Unravelling the Complete Raman Response of Graphene Nanoribbons Discerning the Signature of Edge Passivation.

Controlling the edge morphology and terminations of graphene nanoribbons (GNR) allows tailoring their electronic properties and boosts their application potential. One way of making such structures is encapsulating them inside single-walled carbon nanotubes. Despite the versatility of Raman spectroscopy to resolve strong spectral signals of these systems, discerning the response of long nanoribbons from that of any residual precursor remaining outside after synthesis has been so far elusive. Here, the terrylene dye is used as precursor to make long and ultra-narrow armchair-edged GNR inside nanotubes. The alignment and characteristic length of terrylene encapsulated parallel to the tube's axis facilitates the ribbon formation via polymerization, with high stability up to 750 °C when the hybrid system is kept in high vacuum. A high temperature annealing is used to remove the terrylene external molecules and a subtraction model based on the determination of a scaling factor related to the G-band response of the system is developed. This not only represents a critical step forward toward the analysis of the nanoribbon-nanotube system, but it is a study that enables unraveling the Raman signatures of the individual CH-modes (the signature of edge passivation) for GNR for the first time with unprecedented detail.

Toward a Predominant Substitutional Bonding Environment in B-Doped Single-Walled Carbon Nanotubes.

B-doped single-walled carbon nanotubes have been synthesized from sodium tetraphenyl borate and record incorporation percentages of B heteroatoms have been found in this material as-synthesized. However, carbonaceous impurities, besides other byproducts, can still contain boron and therefore exhibit various types of competing bonding environments. To circumvent this issue, which has constantly hindered a conclusive insight to the existing bonding environments in materials alike, we have employed a purification method, which leaves ∼7% at. of B atoms of the total sample composition almost exclusively in the sp2 configuration. This record B substitutional doping, together with the identification of the competing bonding environments are revealed here unambiguously from X-ray photoelectron spectroscopy. The doping level in the purified tubes is about an order of magnitude larger than in other B-doped single-walled tubes even without purification, and brings the state-of-the-art closer to the controlled applicability of this material.