Mechanical and electrical properties of single-walled carbon nanotubes synthesized by chemical vapor deposition

Despite the tremendous application potentials of carbon nanotubes (CNTs) proposed by researchers in the last two decades, efficient experimental techniques and methods are still in need for controllable production of CNTs in large scale, and for conclusive characterizations of their properties in order to apply CNTs in high accuracy engineering. In this dissertation, horizontally well-aligned high quality single-walled carbon nanotubes (SWCNTs) have been successfully synthesized on St-cut quartz substrate by chemical vapor deposition (CVD). Effective radial moduli (Eradial) of these straight SWCNTs have been measured by using well-calibrated tapping mode and contact mode atomic force microscopy (AFM). It was found that the measured Eradial decreased from 57 to 9 GPa as the diameter of the SWCNTs increased from 0.92 to 1.91 nm. The experimental results were consistent with the recently reported theoretical simulation data. The method used in this mechanical property test can be easily applied to measure the mechanical properties of other low-dimension nanostructures, such as nanowires and nanodots. The characterized sample is also an ideal platform for electrochemical tests. The electrochemical activities of redox probes Fe(CN)63-/4-, Ru(NH3) 63+, Ru(bpy)32+ and protein cytochrome c have been studied on these pristine thin films by using aligned SWCNTs as working electrodes. A simple and high performance electrochemical sensor was fabricated. Flow sensing capability of the device has been tested for detecting neurotransmitter dopamine at physiological conditions with the presence of Bovine serum albumin. Good sensitivity, fast response, high stability and anti-fouling capability were observed. Therefore, the fabricated sensor showed great potential for sensing applications in complicated solution.^

Mechanical and Electrical Properties of Single-walled Carbon Nanotubes Synthesized by Chemical Vapor Deposition

Despite the tremendous application potentials of carbon nanotubes (CNTs) proposed by researchers in the last two decades, efficient experimental techniques and methods are still in need for controllable production of CNTs in large scale, and for conclusive characterizations of their properties in order to apply CNTs in high accuracy engineering. In this dissertation, horizontally well-aligned high quality single-walled carbon nanotubes (SWCNTs) have been successfully synthesized on St-cut quartz substrate by chemical vapor deposition (CVD). Effective radial moduli (Eradial) of these straight SWCNTs have been measured by using well-calibrated tapping mode and contact mode atomic force microscopy (AFM). It was found that the measured Eradial decreased from 57 to 9 GPa as the diameter of the SWCNTs increased from 0.92 to 1.91 nm. The experimental results were consistent with the recently reported theoretical simulation data. The method used in this mechanical property test can be easily applied to measure the mechanical properties of other low-dimension nanostructures, such as nanowires and nanodots. The characterized sample is also an ideal platform for electrochemical tests. The electrochemical activities of redox probes Fe(CN)63-/4-, Ru(NH3)63+, Ru(bpy)32+ and protein cytochrome c have been studied on these pristine thin films by using aligned SWCNTs as working electrodes. A simple and high performance electrochemical sensor was fabricated. Flow sensing capability of the device has been tested for detecting neurotransmitter dopamine at physiological conditions with the presence of Bovine serum albumin. Good sensitivity, fast response, high stability and anti-fouling capability were observed. Therefore, the fabricated sensor showed great potential for sensing applications in complicated solution.

Controlled growth of carbon nanotubes for high performance nanoelectronics

Unique electrical and mechanical properties of single-walled carbon nanotubes (SWNTs) have made them one of the most promising candidates for next-generation nanoelectronics. Efficient utilization of the exceptional properties of SWNTs requires controlling their growth direction (e.g., vertical, horizontal) and morphologies (e.g., straight, junction, coiled). ^ In this dissertation, the catalytic effect on the branching of SWNTs, Y-shaped SWNTs (Y-SWNTs), was investigated. The formation of Y-shaped branches was found to be dependent on the composition of the catalysts. Easier carbide formers have a strong tendency to attach to the sidewall of SWNTs and thus enhance the degree of branching. Y-SWNTs based field-effect transistors (FETs) were fabricated and modulated by the metallic branch of the Y-SWNTs, exhibiting ambipolar characteristics at room temperature. A subthreshold swing of 700 mV/decade and an on/off ratio of 105 with a low off-state current of 10-13 A were obtained. The transport phenomena associated with Y- and cross-junction configurations reveals that the conduction mechanism in the SWNT junctions is governed by thermionic emission at T > 100 K and by tunneling at T < 100 K. ^ Furthermore, horizontally aligned SWNTs were synthesized by the controlled modification of external fields and forces. High performance carbon nanotube FETs and logic circuit were demonstrated utilizing the aligned SWNTs. It is found that the hysteresis in CNTFETs can be eliminated by removing absorbed water molecules on the CNT/SiO2 interface by vacuum annealing, hydrophobic surface treatment, and surface passivation. SWNT “serpentines” were synthesized by utilization of the interaction between drag force from gas flow and Van der Waals force with substrates. The curvature of bent SWNTs could be tailored by adjusting the gas flow rate, and changing the gas flow direction with respect to the step-edges on a single-crystal quartz substrate. Resistivity of bent SWNTs was observed to increase with curvature, which can be attributed to local deformations and possible chirality shift at curved part. ^ Our results show the successful synthesis of SWNTs having controllable morphologies and directionality. The capability of tailoring the electrical properties of SWNTs makes it possible to build an all-nanotube device by integrating SWNTs, having different functionalities, into complex circuits. ^

