We have investigated the growth mechanism of coronene-derived graphene nanoribbons (GNRs) using two different precursors: coronene and a dimer form of coronene, so-called dicoronylene (C48H20). For both of the precursors, the formation of nanoribbon-like materials inside carbon nanotubes (CNTs) was confirmed by transmission electron microscope observations. Experimental and theoretical Raman analysis reveals that the samples also encapsulated dicoronylene and linearly condensed other coronene oligomers, which can be regarded as analogues to GNRs. Interestingly, it was found that the present doping condition of coronene yields dicoronylene prior to encapsulation due to the thermal dimerization of coronene. These results indicate that the dimerization before the encapsulation drives the preferential formation of the coronene-based GNRs within CNTs.
We present an efficient method to extract inner shells of double-wall carbon nanotubes (DWCNTs) in liquid phase. The extraction of inner from outer shells is achieved by cutting the DWCNTs with vigorous sonication in water containing surfactants. The extracted shells are perfectly isolated single-wall carbon nanotubes (SWCNTs) and can be separated using density gradient ultracentrifugation. Statistical analysis using high-resolution transmission electron microscopy reveals that the enrichment of SWCNTs with narrow diameter (0.62-1.0 nm) up to 100% is achieved from highly pure DWCNTs. Furthermore, the (5,4) SWCNTs, which have the diameter of 0.62 nm, are concentrated. Our findings provide a novel way to obtain very narrow, highly isolated SWCNTs with ultraclean surface that have not been obtained in conventional synthesis methods.
Nanotemplated growth of graphene nanoribbons (GNRs) inside carbon nanotubes is a promising mean to fabricate ultrathin ribbons with desired side edge configuration. We report the optical properties of the GNRs formed in single-wall carbon nanotubes. When coronene is used as the precursor, extended GNRs are grown via a high-temperature annealing at 700 °C. Their optical responses are probed through the diazonium-based side-wall functionalization, which effectively suppresses the excitonic absorption peaks of the nanotubes without damaging the inner GNRs. Differential absorption spectra clearly show two distinct peaks around 1.5 and 3.4 eV. These peaks are assigned to the optical transitions between the van Hove singularities in the density of state of the GNRs in qualitative agreement with the first-principles calculations. Resonance Raman spectra and transmission electron microscope observations also support the formation of long GNRs.
We report the thermally induced unconventional cracking of graphene to generate zigzag edges. This crystallography-selective cracking was observed for as-grown graphene films immediately following the cooling process subsequent to chemical vapor deposition (CVD) on Cu foil. Results from Raman spectroscopy show that the crack-derived edges have smoother zigzag edges than the chemically formed grain edges of CVD graphene. Using these cracks as nanogaps, we were also able to demonstrate the carrier tuning of graphene through the electric field effect. Statistical analysis of visual observations indicated that the crack formation results from uniaxial tension imparted by the Cu substrates together with the stress concentration at notches in the polycrystalline graphene films. On the basis of simulation results using a simplified thermal shrinkage model, we propose that the cooling-induced tension is derived from the transient lattice expansion of narrow Cu grains imparted by the thermal shrinkage of adjacent Cu grains.
This report describes the development of a solution-assisted, polymer-free transfer method and the characterization of chemical vapor deposition (CVD)-grown graphene on hexagonal boron nitride. Raman analysis reveals that polymer-free samples have small variations in G- and 2D-mode Raman frequencies and are minimally affected by charge doping as observed for clean exfoliated graphene. Electrical measurements indicate that charge doping, hysteresis, and carrier scattering are suppressed in polymer-free samples. The results demonstrate that this method provides a simple and effective way to prepare clean heterostructures of CVD-grown, large-area graphene and other two-dimensional materials.
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