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Title: CHEMICAL STRUCTURE - NONLINEAR OPTICAL PROPERTY RELATIONSHIPS FOR A SERIES OF TWO-PHOTON ABSORBING FLUORENE MOLECULES.
Creator: Hales, Joel McCajah, Van Stryland, Eric W., University of Central Florida
Abstract / Description: This dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident...
Show moreThis dissertation reports on the investigation of two-photon absorption (2PA) in a series of fluorenyl molecules. Several current and emerging technologies exploit this optical nonlinearity including two-photon fluorescence imaging, three-dimensional microfabrication, site-specific photodynamic cancer therapy and biological caging studies. The two key features of this nonlinearity which make it an ideal candidate for the above applications are its quadratic dependence on the incident irradiance and the improved penetration into absorbing media that it affords. As a consequence of the burgeoning field which exploits 2PA, it is a goal to find materials that exhibit strong two-photon absorbing capabilities. Organic materials are promising candidates for 2PA applications because their material properties can be tailored through molecular engineering thereby facilitating optimization of their nonlinear optical properties. Fluorene derivatives are particularly interesting since they possess high photochemical stability for organic molecules and are generally strongly fluorescent. By systematically altering the structural properties in a series of fluorenyl molecules, we have determined how these changes affect their two-photon absorbing capabilities. This was accomplished through characterization of both the strength and location of their 2PA spectra. In order to ensure the validity of these results, three separate nonlinear characterization techniques were employed: two-photon fluorescence spectroscopy, white-light continuum pump-probe spectroscopy, and the Z-scan technique. In addition, full linear spectroscopic characterization was performed on these molecules along with supplementary quantum chemical calculations to obtain certain molecular properties that might impact the nonlinearity. Different designs in chemical architecture allowed investigation of the effects of symmetry, solvism, donor-acceptor strengths, conjugation length, and multi-branched geometries on the two-photon absorbing properties of these molecules. In addition, the means to enhance 2PA via intermediate state resonances was investigated. To provide plausible explanations for the experimentally observed trends, a conceptually simple three level model was employed. The subsequent correlations found between chemical structure and the linear and nonlinear optical properties of these molecules provided definitive conclusions on how to properly optimize their two-photon absorbing capabilities. The resulting large nonlinearities found in these molecules have already shown promise in a variety of the aforementioned applications.
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Date Issued: 2004
Identifier: CFE0000005, ucf:46103
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0000005

Title: TWO-PHOTON 3D OPTICAL DATA STORAGE VIA FLUORESCENCE MODULATION OF FLUORENE DYES BY PHOTOCHROMIC DIARYLETHENES.
Creator: Corredor, Claudia, Belfield, Kevin D., University of Central Florida
Abstract / Description: Three-dimensional (3D) optical data storage based on two-photon processes provides highly confined excitation in a recording medium and a mechanism for writing and reading data with less cross talk between multiple memory layers, due to the quadratic dependence of two photon absorption (2PA) on the incident light intensity. The capacity for highly confined excitation and intrinsic 3D resolution affords immense information storage capacity (up to 1012 bits/cm3). Recently, the use of...
Show moreThree-dimensional (3D) optical data storage based on two-photon processes provides highly confined excitation in a recording medium and a mechanism for writing and reading data with less cross talk between multiple memory layers, due to the quadratic dependence of two photon absorption (2PA) on the incident light intensity. The capacity for highly confined excitation and intrinsic 3D resolution affords immense information storage capacity (up to 1012 bits/cm3). Recently, the use of photochromic materials for 3D memory has received intense interest because of several major advantages over current optical systems, including their erasable/rewritable capability, high resolution, and high sensitivity. This work demonstrates a novel two-photon 3D optical storage system based on the modulation of the fluorescence emission of a highly efficient two-photon absorbing fluorescent dye (fluorene derivative) and a photochromic compound (diarylethene). The feasibility of using efficient intermolecular Förster Resonance Energy Transfer (RET) from the non-covalently linked two-photon absorbing fluorescent fluorene derivative to the photochromic diarylethene as a novel read-out method in a two-photon optical data storage system was explored. For the purpose of the development of this novel two-photon 3D optical storage system, linear and two-photon spectroscopic characterization of commercial diarylethenes in solution and in a polymer film and evidence of their cyclization (O→C) and cycloreversion (C→O) reactions induced by two-photon excitation were undertaken. For the development of a readout method, Resonance Energy Transfer (RET) from twophoton absorbing fluorene derivatives to photochromic compounds was investigated under one and two-photon excitation. The Förster's distances and critical acceptor concentrations were determined for non-bound donor-acceptor pairs in homogeneous molecular ensembles. To the best of my knowledge, modulation of the two-photon fluorescence emission of a dye by a photochromic diarylethene has not been reported as a mechanism to read the recorded information in a 3D optical data storage system. This system was demonstrated to be highly stable and suitable for recording data in thick storage media. The proposed RET-based readout method proved to be non-destructive (exhibiting a loss of the initial fluorescence emission less than 20% of the initial emission after 10,000 readout cycles). Potential application of this system in a rewritable-erasable optical data storage system was proved. As part of the strategy for the development of diarylethenes optimized for 3D optical data storage, derivatives containing π-conjugated fluorene molecules were synthesized and characterized. The final part of this reasearch demonstrated the photostability of fluorine derivatives showing strong molecular polarizability and high fluorescence quantum yields. These compounds are quite promising for application in RET-based two-photon 3D optical data storage. Hence, the photostability of these fluorene derivatives is a key parameter to establish, and facilitates their full utility in critical applications.
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Date Issued: 2007
Identifier: CFE0001662, ucf:47210
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001662

Title: SINGLET OXYGEN GENERATION USING NEW FLUORENE-BASED PHOTOSENSITIZERS UNDER ONE- AND TWO-PHOTON EXCITATION.
Creator: Andrasik, Stephen, Belfield, Kevin, University of Central Florida
Abstract / Description: Molecular oxygen in its lowest electronically excited state plays an important roll in the field of chemistry. This excited state is often referred to as singlet oxygen and can be generated in a photosensitized process under one- or two-photon excitation of a photosensitizer. It is particularly useful in the field of photodynamic cancer therapy (PDT) where singlet oxygen formation can be used to destroy cancerous tumors. The use of two-photon activated photosensitizers possesses great...
Show moreMolecular oxygen in its lowest electronically excited state plays an important roll in the field of chemistry. This excited state is often referred to as singlet oxygen and can be generated in a photosensitized process under one- or two-photon excitation of a photosensitizer. It is particularly useful in the field of photodynamic cancer therapy (PDT) where singlet oxygen formation can be used to destroy cancerous tumors. The use of two-photon activated photosensitizers possesses great potential in the field of PDT since near-IR light is used to activate the sensitizer, resulting in deeper penetration of light into biological tissue, less photo-bleaching of the sensitizer, and greatly improved resolution of excitation. The synthesis and photophysical characterization of new fluorene-based photosensitizers for efficient singlet oxygen production were investigated. The spectral properties for singlet oxygen production were measured at room temperature and 77 K. Two-photon absorption (2PA) cross-sections of the fluorene derivatives were measured by the open aperture Z-scan method. The quantum yields of singlet oxygen generation under one- and two-photon excitation (ΦΔ and 2PAΦΔ, respectively) were determined by the direct measurement of singlet oxygen luminescence at ≈ 1270 nm. The values of ΦΔ were independent of excitation wavelength, ranging from 0.6 - 0.9. The singlet oxygen quantum yields under two-photon excitation were 2PAΦΔ ≈ ½ΦΔ, indicating that the two processes exhibited the same mechanism of singlet oxygen production, independent of the mechanism of photon absorption.
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Date Issued: 2007
Identifier: CFE0001860, ucf:47411
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001860

