1 research outputs found
Photoluminescence Dynamics of Aryl sp<sup>3</sup> Defect States in Single-Walled Carbon Nanotubes
Photoluminescent
defect states introduced by sp<sup>3</sup> functionalization
of semiconducting carbon nanotubes are rapidly emerging as important
routes for boosting emission quantum yields and introducing new functionality.
Knowledge of the relaxation dynamics of these states is required for
understanding how functionalizing agents (molecular dopants) may be
designed to access specific behaviors. We measure photoluminescence
(PL) decay dynamics of sp<sup>3</sup> defect states introduced by
aryl functionalization of the carbon nanotube surface. Results are
given for five different nanotube chiralities, each doped with a range
of aryl functionality. We find that the PL decays of these sp<sup>3</sup> defect states are biexponential, with both components relaxing
on time scales of ∼100 ps. Exciton trapping at defects is found
to increases PL lifetimes by a factor of 5–10, in comparison
to those for the free exciton. A significant chirality dependence
is observed in the decay times, ranging from 77 ps for (7,5) nanotubes
to >600 ps for (5,4) structures. The strong correlation of time
constants
with emission energy indicates relaxation occurs <i>via</i> multiphonon decay processes, with close agreement to theoretical
expectations. Variation of the aryl dopant further modulates decay
times by 10–15%. The aryl defects also affect PL lifetimes
of the free <i>E</i><sub>11</sub> exciton. Shortening of
the <i>E</i><sub>11</sub> bright state lifetime as defect
density increases provides further confirmation that defects act as
exciton traps. A similar shortening of the <i>E</i><sub>11</sub> dark exciton lifetime is found as defect density increases,
providing strong experimental evidence that dark excitons are also
trapped at such defect sites