Browsing by Subject "Nanostructures."

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Open Access
Atomic layer deposition of metal oxide thin films and nanostructures
(2013) Dönmez, İnci
With the continuing scaling down of microelectronic integrated circuits and increasing need for three-dimensional stacking of functional layers, novel or improved growth techniques are required to deposit thin films with high conformality and atomic level thickness control. As being different from other thin film deposition techniques, atomic layer deposition (ALD) is based on selflimiting surface reactions. The self-limiting film growth mechanism of ALD ensures excellent conformality and large area uniformity of deposited films. Additionally, film thickness can be accurately controlled by the number of sequential surface reactions. Gallium oxide (Ga2O3) thin films were deposited by plasma-enhanced ALD (PEALD) using trimethylgallium as the gallium precursor and oxygen plasma as the oxidant. A wide ALD temperature window was observed from 100 to 400 °C, where the deposition rate was constant at ~0.53 Å/cycle. The deposition parameters, composition, crystallinity, surface morphology, optical and electrical properties were studied for as-deposited and annealed Ga2O3 films. In order to investigate the electrical properties of the deposited films, metal-oxide-semiconductor capacitor structures were fabricated for a variety of film thicknesses and annealing temperatures. Ga2O3 films exhibited decent dielectric properties after crystallization upon annealing. Dielectric constant was increased with film thickness and decreased slightly with increasing annealing temperature. As an additional PEALD experiment, deposition parameters of In2O3 thin films were studied as well, using the precursors of cyclopentadienyl indium and O2 plasma. Initial results of this experiment effort are also presented. Accurate thickness control, along with high uniformity and conformality offered by ALD makes this technique quite promising for the deposition of conformal coatings on nanostructures. This thesis also deals with the synthesis of metal oxide nanotubes using organic nanofiber templates. Combination of electrospinning and ALD processes provided an opportunity to precisely control both diameter and wall thickness of the synthesized nanotubes. As a proof-ofconcept, hafnia (HfO2) nanotubes were synthesized using three-step approach: (i) preparation of the nylon 6,6 nanofiber template by electrospinning, (ii) conformal deposition of HfO2 on the electrospun polymer template via ALD using the precursors of tetrakis(dimethylamido)hafnium and water at 200 °C, and (iii) removal of the organic template by calculation to obtain freestanding HfO2 nanotubes (hollow nanofibers). When the same deposition procedure was applied on nanofibers with different average fiber diameters, thinner HfO2 wall thicknesses were obtained for the templates having smaller diameters due to insufficient exposure of precursor molecules to saturate their extremely large surface area. Thus, “exposure mode” was applied to obtain the desired wall thickness while coating high-surface area nanofibers. We present the experimental efforts including film deposition parameters, structural, elemental, and morphological properties of HfO2 nanotubes.
Open Access
Cascading and modifying nonradiative energy transfer mechanisms in strong coupling region of plasmons and excitons in semiconductor quantum dots
(2010) Akın, Onur
Nonradiative energy transfer finds important applications in nanophotonics and nanobiotechnology including nanoscale optical waveguiding and biological nanosensors. Various fluorophores can take part in such energy transfer interactions in close proximity of each other. Their emission kinetics can be strongly modified and controlled as a result. For example, colloidal semiconductor quantum dots, also known as nanocrystals, have widely been shown to serve as donors and acceptors among themselves or with other fluorescent species to transfer excitation energy nonradiatively. In their close proximity, emission characteristics of such fluorophores can also be altered when coupled with plasmonic structures, e.g., metal nanoparticles. One favored result of these plasmon-exciton interactions is the emission enhancement. In principle it is possible to plasmon-couple acceptor-donor pairs of nonradiative energy transfer to modify their transfer rate. Such plasmon-mediated energy transfer has been demonstrated, where both acceptor-donor pairs are plasmoncoupled. In these cases, however, the resulting plasmon-exciton interactions are not controlled to take place either at the donor site or the acceptor site but at both of the sites. Therefore, it has previously not been possible to identify the coupled interactions. In this thesis, we propose and demonstrate cascaded plasmonic - nonradiative energy transfer interactions that are controlled by selectively plasmon-coupling either only the donor quantum dots or only the acceptor quantum dots. For that, we designed a novel self-assembly architecture of our hybrid layered systems of semiconductor nanocrystals and metal nanoparticles in a bottom-up fashion through precise spatial and spectral control. This scheme uniquely allowed for the ability to spatially control plasmonexciton interactions to take place either at the “start” site (donors) or “finish” site (acceptors) of the energy transfer. This control was achieved by placing the plasmonic layer in the right proximity of the donors (for strong donor-exciton plasmon-coupling) while sufficiently being far away from the acceptors (for weak acceptor-exciton plasmon-coupling), or vice versa. Here we comparatively studied and analyzed consequent modifications of quantum dot emission kinetics in response to both cases of plasmon-coupling to only the donors and to only the acceptors through steady-state and time-resolved photoluminescence measurements, along with their lifetime and rate calculations. Such cascaded energy transfer interactions in the strong exciton-plasmon coupling region hold great promise for innovative near-field photonic devices and biological tags. system.