Title: MICRO-OPTIC-SPECTRAL-SPATIAL-ELEMENTS (MOSSE).
Creator: Mehta, Alok, Johnson, Eric, University of Central Florida
Abstract / Description: Over a wide range of applications, optical systems have utilized conventional optics in order to provide the ability to engineer the properties of incident infra-red fields in terms of the transmitted field spectral, spatial, amplitude, phase, and polarization characteristics. These micro/nano-optical elements that provide specific optical functionality can be categorized into subcategories of refractive, diffractive, multi-layer thin film dichroics, 3-D photonic crystals, and polarization...
Show moreOver a wide range of applications, optical systems have utilized conventional optics in order to provide the ability to engineer the properties of incident infra-red fields in terms of the transmitted field spectral, spatial, amplitude, phase, and polarization characteristics. These micro/nano-optical elements that provide specific optical functionality can be categorized into subcategories of refractive, diffractive, multi-layer thin film dichroics, 3-D photonic crystals, and polarization gratings. The feasibility of fabrication, functionality, and level of integration which these elements can be used in an optical system differentiate which elements are more compatible with certain systems than others. With enabling technologies emerging allowing for a wider range of options when it comes to lithographic nano/micro-patterning, dielectric growth, and transfer etching capabilities, optical elements that combine functionalities of conventional optical elements can be realized. Within this one class of optical elements, it is possible to design and fabricate components capable of tailoring the spectral, spatial, amplitude, phase, and polarization characteristics of desired fields at different locations within an optical system. Optical transmission filters, polarization converting elements, and spectrally selective reflecting components have been investigated over the course of this dissertation and have been coined MOSSE,' which is an acronym for micro-optic-spectral-spatial-elements. Each component is developed and fabricated on a wafer scale where the thin film deposition, lithographic exposure, and transfer etching stages are decoupled from each other and performed in a sequential format. This facilitates the ability to spatially vary the optical characteristics of the different MOSSE structures across the surface of the wafer itself.
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Date Issued: 2007
Identifier: CFE0001962, ucf:47457
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001962

Title: SYNTHESIS OF NOVEL FLUORENE-BASED TWO-PHOTON ABSORBING MOLECULES AND THEIR APPLICATIONS IN OPTICAL DATA STORAGE, MICROFABRICATION, AND STIMULATED EMISSION DEPLETION.
Creator: Yanez, Ciceron, Belfield, Kevin, University of Central Florida
Abstract / Description: Two-photon absorption (2PA) has been used for a number of scientific and technological applications, exploiting the fact that the 2PA probability is directly proportional to the square of the incident light intensity (while one-photon absorption bears a linear relation to the incident light intensity). This intrinsic property of 2PA leads to 3D spatial localization, important in fields such as optical data storage, fluorescence microscopy, and 3D microfabrication. The spatial confinement that...
Show moreTwo-photon absorption (2PA) has been used for a number of scientific and technological applications, exploiting the fact that the 2PA probability is directly proportional to the square of the incident light intensity (while one-photon absorption bears a linear relation to the incident light intensity). This intrinsic property of 2PA leads to 3D spatial localization, important in fields such as optical data storage, fluorescence microscopy, and 3D microfabrication. The spatial confinement that 2PA enables has been used to induce photochemical and photophysical events in increasingly smaller volumes and allowed nonlinear, 2PA-based, technologies to reach sub-diffraction limit resolutions. The primary focus of this dissertation is the development of novel, efficient 2PA, fluorene-based molecules to be used either as photoacid generators (PAGs) or fluorophores. A second aim is to develop more effective methods of synthesizing these compounds. As a third and final objective, the new molecules were used to develop a write-once-read many (WORM) optical data storage system, and stimulated emission depletion probes for bioimaging. In Chapter I, the microwave-assisted synthesis of triarylsulfonium salt photoacid generators (PAGs) from their diphenyliodonium counterparts is reported. The microwave-assisted synthesis of these novel sulfonium salts afforded reaction times 90 to 420 times faster than conventional thermal conditions, with photoacid quantum yields of new sulfonium PAGs ranging from 0.01 to 0.4. These PAGs were used to develop a fluorescence readout-based, nonlinear three-dimensional (3D) optical data storage system (Chapter II). In this system, writing was achieved by acid generation upon two-photon absorption (2PA) of a PAG (at 710 or 730 nm). Readout was then performed by interrogating two-photon absorbing dyes, after protonation, at 860 nm. Two-photon recording and readout of voxels was demonstrated in five and eight consecutive, crosstalk-free layers within a polymer matrix, generating a data storage capacity of up to 1.8 x 1013 bits/cm3. The possibility of using these PAGs in microfabrication is described in Chapter III, where two-photon induced cationic ring-opening polymerization (CROP) crosslinking of an SU8 resin is employed to produce free-standing microstructures. Chapter IV describes the investigation of one- and two-photon stimulated emission transitions by the fluorescence quenching of a sulfonyl-containing fluorene compound in solution at room temperate using a picosecond pump-probe technique. The nature of stimulated transitions under various fluorescence excitation and quenching conditions were analyzed theoretically, and good agreement with experimental data was demonstrated. Two-photon stimulated transitions S1 to S0 were shown at 1064 nm. The two-photon stimulated emission cross section of the sulfonyl fluorophore was estimated as aproximately 240 - 280 GM, making this compound a good candidate for use in two-photon stimulated emission depletion (STED) microscopy.
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Date Issued: 2009
Identifier: CFE0002913, ucf:48003
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0002913

