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.

Biological materials : Part A. tuning LCST of raft copolymers and gold/copolymer hybrid nanoparticles and Part B. biobased nanomaterials

The research described in this dissertation is comprised of two major parts. The first part studied the effects of asymmetric amphiphilic end groups on the thermo-response of diblock copolymers of (oligo/di(ethylene glycol) methyl ether (meth)acrylates, OEGA/DEGMA) and the hybrid nanoparticles of these copolymers with a gold nanoparticle core. Placing the more hydrophilic end group on the more hydrophilic block significantly increased the cloud point compared to a similar copolymer composition with the end group placement reversed. For a given composition, the cloud point was shifted by as much as 28 °C depending on the placement of end groups. This is a much stronger effect than either changing the hydrophilic/hydrophobic block ratio or replacing the hydrophilic acrylate monomer with the equivalent methacrylate monomer. The temperature range of the coil-globule transition was also altered. Binding these diblock copolymers to a gold core decreased the cloud point by 5-15 °C and narrowed the temperature range of the coil-globule transition. The effects were more pronounced when the gold core was bound to the less hydrophilic block. Given the limited numbers of monomers that are approved safe for in vivo use, employing amphiphilic end group placement is a useful tool to tune a thermo-response without otherwise changing the copolymer composition. The second part of the dissertation investigated the production of value-added nanomaterials from two biorefinery “wastes”: lignin and peptidoglycan. Different solvents and spinning methods (melt-, wet-, and electro-spinning) were tested to make lignin/cellulose blended and carbonized fibers. Only electro-spinning yielded fibers having a small enough diameter for efficient carbonization ( Peptidoglycan (a bacterial cell wall material) was copolymerized with poly-(3-hydroxybutyrate), a common polyhydroxyalkanoate produced by bacteria with the objective of determining if a useful material could be obtained with a less rigorous work-up on harvesting polyhydroxyalkanoates. The copolyesteramide product having 25 wt.% peptidoglycan from a highly purified peptidoglycan increased thermal stability by 100-200 °C compared to the poly-(3-hydroxybutyrate) control, while a less pure peptidoglycan, harvested from B. megaterium (ATCC 11561), gave a 25-50 °C increase in thermal stability. Both copolymers absorbed more moisture than pure poly-(3-hydroxybutyrate). The results suggest that a less rigorously harvested and purified polyhydroxyalkanoate might be useful for some applications.

Bluetooth Enabled Ad-hoc Networks: Performance Evaluation of a Self-healing Scatternet Formation Protocol

Bluetooth wireless technology is a robust short-range communications system designed for low power (10 meter range) and low cost. It operates in the 2.4 GHz Industrial Scientific Medical (ISM) band and it employs two techniques for minimizing interference: a frequency hopping scheme which nominally splits the 2.400 - 2.485 GHz band in 79 frequency channels and a time division duplex (TDD) scheme which is used to switch to a new frequency channel on 625 μs boundaries. During normal operation a Bluetooth device will be active on a different frequency channel every 625 μs, thus minimizing the chances of continuous interference impacting the performance of the system. The smallest unit of a Bluetooth network is called a piconet, and can have a maximum of eight nodes. Bluetooth devices must assume one of two roles within a piconet, master or slave, where the master governs quality of service and the frequency hopping schedule within the piconet and the slave follows the master’s schedule. A piconet must have a single master and up to 7 active slaves. By allowing devices to have roles in multiple piconets through time multiplexing, i.e. slave/slave or master/slave, the Bluetooth technology allows for interconnecting multiple piconets into larger networks called scatternets. The Bluetooth technology is explored in the context of enabling ad-hoc networks. The Bluetooth specification provides flexibility in the scatternet formation protocol, outlining only the mechanisms necessary for future protocol implementations. A new protocol for scatternet formation and maintenance - mscat - is presented and its performance is evaluated using a Bluetooth simulator. The free variables manipulated in this study include device activity and the probabilities of devices performing discovery procedures. The relationship between the role a device has in the scatternet and it’s probability of performing discovery was examined and related to the scatternet topology formed. The results show that mscat creates dense network topologies for networks of 30, 50 and 70 nodes. The mscat protocol results in approximately a 33% increase in slaves/piconet and a reduction of approximately 12.5% of average roles/node. For 50 node scenarios the set of parameters which creates the best determined outcome is unconnected node inquiry probability (UP) = 10%, master node inquiry probability (MP) = 80% and slave inquiry probability (SP) = 40%. The mscat protocol extends the Bluetooth specification for formation and maintenance of scatternets in an ad-hoc network.

