Aiming
to unravel the relationship between chemical configuration
and electronic structure of sp<sup>3</sup> defects of aryl-functionalized
(6,5) single-walled carbon nanotubes (SWCNTs), we perform low-temperature
single nanotube photoluminescence (PL) spectroscopy studies and correlate
our observations with quantum chemistry simulations. We observe sharp
emission peaks from individual defect sites that are spread over an
extremely broad, 1000–1350 nm, spectral range. Our simulations
allow us to attribute this spectral diversity to the occurrence of
six chemically and energetically distinct defect states resulting
from topological variation in the chemical binding configuration of
the monovalent aryl groups. Both PL emission efficiency and spectral
line width of the defect states are strongly influenced by the local
dielectric environment. Wrapping the SWCNT with a polyfluorene polymer
provides the best isolation from the environment and yields the brightest
emission with near-resolution limited spectral line width of 270 μeV,
as well as spectrally resolved emission wings associated with localized
acoustic phonons. Pump-dependent studies further revealed that the
defect states are capable of emitting single, sharp, isolated PL peaks
over 3 orders of magnitude increase in pump power, a key characteristic
of two-level systems and an important prerequisite for single-photon
emission with high purity. These findings point to the tremendous
potential of sp<sup>3</sup> defects in development of room temperature
quantum light sources capable of operating at telecommunication wavelengths
as the emission of the defect states can readily be extended to this
range <i>via</i> use of larger diameter SWCNTs