Synthesis of copper carbon nanotube composite and its electrical conductivity measurement

The matrices in which Multi Walled Carbon Nanotubes (MWCNTs) are incorporated to produce composites with improved electrical properties can be polymer, metal or metal oxide. Most composites containing CNTs are polymer based because of its flexibility in fabrication. Very few investigations have been focused on CNT-metal composites due to fabrication difficulties, such as achievement of homogeneous distribution of MWCNTs and poor interfacial bonding between MWCNTs and the metal matrix. In an effort to overcome poor interfacial bonding for the Cu - MWCNT composite, silver (Ag) and nickel (Ni) resinates have been incorporated in the ball milling stage. Composites of MWCNT (16, 12, and 8 Vol %) - Cu+Ag+Ni were pelleted at 20,000 psi (669.4 Mpa) and sintered at 950 °C. The electrical conductivity results measured by four probe meter showed that the conductivity decreases with increase in the porosity. Moreover from these results it can also be stated that an addition of optimum value of (12 Vol %) MWCNT leads to high electrical conductivity (9.26E+07 s-m"), which is 50% greater than the conductivity of Cu. It is anticipated that the conductivity can be increased substantially with hot isostatic pressing of the pellet.

Carbon nanotube reinforced aluminum based nanocomposite fabricated by thermal spray forming

The present research concentrates on the fabrication of bulk aluminum matrix nanocomposite structures with carbon nanotube reinforcement. The objective of the work was to fabricate and characterize multi-walled carbon nanotube (MWCNT) reinforced hypereutectic Al-Si (23 wt% Si, 2 wt% Ni, 1 wt% Cu, rest Al) nanocomposite bulk structure with nanocrystalline matrix through thermal spray forming techniques viz. plasma spray forming (PSF) and high velocity oxy-fuel (HVOF) spray forming. This is the first research study, which has shown that thermal spray forming can be successfully used to synthesize carbon nanotube reinforced nanocomposites. Microstructural characterization based on quantitative microscopy, scanning and transmission electron microscopy (SEM and TEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), Raman spectroscopy and X ray photoelectron spectroscopy (XPS) confirms (i) retention and macro/sub-macro level homogenous distribution of multiwalled carbon nanotubes in the Al-Si matrix and (ii) evolution of nanostructured grains in the matrix. Formation of ultrathin β-SiC layer on MWCNT surface, due to chemical reaction of Si atoms diffusing from Al-Si alloy and C atoms from the outer walls of MWCNTs has been confirmed theoretically and experimentally. The presence of SiC layer at the interface improves the wettability and the interfacial adhesion between the MWCNT reinforcement and the Al-Si matrix. Sintering of the as-sprayed nanocomposites was carried out in an inert environment for further densification. As-sprayed PSF nanocomposite showed lower microhardness compared to HVOF, due to the higher porosity content and lower residual stress. The hardness of the nanocomposites increased with sintering time due to effective pore removal. Uniaxial tensile test on CNT-bulk nanocomposite was carried out, which is the first ever study of such nature. The tensile test results showed inconsistency in the data attributed to inhomogeneous microstructure and limitation of the test samples geometry. The elastic moduli of nanocomposites were computed using different micromechanics models and compared with experimentally measured values. The elastic moduli of nanocomposites measured by nanoindentation technique, increased gradually with sintering attributed to porosity removal. The experimentally measured values conformed better with theoretically predicted values, particularly in the case of Hashin-Shtrikman bound method.

Electrical Transport Properties of Multilayered Single-Walled Carbon Nanotube Films

An improved layer-by-layer vacuum filtration method was adopted for the fabrication of single-walled carbon nanotube (SWCNT) films aiming at a series of SWCNT films with controllable thickness and density. The electrical transport properties of the multilayered SWCNT films have been investigated. With the constant film density, the decrease of the layer number of the SWCNT film results in an increase of the temperature coefficient of resistance (TCR). SWCNT film with 95% metallic nanotubes has shown a lower TCR than that of the SWCNT films with a low percentage of metallic nanotubes. The effect of thermal annealing and subsequent acid (HNO3) treatment on the electrical properties of the SWCNT films has also been investigated.

