the oligomer as a result of the orbital stabilization at the LC-wPBE level. The broadening of the HOMO-LUMO band gap for the T1 exciton compared to the charged states is associated with the inverted bond length alternation observed at this level. The molecular orbital energetics are investigated to identify the relationships between state localization and the corresponding orbital structure.In Chapter 7, we investigate the effect of various conformational defects of trans and cis nature on the energetics and localization of the charged P+ and P- excitations in PPV and MEH-PPV. We observe that the extent of self-trapping for P+ and P- polarons is highly sensitive on molecular and structural conformations, and distribution of atomic charges within the polymers. The particle-hole symmetry is broken with the introduction of trans defects and inclusion of the polarizable environment in consistent with experiment. The differences in the behavior of PPV and MEH-PPV is rationalized based on their orbital energetics and atomic charge distributions. We show these isomeric defects influence the behavior and drift mobilities of the charge carriers in substituted PPVs.
Show less
Date Issued: 2013
Identifier: CFE0005110, ucf:50722
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005110

Title: Fluorescence Lifetime Imaging and Spectroscopy Aided Tracking of ZnO and CdS:Mn/ZnS/ N-acetyl cysteine (NAC) Quantum Dots in Citrus Plants.
Creator: Washington, Torus, Gesquiere, Andre, Rajaraman, Swaminathan, Zhai, Lei, University of Central Florida
Abstract / Description: In this thesis, we present an efficacious way of tracking nanoparticle movement in plant tissue through the use of fluorescence lifetime imaging (FLIM) and spectroscopy as well as a review of nanoparticle uptake in plants and the proposed mechanisms governing them. Given the increasing number of nanomaterials in agriculture and society as a whole, proper imaging tools and proactive measures must be taken to track nanoparticle movement in plant tissues and create infrastructure and products to...
Show moreIn this thesis, we present an efficacious way of tracking nanoparticle movement in plant tissue through the use of fluorescence lifetime imaging (FLIM) and spectroscopy as well as a review of nanoparticle uptake in plants and the proposed mechanisms governing them. Given the increasing number of nanomaterials in agriculture and society as a whole, proper imaging tools and proactive measures must be taken to track nanoparticle movement in plant tissues and create infrastructure and products to keep things sustainable and safe. Herein we report a ZnO comparable nanoparticle(-) a CdS:Mn/ZnS/ N-acetyl cysteine (NAC) quantum dot(-) which boasts longer lifetimes and suitable fluorescent properties above ZnO to properly delineate from plant tissue fluorescence of chlorophyll and cinnamic acids. In addition to FLIM mapping, quantum dot localization in plant vascular tissue was clearly seen and confirmed via characteristic emission spectra and time correlated single photon counting decay curves (TCSPC). Most quantum dots were seen to reside in the xylem. Plant age and structure was seen to affect uptake. QD size likely restricted extensive translocation. Inhibitive effects of QDs were likely water and mechanical stress. We surmise that travel of the cadmium quantum dots up the leaf and branch plant tissues is likely most governed by diffusion as the quantum dots bound to the cell structures create a diffusion gradient which aids travel up the leaf.
Show less
Date Issued: 2017
Identifier: CFE0006820, ucf:51772
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006820

Title: Mechanism of Actin Bundle Assembly, Mechanics and Structure by Ion Interaction.
Creator: Castaneda, Nicholas, Kang, Hyeran, Huo, Qun, Gesquiere, Andre, University of Central Florida
Abstract / Description: The assembly of actin filaments into bundles plays an essential role in mechanical strength and dynamic reorganization of cytoskeleton. Divalent counterions at high concentrations promote bundle formation through electrostatic attraction between charged filaments. Although it has been hypothesized that specific cation interactions may contribute to salt-induced bundling, molecular mechanisms of how salt modulates bundle assembly and mechanics are not well established. Here we determine the...
Show moreThe assembly of actin filaments into bundles plays an essential role in mechanical strength and dynamic reorganization of cytoskeleton. Divalent counterions at high concentrations promote bundle formation through electrostatic attraction between charged filaments. Although it has been hypothesized that specific cation interactions may contribute to salt-induced bundling, molecular mechanisms of how salt modulates bundle assembly and mechanics are not well established. Here we determine the mechanical and dynamic properties of actin bundles with physiologically relevant cations. Using total internal reflection fluorescence (TIRF) microscopy, we measure the bending stiffness of actin bundles determined by persistence length analysis. We characterize real-time formation of bundles by dynamic light scattering intensity and direct visualization using TIRF microscopy. Our results show that divalent cations modulate bundle stiffness as well as time-dependent average bundle size. Furthermore, molecular dynamic simulations propose specificity for cation binding on actin filaments to form bundles. The work suggests that cation interactions serve a regulatory function in bundle assembly dynamics, mechanics, and structure.
Show less
Date Issued: 2017
Identifier: CFE0006572, ucf:51307
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006572

