A1 Refereed original research article in a scientific journal
Stochastic Formation of Quantum Defects in Carbon Nanotubes
Authors: Ma C, Schrage CA, Gretz J, Akhtar A, Sistemich L, Schnitzler L, Li H, Tschulik K, Flavel BS, Kruss S
Publisher: AMER CHEMICAL SOC
Publication year: 2023
Journal: ACS Nano
Journal name in source: ACS NANO
Journal acronym: ACS NANO
Volume: 17
First page : 15989
Last page: 15998
Number of pages: 10
ISSN: 1936-0851
DOI: https://doi.org/10.1021/acsnano.3c04314
Abstract
Small perturbations in the structureof materials significantlyaffect their properties. One example is single wall carbon nanotubes(SWCNTs), which exhibit chirality-dependent near-infrared (NIR) fluorescence.They can be modified with quantum defects through the reaction withdiazonium salts, and the number or distribution of these defects determinestheir photophysics. However, the presence of multiple chiralitiesin typical SWCNT samples complicates the identification of defect-relatedemission features. Here, we show that quantum defects do not affectaqueous two-phase extraction (ATPE) of different SWCNT chiralitiesinto different phases, which suggests low numbers of defects. Forbulk samples, the bandgap emission (E-11) of monochiral(6,5)-SWCNTs decreases, and the defect-related emission feature (E-11*) increases with diazonium salt concentration and representsa proxy for the defect number. The high purity of monochiral samplesfrom ATPE allows us to image NIR fluorescence contributions (E-11 = 986 nm and E-11* = 1140 nm) on the single SWCNTlevel. Interestingly, we observe a stochastic (Poisson) distributionof quantum defects. SWCNTs have most likely one to three defects (forlow to high (bulk) quantum defect densities). Additionally, we verifythis number by following single reaction events that appear as discretesteps in the temporal fluorescence traces. We thereby count singlereactions via NIR imaging and demonstrate that stochasticity playsa crucial role in the optical properties of SWCNTs. These resultsshow that there can be a large discrepancy between ensemble and singleparticle experiments/properties of nanomaterials.
Small perturbations in the structureof materials significantlyaffect their properties. One example is single wall carbon nanotubes(SWCNTs), which exhibit chirality-dependent near-infrared (NIR) fluorescence.They can be modified with quantum defects through the reaction withdiazonium salts, and the number or distribution of these defects determinestheir photophysics. However, the presence of multiple chiralitiesin typical SWCNT samples complicates the identification of defect-relatedemission features. Here, we show that quantum defects do not affectaqueous two-phase extraction (ATPE) of different SWCNT chiralitiesinto different phases, which suggests low numbers of defects. Forbulk samples, the bandgap emission (E-11) of monochiral(6,5)-SWCNTs decreases, and the defect-related emission feature (E-11*) increases with diazonium salt concentration and representsa proxy for the defect number. The high purity of monochiral samplesfrom ATPE allows us to image NIR fluorescence contributions (E-11 = 986 nm and E-11* = 1140 nm) on the single SWCNTlevel. Interestingly, we observe a stochastic (Poisson) distributionof quantum defects. SWCNTs have most likely one to three defects (forlow to high (bulk) quantum defect densities). Additionally, we verifythis number by following single reaction events that appear as discretesteps in the temporal fluorescence traces. We thereby count singlereactions via NIR imaging and demonstrate that stochasticity playsa crucial role in the optical properties of SWCNTs. These resultsshow that there can be a large discrepancy between ensemble and singleparticle experiments/properties of nanomaterials.
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