Growth, modification and integration of carbon nanotubes into molecular electronics

Molecules are the smallest possible elements for electronic devices, with active elements for such devices typically a few Angstroms in footprint area. Owing to the possibility of producing ultrahigh density devices, tremendous effort has been invested in producing electronic junctions by using various types of molecules. The major issues for molecular electronics include (1) developing an effective scheme to connect molecules with the present micro- and nano-technology, (2) increasing the lifetime and stabilities of the devices, and (3) increasing their performance in comparison to the state-of-the-art devices. In this work, we attempt to use carbon nanotubes (CNTs) as the interconnecting nanoelectrodes between molecules and microelectrodes. The ultimate goal is to use two individual CNTs to sandwich molecules in a cross-bar configuration while having these CNTs connected with microelectrodes such that the junction displays the electronic character of the molecule chosen. We have successfully developed an effective scheme to connect molecules with CNTs, which is scalable to arrays of molecular electronic devices. To realize this far reaching goal, the following technical topics have been investigated. 1. Synthesis of multi-walled carbon nanotubes (MWCNTs) by thermal chemical vapor deposition (T-CVD) and plasma-enhanced chemical vapor deposition (PECVD) techniques (Chapter 3). We have evaluated the potential use of tubular and bamboo-like MWCNTs grown by T-CVD and PE-CVD in terms of their structural properties. 2. Horizontal dispersion of MWCNTs with and without surfactants, and the integration of MWCNTs to microelectrodes using deposition by dielectrophoresis (DEP) (Chapter 4). We have systematically studied the use of surfactant molecules to disperse and horizontally align MWCNTs on substrates. In addition, DEP is shown to produce impurityfree placement of MWCNTs, forming connections between microelectrodes. We demonstrate the deposition density is tunable by both AC field strength and AC field frequency. 3. Etching of MWCNTs for the impurity-free nanoelectrodes (Chapter 5). We show that the residual Ni catalyst on MWCNTs can be removed by acid etching; the tip removal and collapsing of tubes into pyramids enhances the stability of field emission from the tube arrays. The acid-etching process can be used to functionalize the MWCNTs, which was used to make our initial CNT-nanoelectrode glucose sensors. Finally, lessons learned trying to perform spectroscopic analysis of the functionalized MWCNTs were vital for designing our final devices. 4. Molecular junction design and electrochemical synthesis of biphenyl molecules on carbon microelectrodes for all-carbon molecular devices (Chapter 6). Utilizing the experience gained on the work done so far, our final device design is described. We demonstrate the capability of preparing patterned glassy carbon films to serve as the bottom electrode in the new geometry. However, the molecular switching behavior of biphenyl was not observed by scanning tunneling microscopy (STM), mercury drop or fabricated glassy carbon/biphenyl/MWCNT junctions. Either the density of these molecules is not optimum for effective integration of devices using MWCNTs as the nanoelectrodes, or an electroactive contaminant was reduced instead of the ionic biphenyl species. 5. Self-assembly of octadecanethiol (ODT) molecules on gold microelectrodes for functional molecular devices (Chapter 7). We have realized an effective scheme to produce Au/ODT/MWCNT junctions by spanning MWCNTs across ODT-functionalized microelectrodes. A percentage of the resulting junctions retain the expected character of an ODT monolayer. While the process is not yet optimized, our successful junctions show that molecular electronic devices can be fabricated using simple processes such as photolithography, self-assembled monolayers and dielectrophoresis.

Fixed block configuration GDDs with block size 6 and (3, r)-regular graphs

Chapter 1 is used to introduce the basic tools and mechanics used within this thesis. Most of the definitions used in the thesis will be defined, and we provide a basic survey of topics in graph theory and design theory pertinent to the topics studied in this thesis. In Chapter 2, we are concerned with the study of fixed block configuration group divisible designs, GDD(n; m; k; λ1; λ2). We study those GDDs in which each block has configuration (s; t), that is, GDDs in which each block has exactly s points from one of the two groups and t points from the other. Chapter 2 begins with an overview of previous results and constructions for small group size and block sizes 3, 4 and 5. Chapter 2 is largely devoted to presenting constructions and results about GDDs with two groups and block size 6. We show the necessary conditions are sufficient for the existence of GDD(n, 2, 6; λ1, λ2) with fixed block configuration (3; 3). For configuration (1; 5), we give minimal or nearminimal index constructions for all group sizes n ≥ 5 except n = 10, 15, 160, or 190. For configuration (2, 4), we provide constructions for several families ofGDD(n, 2, 6; λ1, λ2)s. Chapter 3 addresses characterizing (3, r)-regular graphs. We begin with providing previous results on the well studied class of (2, r)-regular graphs and some results on the structure of large (t; r)-regular graphs. In Chapter 3, we completely characterize all (3, 1)-regular and (3, 2)-regular graphs, as well has sharpen existing bounds on the order of large (3, r)- regular graphs of a certain form for r ≥ 3. Finally, the appendix gives computational data resulting from Sage and C programs used to generate (3, 3)-regular graphs on less than 10 vertices.