Title: Spray_Deposited Titanium-Oxide Films For Infrared Optics, Photonics, And Solar Cell Applications.
Creator: Alhasan, Sarmad, Peale, Robert, Sundaram, Kalpathy, Mikhael, Wasfy, Abdolvand, Reza, Kar, Aravinda, University of Central Florida
Abstract / Description: Self-assembled TiO2 foam-like films, were grown by the water based Streaming Process for ElectrodelessElectrochemical Deposition (SPEED). The morphology of the 1 m thick films consistsof a tangled ropy structure with individual strands of 200 nm diameter and open pores of 0.1to 3 micron dimensions. Such films are advantageous for proposed perovskite solar cell comprisingCH3NH3PbI3 absorber with additional inorganic films as contact and conduction layers,all deposited by SPEED. Lateral film...
Show moreSelf-assembled TiO2 foam-like films, were grown by the water based Streaming Process for ElectrodelessElectrochemical Deposition (SPEED). The morphology of the 1 m thick films consistsof a tangled ropy structure with individual strands of 200 nm diameter and open pores of 0.1to 3 micron dimensions. Such films are advantageous for proposed perovskite solar cell comprisingCH3NH3PbI3 absorber with additional inorganic films as contact and conduction layers,all deposited by SPEED. Lateral film resistivity is in the range 20 - 200 k-cm, increasing withgrowth temperature, while sheet resistance is in the range 2 ?? 20 108 /Sq. Xray diffractionconfirms presence of TiO2 crystals of orthorhombic class (Brookite). UV-vis spectroscopy showshigh transmission below the expected 3.2 eV TiO2 bandgap. Transmittance increases with growthtemperature. This is a Ropy TiO2 thin film.We also prepared a Smooth TiO2 thin film. Self-assembled TiO2 film deposited by aqueous-spraydeposition was investigated to evaluate morphology, crystalline phase, and infrared optical constants.The Anatase nano-crystalline film had 10 nm characteristic surface roughness sparselypunctuated by defects of not more than 200 nm amplitude. The film is highly transparent throughoutthe visible to wavelengths of 12 m. The indirect band gap was determined to be 3.2 eV. Importantfor long-wave infrared applications is that dispersion in this region is weak compared with themore commonly used dielectic SiO2 for planar structures. The low-cost, large-area, atmosphericpressure,chemical spray deposition method allows conformal fabrication on flexible substrates forlong-wave infrared photonics.For comparison TiO2 films deposited by electron-beam evaporation were evaluated to determinemorphology, crystalline phase, and optical transparency.The evaporated TiO2 film was amorphous but crystallized into Anatase phase after annealing.Such film is attractive as electron conductor of unprecedented thinness and flexibility for proposedperovskite solar cell comprising CH3NH3PbI3 absorber with additional inorganic films as contactand conduction layers. The spray deposition method would allow conformal solar cell fabricationon flexible substrates for wearable power generation. Band gap of Evaporated TiO2 film is 4.0 eV.We prepared BaTiO3 thin film to know infrared pyroelectric response.Self-assembled nano-crystalline BaTiO3 films on stainless steel foil substrates, were grown by thewater based Streaming Process for Electrodeless Electrochemical Deposition (SPEED). SPEED isan aqueous process that deposits self-assembled nano-crystalline inorganic thin films over largeareas, without a vacuum, providing a scalable and manufacturing friendly process to fabricatedurable films. The morphology of the 1m thick films comprises single crystals of micron dimensionsimbedded in a matrix of nanocrystals. XRD confirms presence of BaTiO3 crystals ofhexagonal phase for samples annealed at 500C. Subsequent annealing at 600C transforms thefilm to the cubic phase. Potential applications include dielectric layers, capacitors, waveguides,ferroelectric RAM, pyroelectric infrared detectors, and phosphors. Characterization of infraredpyroelectric response at 10m wavelength shows an initially good sensitivity that reversibly decaysover a period of days due to water vapor absorption. A short-lived photo-response due topoling of the hydrated sample is also observed. We studied BaTiO3 to know hysteresis loop.Pyroelectric photoresponse of aqueous spray deposited thin films containing BaTiO3 nano-crystalsis reported. X-ray diffraction data indicate the presence of hexagonal BaTiO3 nano-crystals with20 nm crystalline domains in a matrix of some as yet unidentified nano-crystalline material.When the film is annealed at 600C, the X-ray pattern changes significantly and indicates a conversionto one of the non-hexagonal phases of BaTiO3 as well as a complete change in the matrix.With suitable amplifier, the measured photoresponse was 40V/W.Ferroelectric hysteresis on a film with significant presence of hexagonal BaTiO3 shows saturatedpolarization which is about 5-times smaller than for the bulk tetragonal phase.
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Date Issued: 2017
Identifier: CFE0006710, ucf:51899
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006710

Title: SYNTHESIS AND APPLICATIONS OF RING OPENING METATHESIS POLYMERIZATION BASED FUNCTIONAL BLOCK COPOLYMERS.
Creator: Biswas, Sanchita, Belfield, Kevin, University of Central Florida
Abstract / Description: Ring opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the...
Show moreRing opening metathesis polymerization (ROMP) is established as one of the efficient controlled living polymerization methods which have various applications in polymer science and technology fields. The research presented in this dissertation addresses several applications of multifunctional well-defined norbornene-based block copolymers synthesized by ROMP using ruthenium-based Grubbs catalysts. These novel block copolymers were applied to stabilize maghemite nanoparticles, creating the superparamagnetic polymeric nanocomposites. The J-aggregation properties of the porphyrin dyes were improved via self-assembly with a customized norbornene polymer. Novel multimodal copolymer probes were synthesized for two-photon fluorescence integrin-targeted bioimaging. In Chapter 1 a brief overview of ROMP along with ruthenium metal catalysts and selected applications of the polymers related to this research is presented. Superparamagnetic maghemite nanoparticles are important in biotechnology fields, such as enhanced magnetic resonance imaging (MRI), magnetically controlled drug delivery, and biomimetics. However, cluster formation and eventual loss of nano-dimensions is a major obstacle for these materials. Chapter 2 presents a solution to this problem through nanoparticles stabiulized in a polymer matrix. The synthesis and chracterization of novel diblock copolymers, consisting of epoxy pendant anchoring groups to chelate maghemite nanoparticles and steric stabilizing groups, as well as generation of nanocomposites and their characterization, including surface morphologies and magnetic properties, is discussed in Chapter 2. In Chapter 3, further improvement of the nanocomposites by ligand modification and the synthesis of pyrazole-templated diblock copolymers and their impact to stabilize the maghemite nanocomposite are presented. Additionally, the organic soluble magnetic nanocomposites with high magnetizations were encapsulated in an amphiphilic copolymer and dispersed in water to assess their water stability by TEM. To gain a preliminary measure of biocopatibility of the micelle-encapsulated polymeric magnetic nanocomposites, cell-viability was determined. In Chapter 4, aggregation behaviors of two porphyrin-based dyes were investigated. A new amphiphilic homopolymer containing secondary amine moieties was synthesized and characterized. In low pH, the polymer became water soluble and initiated the stable J-aggregation of the porphyrin. Spectroscopic data supported the aggregation behavior. Two photon fluorescence microscopy (2PFM) has become a powerful technique in bioimaging for non-invasive imaging and potential diagnosis and treatment of a number of diseases via excitation in the near-infrared (NIR) region. The fluorescence emission upon two-photon absorption (2PA) is quadratically dependent with the intensity of excitation light (compared to the linear dependence in the case of one-photon absoprtion), offering several advantages for biological applications over the conventional one-photon absorption (1PA) due to the high 3D spatial resolution that is confined near the focal point along with less photodamage and interference from the biological tissues at longer wavelength (~700-900 nm). Hence, efficient 2PA absorbing fluorophores conjugated with specific targeting moieties provides an even better bioimaging probe to diagnose desired cellular processes or areas of interest The αVβ3 integrin adhesive protein plays a significant role in regulating angiogenesis and is over-expressed in uncontrolled neovascularization during tumor growth, invasion, and metastasis. Cyclic-RGD peptides are well-known antagonists of αVβ3 integrin which suppress the angiogenesis process, thus preventing tumor growth. In Chapter 5 the synthesis, photophysical studies and bioimaging is reported for a versatile norbornene-based block copolymer multifunctional scaffold containing biocompatible (PEG), two-photon fluorescent (fluorenyl), and targeting (cyclic RGD peptide) moieties. This water-soluble polymeric multi scaffold probe with negligible cytotoxicity exhibited much stronger fluorescence and high localization in U87MG cells (that overexpress integrin) compared to control MCF7 cells. The norbornene-based polymers and copolymers have quite remarkable versatility for the creation of advanced functional magnetic, photonic, and biophotonic materials.
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Date Issued: 2010
Identifier: CFE0003065, ucf:48296
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0003065

