Comparative Evaluation of Encapsulation Methods for Endohedral Doping of Single-Wall Carbon Nanotubes

Single wall carbon nanotubes (SWCNTs) are promising building blocks for nanoelectronic and optoelectronic devices, yet reliable and stable doping, particularly n type, remains challenging due to strong environmental sensitivity and competing extrinsic effects. Encapsulation of charge transfer molecules within the SWCNT cavity offers a promising route to stable doping while preserving the nanotubes outer surface for subsequent processing. Here, we systematically investigate the filling of arc discharge SWCNTs with the electron donor tetrathiafulvalene and electron acceptor tetracyanoquinodimethane, comparing different methods for filling, including melt filling, solution reflux, and vacuum phase sublimation. We follow the entire processing workflow from raw, unfilled powders to aqueous dispersions and employ density gradient ultracentrifugation to separate filled from empty nanotubes as well as metallic from semiconducting ones. Encapsulation efficiency and electronic modification are assessed using absorption spectroscopy, resonant Raman scattering, thermogravimetric analysis, and electron paramagnetic resonance. Finally, we introduce a complementary vacuum-phase method that removes externally adsorbed molecules without extensive solvent washing, enabling cleaner encapsulated systems.