Title: The effect of electron-hole pairs in semiconductor and topological insulator nanostructures on plasmon resonances and photon polarizations.
Creator: Paudel, Hari, Leuenberger, Michael, Rahman, Talat, Saha, Haripada, Gesquiere, Andre, University of Central Florida
Abstract / Description: The generation of electron-hole pairs in materials has great importance. In directbandgap semiconductor materials, the mechanism of radiative recombination of electron-holepairs leads to the emission of photons, which is the basis of Light Emitting Diodes(LEDs). The excitation of electron-hole pairs by absorption of photons is the active processin photodiodes, solar cells, and other semiconductor photodetector devices. In optoelectronicdevices such as optical switches which are based on...
Show moreThe generation of electron-hole pairs in materials has great importance. In directbandgap semiconductor materials, the mechanism of radiative recombination of electron-holepairs leads to the emission of photons, which is the basis of Light Emitting Diodes(LEDs). The excitation of electron-hole pairs by absorption of photons is the active processin photodiodes, solar cells, and other semiconductor photodetector devices. In optoelectronicdevices such as optical switches which are based on transmission and reflection of the photons,electron-hole pairs excitation is a key for the device performance. Diodes and transistorsare also great discoveries in electronics which rely on the generation and recombination ofelectron-hole pairs at p-n junctions. In three-dimensional topological insulators (3D TIs)materials nanostructures excitation of electron-hole pairs can be utilized for the quantummemory, quantum information and quantum teleportation. In two-dimensional (2D) layeredmaterials like graphene, MoS_2, MoSe_2, WS_2 and WSe_2 generation and recombination ofelectron hole pairs is main process at p-n junctions, infrared detectors and sensors.This PhD thesis is concerned with the physics of different types of electron-hole pairsin various materials, such as wide-bandgap semiconductors, 3D topological insulators, andplasmonic excitations in metallic nanostructures. The materials of interest are wide bandgap semiconductors such as TiO_2 , 3D TIs such as Pb_1?xSn_xTe and the 2D layered materials such as MoS_2 and MoO_3. We study the electronic and optical properties in bulk and nanostructures and find applications in the area of semiclassical and quantum information processing. One of the interesting applications we focus in this thesis is shift in surface plasmon resonance due to reduction in index of refraction of surrounding dielectric environment which inturns shifts the wavelength of surface plasmon resonance up to 125 nm for carrier density of10^22/cm^3. Employing this effect, we present a model of a light controlled plasmon switching using a hybrid metal-dielectric heterostructures.In 3D TIs nanostructures, the time reversible spin partners in the valence and conductionband can be coupled by a left and a right handed circular polarization of the light.Such coupling of light with electron-hole pair polarization provides an unique opportunityto utilize 3D TIs in quantum information processing and spintronics devices. We present a model of a 3D TI quantum dot made of spherical core-bulk heterostructure. When a 3D TI QD is embedded inside a cavity, the single-photon Faraday rotation provides the possibility to implement optically mediated quantum teleportation and quantum information processing with 3D TI QDs, where the qubit is defined by either an electron-hole pair, a single electron spin, or a single hole spin in a 3D TI QD.Due to excellent transport properties in single and multiple layers of 2D layeredmaterials, several efforts have demonstrated the possibility to engineer electronic and optoelectronic devices based on MoS_2. In this thesis, we focus on theoretical and experimental study of electrical property and photoluminescence tuning, both in a single-layer of MoS_2.We present theoretical analysis of experimental results from the point of view of stability of MoO_3 defects in MoS_2 single layer and bandstructures calculation. In experiment, the electrical property of a single layer of MoS_2 can be tuned from semiconducting to insulating regime via controlled exposure to oxygen plasma. The quenching of photoluminescence of asingle sheet of MoS_2 has also been observed upon exposure to oxygen plasmas. We calculatethe direct to indirect band gap transitions by going from MoS_2 single sheet to MoO_3 singlesheet during the plasma exposure, which is due to the formation of MoO_3 rich defect domainsinside a MoS_2 sheet.
Show less
Date Issued: 2014
Identifier: CFE0005397, ucf:50454
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005397

Title: Zinc Sulfide:manganese doped Quantum rods for detection of metal ions and a business model for future sales.
Creator: Teblum, Andrew, Santra, Swadeshmukul, Gesquiere, Andre, Soskin, Mark, University of Central Florida
Abstract / Description: Hexavalent chromium is an extremely carcinogenic chemical that has been widely produced in the United States. This has led to major waste contamination and pollution throughout the country. According to the Environmental Working Group Hexavalent chromium has been found in 89% of city tap water. Most people believe they are safe using regular home filter systems however that is not true. A more expensive ion exchange water treatment unit is required. Therefore to protect yourselves from this...
Show moreHexavalent chromium is an extremely carcinogenic chemical that has been widely produced in the United States. This has led to major waste contamination and pollution throughout the country. According to the Environmental Working Group Hexavalent chromium has been found in 89% of city tap water. Most people believe they are safe using regular home filter systems however that is not true. A more expensive ion exchange water treatment unit is required. Therefore to protect yourselves from this carcinogenic metal a reliable test is required. In this study we have developed a Zinc Sulfide Manganese doped Quantum Rod technology to detect for presence of chromate and other harmful transitional metals in drinking water. Quantum Rods were synthesized using a hydrothermal reaction method. They were fully characterized using UV-visible absorption spectroscopy, fluorescence emission spectroscopy, X-ray Photoelectric Spectroscopy (XPS) and High Resolution Transmission Electron Microscopy (HRTEM). Quantum Rod metal detection studies were done with 28 different ions in a 96-well fluorescent plate reader. Results show that highest sensitivity to 8 ions including the toxic ions of chromate and mercury allowing us to create a sensor to detect these items.
Show less
Date Issued: 2014
Identifier: CFE0005268, ucf:50569
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005268