Open Access
Cell penetrating peptide amphiphile integrated liposomal systems for enhanced delivery of cargo to tumor cells
(2013) Kılınç, Murat
Liposomes have been extensively utilized as effective nanocarriers due to their enhanced solubility, higher stability and greater ability to facilitate the slow release of encapsulated drugs compared to free drug administrations. Liposomes are also preferred as drug vectors due to their non-toxic nature, biodegradability and structural resemblance to the cell membrane. However, their low internalization efficiencies pose an important challenge for their use in drug delivery applications. Internalization issues inherent in many liposomal systems can be circumvented by the use of cell penetrating peptides, which non-covalently attach on the liposome surface and greatly enhance liposomal uptake in a receptor- and charge-dependent manner. In this study, we examined the liposomal dynamics effected through the integration of an amphiphilic cell penetrating peptide into a simple liposome system. Peptide amphiphiles with a cell penetrating arginine-rich domain were incorporated into liposomal membranes formed by negatively charged dioleoylphosphoglycerol (DOPG) phospholipids in the presence of cholesterol. Throughout the present study, we sought to analyze the effect of peptide incorporation on (a) the physical characteristics, such as size, surface potential and membrane polarity, of the liposomal membrane, (b) the alterations in the encapsulation and delivery mechanisms of hydrophilic (Rhodamine B) and hydrophobic (Nile Red) drug models and (c) the enhancement of therapeutic capability in liposomes loaded with the drugs Doxorubicin-HCl and Paclitaxel. Our results revealed that the modification of liposomes by cell penetrating peptide amphiphiles results in the improvement of cargo delivery and the enhancement of the therapeutic effects of the anticancer drugs Doxurubicin and Paclitaxel.
Open Access
Design and development of novel large scale applications in micro/nanophotonics and nanobiotechnology
(2014) Özgür, Erol
Developments in micro/nanophotonics and nanobiotechnology creates new opportunities regarding development of devices with unprecedented capabilities, which could improve human civilization substantially. On the other hand, a certain level of maturity in transforming these possibilities into reality still requires considerable efforts. One of the main problems of these novel technologies is that their practical know-how is so scarce that they could only be utilized within strictly determined laboratory conditions, and by highly sophisticated scientists. This thesis focuses on large scale applications at the intersection of microphotonics and nanobiotechnology, and also in nanophotonics. On microphotonics side, optical microresonators with toroidal shape were successfully fabricated and optically integrated. Having an extremely high sensitivity towards perturbations in their environments, these microcavities could be used as biological sensors; however, they are also very sensitive for nonspecific interactions. Thus, a novel surface chemistry enabling bioconjugation of molecular probes without compromising their sensitivity and enhancing their selectivity was developed, based on methylphosphonate containing silane modification of the microtoroid surface. After this functionalization, microtoroids were used in biodetection in complex media. Also, a macroscopic photodetection device composed on intrinsically aligned semiconducting selenium nanowires were demonstrated. This device could be considered as a novel and efficient demonstration of nanowire integration to the macroscopic world. Together with the research on biosensors, these are important large scale applications of emergent science of our age.
