Carbon nanostructure based electrodes for high efficiency dye sensitized solar cell

Synthesis and functionalization of large-area graphene and its structural, electrical and electrochemical properties has been investigated. First, the graphene films, grown by thermal chemical vapor deposition (CVD), contain three to five atomic layers of graphene, as confirmed by Raman spectroscopy and high-resolution transmission electron microscopy. Furthermore, the graphene film is treated with CF4 reactive-ion plasma to dope fluorine ions into graphene lattice as confirmed by X-ray photoelectron spectroscopy (XPS) and UV-photoemission spectroscopy (UPS). Electrochemical characterization reveals that the catalytic activity of graphene for iodine reduction enhanced with increasing plasma treatment time, which is attributed to increase in catalytic sites of graphene for charge transfer. The fluorinated graphene is characterized as a counter-electrode (CE) in a dye-sensitized solar cell (DSSC) which shows ~ 2.56% photon to electron conversion efficiency with ~11 mAcm−2 current density. Second, the large scale graphene film is covalently functionalized with HNO3 for high efficiency electro-catalytic electrode for DSSC. The XPS and UPS confirm the covalent attachment of C-OH, C(O)OH and NO3- moieties with carbon atoms through sp2-sp3 hybridization and Fermi level shift of graphene occurs under different doping concentrations, respectively. Finally, CoS-implanted graphene (G-CoS) film was prepared using CVD followed by SILAR method. The G-CoS electro-catalytic electrodes are characterized in a DSSC CE and is found to be highly electro-catalytic towards iodine reduction with low charge transfer resistance (Rct ~5.05 Ωcm 2) and high exchange current density (J0~2.50 mAcm -2). The improved performance compared to the pristine graphene is attributed to the increased number of active catalytic sites of G-CoS and highly conducting path of graphene. We also studied the synthesis and characterization of graphene-carbon nanotube (CNT) hybrid film consisting of graphene supported by vertical CNTs on a Si substrate. The hybrid film is inverted and transferred to flexible substrates for its application in flexible electronics, demonstrating a distinguishable variation of electrical conductivity for both tension and compression. Furthermore, both turn-on field and total emission current was found to depend strongly on the bending radius of the film and were found to vary in ranges of 0.8 - 3.1 V/μm and 4.2 - 0.4 mA, respectively.

Acoustic Manipulation and Alignment of Particles for Applications in Separation, Micro-Templating, and Device Fabrication

This dissertation studies the manipulation of particles using acoustic stimulation for applications in microfluidics and templating of devices. The term particle is used here to denote any solid, liquid or gaseous material that has properties, which are distinct from the fluid in which it is suspended. Manipulation means to take over the movements of the particles and to position them in specified locations. Using devices, microfabricated out of silicon, the behavior of particles under the acoustic stimulation was studied with the main purpose of aligning the particles at either low-pressure zones, known as the nodes or high-pressure zones, known as anti-nodes. By aligning particles at the nodes in a flow system, these particles can be focused at the center or walls of a microchannel in order to ultimately separate them. These separations are of high scientific importance, especially in the biomedical domain, since acoustopheresis provides a unique approach to separate based on density and compressibility, unparalleled by other techniques. The study of controlling and aligning the particles in various geometries and configurations was successfully achieved by controlling the acoustic waves. Apart from their use in flow systems, a stationary suspended-particle device was developed to provide controllable light transmittance based on acoustic stimuli. Using a glass compartment and a carbon-particle suspension in an organic solvent, the device responded to acoustic stimulation by aligning the particles. The alignment of light-absorbing carbon particles afforded an increase in visible light transmittance as high as 84.5%, and it was controlled by adjusting the frequency and amplitude of the acoustic wave. The device also demonstrated alignment memory rendering it energy-efficient. A similar device for suspended-particles in a monomer enabled the development of electrically conductive films. These films were based on networks of conductive particles. Elastomers doped with conductive metal particles were rendered surface conductive at particle loadings as low as 1% by weight using acoustic focusing. The resulting films were flexible and had transparencies exceeding 80% in the visible spectrum (400-800 nm) These films had electrical bulk conductivities exceeding 50 S/cm.