Title: TWO-PHOTON CROSS SECTION ENHANCEMENT OF PHOTOCHROMIC COMPOUNDS FOR USE IN 3D OPTICAL DATA STORAGE.
Creator: Luchita, Gheorghe, Belfield, Kevin, University of Central Florida
Abstract / Description: Rewritable photochrome-based 3D optical data storage requires photochromic molecules with high two-photon absorption (2PA) cross sections. Currently, the low value of two-photon absorption cross sections of existing photochromes makes them unsuitable for practical application in 3D data storage. Worldwide attempts to increase the cross section of photochromic molecules by altering the chemical structure have yielded poor results. In this work, two ways to increase the two-photon absorption...
Show moreRewritable photochrome-based 3D optical data storage requires photochromic molecules with high two-photon absorption (2PA) cross sections. Currently, the low value of two-photon absorption cross sections of existing photochromes makes them unsuitable for practical application in 3D data storage. Worldwide attempts to increase the cross section of photochromic molecules by altering the chemical structure have yielded poor results. In this work, two ways to increase the two-photon absorption cross sections of photochromes were investigated. In the first method, partial success demonstrated by extending the conjugation of a photochromic molecule, a high two-photon absorption cross section of the closed form isomer and high photoconversion to the closed form were realized. At the same time, a decrease in photoswitching quantum yield and low photoconversion to open form was observed. A discussion is provided to explain the results, suggesting that the proposed method of extending the conjugation may not solve the problem. For this reason a new method for effective two-photon absorption cross section enhancement of photochromes was proposed. As a proof of principle, a new two-photon absorbing dye with a hydrogen bonding moiety was synthesized and used for the formation of supramolecular structures with a photochromic compound. Theoretical reasoning and experimental demonstration of energy transfer from the dye to the photochrome under one and two-photon excitation confirmed the practical value of the method. The effects of a 2PA dye on the photochromic properties of a diarylethene were investigated using a model compound to simplify data analysis. Formation of supramolecular structures was revealed using 1H NMR spectroscopic methods. The model compound, having the same hydrogen bonding moiety as 2PA dye, has been demonstrated to bind with photochrome molecules at very low concentrations. Photochromic properties of 2,3-bis(2,4,5-trimethyl-3-thienyl)maleimide, including conversions at the photostationary state, extinction coefficients, photoisomerization reaction rates and quantum yields, were shown to be affected by hydrogen bonding with the model compound - 2,6-bis-(acetamido)pyridine. The extent of this change was determined and discussed, demonstrating a balanced supramolecular strategy to modulate photochemical and photophysical properties of this important class of photochromic material.
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Date Issued: 2011
Identifier: CFE0003928, ucf:48695
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0003928

Title: Broadband Coherent Perfect Absorption in One-Dimensional Optical Systems.
Creator: Villinger, Massimo Maximilian, Abouraddy, Ayman, Dogariu, Aristide, Fathpour, Sasan, University of Central Florida
Abstract / Description: Absorption plays a critical role in a variety of optical applications (-) sometimes it is desirable to minimize it as in optical fibers and waveguides, or to enhance it as in solar cells and photodetectors. We describe here a new optical scheme that controllably produces high optical absorption over a broad wavelength range (hundreds of nm) in systems that have low intrinsic absorption over the same range. This effect, 'coherent perfect absorption' or CPA, arises from a subtle interplay...
Show moreAbsorption plays a critical role in a variety of optical applications (-) sometimes it is desirable to minimize it as in optical fibers and waveguides, or to enhance it as in solar cells and photodetectors. We describe here a new optical scheme that controllably produces high optical absorption over a broad wavelength range (hundreds of nm) in systems that have low intrinsic absorption over the same range. This effect, 'coherent perfect absorption' or CPA, arises from a subtle interplay between interference and absorption of two beams incident on a weakly absorbing medium. In the first part of this study, we present an analytical model that captures the relevant physics of CPA in one-dimensional photonic structures. This model elucidates an absorption-mediated interference effect that underlies CPA (-) an effect that is normally forbidden in Hermitian systems, but is allowed when conservation of energy is violated due to the inclusion of loss. As a concrete example, we consider a Fabry-P(&)#233;rot resonator containing a lossy dielectric and confirm this model through a computational study of a 1-micron-thick silicon layer in a cavity formed of dispersive mirrors with aperiodic multilayer design. We confirm that one may achieve 100% absorption in this thin silicon layer (whose intrinsic absorption is only ~ 3%) in the near-infrared. We then design two device models using few-micron-thick aperiodic planar dielectric mirrors and demonstrate (computationally, as well as experimentally) spectrally flat, coherently enhanced absorption at the theoretical limit in a 2-micron-thick film of polycrystalline silicon embedded in symmetric and asymmetric cavities. This coherent effect is observed over an octave-spanning wavelength range of ~800 (-) 1600 nm utilizing incoherent light in the near-infrared, exploiting mirrors that have wavelength-dependent reflectivity devised to counterbalance the decline in silicon's intrinsic absorption at long wavelengths. We anticipate that the design principles established here may be extended to other materials, broader spectral ranges, and large surface areas. Finally, we study the effect of the angle of incidence on CPA in planar structures. The results of this study point to a path for realizing CPA in such systems continuously over large bandwidths.
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Date Issued: 2015
Identifier: CFE0006059, ucf:50985
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006059

Title: In Actu Et In Silicio: Linear and Nonlinear Photophysical Characterization of a Novel Europium Complex, and Incorporating Computational Calculations in the Analysis of Novel Organic Compounds.
Creator: Woodward, Adam, Belfield, Kevin, Campiglia, Andres, Harper, James, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description: Despite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before...
Show moreDespite not being a tangible substance, light is becoming an increasingly valuable tool in numerous areas of science and technology: the use of laser excitation of a fluorescent probe can generate incredibly detailed images of cellular structures without the need for large amounts of dissection; new types of solar cells are being produced using organic dyes to harvest light; computer data can be stored by inducing a chemical change in a compound through irradiation with light. However, before any of these materials can be applied in such a way, their properties must first be analyzed for them to be deemed viable.The focus of this dissertation is the photophysical characterization, linear and nonlinear, of a several novel organic compounds, and a europium complex, as well as using quantum chemical calculation techniques to understand some of the phenomena that are witnessed and begin to develop predictive capability. The nonlinear characterization of compounds utilizes wavelengths outside of their linear absorption range, where a focused beam can achieve the same excitation as one at half the wavelength, though this effect has a quadratic dependence on power.The potential for nonlinear excitation, or two-photon absorption (2PA), is becoming of increasing interest and importance for organic chromophores. Exciting only a small volume of material at a focal point makes it possible to nondestructively image samples in 3-dimensions, record data in multiple layers, and fabricate intricate structures through photopolymerization reactions.Lanthanides such as europium are known to exhibit sharp emission bands when excited, typically through an antenna effect due to the low probability of achieving direct excitation. This emission is long-lived, and through gating systems can readily be separated from background noise and autofluorescence (often observed in biological samples) that have much shorter lifetimes. Thus, one of the foci of this dissertation is the photophysical investigation of a series of novel lanthanide complexes, with particular attention to a europium complex.
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Date Issued: 2014
Identifier: CFE0005908, ucf:50891
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005908