Open Access
Fabrication of an on-chip nanowire device with controllable nanogap for manipulation, capturing, and electrical characterization of nanoparticles
(2008) Uran, Can
One of the major challenges in nanofabrication commonly arises from the necessity to integrate nanostructures (e.g., nanoparticles) on the same chip with microcomponents (e.g., microelectrodes) that are orders-of-magnitude larger in size. For example, in order to make electrical contacts to colloidally synthesized nanoparticles (typically 1-100 nm in size) by integrating them with microelectrodes (typically in the few micrometers range on the critical side), a large size mismatch that easily ranges from 1:10 to 1:10,000 is required to be handled delicately for successful nano-to-micro integration. This necessitates the ability to manipulate and integrate nanoparticles with a sufficient level of precision on the microchip. In this thesis, to provide a convenient solution to this challenging problem, we proposed and demonstrated for the first time an onchip nanowire device that features a controllable nanogap in its architecture for capturing and electrical characterization of nanoparticles in the gap, all fully integrated on the same microchip. Our innovative approach relies on the use of dielectrophoretic electric-field assisted self-assembly of our segmented nanowires to construct a nanoscale device platform. For this purpose, we synthesized gold-silver-gold segmented nanowires and dielectrophoretically aligned them across our microfabricated array of electrodes. Subsequently, we selectively removed the middle silver segment to open a gap in the nanometer size between the self-aligned gold end segments. Using dielectrophoretic assembly once more, we captured nanoparticles in these nanogaps for further electrical characterization. One of the key benefits in our approach was that the aligned nanowires automatically provided electrical contacts to the captured nanoparticles to allow for electrical probing at the nanoscale. Our innovative approach enabled convenient full integration from nanoparticles to nanowires to microelectrodes to macroprobes on a single chip, spanning a size range of more than six orders of magnitude.
Open Access
Fabrication of novel core-shell nanostructures for photonics applications
(2013) Khudiyev, Tural
Developments in nanoscale fabrication and characterization techniques have led to fundamental changes in the scientific understanding of many fields, and novel nanostructures have been utilized to investigate the conceptual underpinnings behind a diverse array of natural phenomena. However, nanofabrication methods are frequently hindered by issues such as misalignment, small batch sizes, high production costs and constraints in material choice or nanostructure diversity, which decrease their potential utility and prevent their widespread application in nanoscale optics and photonics. In this work, a new top-down nanofabrication method is described, which is called Iterative Size Reduction (ISR), where step-by-step reduction is utilized to decrease structure dimensions from macro- to nanosizes and produce indefinitely long one-dimensional core-shell nanostructures with properties highly suitable for use in optical applications. Plateau-Rayleigh instabilities are then utilized to thermally degrade ISR-produced nanowire arrays into complex core-shell schemes, which are produced successively in a hitherto-undescribed transitory region between core-shell nanowires and core-shell nanospheres. A diverse array of optical phenomena have been observed on fabricated novel core-shell nano-platforms, which are utilized in the design of novel nanostructures for emerging photonics applications. Briefly, (a) the resonant Mie scattering behavior is characterized on glass-polymer nanostructures and these nanostructures are designed for large-area structural coloration, (b) a novel non-resonant Mie scattering regime responsible for the scattering characteristics exhibited by all-polymer core-shell nanowires is described, (c) a nanoscale analogue to the thin film interference phenomenon is demonstrated that occurs on the core-shell boundary of ISR-produced micro- and nanostructures, (d) an unusual photonic crystal structure observed in the neck feathers of mallard drakes is investigated and imitated, (e) a series of all-polymer core-shell nanowires to function as novel light-trapping platforms and sensors are engineered and (f) the generation of supercontinuum light in well-ordered arrays of As2Se3 nanowires is reported.
Open Access
Hot electron interactions in nanostructures
(1997) Kaya, Ismet Inonu
Modern semiconductor growth and processing techiques have provided the capability of fabricating a huge variety of devices which have atomically precise layered structures and lateral patterns with nanometer sizes. This not only provided novel device possibilités but also opened a new field in condensed matter physics, so called mesoscopics. It does not seem likely that the mesoscopic electronic devices will be available in the near future. Two main obstacles for mesoscopic electronics are the low temperature requirements and the breakdown of the phase coherence of the carriers as their energies exceed the Fermi level. This strongly suggests the investigation of the excited carriers with energies well in excess of their thermal equilibrium energy as the dimensions shrink. In this thesis, the interactions of hot electrons in semiconductor and metal structures with deep submicron characteristic dimensions have been studied. Tunneling Hot Electron Transfer Amplifier (THETA) constructed by abrupt semiconductur heterojunctions is a perfect system to analyze the interaction of hot electrons with cold electrons and the other possible excitations in solids. Recently, it has been discovered that an electron multiplication effect took place in such devices under certain conditions and resulted in a transfer ratio of greater than unity. In this work a novel fabrication technique has been developed. It would make it possible to utilize this effect for fabrication of a high frequency oscillator in the THz regime, in a future work. In addition, a kind of lateral THETA device has been constructed using a Two Dimensional Electron Gas structure. Electron multiplication effect for the first time has been observed in 2DEG structures. Moreover, the dependence of the effect on parameters such as injection energy, emitter and collector barrier heights and electron transit length has been investigated. The other direction of the work has been the investigation of metal wires under extremely high current densities. A strong nonlinearity in conductivity is introduced when a free standing submicrometer wire is biased to heat upto very high temperatures. The geometry of two crossing wires has been investigated under this condition.