Enhanced zinc oxide and graphene nanostructures for electronics and sensing applications

Zinc oxide and graphene nanostructures are important technological materials because of their unique properties and potential applications in future generation of electronic and sensing devices. This dissertation investigates a brief account of the strategies to grow zinc oxide nanostructures (thin film and nanowire) and graphene, and their applications as enhanced field effect transistors, chemical sensors and transparent flexible electrodes. Nanostructured zinc oxide (ZnO) and low-gallium doped zinc oxide (GZO) thin films were synthesized by a magnetron sputtering process. Zinc oxide nanowires (ZNWs) were grown by a chemical vapor deposition method. Field effect transistors (FETs) of ZnO and GZO thin films and ZNWs were fabricated by standard photo and electron beam lithography processes. Electrical characteristics of these devices were investigated by nondestructive surface cleaning, ultraviolet irradiation treatment at high temperature and under vacuum. GZO thin film transistors showed a mobility of ∼5.7 cm2/V·s at low operation voltage of <5 V and a low turn-on voltage of ∼0.5 V with a sub threshold swing of ∼85 mV/decade. Bottom gated FET fabricated from ZNWs exhibit a very high on-to-off ratio (∼106) and mobility (∼28 cm2/V·s). A bottom gated FET showed large hysteresis of ∼5.0 to 8.0 V which was significantly reduced to ∼1.0 V by the surface treatment process. The results demonstrate charge transport in ZnO nanostructures strongly depends on its surface environmental conditions and can be explained by formation of depletion layer at the surface by various surface states. A nitric oxide (NO) gas sensor using single ZNW, functionalized with Cr nanoparticles was developed. The sensor exhibited average sensitivity of ∼46% and a minimum detection limit of ∼1.5 ppm for NO gas. The sensor also is selective towards NO gas as demonstrated by a cross sensitivity test with N2, CO and CO2 gases. Graphene film on copper foil was synthesized by chemical vapor deposition method. A hot press lamination process was developed for transferring graphene film to flexible polymer substrate. The graphene/polymer film exhibited a high quality, flexible transparent conductive structure with unique electrical-mechanical properties; ∼88.80% light transmittance and ∼1.1742Ω/sq k sheet resistance. The application of a graphene/polymer film as a flexible and transparent electrode for field emission displays was demonstrated.

Embedded heat pipes in cofired ceramic substrates for enhanced thermal management of electronics

A novel and new thermal management technology for advanced ceramic microelectronic packages has been developed incorporating miniature heat pipes embedded in the ceramic substrate. The heat pipes use an axially grooved wick structure and water as the working fluid. Prototype substrate/heat pipe systems were fabricated using high temperature co-fired ceramic (alumina). The heat pipes were nominally 81 mm in length, 10 mm in width, and 4 mm in height, and were charged with approximately 50–80 μL of water. Platinum thick film heaters were fabricated on the surface of the substrate to simulate heat dissipating electronic components. Several thermocouples were affixed to the substrate to monitor temperature. One end of the substrate was affixed to a heat sink maintained at constant temperature. The prototypes were tested and shown to successful and reliably operate with thermal loads over 20 Watts, with thermal input from single and multiple sources along the surface of the substrate. Temperature distributions are discussed for the various configurations and the effective thermal resistance of the substrate/heat pipe system is calculated. Finite element analysis was used to support the experimental findings and better understand the sources of the system's thermal resistance. ^

Resource allocation in multi-user telecommunication networks

This dissertation discussed resource allocation mechanisms in several network topologies including infrastructure wireless network, non-infrastructure wireless network and wire-cum-wireless network. Different networks may have different resource constrains. Based on actual technologies and implementation models, utility function, game theory and a modern control algorithm have been introduced to balance power, bandwidth and customers' satisfaction in the system. ^ In infrastructure wireless networks, utility function was used in the Third Generation (3G) cellular network and the network was trying to maximize the total utility. In this dissertation, revenue maximization was set as an objective. Compared with the previous work on utility maximization, it is more practical to implement revenue maximization by the cellular network operators. The pricing strategies were studied and the algorithms were given to find the optimal price combination of power and rate to maximize the profit without degrading the Quality of Service (QoS) performance. ^ In non-infrastructure wireless networks, power capacity is limited by the small size of the nodes. In such a network, nodes need to transmit traffic not only for themselves but also for their neighbors, so power management become the most important issue for the network overall performance. Our innovative routing algorithm based on utility function, sets up a flexible framework for different users with different concerns in the same network. This algorithm allows users to make trade offs between multiple resource parameters. Its flexibility makes it a suitable solution for the large scale non-infrastructure network. This dissertation also covers non-cooperation problems. Through combining game theory and utility function, equilibrium points could be found among rational users which can enhance the cooperation in the network. ^ Finally, a wire-cum-wireless network architecture was introduced. This network architecture can support multiple services over multiple networks with smart resource allocation methods. Although a SONET-to-WiMAX case was used for the analysis, the mathematic procedure and resource allocation scheme could be universal solutions for all infrastructure, non-infrastructure and combined networks. ^