Title: Mode Evolution in Fiber Based Devices for Optical Communication Systems.
Creator: Huang, Bin, Li, Guifang, Amezcua Correa, Rodrigo, Abouraddy, Ayman, Chen, Haoshuo, University of Central Florida
Abstract / Description: Space division multiplexing (SDM) is the most promising way of increasing the capacity of a single fiber. To enable the few mode fiber (FMF) or multi-mode fiber (MMF) transmission system, several major challenges have to be overcome. One is the urgent need of ideal mode multiplexer, the second is the perfect amplification for all spatial modes, another one is the modal delay spread (MDS) due to group velocity difference of spatial modes. The main subject of this dissertation is to model,...
Show moreSpace division multiplexing (SDM) is the most promising way of increasing the capacity of a single fiber. To enable the few mode fiber (FMF) or multi-mode fiber (MMF) transmission system, several major challenges have to be overcome. One is the urgent need of ideal mode multiplexer, the second is the perfect amplification for all spatial modes, another one is the modal delay spread (MDS) due to group velocity difference of spatial modes. The main subject of this dissertation is to model, fabricate and characterize the mode multiplexer for FMF transmission. First, we designed a novel resonant mode coupler (structured directional coupler pair). After that, we studied the adiabatic mode multiplexer (photonic lantern). 6-mode photonic lantern using graded-index (GI) MMFs is proposed and demonstrated, which alleviates the adiabatic require-ment and improves mode selectivity. Then, 10-mode photonic lantern is demonstrated using novel double cladding micro-structured drilling-hole preform, which alleviates the adiabatic requirement and demonstrate a feasible way to scale up the lantern modes. Also, multi-mode photonic lantern is studied for high order input modes. In addition, for the perfect amplification of the modes, cladding pump method is demonstrated. The mode selective lantern designed and fabricated can be used for the characterization of few mode amplifier with swept wavelength interferometer (SWI). Also, we demonstrated the application of the use of the few mode amplifier for the turbulence-resisted preamplified receiver. Besides, for the reduction of MDS, the long period grating for introducing strong mode mixing is demonstrated.
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Date Issued: 2017
Identifier: CFE0006884, ucf:51720
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006884

Title: Synthesis of Fluorene-based derivatives, Characterization of Optical properties and their Applications in Two-photon Fluorescence Imaging and Photocatalysis.
Creator: Githaiga, Grace, Belfield, Kevin, Patino Marin, Pedro, Chumbimuni Torres, Karin, Zou, Shengli, Cheng, Zixi, University of Central Florida
Abstract / Description: The two-photon absorption (2PA) phenomenon has attracted attention from various fields ranging from chemistry and biology to optics and engineering. Two of the common NLO applications in which organic materials have been used are three-dimensional (3D) fluorescence imaging and optical power limiting. Two-photon absorbing materials are, therefore, in great demand to meet the needs of emerging technologies. Organic molecules show great promise to meet this need as they can be customized through...
Show moreThe two-photon absorption (2PA) phenomenon has attracted attention from various fields ranging from chemistry and biology to optics and engineering. Two of the common NLO applications in which organic materials have been used are three-dimensional (3D) fluorescence imaging and optical power limiting. Two-photon absorbing materials are, therefore, in great demand to meet the needs of emerging technologies. Organic molecules show great promise to meet this need as they can be customized through molecular engineering, and as the development of two-photon materials that suit practical application intensifies, so does research to meet this need. However, there remains some uncertainty in the particulars of design criteria for molecules with large 2PA cross sections at desired wavelengths, as such research to understand structure-property relationships is matter of significant importance. As a result, the full potential of 2PA materials has not been fully exploited. Several strategies to enhance the magnitude and tune the wavelength of 2PA have been reported for ?-conjugated organic molecules. On this account, we have designed novel fluorophores using the fluorene moiety and modified it to tune the properties of the compounds.Chapter 2 of this dissertation reports the successful application of fluorene-based compounds in photocatalysis; a process that involves the decomposition of organic compounds into environmentally friendly carbon dioxide and water attesting to the photostability of the fluorene moiety. A facile organic nanoparticle preparation method is reported in chapter 3 using the reprecipitation method, whose surface was then modified using a naturally occurring surfactant, Lecithin, and were then successfully used in fluorescence cell imaging. Chapter 4 reports the design and synthesis of a fluorene-based compound using an acceptor, s-indacene-1, 3, 5, 7(2H, 6H)-tetra one, or Janus Dione, a moiety that is relatively new and that has not been fully exploited despite its very attractive features. Owing to the hydrophobicity of this compound, notwithstanding its unprecedented 2PA cross section, it was not applicable in fluorescence cell imaging but provided the tenets for the design of related derivative. This limitation was circumvented in the concluding chapter by tuning the compound's hydrophilicity. The hydrophilic Janus dione probe was then used as envisioned for cell imaging as the dual prerequisites for fluorescence imaging probes; large 2PA cross sections and high fluorescence quantum yields were met.
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Date Issued: 2015
Identifier: CFE0005620, ucf:50207
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005620

Title: Squaraine dyes, design and synthesis for various functional materials applications.
Creator: Zhang, Yuanwei, Belfield, Kevin, Campiglia, Andres, Zou, Shengli, Frazer, Andrew, Cheng, Zixi, University of Central Florida
Abstract / Description: This dissertation contains the synthesis and characterization of squaraine based new functional materials. In the first part of this thesis work, a water soluble benzothiazolium squaraine dye was synthesized with pyridium pendents, and controlled aggregation properties were achieved. After formation of partially reversible J-aggregation on a polyelectrolyte (poly(acryl acid) sodium salt) template, the nonlinear, two-photon absorption cross section per repeat unit was found to be above 30-fold...
Show moreThis dissertation contains the synthesis and characterization of squaraine based new functional materials. In the first part of this thesis work, a water soluble benzothiazolium squaraine dye was synthesized with pyridium pendents, and controlled aggregation properties were achieved. After formation of partially reversible J-aggregation on a polyelectrolyte (poly(acryl acid) sodium salt) template, the nonlinear, two-photon absorption cross section per repeat unit was found to be above 30-fold enhanced compared with nonaggregate and/or low aggregates. Using a similar strategy, sulfonate anions were introduced into the squaraine structure, and the resulting compounds exhibited good water solubilities. A 'turn on' fluorescence was discovered when these squaraine dyes interacted with bovine serum albumin (BSA), titration studies by BSA site selective reagents show these squaraine dyes can bind to both site I and II of BSA, with a preference of site II. Introduction of these squaraine dyes to BSA nanoparticles generated near-IR protein nano fabricates, and cell images were collected. Metal sensing properties were also studied using the sulfonates containing a benzoindolium squaraine dye, and the linear response of the absorption of the squaraine dye to the concentration of Hg2+ makes it a good heavy metal-selective sensing material that can be carried out in aqueous solution. Later, a squaraine scaffold was attached to deoxyribonucleosides by Sonogashira coupling reactions, in which the reaction conditions were modified. Iodo-deoxyuridine and bromo-deoxyadenosine were used as the deoxyribonucleosides building blocks, and the resulting squaraine dye-modified deoxyribonucleosides exhibited near-IR absorption and emission properties due to the squaraine chromophore. Interestingly, these non-natural deoxyribonucleosdies showed viscosity dependent photophysical properties, which make them nice candidates for fluorescence viscosity sensors at the cellular level. After incubation with cells, these viscosity sensors were readily uptaken by cell, and images were obtained showing regions of high viscosity in cells.
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Date Issued: 2013
Identifier: CFE0005451, ucf:50369
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005451