Experimental and theoretical study of microstructure effect on piezoelectric property of one dimensional ZnO nanostructures

Emerging nanogenerators have attracted the attention of the research community, focusing on energy generation using piezoelectric nanomaterials. Nanogenerators can be utilized for powering NEMS/MEMS devices. Understanding the piezoelectric properties of ZnO one-dimensional materials such as ZnO nanobelts (NBs) and Nanowires (NWs) can have a significant impact on the design of new devices. The goal of this dissertation is to study the piezoelectric properties of one-dimensional ZnO nanostructures both experimentally and theoretically. First, the experimental procedure for producing the ZnO nanostructures is discussed. The produced ZnO nanostructures were characterized using an in-situ atomic force microscope and a piezoelectric force microscope. It is shown that the electrical conductivity of ZnO NBs is a function of applied mechanical force and its crystalline structure. This phenomenon was described in the context of formation of an electric field due to the piezoelectric property of ZnO NBs. In the PFM studies, it was shown that the piezoelectric response of the ZnO NBs depends on their production method and presence of defects in the NB. Second, a model was proposed for making nanocomposite electrical generators based on ZnO nanowires. The proposed model has advantages over the original configuration of nanogenerators which uses an AFM tip for bending the ZnO NWs. Higher stability of the electric source, capability for producing larger electric fields, and lower production costs are advantages of this configuration. Finally, piezoelectric properties of ZnO NBs were simulated using the molecular dynamics (MD) technique. The size-scale effect on piezoelectric properties of ZnO NBs was captured, and it is shown that the piezoelectric coefficient of ZnO NBs decreases by increasing their lateral dimensions. This phenomenon is attributed to the surface charge redistribution and compression of unit cells that are placed on the outer shell of ZnO NBs.

MODELING AND PROTOCOL DESIGN FOR EMERGING WIRELESS SYSTEMS

Mobile Mesh Network based In-Transit Visibility (MMN-ITV) system facilitates global real-time tracking capability for the logistics system. In-transit containers form a multi-hop mesh network to forward the tracking information to the nearby sinks, which further deliver the information to the remote control center via satellite. The fundamental challenge to the MMN-ITV system is the energy constraint of the battery-operated containers. Coupled with the unique mobility pattern, cross-MMN behavior, and the large-spanned area, it is necessary to investigate the energy-efficient communication of the MMN-ITV system thoroughly. First of all, this dissertation models the energy-efficient routing under the unique pattern of the cross-MMN behavior. A new modeling approach, pseudo-dynamic modeling approach, is proposed to measure the energy-efficiency of the routing methods in the presence of the cross-MMN behavior. With this approach, it could be identified that the shortest-path routing and the load-balanced routing is energy-efficient in mobile networks and static networks respectively. For the MMN-ITV system with both mobile and static MMNs, an energy-efficient routing method, energy-threshold routing, is proposed to achieve the best tradeoff between them. Secondly, due to the cross-MMN behavior, neighbor discovery is executed frequently to help the new containers join the MMN, hence, consumes similar amount of energy as that of the data communication. By exploiting the unique pattern of the cross-MMN behavior, this dissertation proposes energy-efficient neighbor discovery wakeup schedules to save up to 60% of the energy for neighbor discovery. Vehicular Ad Hoc Networks (VANETs)-based inter-vehicle communications is by now growingly believed to enhance traffic safety and transportation management with low cost. The end-to-end delay is critical for the time-sensitive safety applications in VANETs, and can be a decisive performance metric for VANETs. This dissertation presents a complete analytical model to evaluate the end-to-end delay against the transmission range and the packet arrival rate. This model illustrates a significant end-to-end delay increase from non-saturated networks to saturated networks. It hence suggests that the distributed power control and admission control protocols for VANETs should aim at improving the real-time capacity (the maximum packet generation rate without causing saturation), instead of the delay itself. Based on the above model, it could be determined that adopting uniform transmission range for every vehicle may hinder the delay performance improvement, since it does not allow the coexistence of the short path length and the low interference. Clusters are proposed to configure non-uniform transmission range for the vehicles. Analysis and simulation confirm that such configuration can enhance the real-time capacity. In addition, it provides an improved trade off between the end-to-end delay and the network capacity. A distributed clustering protocol with minimum message overhead is proposed, which achieves low convergence time.

Translation Studies on an Annular Field Reversed Configuration Device for Space Propulsion

This research investigated annular field reversed configuration (AFRC)devices for high power electric propulsion by demonstrating the acceleration of these plasmoids using an experimental prototype and measuring the plasmoid's velocity, impulse, and energy efficiency. The AFRC plasmoid translation experiment was design and constructed with the aid of a dynamic circuit model. Two versions of the experiment were built, using underdamped RLC circuits at 10 kHz and 20 kHz. Input energies were varied from 100 J/pulse to 1000 J/pulse for the 10 kHz bank and 100 J/pulse for the 20 kHz bank. The plasmoids were formed in static gas fill of argon, from 1 mTorr to 50 mTorr. The translation of the plasmoid was accomplished by incorporating a small taper into the outer coil, with a half angle of 2°. Magnetic field diagnostics, plasma probes, and single-frame imaging were used to measure the plasmoid's velocity and to diagnose plasmoid behavior. Full details of the device design, construction, and diagnostics are provided in this dissertation. The results from the experiment demonstrated that a repeatable AFRC plasmoid was produced between the coils, yet failed to translate for all tested conditions. The data revealed the plasmoid was limited in lifetime to only a few (4-10) μs, too short for translation at low energy. A global stability study showed that the plasma suffered a radial collapse onto the inner wall early in its lifecycle. The radial collapse was traced to a magnetic pressure imbalance. A correction made to the circuit was successful in restoring an equilibrium pressure balance and prolonging radial stability by an additional 2.5 μs. The equilibrium state was sufficient to confirm that the plasmoid current in an AFRC reaches a steady-state prior to the peak of the coil currents. This implies that the plasmoid will always be driven to the inner wall, unless it translates from the coils prior to peak coil currents. However, ejection of the plasmoid before the peak coil currents results in severe efficiency losses. These results demonstrate the difficulty in designing an AFRC experiment for translation as balancing the different requirements for stability, balance, and efficient translation can have competing consequences.