Segmental body composition determination through a bioelectrical very large scale integration (VLSI) system

The purpose of this investigation was to develop new techniques to generate segmental assessments of body composition based on Segmental Bioelectrical Impedance Analysis (SBIA). An equally important consideration was the design, simulation, development, and the software and hardware integration of the SBIA system. This integration was carried out with a Very Large Scale Integration (VLSI) Field Programmable Gate Array (FPGA) microcontroller that analyzed the measurements obtained from segments of the body, and provided full body and segmental Fat Free Mass (FFM) and Fat Mass (FM) percentages. Also, the issues related to the estimate of the body's composition in persons with spinal cord injury (SCI) were addressed and investigated. This investigation demonstrated that the SBIA methodology provided accurate segmental body composition measurements. Disabled individuals are expected to benefit from these SBIA evaluations, as they are non-invasive methods, suitable for paralyzed individuals. The SBIA VLSI system may replace bulky, non flexible electronic modules attached to human bodies. ^

Realization of Differentiated Quality of Service for Wideband Code Division Multiple Access Core Network

The development of 3G (the 3rd generation telecommunication) value-added services brings higher requirements of Quality of Service (QoS). Wideband Code Division Multiple Access (WCDMA) is one of three 3G standards, and enhancement of QoS for WCDMA Core Network (CN) becomes more and more important for users and carriers. The dissertation focuses on enhancement of QoS for WCDMA CN. The purpose is to realize the DiffServ (Differentiated Services) model of QoS for WCDMA CN. Based on the parallelism characteristic of Network Processors (NPs), the NP programming model is classified as Pool of Threads (POTs) and Hyper Task Chaining (HTC). In this study, an integrated programming model that combines both of the two models was designed. This model has highly efficient and flexible features, and also solves the problems of sharing conflicts and packet ordering. We used this model as the programming model to realize DiffServ QoS for WCDMA CN. ^ The realization mechanism of the DiffServ model mainly consists of buffer management, packet scheduling and packet classification algorithms based on NPs. First, we proposed an adaptive buffer management algorithm called Packet Adaptive Fair Dropping (PAFD), which takes into consideration of both fairness and throughput, and has smooth service curves. Then, an improved packet scheduling algorithm called Priority-based Weighted Fair Queuing (PWFQ) was introduced to ensure the fairness of packet scheduling and reduce queue time of data packets. At the same time, the delay and jitter are also maintained in a small range. Thirdly, a multi-dimensional packet classification algorithm called Classification Based on Network Processors (CBNPs) was designed. It effectively reduces the memory access and storage space, and provides less time and space complexity. ^ Lastly, an integrated hardware and software system of the DiffServ model of QoS for WCDMA CN was proposed. It was implemented on the NP IXP2400. According to the corresponding experiment results, the proposed system significantly enhanced QoS for WCDMA CN. It extensively improves consistent response time, display distortion and sound image synchronization, and thus increases network efficiency and saves network resource.^

Field programmable gate array based target detection and gesture recognition

The move from Standard Definition (SD) to High Definition (HD) represents a six times increases in data, which needs to be processed. With expanding resolutions and evolving compression, there is a need for high performance with flexible architectures to allow for quick upgrade ability. The technology advances in image display resolutions, advanced compression techniques, and video intelligence. Software implementation of these systems can attain accuracy with tradeoffs among processing performance (to achieve specified frame rates, working on large image data sets), power and cost constraints. There is a need for new architectures to be in pace with the fast innovations in video and imaging. It contains dedicated hardware implementation of the pixel and frame rate processes on Field Programmable Gate Array (FPGA) to achieve the real-time performance. ^ The following outlines the contributions of the dissertation. (1) We develop a target detection system by applying a novel running average mean threshold (RAMT) approach to globalize the threshold required for background subtraction. This approach adapts the threshold automatically to different environments (indoor and outdoor) and different targets (humans and vehicles). For low power consumption and better performance, we design the complete system on FPGA. (2) We introduce a safe distance factor and develop an algorithm for occlusion occurrence detection during target tracking. A novel mean-threshold is calculated by motion-position analysis. (3) A new strategy for gesture recognition is developed using Combinational Neural Networks (CNN) based on a tree structure. Analysis of the method is done on American Sign Language (ASL) gestures. We introduce novel point of interests approach to reduce the feature vector size and gradient threshold approach for accurate classification. (4) We design a gesture recognition system using a hardware/ software co-simulation neural network for high speed and low memory storage requirements provided by the FPGA. We develop an innovative maximum distant algorithm which uses only 0.39% of the image as the feature vector to train and test the system design. Database set gestures involved in different applications may vary. Therefore, it is highly essential to keep the feature vector as low as possible while maintaining the same accuracy and performance^

