Optical properties of carbon nanotubes

Open Access
Chen, Gugang
Graduate Program:
Doctor of Philosophy
Document Type:
Date of Defense:
October 07, 2003
Committee Members:
  • Peter C Eklund, Committee Chair
  • Gerald Dennis Mahan, Committee Member
  • Vincent Henry Crespi, Committee Member
  • Thomas E Mallouk, Committee Member
  • reflectance
  • SWNTs
  • chemical doping
  • optical properties
  • DWNTs
  • peapods
  • nanotubes
  • transmission
  • Raman
  • HiPCO
This thesis addresses the optical properties of novel carbon filamentary nanomaterials: single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), and SWNTs with interior C60 molecules (peapods). Optical reflectance spectra of bundled SWNTs are discussed in terms of their electronic energy band structure. An Effective Medium Model for a composite material was found to provide a reasonable description of the spectra. Furthermore, we have learned from optical absorption studies of DWNTs and C60-peapods that the host tube and the encapsulant interact weakly; small shifts in interband absorption structure were observed. Resonant Raman scattering studies on SWNTs synthesized via the HiPCO process show that the zone-folding approximation for phonons and electrons works reasonably well, even for small diameter (d < 1 nm) tubes. The energy of optical transitions between van Hove singularities in the electronic density of states computed from the zone-folding model agree well with the resonant conditions for Raman scattering. Small diameter tubes were found to exhibit additional sharp Raman bands in the frequency range 500 - 1200 cm-1 with an, as yet, undetermined origin. The Raman spectrum of a DWNT was found to be well described by a superposition of the Raman spectra expected for inner and outer tubes, i.e., no charge transfer occurs and the weak van der Waals (vdW) interaction between tubes does not have significant impact on the phonons. A ~7 cm-1 downshift of the small diameter, inner-tube tangential mode frequency was observed, however, but attributed to a tube wall curvature effect, rather than the vdW interaction. Finally, we studied the chemical doping of DWNTs, where the dopant (Br anions) is chemically bound to the outside of the outer tube. The doped DWNT system is a model for a cylindrical molecular capacitor. We found experimentally that 90% of the positive charge resides on the outer tube, so that most of electric field on the inner tube is screened, i.e., we have observed a molecular Faraday cage effect. A self-consistent theoretical model in the tight-binding approximation with a classical electrostatic energy term is in good agreement with our experimental results.