Photophysics of Individual Single-Walled Carbon Nanotubes

Abstract

Single-walled carbon nanotubes (SWNTs) are cylindrical graphitic molecules that have remained at the forefront of nanomaterials research since 1991, largely due to their exceptional and unusual mechanical, electrical, and optical properties. The motivation for understanding how nanotubes interact with light (i.e., SWNT photophysics) is both fundamental and applied. Individual nanotubes may someday be used as superior near-infrared fluorophores, biological tags and sensors, and components for ultrahigh-speed optical communications systems. Establishing an understanding of basic nanotube photophysics is intrinsically significant and should enable the rapid development of such innovations. Unlike conventional molecules, carbon nanotubes are synthesized as heterogeneous samples, composed of molecules with different diameters, chiralities, and lengths. Because a nanotube can be either metallic or semiconducting depending on its particular molecular structure, SWNT samples are also mixtures of conductors and semiconductors. Early progress in understanding the optical characteristics of SWNTs was limited because nanotubes aggregate when synthesized, causing a mixing of the energy states of different nanotube structures. Recently, significant improvements in sample preparation have made it possible to isolate individual nanotubes, enabling many advances in characterizing their optical properties. In this Account, single-molecule confocal microscopy and spectroscopy were implemented to study the fluorescence from individual nanotubes. Single-molecule measurements naturally circumvent the difficulties associated with SWNT sample inhomogeneities. Intrinsic SWNT photoluminescence has a simple narrow Lorentzian line shape and a polarization dependence, as expected for a one-dimensional system. Although the local environment heavily influences the optical transition wavelength and intensity, single nanotubes are exceptionally photostable. In fact, they have the unique characteristic that their single molecule fluorescence intensity remains constant over time; SWNTs do not "blink" or photobleach under ambient conditions. In addition, transient absorption spectroscopy was used to examine the relaxation dynamics of photoexcited nanotubes and to elucidate the nature of the SWNT excited state. For metallic SWNTs, very fast initial recovery times (300-500 fs) corresponded to excited-state relaxation. For semiconducting SWNTs, an additional slower decay component was observed (50-100 ps) that corresponded to electron-hole recombination. As the excitation intensity was increased, multiple electron-hole pairs were generated in the SWNT; however, these e-h pairs annihilated each other completely in under 3 ps. Studying the dynamics of this annihilation process revealed the lifetimes for one, two, and three e-h pairs, which further confirmed that the photoexcitation of SWNTs produces not free electrons but rather one-dimensional bound electron-hole pairs (i.e., excitons). In summary, nanotube photophysics is a rapidly developing area of nanomaterials research. Individual SWNTs exhibit robust and unexpectedly unwavering single-molecule fluorescence in the near-infrared, show fast relaxation dynamics, and generate excitons as their optical excited states. These fundamental discoveries should enable the development of novel devices based on the impressive photophysical properties of carbon nanotubes, especially in areas like biological imaging. Many facets of nanotube photophysics still need to be better understood, but SWNTs have already proven to be an excellent starting material for future nanophotonics applications.