Synthetic Approaches to Flexible Fluorescent Conjugated Polymers

Conjugated polymers (CPs) are intrinsically fluorescent materials that have been used for various biological applications including imaging, sensing, and delivery of biologically active substances. The synthetic control over flexibility and biodegradability of these materials aids the understanding of the structure-function relationships among the photophysical properties, the self-assembly behaviors of the corresponding conjugated polymer nanoparticles (CPNs), and the cellular behaviors of CPNs, such as toxicity, cellular uptake mechanisms, and sub-cellular localization patterns. Synthetic approaches towards two classes of flexible CPs with well-preserved fluorescent properties are described. The synthesis of flexible poly(p-phenylenebutadiynylene)s (PPBs) uses competing Sonogashira and Glaser coupling reactions and the differences in monomer reactivity to incorporate a small amount (~10%) of flexible, non-conjugated linkers into the backbone. The reaction conditions provide limited control over the proportion of flexible monomer incorporation. Improved synthetic control was achieved in a series of flexible poly(p-phenyleneethynylene)s (PPEs) using modified Sonogashira conditions. In addition to controlling the degree of flexibility, the linker provides disruption of backbone conjugation that offers control of the length of conjugated segments within the polymer chain. Therefore, such control also results in the modulation of the photophysical properties of the materials. CPNs fabricated from flexible PPBs are non-toxic to cells, and exhibit subcellular localization patterns clearly different from those observed with non-flexible PPE CPNs. The subcellular localization patterns of the flexible PPEs have not yet been determined, due to the toxicity of the materials, most likely related to the side-chain structure used in this series. The study of the effect of CP flexibility on self-assembly reorganization upon polyanion complexation is presented. Owing to its high rigidity and hydrophobicity, the PPB backbone undergoes reorganization more readily than PPE. The effects are enhanced in the presence of the flexible linker, which enables more efficient π-π stacking of the aromatic backbone segments. Flexibility has minimal effects on the self-assembly of PPEs. Understanding the role of flexibility on the biophysical behaviors of CPNs is key to the successful development of novel efficient fluorescent therapeutic delivery vehicles.

Flexible pavement layer moduli determination : an adaptive artificial neural network approach

The estimation of pavement layer moduli through the use of an artificial neural network is a new concept which provides a less strenuous strategy for backcalculation procedures. Artificial Neural Networks are biologically inspired models of the human nervous system. They are specifically designed to carry out a mapping characteristic. This study demonstrates how an artificial neural network uses non-destructive pavement test data in determining flexible pavement layer moduli. The input parameters include plate loadings, corresponding sensor deflections, temperature of pavement surface, pavement layer thicknesses and independently deduced pavement layer moduli.

Embedded Heat Pipes in Cofired Ceramic Substrates for Enhanced Thermal Management of Electronics

A novel and new thermal management technology for advanced ceramic microelectronic packages has been developed incorporating miniature heat pipes embedded in the ceramic substrate. The heat pipes use an axially grooved wick structure and water as the working fluid. Prototype substrate/heat pipe systems were fabricated using high temperature co-fired ceramic (alumina). The heat pipes were nominally 81 mm in length, 10 mm in width, and 4 mm in height, and were charged with approximately 50-80 mL of water. Platinum thick film heaters were fabricated on the surface of the substrate to simulate heat dissipating electronic components. Several thermocouples were affixed to the substrate to monitor temperature. One end of the substrate was affixed to a heat sink maintained at constant temperature. The prototypes were tested and shown to successful and reliably operate with thermal loads over 20 Watts, with thermal input from single and multiple sources along the surface of the substrate. Temperature distributions are discussed for the various configurations and the effective thermal resistance of the substrate/heat pipe system is calculated. Finite element analysis was used to support the experimental findings and better understand the sources of the system's thermal resistance.

Improved Electronics for the Hall A Detectors at JLab: Summing Modules and VDC Amplifier/Discriminator Cards

Testing of summing electronics and VDC A/D Cards was performed to assure proper functioning and operation within defined parameters. In both the summing modules and the VDC A/D cards, testing for minimum threshold voltage for each channel and crosstalk between neighboring channels was performed. Additionally, the modules were installed in Hall A with input signals from shower detectors arranged to establish a trigger by summing signals together with the use of tested modules. Testing involved utilizing a pulser to mimic PMT signals, a discriminator, an attenuator, a scaler, a level translator, an oscilloscope, a high voltage power supply, and a special apparatus used to power and send signal to the A/D cards. After testing, modules were obtained that meet necessary criteria for use in the APEX experiment, and the A/D cards obtained were determined to have adequate specifications for their utilization, with specific results included in the appendix.