Title: A Complete Approach to Predict Biodistribution of Nanomaterials Within Animal Species from In-vitro Data.
Creator: Price, Edward, Gesquiere, Andre, Huo, Qun, Kolpashchikov, Dmitry, Rex, Matthew, Ebert, Steven, University of Central Florida
Abstract / Description: Smart drug-design for antibody and nanomaterial-based therapies allows for optimization of drug efficacy and more efficient early-stage pre-clinical trials. The ideal drug must display maximum efficacy at target tissue sites, but to track and predict distribution to these sites, one must have a mechanistic understanding of the kinetics involved with the individual cells of the tissue itself. This process can be tracked through biological simulations coupled with in-vitro approaches, which...
Show moreSmart drug-design for antibody and nanomaterial-based therapies allows for optimization of drug efficacy and more efficient early-stage pre-clinical trials. The ideal drug must display maximum efficacy at target tissue sites, but to track and predict distribution to these sites, one must have a mechanistic understanding of the kinetics involved with the individual cells of the tissue itself. This process can be tracked through biological simulations coupled with in-vitro approaches, which result in a rapid and efficient in-depth understanding of drug transport within tissue vasculature and cellular environment. As a result, it becomes possible to predict drug biodistribution within live animal tissue cells without the need for animal studies. Herein, we use in-vitro assays to translate transport kinetics to whole-body animal simulations to predict drug distribution from vasculature into individual tissue cells for the first time. Our approach is based on rate constants obtained from an in-vitro assay that accounts for cell-induced degradation, which are translated to a complete animal simulation to predict nanomedicine biodistribution at the single cell level. This approach delivers predictions for therapies of varying size and type for multiple species of animals solely from in-vitro data. Thus, we expect this work to assist in refining, reducing, and replacing animal testing, while at the same time, giving scientists a new perspective during early stages of drug development.
Show less
Date Issued: 2019
Identifier: CFE0007900, ucf:52747
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007900

Title: Light Scattering Property of Gold Nanoparticles with Applications to Biomolecule Detection and Analysis.
Creator: Zheng, Tianyu, Huo, Qun, Zou, Shengli, Gesquiere, Andre, Kang, Hyeran, Zhai, Lei, University of Central Florida
Abstract / Description: Gold nanoparticles (AuNPs) have unique optical and chemical properties. Dynamic light scattering (DLS) is an analytical tool used routinely for nanoparticle size measurement. The combined use of AuNPs and DLS has led to a novel analytical assay technology called D2Dx (from diameter to diagnostics). Herein, my dissertation highlights the extended use of D2Dx for biomolecule detection and analysis. Under this general theme, Chapter 1 provides some background information of AuNPs, DLS, the...
Show moreGold nanoparticles (AuNPs) have unique optical and chemical properties. Dynamic light scattering (DLS) is an analytical tool used routinely for nanoparticle size measurement. The combined use of AuNPs and DLS has led to a novel analytical assay technology called D2Dx (from diameter to diagnostics). Herein, my dissertation highlights the extended use of D2Dx for biomolecule detection and analysis. Under this general theme, Chapter 1 provides some background information of AuNPs, DLS, the principle of D2Dx technique and its potential applications. Chapter 2 summarizes a study on the effect of AuNP concentrations and laser power on the hydrodynamic size measurement of AuNPs by DLS. This study demonstrated the multiple scattering effect on DLS analysis, and how to use the exceptionally high sensitivity of DLS in AuNP aggregate detection for bioassay design and development. Chapter 3 explores a cooperative interaction between AuNP and certain proteins in blood serum that are key to the immune system, leading to a novel diagnostic tool that can conveniently monitor the humoral immunity development from neonates to adults and detect active infections in animals. Chapter 4 reports an application of D2Dx technique for acute viral infection detection based on the active immune responses elicited from mouse models infected with influenza virus. Chapter 5 describes another application of D2Dx for prostate cancer detection. The D2Dx assay identifies prostate cancer patients from non-cancer controls with improved specificity and sensitivity than PSA test. Chapter 6 demonstrates the use of AuNPs and DLS for hydrodynamic size measurement of protein disulfide isomerase with two different conformations. Chapter 7 investigates the concentration-dependent self-assembling behavior of ribostamycin through its interaction with AuNPs in aqueous solution. Overall, this dissertation established several lines of applications of using AuNPs and DLS for biomolecular research and in vitro diagnostics.
Show less
Date Issued: 2018
Identifier: CFE0007385, ucf:52056
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007385