Open Access
Light scattering from core-shell nano-structures : structural coloration
(2013) Dolaş, Muhammet Halit
In this work, we produced kilometer-long semiconducting cylindrical nanostructures by using a top-to-bottom nano-fabrication technique which was recently developed in our research group. Comparison of commonly used methods of producing nano-structures such as electrospinning and nano-imprint lithography versus iterative thermal size reduction (ISR) is done in terms of uniformity, geometry control, multi-material compatibility, yield and device integrability. While the others cannot fulfil all requirements, ISR shows impressive results in all aspects. From very beginning to end, all steps of production and characterization of nano-wires produced by ISR, the design, chalcogenide glass production, preform preparation, fiber drawing, iterative size reduction, chemical etching and imaging are explained in details. In addition, production and characterization of nanospheres by in-fiber fluid instability which is based on Plateau-Rayleigh instability is also demonstrated. Theoretical study on scattering from small particles, Mie scattering, which is one of the mechanisms for structural coloration together with thin film interference, multilayer interference, diffraction grating and photonic crystals is done. Structural coloration due to scattering from small particles is simulated using Finite Domain Time Difference (FDTD) method and compared with theoretical results estimated for nano-wire and nano-sphere cases. Results are confirmed with observation of structural coloration by taking dark field optical microscopy images of the final products of ISR and in-fiber fluid instability processes
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Novel design-based complex nanostructures in hybrid core-shell architectures for high-efficiency light generation
(2010) Özel, İlkem Özge
Recent developments in nanoscience and nanotechnology have given rise to the discovery of hybrid nanostructured multi-component materials that serve several tasks all at once. A very important and rapidly growing field of these materials is the development of highly efficient fluorophores to meet the urgent demand of low-energy consuming, high-quality light emitters for future solid-state lighting applications. Such hybrid nanomaterials are entailed to exhibit extraordinary optoelectronic properties compared to the bulk case of their single components such as enhanced quantum efficiency, tunable multi-color emission, and reduction of multiple processing steps. Herein, to address these requirements, we propose and demonstrate novel design-based complex nanomaterials in hybrid multi-shell architectures for high-efficiency light generation. These requirements are made possible by using the concept of hybrid core-shell-… nanostructures comprising at least two units, including hybrid metalcore/dielectric-shell nanoparticles furnished with an outer shell of semiconductor nanocrystals for enhanced emission and different conjugated polymers forming a single multi-polymer nanoparticle and emitting simultaneously at different wavelengths. In the first part of this thesis, we developed and demonstrated Au-silica core/shell nanoparticles that successfully assemble CdTe nanocrystals right on their silica shells for enhanced plasmonexciton interactions, while solving the common problems of lacking control in dielectric spacing and limited film thickness typically encountered in such plasmon-coupled nanocrystals. Here we present the synthesis and characterization results of this new set of multi-shell decorated nanoparticle composites with a tunable dielectric spacing thickness of silica shell precisely controlled by synthesis to optimize plasmon-exciton interactions for enhanced emission. Experimental data obtained from steady-state and time-resolved photoluminescence measurements together with extensive computational analysis clearly verify the strong plasmon-exciton interactions in these designbased multi-shell nanocomposites. In the second part, we construct bi-polymer nanoparticle systems in various architectures of core/shells, for each of which thorough investigations of the non-radiative energy transfer mechanisms are made. Here we present the synthesis and characterization results of these core/shell bi-polymer nanoassemblies. The flexibility of designing such bipolymer nanostructures allows for the optimization of maximum energy transfer efficiency. This concept of complex hybrid nanostructures for high-efficiency light generation opens up new paths for optoelectronic devices and nanophotonics applications including those in solid-state lighting.
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Novel multichromophoric energy transfer cassettes based on functionalized BODIPY dyes
(2012) Çeltek, Gizem
Energy necessity is one of the leading problems in the world due to the developing technologies and strategies. There are many energy sources, which are being used for years, however; conversion and transfer of the energy is a problem in many fields due to energy loss. In this manner, the efficiency of energy transfer is very crucial. For this purpose, we have designed multichromophoric molecules, which can absorb the light with donor parts, then transfer the energy to the acceptor site. During this process, energy loss is tried to be prevented by lowering the distance between the donor and acceptor Boradiazaindacene (BODIPY) molecules. Three different energy transfer cassettes are synthesized and characterized. The design of the supramolecule, in means of spectral overlap and distance between the donor and the acceptor site are observed to affect the energy transfer efficiency. Through functional design, these molecules absorb and emit light in different wavelengths. Substation of distyryl and tetrastyryl groups to the acceptor BODIPY core changes the emission and absorption maxima. Increasing number of styryl groups attached to the molecule shifts the spectrum to the red part of the visible region. Through rational design, these molecules can be used in applications of energy transfer and broad spectrum absorber purposes.
