Functional surface chemistry of carbon-based nanostructures

The recently discovered abilities to synthesize single-walled carbon nanotubes and prepare single layer graphene have spurred interest in these sp2-bonded carbon nanostructures. In particular, studies of their potential use in electronic devices are many as silicon integrated circuits are encountering processing limitations, quantum effects, and thermal management issues due to rapid device scaling. Nanotube and graphene implementation in devices does come with significant hurdles itself. Among these issues are the ability to dope these materials and understanding what influences defects have on expected properties. Because these nanostructures are entirely all-surface, with every atom exposed to ambient, introduction of defects and doping by chemical means is expected to be an effective route for addressing these issues. Raman spectroscopy has been a proven characterization method for understanding vibrational and even electronic structure of graphene, nanotubes, and graphite, especially when combined with electrical measurements, due to a wealth of information contained in each spectrum. In Chapter 1, a discussion of the electronic structure of graphene is presented. This outlines the foundation for all sp2-bonded carbon electronic properties and is easily extended to carbon nanotubes. Motivation for why these materials are of interest is readily gained. Chapter 2 presents various synthesis/preparation methods for both nanotubes and graphene, discusses fabrication techniques for making devices, and describes characterization methods such as electrical measurements as well as static and time-resolved Raman spectroscopy. Chapter 3 outlines changes in the Raman spectra of individual metallic single-walled carbon nantoubes (SWNTs) upon sidewall covalent bond formation. It is observed that the initial degree of disorder has a strong influence on covalent sidewall functionalization which has implications on developing electronically selective covalent chemistries and assessing their selectivity in separating metallic and semiconducting SWNTs. Chapter 4 describes how optical phonon population extinction lifetime is affected by covalent functionalization and doping and includes discussions on static Raman linewidths. Increasing defect concentration is shown to decrease G-band phonon population lifetime and increase G-band linewidth. Doping only increases G-band linewidth, leaving non-equilibrium population decay rate unaffected. Phonon mediated electron scattering is especially strong in nanotubes making optical phonon decay of interest for device applications. Optical phonon decay also has implications on device thermal management. Chapter 5 treats doping of graphene showing ambient air can lead to inadvertent Fermi level shifts which exemplifies the sensitivity that sp2-bonded carbon nanostructures have to chemical doping through sidewall adsorption. Removal of this doping allows for an investigation of electron-phonon coupling dependence on temperature, also of interest for devices operating above room temperature. Finally, in Chapter 6, utilizing the information obtained in previous chapters, single carbon nanotube diodes are fabricated and characterized. Electrical performance shows these diodes are nearly ideal and photovoltaic response yields 1.4 nA and 205 mV of short circuit current and open circuit voltage from a single nanotube device. A summary and discussion of future directions in Chapter 7 concludes my work

Performance and Photovoltaic Response of Polymer-Doped Carbon Nanotube <i>p−n</i> Diodes

Two terminal abrupt junction diodes are fabricated from single semiconducting carbon nanotubes with simple photopatterned polymer layers defining air-stable p- and n-regions. These intratube diodes show nearly ideal behavior with relatively low series resistance and no sign of Zener breakdown at room temperature. Spatial doping profiles measured by micro-Raman spectroscopy and selective electrochemical gating of the n-region indicate that diode performance depends strongly on relative doping levels. A short circuit current of 1.4 nA with an open circuit voltage of 205 mV are measured when illuminated to saturation

Bubbling and Foaming Assisted Clearing of Mucin Plugs in Microfluidic Y-Junctions

Microfluidic Y-junctions were used to study mechanical mechanisms involved in pig gastric mucin (PGM) plug removal from within one of two bifurcation branches with 2-phase air and liquid flow. Water control experiments showed moderate plug removal due to shear from vortex formation in the blockage branch and suggest a PGM yield stress of 35 Pa, as determined by computational fluid dynamics. Addition of hexadecyltrimethylammonium bromide (CTAB) surfactant improved clearing effectiveness due to bubbling in 1 mm diameter channels and foaming in 500 μm diameter channels. Plug removal mechanisms have been identified as vortex shear, bubble scouring, and then foam scouring as air flow rate is increased with constant liquid flow. The onset of bubbling and foaming is attributed to a flow regime transition from slug to slug-annular. Flow rates explored for 1 mm channels are typically experienced by bronchioles in generations 8 and 9 of lungs. Results have implications on treatment of cystic fibrosis and other lung diseases