Title: Photophysical and photochemical factors affecting multi-photon direct laser writing using the cross-linkable epoxide SU-8.
Creator: Williams Jr., Henry, Kuebler, Stephen, Elsheimer, Seth, Zhai, Lei, Liao, Yi, Heinrich, Helge, University of Central Florida
Abstract / Description: For the past decade, the epoxy based photoresist SU-8 has been used commercially and in the lab for fabricating micro- and nano-structures. Investigators have studied how processing parameters such as pre- and post-exposure bake temperatures affect the resolution and quality of SU-8 structures patterned using ultraviolet or x-ray lithography. Despite the advances in understanding the phenomena, not all of them have been explored, especially those that are specific to multi-photon direct laser...
Show moreFor the past decade, the epoxy based photoresist SU-8 has been used commercially and in the lab for fabricating micro- and nano-structures. Investigators have studied how processing parameters such as pre- and post-exposure bake temperatures affect the resolution and quality of SU-8 structures patterned using ultraviolet or x-ray lithography. Despite the advances in understanding the phenomena, not all of them have been explored, especially those that are specific to multi-photon direct laser writing (mpDLW). Unlike conventional exposure techniques, mpDLW is an inherently three-dimensional (3D) process that is activated by nonlinear absorption of light.This dissertation reports how several key processing parameters affect mpDLW using SU-8 including pre-exposure bake duration, focal depth, incident laser power, focal-point scan speed, and excitation wavelength. An examination of solvent content of films at various stages in the mpDLW by 1H-NMR shows that even moderate solvent content (over 1 wt-%) affects film viscosity and photoacid diffusion lengths, and can greatly affect the overall fidelity of small features. A study of micro-fabricated feature size versus writing depth in the material shows that even slight refractive index mismatch between SU-8 and the medium between it and the focusing objective introduces spherical aberration that distorts the focus, causing feature size to decrease or even increase in size with writing depth, depending on the average exposure power used. Proper adjustment of the average exposure power was demonstrated as a means to fabricate more uniform features with writing depth. Third, when varying the power and scan speed, it was observed that the feature-size scales with these two parameters in a manner that is consistent with a three-photon absorption mechanism at an excitation wavelength of 800 nm. When aniiiexcitation wavelength of 725 nm is used, the feature-size scaling becomes consistent with that of two photon absorption. This shows that the photoinitiators in the SU-8 can be activated by either two- or three-photon absorption over this wavelength range. Using an irradiance of ~2 TW cm-2 and elongated femtosecond pulses resulted in an observed fourth order power dependence. This observation is in agreement with the literature and suggests that the effective absorptive nonlinearity is also sensitive to pulse duration. These findings will be useful for creating accurate models of the process of mpDLW in SU-8. These models could be used to optimize the processing parameters and develop new processing methods and materials for high-resolution fabrication of robust 3D microstructures. Some of the findings were used to develop a method for fabricating functional microlenses on the tip of optical fibers. This approach opens a new route to functional integrated photonic devices.
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Date Issued: 2013
Identifier: CFE0005441, ucf:50403
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0005441

Title: Peak Power Scaling of Nanosecond Pulses in Thulium based Fiber Lasers.
Creator: Gaida, Christian, Richardson, Martin, Shah, Lawrence, Amezcua Correa, Rodrigo, University of Central Florida
Abstract / Description: Thulium based fiber lasers represent a promising alternative for pulse energy scaling and highpeak power generation with ytterbium based systems at 1 micrometer. Advantages of thulium arise fromthe operation at longer wavelengths and a large gain bandwidth (1.8-2.1 micrometer). Nonlinear effects,such as self phase modulation, stimulated Raman scattering and stimulated Brillouin scattering generally limit peak power scaling in fiber lasers. The longer wavelength of thulium fiber lasersand...
Show moreThulium based fiber lasers represent a promising alternative for pulse energy scaling and highpeak power generation with ytterbium based systems at 1 micrometer. Advantages of thulium arise fromthe operation at longer wavelengths and a large gain bandwidth (1.8-2.1 micrometer). Nonlinear effects,such as self phase modulation, stimulated Raman scattering and stimulated Brillouin scattering generally limit peak power scaling in fiber lasers. The longer wavelength of thulium fiber lasersand large mode field areas can significantly increase the nonlinear thresholds. Compared to 1 micrometer systems, thulium fiber lasers enable single mode guidance for two times larger mode field diameterin step index fibers. Similar behavior is expected for index guiding thulium doped photonic crystalfibers.In this work a novel thulium doped rod type photonic crystal fiber design with large mode field diameter (>50 micrometer) was first characterized in CW-lasing configuration and then utilized as finalamplifier in a two stage master oscillator power amplifier. The system generated MW-level peakpower at 6.5ns pulse duration and 1kHz repetition rate. This world record performance exemplifiesthe potential of thulium fiber lasers to supersede ytterbium based systems for very high peak powergeneration in the future.As part of this work a computer model for the transient simulation of pulsed amplification inthulium based fiber lasers was developed. The simulations are in good agreement with the experimentalresults. The computer model can be used for efficient optimization of future thulium basedfiber amplifier designs.
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Date Issued: 2013
Identifier: CFE0004845, ucf:49699
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004845

Title: HIGH-SPEED MODELOCKED SEMICONDUCTOR LASERS AND APPLICATIONS IN COHERENT PHOTONIC SYSTEMS.
Creator: Lee, Wangkuen, Delfyett, Peter, University of Central Florida
Abstract / Description: 1.55-µm high-speed modelocked semiconductor lasers are theoretically and experimentally studied for various coherent photonic system applications. The modelocked semiconductor lasers (MSLs) are designed with high-speed (>5 GHz) external cavity configurations utilizing monolithic two-section curved semiconductor optical amplifiers. By exploiting the saturable absorber section of the monolithic device, passive or hybrid mode-locking techniques are used to generate short optical pulses with...
Show more1.55-µm high-speed modelocked semiconductor lasers are theoretically and experimentally studied for various coherent photonic system applications. The modelocked semiconductor lasers (MSLs) are designed with high-speed (>5 GHz) external cavity configurations utilizing monolithic two-section curved semiconductor optical amplifiers. By exploiting the saturable absorber section of the monolithic device, passive or hybrid mode-locking techniques are used to generate short optical pulses with broadband optical frequency combs. Laser frequency stability is improved by applying the Pound-Drever-Hall (PDH) frequency stabilization technique to the MSLs. The improved laser performance after the frequency stabilization (a frequency drifting of less than 350 MHz), is extensively studied with respect to the laser linewidth (~ 3 MHz), the relative intensity noise (RIN) (< -150 dB/Hz), as well as the modal RIN (~ 3 dB reduction). MSL to MSL, and tunable laser to MSL synchronization is demonstrated by using a dual-mode injection technique and a modulation sideband injection technique, respectively. Dynamic locking behavior and locking bandwidth are experimentally and theoretically studied. Stable laser synchronization between two MSLs is demonstrated with an injection seed power on the order of a few microwatt. Several coherent heterodyne detections based on the synchronized MSL systems are demonstrated for applications in microwave photonic links and ultra-dense wavelength division multiplexing (UD-WDM) system. In addition, efficient coherent homodyne balanced receivers based on synchronized MSLs are developed and demonstrated for a spectrally phase-encoded optical CDMA (SPE-OCDMA) system.
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Date Issued: 2007
Identifier: CFE0001703, ucf:47326
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0001703