Synthetic approaches to flexible fluorescent conjugated polymers

Conjugated polymers (CPs) are intrinsically fluorescent materials that have been used for various biological applications including imaging, sensing, and delivery of biologically active substances. The synthetic control over flexibility and biodegradability of these materials aids the understanding of the structure-function relationships among the photophysical properties, the self-assembly behaviors of the corresponding conjugated polymer nanoparticles (CPNs), and the cellular behaviors of CPNs, such as toxicity, cellular uptake mechanisms, and sub-cellular localization patterns. ^ Synthetic approaches towards two classes of flexible CPs with well-preserved fluorescent properties are described. The synthesis of flexible poly( p-phenylenebutadiynylene)s (PPBs) uses competing Sonogashira and Glaser coupling reactions and the differences in monomer reactivity to incorporate a small amount (∼10%) of flexible, non-conjugated linkers into the backbone. The reaction conditions provide limited control over the proportion of flexible monomer incorporation. Improved synthetic control was achieved in a series of flexible poly(p-phenyleneethynylene)s (PPEs) using modified Sonogashira conditions. In addition to controlling the degree of flexibility, the linker provides disruption of backbone conjugation that offers control of the length of conjugated segments within the polymer chain. Therefore, such control also results in the modulation of the photophysical properties of the materials. ^ CPNs fabricated from flexible PPBs are non-toxic to cells, and exhibit subcellular localization patterns clearly different from those observed with non-flexible PPE CPNs. The subcellular localization patterns of the flexible PPEs have not yet been determined, due to the toxicity of the materials, most likely related to the side-chain structure used in this series. ^ The study of the effect of CP flexibility on self-assembly reorganization upon polyanion complexation is presented. Owing to its high rigidity and hydrophobicity, the PPB backbone undergoes reorganization more readily than PPE. The effects are enhanced in the presence of the flexible linker, which enables more efficient π-π stacking of the aromatic backbone segments. Flexibility has minimal effects on the self-assembly of PPEs. Understanding the role of flexibility on the biophysical behaviors of CPNs is key to the successful development of novel efficient fluorescent therapeutic delivery vehicles.^

Bionano Electronics: Magneto-Electric Nanoparticles for Drug Delivery, Brain Stimulation and Imaging Applications

Nanoparticles are often considered as efficient drug delivery vehicles for precisely dispensing the therapeutic payloads specifically to the diseased sites in the patient’s body, thereby minimizing the toxic side effects of the payloads on the healthy tissue. However, the fundamental physics that underlies the nanoparticles’ intrinsic interaction with the surrounding cells is inadequately elucidated. The ability of the nanoparticles to precisely control the release of its payloads externally (on-demand) without depending on the physiological conditions of the target sites has the potential to enable patient- and disease-specific nanomedicine, also known as Personalized NanoMedicine (PNM). In this dissertation, magneto-electric nanoparticles (MENs) were utilized for the first time to enable important functions, such as (i) field-controlled high-efficacy dissipation-free targeted drug delivery system and on-demand release at the sub-cellular level, (ii) non-invasive energy-efficient stimulation of deep brain tissue at body temperature, and (iii) a high-sensitivity contrasting agent to map the neuronal activity in the brain non-invasively. First, this dissertation specifically focuses on using MENs as energy-efficient and dissipation-free field-controlled nano-vehicle for targeted delivery and on-demand release of a anti-cancer Paclitaxel (Taxol) drug and a anti-HIV AZT 5’-triphosphate (AZTTP) drug from 30-nm MENs (CoFe2O4-BaTiO3) by applying low-energy DC and low-frequency (below 1000 Hz) AC fields to separate the functions of delivery and release, respectively. Second, this dissertation focuses on the use of MENs to non-invasively stimulate the deep brain neuronal activity via application of a low energy and low frequency external magnetic field to activate intrinsic electric dipoles at the cellular level through numerical simulations. Third, this dissertation describes the use of MENs to track the neuronal activities in the brain (non-invasively) using a magnetic resonance and a magnetic nanoparticle imaging by monitoring the changes in the magnetization of the MENs surrounding the neuronal tissue under different states. The potential therapeutic and diagnostic impact of this innovative and novel study is highly significant not only in HIV-AIDS, Cancer, Parkinson’s and Alzheimer’s disease but also in many CNS and other diseases, where the ability to remotely control targeted drug delivery/release, and diagnostics is the key.