Title: nanoengineered energy harvesting and storage devices.
Creator: Li, Chao, Thomas, Jayan, Zhai, Lei, Yang, Yang, Gesquiere, Andre, Dong, Yajie, Sun, Wei, University of Central Florida
Abstract / Description: Organic and perovskite solar cells have recently attracted significant attention due to itsflexibility, ease of fabrication and excellent performance. In order to realize even betterperformance for organic and perovskite solar cells, rejuvenated effort towards developingnanostructured electrodes and high quality active layer is necessary.In this dissertation, several strategic directions of enhancing the performance of organicand perovskite solar cells are investigated. An introduction and...
Show moreOrganic and perovskite solar cells have recently attracted significant attention due to itsflexibility, ease of fabrication and excellent performance. In order to realize even betterperformance for organic and perovskite solar cells, rejuvenated effort towards developingnanostructured electrodes and high quality active layer is necessary.In this dissertation, several strategic directions of enhancing the performance of organicand perovskite solar cells are investigated. An introduction and background of organic andperovskite solar cells, which includes motivation, classification and working principles,nanostructured electrode materials and solvent effect on active materials, and devices fabrication,are presented. A facile method, called Spin-on Nanoprinting (SNAP), to fabricate highly orderedZnO-AgNW-ZnO electrode is introduced to enhance the performance of organic solar cell.Subsequently, a ternary solvent method is developed to fabricate high Voc thieno[3,4-b]thiophene/benzodithiophene (PTB7) and indene-C60 bisadduct (ICBA)solar cells. Theperformance of the devices improved about 20% compared to those made by binary solventmethod. In order to understand the fundamental properties of the materials ruling theperformance of the PSCs tested, AFM-based nanoscale characterization techniques includingPulsed-Force-Mode AFM (PFM-AFM) and Mode-Synthesizing AFM (MSAFM) are introduced.These methods are used to study the morphology and physical properties of the structuresconstitutive of the active layers of the PSCs. Conductive-AFM (cAFM) studies reveal localvariations in conductivity in the donor and acceptor phases as well as an increase in photocurrentmeasured in the PTB7:ICBA sample obtained with the ternary solvent processing technique.Moreover, efficient perovskite solar cells with good transparency in the visible wavelength rangehave been developed by a facile and low-temperature PCBM-assisted perovskite growth method.This method results in the formation of perovskite-PCBM hybrid material at the grain boundaries which is observed by EELS mapping and confirmed by steady-state photoluminescence (PL)spectra and transient photocurrent (TP) measurements. This method involves fewer steps andtherefore is less expensive and time consuming than other reported methods. In addition, wereport an all solid state, energy harvesting and storing (ENHANS) filament which integratesperovskite solar cell (PSC) on top of a symmetric supercapacitor (SSC) via a copper filamentwhich works as a shared electrode for direct charge transfer. Developing ENHANS on a copperfilament provides a low-cost solution for flexible self-sufficient energy systems for wearablesand other portable devices. Finally, a summary of this dissertation as well as some potentialfuture directions are presented.
Show less
Date Issued: 2016
Identifier: CFE0006693, ucf:51912
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006693

Title: Coated Quantum Dots: Engineering of Surface Chemistry for Biomedical and Agricultural Applications.
Creator: Maxwell, Tyler, Santra, Swadeshmukul, Gesquiere, Andre, Harper, James, Zou, Shengli, Leon, Lorraine, University of Central Florida
Abstract / Description: Quantum dots (QDs) are crystalline nanoparticles made from semiconductor material with sizes ranging from 1 to 10 nm in diameter. QDs are attractive fluorophores for bioimaging and sensing due to their size-dependent optical properties, broad absorption bands, high extinction coefficients and superior photostability. The combination of imaging and drug delivery in a single particle can provide valuable information and improve the efficacy of existing treatments. This dissertation highlights...
Show moreQuantum dots (QDs) are crystalline nanoparticles made from semiconductor material with sizes ranging from 1 to 10 nm in diameter. QDs are attractive fluorophores for bioimaging and sensing due to their size-dependent optical properties, broad absorption bands, high extinction coefficients and superior photostability. The combination of imaging and drug delivery in a single particle can provide valuable information and improve the efficacy of existing treatments. This dissertation highlights the use of QDs for biomedical and agricultural applications. Chapter 1 of this dissertation presents a background of QDs and outlines the synthesis methods of producing and functionalizing QDs. A discussion of the advantages and limitations of each method for producing water-soluble QDs and the rationale for the proposed research is also presented. Chapter 2 describes an activatable QD design for tracking of drug delivery for cancer treatment. QDs synthesized by microemulsion (ME) were cross-linked in a one-step procedure. Enhanced binding affinity of the probe to cell lines overexpressing folate receptors was shown through fluorescence microscopy. However, this system is not practical for the large-scale synthesis due to its complexity and can not be translated for clinical development. Chapter 3 presents a sol-gel synthesis method for producing water-soluble QDs utilizing the thiol-based small molecule capping agent as the stabilizer as an alternative to ME technique. This method was designed to be a simple (one-step), cost-effective, and scalable for making both manganese doped CdS and ZnS QDs. QDs were synthesized through sol-gel method with a library of organic thiol coatings and characterized by size, surface charge, stability, and optical properties. These particles were compared to QDs produced from ME synthesis and were found to have similar properties. Chapter 4 reports the sol-gel QDs as slow-release antibiotic delivery system for application as agricultural bactericide. Utilizing electrostatic interactions, the QDs were shown to be capable of improving the leaf adhesion and slowing the rate of release of streptomycin. Chapter 5 presents a summary of the major findings of this research and discusses the future research directions.
Show less
Date Issued: 2019
Identifier: CFE0007681, ucf:52476
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0007681