Title: Characterization of composite broadband absorbing conjugated polymer nanoparticles by steady-state, time-resolved and single particle spectroscopy.
Creator: Bonner, Maxwell, Gesquiere, Andre, Campiglia, Andres, Santra, Swadeshmukul, Hernandez, Florencio, Perez Figueroa, Jesus, Ye, Jingdong, Fernandez-Valle, Cristina, University of...
Show moreBonner, Maxwell, Gesquiere, Andre, Campiglia, Andres, Santra, Swadeshmukul, Hernandez, Florencio, Perez Figueroa, Jesus, Ye, Jingdong, Fernandez-Valle, Cristina, University of Central Florida
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Abstract / Description: As the global economy searches for reliable, inexpensive and environmentally friendly renewable energy resources, energy conservation by means of photovoltaics has seen near exponential growth in the last decade. Compared to state-of-the-art inorganic solar cells, organic photovoltaics (OPVs) composed of conjugated polymers are particularly interesting because of their processability, flexibility and the potential for large area devices at a reduced fabrication cost. It has been extensively...
Show moreAs the global economy searches for reliable, inexpensive and environmentally friendly renewable energy resources, energy conservation by means of photovoltaics has seen near exponential growth in the last decade. Compared to state-of-the-art inorganic solar cells, organic photovoltaics (OPVs) composed of conjugated polymers are particularly interesting because of their processability, flexibility and the potential for large area devices at a reduced fabrication cost. It has been extensively documented that the interchain and intrachain interactions of conjugated polymers complicate the fundamental understanding of the optical and electronic properties in the solid-state (i.e. thin film active layer). These interactions are highly dependent on the nanoscale morphology of the solid-state material, leading to a heterogeneous morphology where individual conjugated polymer molecules obtain a variety of different optoelectronic properties. Therefore, it is of the utmost importance to fundamentally study conjugated polymer systems at the single molecule or nanoparticle level instead of the complex macroscopic bulk level.This dissertation research aims to develop simplified nanoparticle models that are representation of the nanodomains found in the solid-state material, while fundamentally addressing light harvesting, energy transfer and interfacial charge transfer mechanisms and their relationship to the electronic structure, material composition and morphology of the nanoparticle system. In preceding work, monofunctional doped nanoparticles (polymer-polymer) were fabricated with enhanced light harvesting and F?rster energy transfer properties by blending Poly[(o-phenylenevinylene)-alt-(2-methoxy-5-(2-ethylhexyloxy)-p-phenylenevinylene)] (BPPV) and Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) at various MEH-PPV doping ratios. While single particle spectroscopy (SPS) reveals a broad distribution of optoelectronic and photophysical properties, time-correlated single photon counting (TC-SPC) spectroscopy displays multiple fluorescence lifetime components for each nanoparticle composition, resulting from changing polymer chain morphologies and polymer-polymer aggregation. In addition, difunctional doped nanoparticles were fabricated by doping the monofunctional doped nanoparticles with PC60BM ([6,6]-phenyl-C61-butyric acid methyl ester) to investigate competition between intermolecular energy transfer and interfacial charge transfer. Specifically, the difunctional SPS data illustrated enhanced and reduced energy transfer mechanisms that are dependent on the material composition of MEH-PPV and PC60BM. These data are indicative of changes in inter- and intrachain interactions of BPPV and MEH-PPV and their respective nanoscale morphologies. Together, these fundamental studies provide a thorough understanding of monofunctional and difunctional doped nanoparticle photophysics, necessary for understanding the morphological, optoelectronic and photophysical processes that can limit the efficiency of OPVs and provide insight for strategies aimed at improving device efficiencies.
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Date Issued: 2011
Identifier: CFE0004089, ucf:49143
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0004089

Title: EXPERIMENTAL AND THEORETICAL STUDY OF THE OPTICAL PROPERTIES OF SEMICONDUCTOR QUANTUM DOTS.
Creator: Nootz, Gero, Cuenya , Beatriz, University of Central Florida
Abstract / Description: The aim of this dissertation is to gain a better understanding of the unique electronic structure of lead salt quantum dots (QDs) and its influences on the nonlinear optical (NLO) properties as well as the time dynamics of the photogenerated charge carriers. A variety of optical techniques such as Z-scan, two-photon excited fluorescence and time-resolved pump probe spectroscopy are used to measure these properties. The one-photon as well as the degenerate and nondegenerate two-photon...
Show moreThe aim of this dissertation is to gain a better understanding of the unique electronic structure of lead salt quantum dots (QDs) and its influences on the nonlinear optical (NLO) properties as well as the time dynamics of the photogenerated charge carriers. A variety of optical techniques such as Z-scan, two-photon excited fluorescence and time-resolved pump probe spectroscopy are used to measure these properties. The one-photon as well as the degenerate and nondegenerate two-photon absorption (2PA) spectra are measured and the electronic wave functions from a four-band envelope function formalism are used to model the results. We observe local maxima in the 2PA spectra for QD samples of many different sizes at energies where only 1PA is predicted by the model. This is similar to the previously measured transitions in the 1PA spectra which are not predicted by the model but accrue at the energies of the two-photon allowed transitions. Most importantly we observe 2PA peaks for all samples at the energy of the first one-photon allowed transition. This result can only be understood in terms of symmetry breaking and therefore is strong evidence that other transitions, not predicted by the model if the selection rules are left intact, also have the origin in the lifted spatial symmetry of the wave functions. On the other hand, the uniquely symmetric eigenenergies of these quantum-confined energy states in the conduction and valance bands explain the observed trend toward larger two-photon cross-sections as the quantum confinement is increased in smaller QDs. Moreover, this unique feature is shown to reduce the possible relaxation channels for photoexcited carriers, which is confirmed experimentally by the reduced carrier relaxation rate as compared to CdSe QDs which lack this symmetry. Carrier multiplication (CM), a process in which several electrons are excited by the absorption of a single photon is studied in PbS QDs. We show that for PbS QDs with radius smaller than 2.5 nm the parameters of CM get very close to the theoretical optimum. Next-generation solar cells operating under these ideal conditions could potentially have conversion efficiency of up to 42%. This compares favorably to the 30% efficiency limit of a single junction silicon solar cell.
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Date Issued: 2010
Identifier: CFE0003396, ucf:48413
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0003396