PROOF OF CONCEPT PROTOTYPE FOR A RAILROAD PEDESTRIAN WARNING SYSTEM USING WIRELESS SENSOR NETWORKS

Wireless sensor network is an emerging research topic due to its vast and ever-growing applications. Wireless sensor networks are made up of small nodes whose main goal is to monitor, compute and transmit data. The nodes are basically made up of low powered microcontrollers, wireless transceiver chips, sensors to monitor their environment and a power source. The applications of wireless sensor networks range from basic household applications, such as health monitoring, appliance control and security to military application, such as intruder detection. The wide spread application of wireless sensor networks has brought to light many research issues such as battery efficiency, unreliable routing protocols due to node failures, localization issues and security vulnerabilities. This report will describe the hardware development of a fault tolerant routing protocol for railroad pedestrian warning system. The protocol implemented is a peer to peer multi-hop TDMA based protocol for nodes arranged in a linear zigzag chain arrangement. The basic working of the protocol was derived from Wireless Architecture for Hard Real-Time Embedded Networks (WAHREN).

DESIGN OF EFFICIENT IN-NETWORK DATA PROCESSING AND DISSEMINATION FOR VANETS

By providing vehicle-to-vehicle and vehicle-to-infrastructure wireless communications, vehicular ad hoc networks (VANETs), also known as the “networks on wheels”, can greatly enhance traffic safety, traffic efficiency and driving experience for intelligent transportation system (ITS). However, the unique features of VANETs, such as high mobility and uneven distribution of vehicular nodes, impose critical challenges of high efficiency and reliability for the implementation of VANETs. This dissertation is motivated by the great application potentials of VANETs in the design of efficient in-network data processing and dissemination. Considering the significance of message aggregation, data dissemination and data collection, this dissertation research targets at enhancing the traffic safety and traffic efficiency, as well as developing novel commercial applications, based on VANETs, following four aspects: 1) accurate and efficient message aggregation to detect on-road safety relevant events, 2) reliable data dissemination to reliably notify remote vehicles, 3) efficient and reliable spatial data collection from vehicular sensors, and 4) novel promising applications to exploit the commercial potentials of VANETs. Specifically, to enable cooperative detection of safety relevant events on the roads, the structure-less message aggregation (SLMA) scheme is proposed to improve communication efficiency and message accuracy. The scheme of relative position based message dissemination (RPB-MD) is proposed to reliably and efficiently disseminate messages to all intended vehicles in the zone-of-relevance in varying traffic density. Due to numerous vehicular sensor data available based on VANETs, the scheme of compressive sampling based data collection (CS-DC) is proposed to efficiently collect the spatial relevance data in a large scale, especially in the dense traffic. In addition, with novel and efficient solutions proposed for the application specific issues of data dissemination and data collection, several appealing value-added applications for VANETs are developed to exploit the commercial potentials of VANETs, namely general purpose automatic survey (GPAS), VANET-based ambient ad dissemination (VAAD) and VANET based vehicle performance monitoring and analysis (VehicleView). Thus, by improving the efficiency and reliability in in-network data processing and dissemination, including message aggregation, data dissemination and data collection, together with the development of novel promising applications, this dissertation will help push VANETs further to the stage of massive deployment.

Waterpower : a geophysical and archaeological investigation of the waterpower system at the West Point Foundry, Cold Spring, New York

Waterpower: A Geophysical and Archaeological Investigation of the Waterpower System at the West Point Foundry, Cold Spring, New York, describes the results of ground penetrating radar surveys and archaeological excavation undertaken by Michigan Technological University (MTU) archaeologists during the summer of 2003 at the West Point Foundry, Cold Spring, New York. 2003 constituted MTU's second field season at the foundry. Fieldwork concentrated on the foundry's waterpower system, an intricate network of surface and subsurface drains, races, flumes, waterwheels, turbines, dams, and ponds that powered operations and regulated water flow throughout the site. Archaeologists utilized non-destructive geophysical technology, which expedited survey, facilitated placement of excavation units, and provided a model for future archaeogeophysical research at industrial sites. Features discovered during excavation provided valuable information pertaining to the waterpower system's construction and its functions. Data from ground penetrating radar surveys, archaeological excavation, historical photographs, documents, and maps permitted the development of a provisional chronology of the development of various components of the West Point Foundry's waterpower system. Information gathered during this project serves as an aid in sit interpretation and rehabilitation.