Study of carbon nanotube film and shape memory alloys treatment for sensing and structural vibration control

Structural vibration control is of great importance. Current active and passive vibration control strategies usually employ individual elements to fulfill this task, such as viscoelastic patches for providing damping, transducers for picking up signals and actuators for inputting actuating forces. The goal of this dissertation work is to design, manufacture, investigate and apply a new type of multifunctional composite material for structural vibration control. This new composite, which is based on multi-walled carbon nanotube (MWCNT) film, is potentially to function as free layer damping treatment and strain sensor simultaneously. That is, the new material integrates the transducer and the damping patch into one element. The multifunctional composite was prepared by sandwiching the MWCNT film between two adhesive layers. Static sensing test indicated that the MWCNT film sensor resistance changes almost linearly with the applied load. Sensor sensitivity factors were comparable to those of the foil strain gauges. Dynamic test indicated that the MWCNT film sensor can outperform the foil strain gage in high frequency ranges. Temperature test indicated the MWCNT sensor had good temperature stability over the range of 237 K-363 K. The Young’s modulus and shear modulus of the MWCNT film composite were acquired by nanoindentation test and direct shear test, respectively. A free vibration damping test indicated that the MWCNT composite sensor can also provide good damping without adding excessive weight to the base structure. A new model for sandwich structural vibration control was then proposed. In this new configuration, a cantilever beam covered with MWCNT composite on top and one layer of shape memory alloy (SMA) on the bottom was used to illustrate this concept. The MWCNT composite simultaneously serves as free layer damping and strain sensor, and the SMA acts as actuator. Simple on-off controller was designed for controlling the temperature of the SMA so as to control the SMA recovery stress as input and the system stiffness. Both free and forced vibrations were analyzed. Simulation work showed that this new configuration for sandwich structural vibration control was successful especially for low frequency system.

Functionalized carbon nanotube nanoelectrodes for biomolecular recognition

The objective of this research is to develop nanoscale ultrasensitive transducers for detection of biological species at molecular level using carbon nanotubes as nanoelectrodes. Rapid detection of ultra low concentration or even single DNA molecules are essential for medical diagnosis and treatment, pharmaceutical applications, gene sequencing as well as forensic analysis. Here the use of functionalized single walled carbon nanotubes (SWNT) as nanoscale detection platform for rapid detection of single DNA molecules is demonstrated. The detection principle is based on obtaining electrical signal from a single amine terminated DNA molecule which is covalently bridged between two ends of an SWNT separated by a nanoscale gap. The synthesis, fabrication, chemical functionalization of nanoelectrodes and DNA attachment were optimized to perform reliable electrical characterization these molecules. Using this detection system fundamental study on charge transport in DNA molecule of both genomic and non genomic sequences is performed. We measured an electrical signal of about 30 pA through a hybridized DNA molecule of 80 base pair in length which encodes a portion of sequence of H5N1 gene of avian Influenza A virus. Due the dynamic nature of the DNA molecules the local environment such as ion concentration, pH and temperature significantly influence its physical properties. We observed a decrease in DNA conductance of about 33% in high vacuum conditions. The counterion variation was analyzed by changing the buffer from sodium acetate to tris(hydroxymethyl) aminomethane, which resulted in a two orders of magnitude increase in the conductivity of the DNA. The fabrication of large array of identical SWNT nanoelectrodes was achieved by using ultralong SWNTs. Using these nanoelectrode array we have investigated the sequence dependent charge transport in DNA. A systematic study performed on PolyG - PolyC sequence with varying number of intervening PolyA - PolyT pairs showed a decrease in electrical signal from 180 pA (PolyG - PolyC) to 30 pA with increasing number of the PolyA - PolyT pairs. This work also led to the development of ultrasensitive nanoelectrodes based on enzyme functionalized vertically aligned high density multiwalled CNTs for electrochemical detection of cholesterol. The nanoelectrodes exhibited selectively detection of cholesterol in the presence of common interferents found in human blood.

Enhancement of field emission from multistage structure of carbon nanotube arrays

The field emission measurements for the multistage structured nanotubes (i.e., thin-multiwall and single wall carbon nanotubes grown on multiwall carbon nanotubes) were carried out and a low turn-on field of ~0.45 V/ μm, high emission current of 450 μA at a field of IV/μm and a large field enhancement factor of ~26200 were obtained. The thin multiwall carbon nanotubes (thin-MWNTs) and single wall carbon nanotubes (SWNTs) were grown on the regular arrays of vertically aligned multi wall carbon nanotubes (MWNTs) on porous silicon substrate by Chemical Vapor Deposition (CVD) method. The thin-MWNTs and SWNTs grown on MWNTs in this way have a multistage structure which gives higher enhancement of the electric field and hence the electron field emission.