Raman spectra of unfilled and filled carbon nanotubes: Theory

TL;DR

This theoretical study investigates how electron-phonon and phonon-phonon interactions influence the Raman spectra of filled and unfilled carbon nanotubes, revealing effects of filling atoms and metallic or semiconducting nature on spectral features.

Contribution

The paper provides a detailed theoretical analysis of Raman spectral features in filled and unfilled carbon nanotubes, highlighting the effects of filling atoms and interactions on peak shapes and positions.

Findings

Filling atoms can cause broadening or emergence of new peaks in Raman spectra.

Metallic nanotubes exhibit Breit-Wigner-Fano line shapes in the G-band due to plasmon excitation.

Semiconducting nanotubes generally show Lorentzian peaks, with possible BWF features when filled with donor atoms.

Abstract

The Raman spectra of two G-bands and a radial breathing mode (RBM) of unfilled and filled single-wall semiconducting and metallic carbon nanotubes have been investigated theoretically, in the presence of electron-phonon and phonon-phonon interactions. Excitation of low frequency optical plasmons in the metallic nanotube is responsible for the peak known as the Breit-Wigner-Fano (BWF) line shape in the G-band Raman spectra. In a filled nanotube there is an additional peak due to excitation of the phonon of the filling atom or molecule. Positions, shapes and relative strengths of these Raman peaks depend on the phonon frequencies of the nanotube and that of the filling atoms, and strengths and forms of the plasmon-phonon and phonon-phonon interactions. For example, filling atoms with phonon frequency close to the RBM frequency of the nanotube may broaden and lower the RBM Raman peak to such an extent that it may become barely visible. Hybridization between the G-bands and the filling atom phonon is also strong when these two frequencies are close to each other and it has important effects on the G-band and the BWF line shapes. When the phonon frequency of the filling atom is far from the RBM and G-band frequencies, it gives rise to a separate peak with modest effects on the RBM and G-band spectra. Raman spectra of semiconducting unfilled and filled nanotubes have similar behavior as those of metallic nanotubes except that normally they have Lorentzian line shapes and do not show a BWF line shape. However, if a semiconducting nanotube is filled with donor atoms, it is predicted that the BWF type line shape may be observed near the RBM, or the G-band or the filling atom Raman peak.