(Invited) Kinetics and Thermodynamics of Swcnts and Bnnts Encapsulation with α-Sexithiophene in Liquid Phase

Abstract

Single-Walled Carbon Nanotubes (SWNTs) and Boron Nitride Nanotubes (BNNTs) come with hollow 1D centers, which can serve to define narrow spaces for encapsulating small organic dyes. The encapsulation process is of scientific interest because it can be used to tailor the optical properties of the resulting dyes@NTs nanohybrids. Past works have shown that the dyes@SWCNT exhibits a strongly enhanced Raman scattering cross section, while the dyes@BNNTs do emit robust, generally red-shifted, luminescence at wavelengths down to the near-IR. In both cases, the nanotube protects the encapsulated dyes from photobleaching, provides high confinement, and reinforces intermolecular interactions between dyes into specific aggregation states.Here, we compare the liquid phase encapsulation process of α-sexithiophene (6T), which is a conjugated rod-like dye, inside SWCNTs and BNNTs. Raman and luminescence imaging experiments are used to monitor the 6T encapsulation process of a large ensemble of individual nanotubes in liquid-phase. This method probes statistically the encapsulation kinetics using hundreds of individual nanotubes according to various parameters (dye concentration and temperature). The results highlight a kinetic model in which single and double aggregates is formed sequentially. This kinetics and the associated thermodynamic parameters for the 6T encapsulation will be presented and discussed so as to gain a better control over the emission properties of the nanohybrids.