Novel Techniques for Optical Characterization of Single-Walled Carbon Nanotube Samples
Streit, Jason Kyle
Weisman, R. Bruce
Doctor of Philosophy
Photoluminescence spectroscopy has emerged as a powerful tool for characterizing the structure and optical properties of single-walled carbon nanotube (SWCNT) samples. This thesis will discuss the development and application of new fluorescence-based methods designed to fully characterize bulk SWCNT suspensions by length and structural composition. An efficient new method is demonstrated to measure length distributions of aqueous SWCNT samples by analyzing the diffusional motions of many individual nanotubes captured in sequences of short-wave infrared (SWIR) fluorescence images. This method, termed length analysis by nanotube diffusion (LAND), provides distributions in very good agreement with those obtained by conventional atomic force microscopy analysis. A novel microscopy technique is described to measure the peak emission wavelengths of many individual nanotubes without the use of a spectrometer. We exploit the chromatic aberration of an objective lens to deduce emission wavelength from focal depth. Spectral measurements successfully reproduce bulk emission spectra and also provide relative abundances of specific SWCNT structures. A new approach is applied to find nanotube concentrations by directly counting SWCNTs in SWIR fluorescence images. Concentrations are used to rigorously determine absolute absorption cross sections for the E11 and E22 electronic transitions of the (6,5), (7,5), (7,6), (8,6), (8,7) and (9,7) SWCNT species. It is found that the absorption cross section per carbon atom decreases with increasing nanotube diameter. Finally, the spectral analysis of fluorescence fluctuations (SAFF) method is developed and used to characterize SWCNT samples by structural composition, sample quality, and aggregation state. Fluorescence spectra are sequentially measured from small volumes of slowly flowing dilute samples and the intensity fluctuations resulting from small statistical variations in nanotube concentration are analyzed. The ratio of the squared mean intensity to variance of intensity is plotted as a function of wavelength to give a relative concentration spectrum, reflecting the number of particles contributing to the emission at each wavelength. In addition, mean intensity is divided by abundance to obtain fluorescence efficiency values for all species represented in the sample. Intensity correlations between different emission wavelengths are used to detect the formation of loose nanotube aggregates and also study the broadening components of individual emission line widths.