Title: ELECTRO-OPTICAL AND ALL-OPTICAL SWITCHING IN MULTIMODE INTERFERENCE WAVEGUIDES INCORPORATING SEMICONDUCTOR NANOSTRUCTURES.
Creator: Bickel, Nathan, LiKamWa, Patrick, University of Central Florida
Abstract / Description: The application of epitaxially grown, III-V semiconductor-based nanostructures to the development of electro-optical and all-optical switches is investigated through the fabrication and testing of integrated photonic devices designed using multimode interference (MMI) waveguides. The properties and limitations of the materials are explored with respect to the operation of those devices through electrical carrier injection and optical pumping. MMI waveguide geometry was employed as it offered...
Show moreThe application of epitaxially grown, III-V semiconductor-based nanostructures to the development of electro-optical and all-optical switches is investigated through the fabrication and testing of integrated photonic devices designed using multimode interference (MMI) waveguides. The properties and limitations of the materials are explored with respect to the operation of those devices through electrical carrier injection and optical pumping. MMI waveguide geometry was employed as it offered advantages such as a very compact device footprint, low polarization sensitivity, large bandwidth and relaxed fabrication tolerances when compared with conventional single-mode waveguide formats. The first portion of this dissertation focuses on the characterization of the materials and material processing techniques for the monolithic integration of In0.15Ga0.85As/GaAs self-assembled quantum dots (SAQD) and InGaAsP/InGaAsP multiple quantum wells (MQW). Supplemental methods for post-growth bandgap tuning and waveguide formation were developed, including a plasma treatment process which is demonstrated to reliably inhibit thermally induced interdiffusion of Ga and In atoms in In0.15Ga0.85As/GaAs quantum dots. The process is comparable to the existing approach of capping the SAQD wafer with TiO2, while being simpler to implement along-side companion techniques such as impurity free vacancy disordering. Study of plasma-surface interactions in both wafer structures suggests that the effect may be dependent on the composition of the contact layer. The second portion of this work deals with the design, fabrication, and the testing of MMI switches which are used to investigate the limits of electrical current control when employing SAQD as the active core material. A variable power splitter based on a 3-dB MMI coupler is used to analyze the effects of sub-microsecond electrical current pulses in relation to carrier and thermal nonlinearities. Electrical current controlled switching of the variable power splitter and a tunable 2 x 2 MMI coupler is also demonstrated. The third part of this dissertation explores the response of In0.15Ga0.85As/GaAs SAQD waveguide structures to photogenerated carriers. Also presented is a simple, but effective, design modification to the 2 x 2 MMI cross-coupler switch that allows control over the carrier distribution within the MMI waveguide. This technique is combined with selective-area bandgap tuning to demonstrate a compact, working, all-optical MMI based switch.
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Date Issued: 2010
Identifier: CFE0003220, ucf:48568
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0003220

Title: Synthesis and Characterization of New Probes for use in Fluorescence and X-ray CT Bioimaging.
Creator: Tang, Simon, Belfield, Kevin, Miles, Delbert, Campiglia, Andres, Zou, Shengli, Cheng, Zixi, University of Central Florida
Abstract / Description: The pursuit of more suitable drugs intended for possible biological applications are a continuously growing topic of research within the scientific community. One of these suitable qualities includes the need for hydrophilicity and or some appropriate delivery system for the drug to enter into biological systems. A system of analyzing and following these compounds would then, however, be necessary to conduct any kind of mechanistic or interaction studies for he said drug within the biological...
Show moreThe pursuit of more suitable drugs intended for possible biological applications are a continuously growing topic of research within the scientific community. One of these suitable qualities includes the need for hydrophilicity and or some appropriate delivery system for the drug to enter into biological systems. A system of analyzing and following these compounds would then, however, be necessary to conduct any kind of mechanistic or interaction studies for he said drug within the biological system. Just to name a few, fluorescence and X-ray computed tomography (CT) methods allow for imaging of biological systems but require the need of compounds with specific qualities. Finally, even with a means of entering and following a oaded drug, it would not be complete without a way of targeting its intended location. Herein, the first chapter reports the synthesis and characterization of a fluorene-based pyridil bis-?-diketone compound with suitable one- and two-photon fluorescent properties and its encapsulation into Pluronic F127 micelles for the possible application of tracking lysosomes. Next the synthesis and characterization of a BODIPY-based fluorophore with excellent fluorescence ability is reported. This compound was conjugated to two triphenylphosphine (TPP) groups and is shown as a potential mitochondria probe within HCT-116 cells. Finally, the synthesis and characterization of diatrizoic acid (DA) based derivatives conjugated to silica nanoparticles, as well as unconjugated, are reported as potential CT contrast agents. The derivatives were also functionalized with maleimide moieties facilitating subsequent potential bioconjugation of a targeting protein via a thiol group.
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Date Issued: 2015
Identifier: CFE0006056, ucf:50961
Format: Document (PDF)
PURL: http://purl.flvc.org/ucf/fd/CFE0006056

two-photon absorption (9)	+ -
Two-Photon Absorption (7)	+ -
Two-photon absorption (5)	+ -
integrated photonics (5)	+ -
nonlinear optics (5)	+ -

photonics (5)	+ -
Photonics (4)	+ -
Integrated photonics (3)	+ -
Two-photon (3)	+ -
optical data storage (3)	+ -
optics (3)	+ -
photonic crystals (3)	+ -
semiconductors (3)	+ -
Fiber Laser (2)	+ -
Optics (2)	+ -
Quantum dots (2)	+ -
SU-8 (2)	+ -
Spectroscopy (2)	+ -
Two Photon Absorption (2)	+ -
bioimaging (2)	+ -
fluorescence microscopy (2)	+ -
frequency combs (2)	+ -
micro-optics (2)	+ -
microfabrication (2)	+ -
multimode interference (2)	+ -
nanophotonics (2)	+ -
nonlinear spectroscopy (2)	+ -
optoelectronics (2)	+ -
photostability (2)	+ -
silicon photonics (2)	+ -

ETD Collection (71)	+ -
Honors Collection (1)	+ -

University of Central Florida (72)	+ -
Belfield, Kevin (17)	+ -
Zou, Shengli (10)	+ -
Fathpour, Sasan (9)	+ -
Campiglia, Andres (8)	+ -

Likamwa, Patrick (8)	+ -
Schoenfeld, Winston (7)	+ -
Cheng, Zixi (6)	+ -
Christodoulides, Demetrios (6)	+ -
Delfyett, Peter (6)	+ -
Peale, Robert (6)	+ -
Abouraddy, Ayman (5)	+ -
Amezcua Correa, Rodrigo (5)	+ -
Frazer, Andrew (5)	+ -
Hernandez, Florencio (5)	+ -
Kuebler, Stephen (5)	+ -
Gesquiere, Andre (4)	+ -
Li, Guifang (4)	+ -
Richardson, Martin (4)	+ -
Vanstryland, Eric (4)	+ -
Hagan, David (3)	+ -
Masunov, Artem (3)	+ -
Van Stryland, Eric (3)	+ -
Zhai, Lei (3)	+ -
Belfield, Kevin D. (2)	+ -
Chumbimuni Torres, Karin (2)	+ -
Harper, James (2)	+ -
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