Title: Photochemistry and Applications of Diels-Alder Adducts and Photoacids in Materials Science.
Creator: Johns, Valentine, Liao, Yi, Miles, Delbert, Zou, Shengli, Gesquiere, Andre, Su, Ming, University of Central Florida
Abstract / Description: Utilizing light as an energy source for reactions has intrigued many chemists. This has led to the development of the principles of photochemistry. The Photo retro Diels Alder (PrDA) reaction is one such system that has potential for use in materials science as well as in the life sciences. However, there was no guide to predict whether a compound could undergo the PrDA reaction, which limits the widespread use of this reaction. Another system is that of photoacids (molecules that release...
Show moreUtilizing light as an energy source for reactions has intrigued many chemists. This has led to the development of the principles of photochemistry. The Photo retro Diels Alder (PrDA) reaction is one such system that has potential for use in materials science as well as in the life sciences. However, there was no guide to predict whether a compound could undergo the PrDA reaction, which limits the widespread use of this reaction. Another system is that of photoacids (molecules that release protons upon irradiation reversibly). Since most fundamental processes involve proton transfer, these types of photoacids have great potential which is yet to be explored. This thesis describes the design and synthesis of various aromatic DA adducts. These adducts were made to undergo the rDA reaction using UV (Ultra-Violet) light. Experimental results showed that the photoreactivity of these adducts depends on the electron-donating ability of the diene component and the electron-withdrawing ability of the dienophile component. In addition, mechanistic study of this reaction revealed the formation of a charge separated intermediate with a singlet excited state. The potential of the PrDA reaction was also explored in two ways. One was by designing isomeric DA adducts from pentacene and TCNE (tetracyanoethylene) which are capable of switching from one isomer to another via a PrDA process. The other way was the design and synthesis of a polymer with an anthracene diketone moeity which could undergo a PrDA reaction to change from an insulator to a semiconductor. Finally, the syntheses of a number of photoacids which not only become acidic upon irradiation but also respond to visible light reversibly have been explored. A rationale has been developed for the design of photoacids with desired photo-induced response. While electron donating and accepting groups in strategic positions help tune the pH; using different combinations of ethanol and water affect the rate of the forward and the backward processes. A photoacid monomer was also incorporated into three photoacid polymers which respond to visible light reversibly, hence promising widespread applications of these photoacids.
Show less
Date Issued: 2012
Identifier: CFE0004556, ucf:49235
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004556

Title: Electronic and Optoelectronic Transport Properties of Carbon Nanotube/Organic Semiconductor Devices.
Creator: Sarker, Biddut, Khondaker, Saiful, Schulte, Alfons, Stolbov, Sergey, Gesquiere, Andre, University of Central Florida
Abstract / Description: Organic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising...
Show moreOrganic field effect transistors (OFETs) are of significant research interest due to their promising applications in large area, low-cost electronic devices such as flexible displays, sensor arrays, and radio-frequency identification tags. A major bottleneck in fabricating high-performance OFET is the large interfacial barrier between the metal electrodes and organic semiconductors (OSC) which results in an inefficient charge injection. Carbon nanotubes (CNTs) are considered to be a promising electrode material which can address this challenge.In this dissertation, we demonstrate fabrication of high-performance OFETs using aligned array CNT electrodes and investigate the detailed electronic transport properties of the fabricated devices. The OFETs with CNT electrodes show a remarkable enhancement in the device performance such as high mobility, high current on-off ratio, higher cutoff frequency, absence of short channel effect and better charge carrier injection than those OFETs with metal electrodes. From the low temperature transport measurements, we show that the charge injection barrier at CNT/OSC interface is smaller than that of the metal/OSC interface. A transition from direct tunneling to Fowler-Nordheim tunneling observed in CNT/OSC system shows further evidence of low injection barrier. A lower activation energy measured for the OFETs with CNT electrodes gives evidence of lower interfacial trap states. Finally, OFETs are demonstrated by directly growing crystalline organic nanowires on aligned array CNT electrodes.In addition to investigating the interfacial barrier at CNT/OSC interface, we also studied photoconduction mechanism of the CNT and CNT/OSC nanocomposite thin film devices. We found that the photoconduction is due to the exciton dissociations and charge carrier separation caused by a Schottky barrier at the metallic electrode/CNT interface and diffusion of the charge carrier through percolating CNT networks. In addition, it is found that photoresponse of the CNT/organic semiconductor can be tuned by changing the weight percentage of CNT into the organic semiconductors.
Show less
Date Issued: 2012
Identifier: CFE0004596, ucf:49217
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004596