Open Access
Novel nanocrystal-integrated LEDs utilizing radiative and nonradiative energy transfer for high-quality efficient light generation
(2011) Nizamoğlu, Sedat
To combat environmental issues escalating with the increasing carbon footprint, combined with the energy problem of limited resources, innovating fundamentally new ways of raising energy efficiency and level of energy utilization is essential to our energy future. Today, to this end, achieving lighting efficiency is an important key because artificial lighting consumes about 19% of total energy generation around the globe. There is a large room for improving lighting efficacy for potential carbon emission cut. However, the scientific challenge is to reach simultaneously high-quality photometric performance. To address these problems, we proposed, developed and demonstrated a new class of color-conversion light emitting diodes (LEDs) integrated with nanophosphors of colloidal quantum dots. The favorable properties of these semiconductor nanocrystal quantum dots, including size-tuneable and narrow-band emission with high photostability, have provided us with the ability of achieving highquality, efficient lighting. Via using custom-design combinations of such nanocrystal emitters, we have shown that targeted white luminescence spectra can be generated with desired high photometric performance, which is important for obtaining application-specific white LEDs, e.g., for indoors lighting, street lighting, and LED-TV backlighting. Furthermore, dipole-dipole coupling capability of these semiconductor nanocrystals has allowed us to realize novel device designs based on Förster-type nonradiative energy transfer. By mastering exciton-exciton interactions in color-conversion LEDs, we have demonstrated enhanced color conversion via recycling of trapped excitons and white light generation based on nonradiative pumping of nanocrystal quantum dots for color conversion. This research work has led to successful demonstrators of semiconductor nanocrystal quantum dots that photometrically outperform conventional rareearth phosphor powders in terms of color rendering, luminous efficacy of optical radiation, color temperature and scotopic/photopic ratio for the first time.
Open Access
Novel wireless RF-bioMEMS implant sensors of metamaterials
(2010) Melik, Rohat
Today approximately one out of ten patients with a major bone fracture does not heal properly because of the inability to monitor fracture healing. Standard radiography is not capable of discriminating whether bone healing is occurring normally or aberrantly. To solve this problem, we proposed and developed a new enabling technology of implantable wireless sensors that monitor mechanical strain on implanted hardware telemetrically in real time outside the body. This is intended to provide clinicians with a powerful capability to asses fracture healing following the surgical treatment. Here we present the proof-of-concept in vitro and ex vivo demonstrations of bio-compatible radio-frequency (RF) micro-electro-mechanical system (MEMS) strain sensors for wireless strain sensing to monitor healing process. The operating frequency of these sensors shifts under mechanical loading; this shift is related to the surface strain of the implantable test material. In this thesis, for the first time, we developed and demonstrated a new class of bio-implant metamaterial-based wireless strain sensors that make use of their unique structural advantages in sensing, opening up important directions for the applications of metamaterials. These custom-design metamaterials exhibit better performance in remote sensing than traditional RF structures (e.g., spiral coils). Despite their small size, these meta-sensors feature a low enough operating frequency to avoid otherwise strong background absorption of soft tissue and yet yield higher Q-factors (because of their splits with high electric field density) compared to the spiral structures. We also designed and fabricated flexible metamaterial sensors to exhibit a high level of linearity, which can also conveniently be used on non-flat surfaces. Innovating on the idea of integrating metamaterials, we proposed and implemented a novel architecture of ‘nested metamaterials’ that incorporate multiple split ring resonators integrated into a compact nested structure to measure strain telemetrically over a thick body of soft tissue. We experimentally verified that this nested metamaterial architecture outperforms classical metamaterial structures in telemetric strain sensing. As a scientific breakthrough, by employing our nested metamaterial design, we succeeded in reducing the electrical length of the sensor chip down to λo/400 and achieved telemetric operation across thick soft tissue with a tissue thickness up to 20 cm, while using only sub-cm implantable chip size (compatible with typical orthopaedic trauma implants and instruments). As a result, with nested metamaterials, we successfully demonstrated wireless strain sensing on sheep’s fractured metatarsal and femur using our sensors integrated on stainless steel fixation plates and on sheep’s spine using directly attached sensors in animal models. This depth of wireless sensing has proved to suffice for a vast portfolio of bone fracture (including spine) and trauma care applications in body, as also supported by ongoing in vivo experiments in live animal models in collaboration with biomechanical and medical doctors. Herein, for all generations of our RF-bioMEMS implant sensors, this dissertation presents a thorough documentation of the device conception, design, modeling, fabrication, device characterization, and system testing and analyses. This thesis work paves the way for “smart” orthopaedic trauma implants, and enables further possible innovations for future healthcare.
