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Measuring electronic Raman scattering (ERS) has become an efficient method for structural characterization of metallic single-wall carbon nanotubes (SWCNT). However, applying this method to other types of SWCNT-based structures, e.g., those with strong van der Waals (VDW) coupling, is currently not well studied. In this work, we combine electron diffraction, Rayleigh and Raman spectroscopies to investigate the ERS process near 36 metallic transitions in 21 individual double-wall carbon nanotubes (DWCNTs) with all types of electronic configurations. We observe the partial suppression of ERS intensity in DWCNTs compared to SWCNTs and mainly attribute it to the effect of dielectric screening of Coulomb interactions. We probe ultra-pure macroscopic multi-chirality DWCNT solutions and identify the role of inhomogeneous broadening in observing ERS peaks in Raman spectra. Based on the experimental findings, we propose an adapted method for the structural identification of DWCNT samples from the ERS data. The obtained results can be generalized to the characterization of the emerging 1D VDW heterostructures based on metallic SWCNTs., DL thanks Prof. S. Rochal and D. Chalin for providing MAPLE code for calculating DWCNT transition energy shifts and W. Van Werveke and M. De Clercq for providing MATLAB code for creating chirality distribution maps. A part of the experimental data (i.e., microscopic Rayleigh and Raman spectra, ED patterns) was obtained and preliminary processed within the framework of Russian Foundation for Basic Research grant 18-32-00397 mol_a. Further data analysis (i.e., developing models for ERS, Raman and Rayleigh spectra fitting) was performed by DL with the support of the postdoctoral grant (12ZP720N) of the Fund for Scientific Research Flanders (FWO). The TEM measurements were performed in the Laboratorio de Microscopias Avanzadas (LMA), Universidad de Zaragoza (Spain). R.A. gratefully acknowledges the support from the Spanish MICINN (PID2019-104739 GB-100/AEI/10.13039/501100011033), Government of Aragon (projects DGA E13-20R (FEDER, EU)) and from the European Union H2020 program “ESTEEM3” (Grant number 823717). V.N.P. acknowledges financial support for NTB calculations from the National Science Fund of Bulgaria under grant KP-06-N38/10 from 06.12.2019. T.T.C acknowledges financial support from Vietnam Academy of Science and Technology (grant number: VAST03.06/22-23). H.N.T, E.F., A.A.Z, J.L.S. and M.P. acknowledge financial support by the ANR GAMBIT project, grant ANR-13-BS10-0014 of the French Agence Nationale de la Recherche. The characterization of the macroscopic UP-DWCNT samples was financially supported by a PhD fellowship for M. Erkens of the Research Foundation of Flanders (FWO, grant number: 11C9220N). D.L. acknowledges the financial support from the University of Antwerp Research Fund (grant BOF KP 43770). D.L., M.A., W.W. and S.C. also acknowledge funding from FWO projects (G040011N, G02112N, G035918N and G036618N).

Graphene nanoribbons with sub-nanometer widths are extremely interesting for nanoscale electronics and devices as they combine the unusual transport properties of graphene with the opening of a band gap due to quantum confinement in the lateral dimension. Strong research efforts are presently paid to grow such nanoribbons. Here we show the synthesis of 6- and 7-armchair graphene nanoribbons, with widths of 0.61 and 0.74 nm, and excitonic gaps of 1.83 and 2.18 eV, by high-temperature vacuum annealing of ferrocene molecules inside single-walled carbon nanotubes. The encapsulation of the so-obtained graphene nanoribbons is proved by atomic resolution electron microscopy, while their assignment is provided by a combination of an extensive wavelength-dependent Raman scattering characterization and quantum-chemical calculations. These findings enable a facile and scalable approach leading to the controlled growth and detailed analysis of well-defined sub-nanometer graphene nanoribbons., Comment: 35 pages, 4 figures

Even though ultrasonication is considered to be an effective method to disperse carbon nanotubes (CNTs), its devastating effects on the nanotubes are often neglected. Here, even mild ultrasonication is found to rapidly extract the inner single-wall CNTs (SWCNTs) from the outer shells of the double-wall CNTs (DWCNTs). As-synthesized DWCNTs are gently solubilized in a surfactant solution, strictly avoiding any ultrasonication, followed by two consecutive density gradient ultracentrifugation (DGU) steps to obtain a purified colloidal solution of isolated DWCNTs. The latter is carefully selected based on in situ resonant Raman (RRS) and fluorescence (PL) spectroscopy, measured as a function of depth directly in the ultracentrifuge tube after DGU. These purified DWCNTs are ultrasonicated in successive time steps while intermittently probing the sample via RRS and PL spectroscopy. These results unravel the very fast increasing yet saturating extraction mechanism that leads to the formation of fluorescing SWCNTs. A statistical high-resolution transmission electron microscopy study confirms the drastic increase in SWCNTs after ultrasonication, and evidences that ultrasonication forms SWCNTs from both the inner and outer shells of the DWCNTs. This study demonstrates how easily ultrasonication extracts SWCNTs from individually solubilized DWCNTs, unavoidably complicating any further spectroscopic studies on DWCNTs severely., 41 pages (64 incl. SI), 9 figures (19 SI figures)

Carbyne, i.e. an infinitely long linear carbon chain (LCC), has been at the focus of a lot of research for quite a while, yet its optical, electronic, and vibrational properties have only recently started to become accessible experimentally thanks to its synthesis inside carbon nanotubes (CNTs). While the role of the host CNT in determining the optical gap of the LCCs has been studied previously, little is known about the excited states of such ultralong LCCs. In this work, we employ the selectivity of wavelength-dependent resonant Raman spectroscopy to investigate the excited states of ultralong LCCs encapsulated inside double-walled CNTs. In addition to the optical gap, the Raman resonance profile shows three additional resonances. Corroborated with DFT calculations on LCCs with up to 100 C-atoms, we assign these resonances to a vibronic series of a different electronic state. Indeed, the calculations predict the existence of two optically allowed electronic states separated by an energy of 0.14-0.22 eV in the limit of an infinite chain, in agreement with the experimental results. Furthermore, among these two states, the one with highest energy is also characterized by the largest electron-vibration couplings, which explains the corresponding vibronic series of overtones.

International audience; Resonant Raman spectroscopy is a widely used technique for single-walled carbon nanotube (SWCNT) characterization, in particular in the radial breathing mode (RBM) range which provides direct information on the structure of the nanotube in resonance. The RBM peak counting method, i.e. acquiring Raman spectrum grids on a substrate with a select set of discrete laser lines and counting RBM peaks as single nanotubes, is frequently used to characterize SWCNT growth samples, despite the many factors that can induce errors in the results. In this work, we cross-characterize the diameter distributions obtained through this methodology with diameter distributions obtained by counting SWCNT diameters in transmission electron microscopy (TEM) and discuss the different results and biases between the techniques. This study is performed on a broad diameter distribution sample, and on two chirality-enriched samples whose chirality distributions are determined by photoluminescence excitation spectroscopy (PLE) and statistical analysis of high resolution TEM (HRTEM) images. We show that the largest differences between the Raman peak counting and TEM diameter distributions stem from the chirality-dependence of SWCNT Raman cross-sections and the patchy vision offered by the use of only a few discrete excitation wavelengths. The effect of the substrate and TEM-related biases are also discussed.