Title: Fabrication and Characterization of Spatially-Variant Self-Collimating Photonic Crystals.
Creator: Digaum, Jennefir, Kuebler, Stephen, Kik, Pieter, Schoenfeld, Winston, Likamwa, Patrick, Gesquiere, Andre, University of Central Florida
Abstract / Description: Spatially-variant photonic crystals (SVPCs) created using materials having a low refractive index are shown to be capable of abruptly controlling light beams with high polarization selectivity. SVPCs are photonic crystals for which the orientation of the unit cell is controllably varied throughout the lattice to control the flow of light. Multi-photon lithography in a photo polymer was used to fabricate three-dimensional SVPCs that direct the flow of light around a 90 degree bend. The optical...
Show moreSpatially-variant photonic crystals (SVPCs) created using materials having a low refractive index are shown to be capable of abruptly controlling light beams with high polarization selectivity. SVPCs are photonic crystals for which the orientation of the unit cell is controllably varied throughout the lattice to control the flow of light. Multi-photon lithography in a photo polymer was used to fabricate three-dimensional SVPCs that direct the flow of light around a 90 degree bend. The optical performance of the SVPCs was characterized using a scanning optical-fiber system that introduced light onto the input face of a structure and measured the intensity of light emanating from the output faces.As a proof-of-concept, SVPCs that can bend a beam at a wavelength of ?0 = 2.94 ?m were fabricated in the photo-polymer SU-8. The SVPCs were shown to direct infrared light of one polarization through a sharp bend, while the other polarization propagated straight through the SVPC, when the volumetric fill-factor is near 50%. The peak-to-peak ratio of intensities of the bent- and straight-through beams was 8:1, and a power efficiency of 8% was achieved. The low efficiency is attributed to optical absorption in SU-8 at ?0 = 2.94 ?m.SVPCs that can bend a beam at telecommunications wavelengths near ?0 = 1.55 ?m were fabricated by multi-photon lithography in the photo-polymer IP-Dip. IP-Dip was chosen over SU 8 to enable fabrication of finer features, as are needed for an SVPC scaled in size to operate at shorter wavelengths. Experimental characterization shows that these particular SVPCs provide effective control of the vertically polarized beam at ?0 = 1.55 ?m, when the volumetric fill-factor is around 46%. The beam bending peak efficiency was found to be 52.5% with a peak-to-peak ratio between the bent- and straight-through beams of 78.7. Additionally, these SVPCs can bend a light beam with a broad bandwidth of 153 nm that encompasses both the C- and S-bands of the telecommunications window. Furthermore, the SVPCs have high tolerance to misalignment, in which an offset of the input beam by as much as 6 ?m causes the beam-bending efficiency to drop no more than 50%. Finally, it is shown that these particular SVPCs can bend beams without significantly distorting the mode profile. This work introduces a new scheme for controlling light that should be useful for integrated photonics.The penultimate chapter discusses nonlinear phenomena that were observed during the optical characterization of the SVPCs using a high peak-power amplified femtosecond laser system. The first of these effects is referred to as "super-collimation", in which the beam bending peak efficiency of certain SVPCs increases with input intensity, reaching as high as 68%. The second effect pertains to nonlinear imaging of light at ?0 = 1.55 ?m scattered from an SVPC and detected using a silicon-CCD camera. This effect enables beam bending within the device to be imaged in real time. The dissertation concludes with an outlook for SVPCs, discussing potential applications and challenges that must be addressed to advance their use in photonics.
Show less
Date Issued: 2016
Identifier: CFE0006527, ucf:51371
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006527

Title: An Adhesive Vinyl-Acrylic Electrolyte and Electrode Binder for Lithium Batteries.
Creator: Tran, Binh, Zhai, Lei, Zou, Shengli, Kuebler, Stephen, Hernandez, Florencio, Gesquiere, Andre, University of Central Florida
Abstract / Description: This dissertation describes a new vinyl-acrylic copolymer that displays great potential for applications in lithium ion batteries by enabling novel, faster, safer and cost-effective processes. Understanding the chemistry of materials and processes related to battery manufacturing allows the design of techniques and methods that can ultimately improve the performance of existing batteries while reducing the cost. The first and second parts of this dissertation focuses on the free radical...
Show moreThis dissertation describes a new vinyl-acrylic copolymer that displays great potential for applications in lithium ion batteries by enabling novel, faster, safer and cost-effective processes. Understanding the chemistry of materials and processes related to battery manufacturing allows the design of techniques and methods that can ultimately improve the performance of existing batteries while reducing the cost. The first and second parts of this dissertation focuses on the free radical polymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA), methyl methacrylate (MMA), and isobutyl vinyl ether (IBVE) monomers to afford a vinyl-acrylic poly(PEGMA-co-MME-co-IBVE) random copolymer and the investigation of its properties as a soluble, amorphous, and adhesive electrolyte that is able to permanently hold 800 times its own weight. Such material properties envision a printable battery manufacturing procedure, since existing electrolytes lack adhesion at a single macromolecular level. Electrolytes can also be used as an electrode binder so long as it has structural integrity and allows ion transfer to and from the active electrode material during insertion/extraction processes. In the third section, the use of this electrolyte as a water-soluble binder for the aqueous fabrication of LiCoO2 cathodes is presented. Results of this study demonstrated the first aqueous process fabrication of thick, flexible, and fully compressed lithium ion battery electrodes by using commercial nickel foam as a supporting current collector. This feat is rather impressive because these properties are far superior to other aqueous binders in terms of material loading per electrode, specific area capacity, durability, and cell resistance. Finally, the fourth section expands on this concept by using the poly(PEGMA-co-MMA-co-IBVE) copolymer for the aqueous fabrication of a low voltage Li4Ti5O12 anode type electrode. Altogether, results demonstrate as a proof of concept that switching the current toxic manufacturing of lithium-ion batteries to an aqueous process is highly feasible. Furthermore, new electrode manufacturing techniques are also deemed possible.
Show less
Date Issued: 2013
Identifier: CFE0004761, ucf:49780
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004761