Open Access
Optical near field interaction of spherical quantum dots
(2012) Amirahmadov, Togay
Nanometer-sized materials can be used to make advanced photonic devices. However, as far as the conventional far-field light is concerned, the size of these photonic devices cannot be reduced beyond the diffraction limit of light, unless emerging optical near-fields (ONF) are utilized. ONF is the localized field on the surface of nanometric particles, manifesting itself in the form of dressed photons as a result of light-matter interaction, which are bound to the material and not massless. In this thesis, we theoretically study a system composed of differentsized quantum dots involving ONF interactions to enable optical excitation transfer. Here this is explained by resonance energy transfer via an optical nearfield interaction between the lowest state of the small quantum dot and the first dipole-forbidden excited state of the large quantum dot via the dressed photon exchange for a specific ratio of quantum dot size. By using the projection operator method, we derived the formalism for the transfered energy from one state to another for strong confinement regime for the first time. We performed numerical analyses of the optical near-field energy transfer rate for spherical colloidal quantum dots made of CdSe, CdTe, CdSe/ZnS and PbSe. We estimated that the energy transfer time to the dipole forbidden states of quantum dot is sufficiently shorter than the radiative lifetime of excitons in each quantum dot. This model of ONF is essential to understanding and designing systems of such quantum dots for use in near-field photonic devices.
Open Access
Optimization of orthogonal reactions on bodipy dyes for one-pot synthesis of light harvesting dendrimers
(2013) Bekdemir, Ahmet
For more than a decade, synthetic organic chemistry has dealt with focusing on highly selective and efficient reactions that can proceed under mild conditions which would then be categorized under the term “orthogonal click chemistry”. These types of reaction have served number of applications for years as in peptide synthesis, homogeneous catalysis and development of supramolecular systems. On the other side, after a partial understanding of how photosynthetic bacteria and plants harvest solar radiation in order to carry their necessary carbon dioxide reduction reaction by converting light to chemical energy, artificial light harvesting systems have captivated a lot attention of scientists. Because today’s one of the biggest and inevitable problems is to discover/invent alternative energy sources/devices for future demands, these artificial light harvesting and solar concentrator systems are highly open for further development and optimization. However, like most other macromolecular systems, synthesis of these kind of devices should be straightforward so as to decrease the cost and to increase the efficiency. At this point, orthogonal click reactions, being mild and efficient synthetic models, can undoubtedly be worthwhile to consider as proper tools for easy preparation of light harvesting molecules. Here we propose a synthesis of thiol, Michael accepting groups, amine and isothiocyanate modified BODIPY dyes for light harvesting cascade preparation. Moreover, the optimization of Michael addition type thiol – ene reaction of these functionalized dyes has been discussed. Among methyl methacrylate, cyanoacetic acid and nitroolefin functionalizations, it was found that nitroolefin attached BODIPY dyes are the most reactive one. The achieved product has been investigated in terms of fluorescence and energy transfer.
