Channeling Excitons to Emissive Defect Sites in Carbon Nanotube Semiconductors beyond the Dilute Regime.

Abstract

The exciton photoluminescence of carbon nanotube semiconductors has been intensively exploited for bioimaging, anticounterfeiting, photodetection, and quantum information science. However, at high concentrations, photoluminescence is lost to self-quenching because of the nearly complete overlap of the absorption and emissive states (∼10 meV Stokes shift). Here we show that by introducing sparse fluorescent quantum defects via covalent chemistry, self-quenching can be efficiently bypassed by means of the new emission route. The defect photoluminescence is significantly red-shifted by 190 meV for p-nitroaryl tailored (6,5)-single-walled carbon nanotubes (SWCNTs) from the native emission of the nanotube. Notably, the defect photoluminescence is more than 34 times brighter than the native photoluminescence of unfunctionalized SWCNTs in the most concentrated nanotube solution tested (2.7 × 1014 nanotubes/mL). Moreover, we show that defect photoluminescence is more resistant to self-quenching than the native state in a dense film, which is the upper limit of concentration. Our findings open opportunities to harness nanotube excitons in highly concentrated systems for applications where photoluminescence brightness and light-collecting efficiency are mutually important.