Title: Novel optical properties of metal nanostructures based on surface plasmons.
Creator: Wang, Haining, Zou, Shengli, Liao, Yi, Kolpashchikov, Dmitry, Gesquiere, Andre, Su, Ming, University of Central Florida
Abstract / Description: Surface plasmons have been attracted extensive interests in recent decades due to the novel properties in nanometer sized dimensions. My work focused on the novel optical properties of metal nanostructures based on surface plasmons using theoretical simulation methods. In the first part, we investigated metal nanofilms and nanorods and demonstrated that extremely low scattering efficiency, high absorption efficiency and propagation with long distance could be obtained by different metal...
Show moreSurface plasmons have been attracted extensive interests in recent decades due to the novel properties in nanometer sized dimensions. My work focused on the novel optical properties of metal nanostructures based on surface plasmons using theoretical simulation methods. In the first part, we investigated metal nanofilms and nanorods and demonstrated that extremely low scattering efficiency, high absorption efficiency and propagation with long distance could be obtained by different metal nanostructures. With a perforated silver film, we demonstrated that an extremely low scattering cross section with an efficiency of less than 1% can be achieved at tunable wavelengths with tunable widths. The resonance wavelength, width, and intensity are influenced by the shape, size and arrangement pattern of the holes, as well as the distance separating the holes along the polarization direction. The extremely low scattering could be used to obtain high absorption efficiency of a two-layer silver nanofilm. Using the discrete dipole approximation method, we achieved enhanced absorption efficiencies, which are close to 100%, at tunable wavelengths in a two-layer silver thin film. The film is composed of a 100 nm thick perforated layer facing the incident light and a 100 nm thick solid layer. Resonance wavelengths are determined by the distances between perforated holes in the first layer as well as the separation between two layers. The resonance wavelengths shift to red with increasing separation distance between two layers or the periodic distance of the hole arrays. Geometries of conical frustum shaped holes in the first layer are critical for the improved absorption efficiencies. When the hole bottom diameter equals the periodic distance and the upper diameter is about one-third of the bottom diameter, close to unit absorption efficiency can be obtained. We examined the electromagnetic wave propagation along a hollow silver nanorod with subwavelength dimensions. The calculations show that light may propagate along the hollow nanorod with growing intensities. The influences of the shape, dimension, and length of the rod on the resonance wavelength and the enhanced local electric field, |E|2, along the rod were investigated. In the second part, a generalized electrodynamics model is proposed to describe the enhancement and quenching of fluorescence signal of a dye molecule placed near a metal nanoparticle (NP). Both the size of the Au NPs and quantum yield of the dye molecule are crucial in determining the emission intensity of the molecule. Changing the size of the metal NP will alter the ratio of the scattering and absorption efficiencies of the metal NP and consequently result in different enhancement or quenching effect to the dye molecule. A dye molecule with a reduced quantum yield indicates that the non-radiative channel is dominant in the decay of the excited dye molecules and the amplification of the radiative decay rate will be easier. In general, the emission intensity will be quenched when the size of metal NP is small and the quantum yield of dye molecule is about unity. A significant enhancement factor will be obtained when the quantum yield of the molecule is small and the particle size is large. When the quantum yield of the dye molecule is less than 10-5, the model is simplified to the surface enhanced Raman scattering equation.
Show less
Date Issued: 2013
Identifier: CFE0004769, ucf:49786
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004769