Open Access
Photocatalytic nanocomposites for increased optical activity
(2008) Tek, Sümeyra
To combat environmental pollution, photocatalytic decomposition provides degradation of organic and inorganic contaminants near the surface of the photocatalyst nanoparticles by converting optical energy of the absorbed light into chemical energy for the redox reactions. However, photocatalytic activities of such semiconductor metal-oxide nanoparticles are limited with their bandgap energy that allows for optical absorption typically in the ultraviolet spectral range. Yet another limitation is that the photocatalytic activity of these semiconductor nanoparticles is substantially reduced when they are immobilized in solid thin films, resulting from their effectively decreased active surface area. But such immobilized nanoparticles are much more desired in industrial applications, e.g., for mass environmental decontamination and outdoors/indoors self-cleaning on large surfaces. To address these issues, in this thesis, we investigated and demonstrated the spectral behavior and time evolution of optical activity curves of immobilized TiO2 and ZnO nanoparticles. We studied the nanoparticle size effect for the optical activity and demonstrated significant increase in the resulting photocatalysis with decreasing the size of such immobilized nanoparticles for the first time. We obtained optimal excitation conditions for TiO2 and ZnO nanocomposite films separately. We achieved maximum optical recovery levels of 93% for TiO2 nanoparticles and 55% for ZnO nanoparticles at the excitation wavelengths of 310 nm and 290 nm, respectively, after optical irradiation with an excitation density of 7.3 J/cm2 , where we observed no optical recovery for their respective negative control groups (with no nanoparticles). In these comparative spectral studies, we showed strong correlation between the differential optical recovery and the photocatalytic activity. For further substantial enhancement in the near ultraviolet and visible spectral ranges, we also proposed and demonstrated the use of a unique combination of TiO2-ZnO nanoparticles integrated together into the same resin. In this novel approach, we observed higher levels of photocatalytic activity under optical irradiation at and above 380 nm compared to the cases of only TiO2 or only ZnO nanocomposite films with the same total metal-oxide nanoparticle density. At 400 nm in the visible, we accomplished an optical recovery level of ~30% with the combination of TiO2-ZnO nanoparticles together while this level was only ~14% for the TiO2 nanoparticles alone and ~3% for the ZnO nanoparticles alone under identical conditions. Even at 440 nm, we obtained ~20% optical recovery using the TiO2-ZnO photocatalytic synergy, despite the optical activity of the single type of nanoparticles alone close to the zero base-line of their control group. These proof-of-concept experimental demonstrations indicate that such TiO2-ZnO combined nanocomposite films hold great promise for efficient environmental decontamination in daylight.
Open Access
Preparation and characterization of ultra thin films containing silver-copper nanoalloys using layer-by-layer deposition technique for antibacterial applications
(2012) Camcı, Merve Taner
The main objective of this master thesis is to explore the preparation, characterization and antibacterial applications of Layer-by-Layer (LbL) assembled ultra thin films containing AgCu nanoalloys. Within this purpose, first part of the research mainly focused on the preparation of Ag nanoparticles and AgCu nanoalloys in order to prevent the oxidation of copper to copper oxide and the formation of polyelectrolyte-AgCu nanoalloy films by Layerby-Layer assembly. Accordingly, Ag nanoparticles and AgCu nanoalloys were synthesized by the chemical reduction of silver and copper salts in aqueous solution with the help of strong reducing agents sodium borohydride or hydrazine hydrate in the presence of complexing agent and stabilizer, then ultra thin polyelectrolyte layers containing pre-prepared AgCu nanoalloys were constructed by Layer-by-Layer deposition technique in different combinations. Also the stability of these nano sized binary alloys in solution phase were prolonged in the presence of third metal zinc as a sacrificial anode. In the second part of the study, characterization of LbL assembled ultra thin polyelectrolyte and metal nanoparticle thin films using Optical (UV-visible) and X-ray Photoelectron Spectroscopy (XPS) was studied. In order to get further information on the optical response of single and bimetallic nanoparticles, Ag nanoparticle and AgCu nanoalloy incorporated ultra thin polyelectrolyte films were investigated by optical spectroscopy. In addition the LbL films were analyzed by Static XPS to extract atomic level chemical information due to elemental and chemical state analysis. In order to get further understanding at the molecular level, samples were analyzed under external bias application by Dynamic XPS and it was shown that Ag and Cu respond in the same way to applying external electrical stimuli when both are in the same environment as a result of alloy formation, as reflected by the same shifts in Ag3d and Cu2p binding energy positions. Lastly, in the third part of the study detailed antibacterial analysis of synthesized monometallic and multimetallic nanoparticle solutions and the organized ultra thin polyelectrolyte layers containing Ag and AgCu nanoclusters against Escherichia coli strain was performed. These approaches enabled us to show the better antibacterial behavior of AgCu nanoalloys as a result of successful synthesis of AgCu nanoalloy without any copper oxide formation as the end product.