Title: Planar Organic Photovoltaic Devices.
Creator: Alzubi, Feras, Khondaker, Saiful, Chow, Lee, Schelling, Patrick, Gesquiere, Andre, University of Central Florida
Abstract / Description: Organic Photovoltaic devices (OPV) are considered to be attractive candidates for clean and renewable energy source because of their potential for low cost of fabrication, easy processing, and their mechanical flexibility. The device efficiency of OPV cells are limited by several factors. Among them are: (i) donor-acceptor interface, (ii) morphology of the materials, (iii) electrode-organic semiconductor (OSC) interface and (iv) device architecture such as active material thickness and...
Show moreOrganic Photovoltaic devices (OPV) are considered to be attractive candidates for clean and renewable energy source because of their potential for low cost of fabrication, easy processing, and their mechanical flexibility. The device efficiency of OPV cells are limited by several factors. Among them are: (i) donor-acceptor interface, (ii) morphology of the materials, (iii) electrode-organic semiconductor (OSC) interface and (iv) device architecture such as active material thickness and electrode separation. Although, the donor-acceptor interface has been studied in detail, the commonly prevalent vertical OPV device structure does not allow a good understanding of the other key issues as the vertical structure limits one of the electrode to be a transparent electrode as well as introducing inseparable relation between the electrodes separation and the active material thickness. In addition, it is also well known that the charge transport in OSC is anisotropic and the charge mobility is better in lateral direction rather than vertical direction. In order to address some of these issues, we fabricated OPV devices in a planar device structure where cathode and anode of dissimilar metals are in-plane with each other and their photovoltaic behaviors were studied. We used poly(3-hexylthiophene) and [6,6]-pheny1 C61-butyric acid methy1 ester (P3HT:PCBM) blend as an active material. In particular, we present a detailed study about the effects of the structural parameters such as the channel length, the active layer thickness, and the work function of the electrodes on the open circuit voltage (Voc), short circuit current (Isc), fill factor (FF) and the power conversion efficiency (PCE).In order to determine the suitable anode and cathode for the planar organic photovoltaic (P-OPV) structure, we first fabricated and measured organic field effect transistor (OFET) devices with different contacts and studied the effect of barrier height at the P3HT:PCBM/electrode interface on the device output and transport properties. The study showed a clear effect of varying the contact material on the charge injection mechanism and on the carriers mobilities. The results have also shown that Au with high hole mobility and on current in the p-channel can be used as an anode (holes extractor) in the P-OPV device while In, Cr, and Ti that showed a reasonable value of electron mobility can be good candidates for cathode (electron extractor). We also found that, Ag, Al, and Mg showed large barrier which resulted in large threshold voltage in the I-V curve making them undesired cathode materials in the P-OPV device. We then fabricated P-OPV devices with Au as an anode material and varied the cathode material to study the effect of the interface between the P3HT:PCBM layer and the cathode material. When Al, Mg, or Ag used as a cathode material no PV behavior was observed, while PV behavior was observed for In, Cr, and Ti cathode materials. The PV behavior and the characteristic parameters including Voc, Isc, FF and PCE were affected by varying the cathode material. The results have shown that the P-OPV device performance can be affected by the cathode material depending on the properties and the work function of the metal.We have also studied the effect of varying the P3HT:PCBM layer thickness at a fixed channel length for Cr and Ti cathode materials and Au as anode. While Voc and FF values do not change, Isc and PCE increase with increasing the layer thickness due to the increase of the light absorption and charges generation. Moreover, we studied the effect of varying the channel length at a fixed film thickness; and showed that the values of Isc and PCE increase with decreasing channel length while Voc and FF maintain the same value. In this thesis we will also present the results on experimentally defining and testing the illuminated area in the P-OPV device by using different measurement set-ups and different electrodes patterns. The results prove that the illuminated area in the P-OPV device is the area enclosed between the two electrodes. Lastly, we will present the effect of the P3HT:PCBM ratio on the P-OPV device performance. We show that 1:2 ratio is the optimized ratio for the P-OPV device. The detailed results in this thesis show a potential opportunity to help improving and understanding the design of OPV device by understanding the effects of the device structural parameters.
Show less
Date Issued: 2013
Identifier: CFE0004804, ucf:49754
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004804

Nanoparticles (2)	+ -
conjugated polymer (2)	+ -
nanoparticle (2)	+ -
2D Layered Materials (1)	+ -
A549 (1)	+ -

Actin (1)	+ -
Action potential (1)	+ -
Cadmium uptake (1)	+ -
Cancer (1)	+ -
Carbon nanotube (1)	+ -
Charge Transport (1)	+ -
Charge injection (1)	+ -
Chrage Transport (1)	+ -
Chromate (1)	+ -
Citrus (Citrus aurantium (1)	+ -
Citrus (Citrus sinesis.) (1)	+ -
Conjugated polymers (1)	+ -
ENHANS (1)	+ -
Electrodes (1)	+ -
Exchange-Correlation Functionals. (1)	+ -
Excited State Dynamics (1)	+ -
Excitons (1)	+ -
Fluorescence (1)	+ -
Fluorescence Lifetime Imaging (1)	+ -
Gel Electrophoresis (1)	+ -
Gold nanoparticle (1)	+ -
L.) (1)	+ -
MDA-MB-231 (1)	+ -
MIA PaCa-2 (1)	+ -
Materials (1)	+ -

Gesquiere, Andre (22)	+ -
University of Central Florida (22)	+ -
Zou, Shengli (5)	+ -
Santra, Swadeshmukul (4)	+ -
Zhai, Lei (4)	+ -

Huo, Qun (3)	+ -
Kang, Hyeran (3)	+ -
Campiglia, Andres (2)	+ -
Hernandez, Florencio (2)	+ -
Hickman, James (2)	+ -
Khondaker, Saiful (2)	+ -
Kolpashchikov, Dmitry (2)	+ -
Kuebler, Stephen (2)	+ -
Liao, Yi (2)	+ -
Rajaraman, Swaminathan (2)	+ -
Saha, Haripada (2)	+ -
Schoenfeld, Winston (2)	+ -
Stolbov, Sergey (2)	+ -
Su, Ming (2)	+ -
Ye, Jingdong (2)	+ -
Abdellatif, Yasmine (1)	+ -
Alzubi, Feras (1)	+ -
Ballantyne, John (1)	+ -
Bonner, Maxwell (1)	+ -
Castaneda, Nicholas (1)	+ -
Chow, Lee (1)	+ -
Clausen, Christian (1)	+ -
Digaum, Jennefir (1)	+ -
Dong, Yajie (1)	+ -
Ebert, Steven (1)	+ -

Search In

Pages

Pages

Sort Results By:

Narrow results by:

Topical Subject

Collection

Type of Resource

Language

Creator

Format

Owner