Open Access
Preparation and characterization of ultra-thin films containing Au and Ag nanoparticles using layer-by-layer deposition technique
(2009) Cönger, Can Pınar
The main objective of this thesis is to investigate the layer-by-layer deposited polyelectrolyte and polyelectrolyte/metal nanoparticle films by using X-ray Photoelectron (XPS) and Optical Spectroscopy (UV-Vis). Within this purpose, in the first part of the study, layer-by-layer deposited single and oppositely charged bilayered films are investigated by XPS. To extract additional information in the molecular level, the samples are analyzed while applying an external voltage bias. It is shown that applying external electrical stimuli to a single polyelectrolyte layer coated Si/SiO2 system responds to the change in the polarity by molecular rearrangements, evidenced by the changes only in the intensity of the corresponding –N + (1s) peak. In the second part of the study, metal nanoparticle (Au and/or Ag) incorporated polyelectrolyte films are investigated by optical spectroscopy. Within this frame, multilayer gold and silver nanaoparticle/polyelectrolyte films are prepared both separately and in bimetallic form. In order to get further understanding about the optical responses of single type of metal nanoparticle incorporated systems, several experimental approaches are followed. These approaches also enable us to control and manipulate the optical properties of these compact structures. The last part focuses on incorporation of metallic ions into layer-by-layer assembled polyelectrolyte matrices through ion-exchange method. It is shown that metal ions can be incorporated and subsequently reduced within this polymer matrix by UV or X-ray irradiation and can also form nanoparticles.
Open Access
Rational design of two photon absorbing Bodipy dyes
(2010) Kılıç, Bilal
Two photon absorption is a nonlinear process which is of particular interest in various applications such as optical data storage, fluorescence imaging, O2 sensing and photodynamic therapy. These applications have created a strong demand for new dyes which have high two photon absorption cross section. In the two- photon absorption process there is an interaction of the two photons which are simultaneously absorbed by materials. For this purpose, we have designed and synthesized a novel class of distyryl-substituted boradiazaindacene (BODIPY) dyes which absorb two one photon in the green or two photons in the near IR regions of the (electromagnetic) spectrum and have D-A-D structure. As expected, as the strength of the donor groups which were introduced to the 3,5 position of the BODIPY core increase, absorption and emission maxima of the BODIPY dyes are shifted in the near IR regions of the spectrum. Furthermore, GM values increase due to the enhancement donor strength of the terminal groups. In summary, we have successfully synthesized a novel class of BODIPY derivatives which have large TPA cross section values.
Open Access
Selective fluorescence sensing of biological thiols using a bodipy based bifunctional probe and the catalytic activity of short peptide amphiphile nanostructures : implications on the oring of life
(2013) Altay, Yiğit
Chemosensor development is an attractive field of modern chemistry and there exist large amount of contribution from all over the world. The biological importance of thiols triggered the development of sensors to differentiate especially cysteine (Cys), homocysteine (Hcy) and glutathione (GSH) which play key roles in biological systems. Concentration of those thiols results in number of diseases and their structural similarity complicates the differentiation. Optical probes especially fluorescent ones are widely employed for that purpose since it offers simplicity, sensitivity and low detection limits as well as real time analysis. BODIPY core is decorated with a Michael acceptor nitro-styrene group to covalent incorporation of thiols and with an aza-crown moiety to recognition of N-terminus of them. The work in this thesis is the first example in which one of them is separated from others or three of them separated from each other’s by chain length difference using fluorescence spectrometry. Formation of short peptides (2-4 aa residues) is considered to be likely under primordial conditions, following a number of scenarios. In this work, it is constructed a short peptide library limiting our choice of amino acids to those believed to be available at larger concentrations such as Gly, Ala, Asp and Cys. It is demonstrated that when acylated at the N-terminus, nanostructures of varying size and shapes were formed. Investigations on the catalytic activity of these nanostructures under different conditions are presented. The findings on the correlation of peptide structure and nanostructure formation and/or catalytic activity are presented.
Open Access
Selective manipulation of ICT and PeT processes in styryl-Bodipy derivatives : applications in molecular logic and fluoerescence sensing of metal ions
(2010) Selçuk, Sencer
Recent developments in the Bodipy chemistry, provided new opportunities for modification of this chromophore which, in turn, using appropriate metal-ligand pairs, allowed the control and manipulation of PeT and ICT mechanisms. Exploiting these mechanisms, we demonstrated that photophysical properties of Bodipy can be shaped as desired using metal cation modulators to obtain absorbance signals in accordance with a digital half-adder circuit. In addition, another Bodipy derivative with a simple and rational design, shown to have emission signals equivalent to AND operation in Boolean logic. A molecular threeinput AND gate was also synthesized taking the advantage of differential binding affinities of metal cations for different ligands. Our work proves that, with careful design, photophysical properties of a single chromophore can be modified as desired. Hence molecular logic gates, and even molecules performing more complex logic operations can be obtained using metal cations as non-annihilating logic inputs.