Double-walled carbon nanotubes (DWNTs), often regarded as the simplest one-dimensional (1D) van der Waals moiré superlattices, are the ideal structures to explore the interlayer coupling, including mechanical and electronical coupling, at the nanoscale in 1D systems. By combining spatial modulation spectroscopy (SMS) and resonant Raman scattering (RRS) experiments on well-identified individual free-standing DWNTs with the calculations of their optical absorption by using the recursion method with non-orthogonal tight-binding (NTB) basis functions, we are able to unambiguously assign the nature, namely mirror transition or cross transition, of each optical transitions in DWNTs. Our study identifies and allows to determine the conditions of the mixing of the electronic states leading to the appearance of cross transitions in the optical absorption of DWNTs, beyond of the so-called Koshino's criteria previously derived. On the other hand, the striking behavior of the resonant excitation profile (REP) of the Raman active modes around the cross transition reveals the strong sensitivity of the modes intensity on the electronic interlayer coupling in DWNTs, emphasizing the relevance of Raman spectroscopy for studying the electronic and mechanical coupling at the nanoscale.

The synthesis of a copolymer derived from poly(3-hexylthiophene), one of the monomers bearing an aniline group, is described. Like the homopolymer, this copolymer is able to functionalize carbon nanotubes by π-stacking of the thiophene units onto the hexagonal network of the nanotubes. It can as well be covalently attached onto carbon nanotube walls without the need for an intermediate chemical step. While the dispersion of non-covalent nanohybrids in THF is stable for only a few hours, one of the covalent nanohybrids is stable for weeks, showing the efficiency of the functionalization. The comparison between the spectroscopic characterization of both covalent and non-covalent systems shows that the copolymer organizes differently at the interface with the nanotubes in each case, in agreement with the effectiveness of the addition reaction.

A search for new relatively easy physicochemical methods for structural identification of carbon nanotubes represents a key challenge. Here, analyzing the experimental data on double-walled carbon nanotubes (DWCNTs) obtained by us and taken from literature, we have expressed the magnitude of elastic coupling between two tubular walls forming a DWCNT as a simple function dependent not only on DWCNT diameters but also on the difference between the chirality angles of the constituent nanotubes. To get this quite unexpected result, which allows us to relate more precisely the structural parameters of a DWCNT with frequencies of its radial breathing-like modes (RBLM), we have developed a new model for the RBLM dynamics that takes into account a possible deposition of water molecules from ambient air onto the DWCNT surface. The comparison between theoretical and experimental RBLM frequencies allows the evaluation of the handedness-dependent contribution in elastic coupling between the layers suggesting that, in the formation of DWCNTs, the layers with the same handedness are privilegeted. Application of the results for identification of DWCNTs is also considered.

Double-walled carbon nanotubes (DWNTs), consisting of two coaxial and weakly van der Waals coupled single-walled carbon nanotubes (SWNTs), are one of the most ideal and fundamental systems to study the effects of inter-tube coupling on the physical properties in one-dimensional structures.On this poster, we report on the investigations of individual, spatially isolated and suspended double-walled carbon nanotubes (DWNTs) by combination of high-resolution electron microscopy, electron diffraction, Rayleigh spectroscopy and Raman spectroscopy (Figure 1) [1,2]. We first present an overview of the effect of the diameters, inter-tube distance and nature (metallic or semiconducting) on the Raman signature (Radial Breathing Like [1,3,4] and Tangential Modes [4-6]) of DWNTs. We then examine the features of tangential modes and find a clear frequency shift of the inner-layer G modes as a function of the inter-tube distance with respect to the corresponding G modes in equivalent single-walled carbon nanotubes (SWNT).[4-6] These results are understood by considering the effects of the relaxation of the layers and the interaction between the relaxed structures.[7] Finally, we study the experimental excitation dependence of the G modes intensity of the constituent inner and outer SWNTs. In particular, we discuss the effects of the quantum interference between different electronic transitions on the observed behaviors.[8]References[1] D.I. Levshov et al., Carbon, 114, 141 (2017). [2] D.I. Levshov et al., Phys Rev. B 96 (2017), 195410.[3] D.I. Levshov et al., Nano Lett. 11(11) (2011), 4800. [4] H.-N. Tran et al., Adv. Nat. Sci. Nanosci. Nanotechnol. (2017), 8, 15018.[5] D. Levshov et al., J. Phys. Chem. C 119(40) (2015), 23196.[6] D.I. Levshov et al., Phys. Status Solidi B 254(11) (2017), 1700251.[7] V.N. Popov et al., Phys. Rev. B 97 (2018), 165417.[8] H.-N. Tran et al., Phys. Rev. B 95 (2017), 95 (20), 205411

Using an experimental approach that combines high-resolution electron microscopy, electron diffraction and optical spectroscopies, including Raman scattering, Rayleigh spectroscopy and photoluminescence, on individual, spatially isolated and suspended (free-standing) single-walled (SWNTs) and double-walled carbon nanotubes (DWNTs), we have been able to investigate their phonons characteristics and optical properties. In this talk, we present an overview of the most significant results obtained via this approach. Particular attention is paid to the study of DWNTs, a coaxial composite of two SWNTs, which provide a unique model system for studying coupling at the nanoscale. We show how such coupling, originating from the van der Waals interaction between the inner and outer nanotubes, plays a crucial role in determining the characteristics of the collective radial breathing-like modes and G modes in DWNTs (for a review see Ref. 1-2). The effects of quantum interference between different electronic transitions on the experimental behavior of the G-modes intensity are discussed [3]. It must be emphasized that the theoretical predictions of Philippe Lambin and his collaborators have been invaluable in understanding a lot of these experimental data [4].

Première femme à avoir accédé au rang de professeur titulaire au Massachussetts Institute of Technology (MIT),Mildred Spiewak Dresselhaus, ou simplement Millie pourla plupart de ses collègues, est l’exemple d’un engagement passionnel et infatigable pour la science en général, la physique en particulier, et pour la reconnaissancede la place des femmes en science.Sa disparition le 20 février 2017 à l’âge de 86 ans, en pleine activité scientifique, a très profondément marqué les communautés de chercheurs engagés dansles nanosciences. Ses contributions à la compréhension du couplage entre propriétés électroniques,vibrationnelles et structurales, dans les différentes formesde carbone sont au centre du développement des nanomatériaux carbonés et de leurs applications.

The goal of this chapter is to review the main information derived from Raman spectroscopy on individual suspended (free-standing) chiralityidentified single-wall carbon nanotubes (SWCNTs) and double-wall carbonnanotubes (DWCNTs) with a special focus on the characteristics of their radial breathing modes and G modes, including their resonance conditions. ForSWCNTs, the different relationships between the radial breathing mode frequency and the inverse of the diameter illustrate the high sensitivity of individual suspended SWCNTs to their environmental conditions. The intrinsicprofiles of the optical longitudinal (LO) and transverse (TO) G modes are unambiguously identified both for metallic and semiconducting chiral and achiral SWCNTs, and the diameter dependence of the LO and TO frequencies are established. In DWCNTs, the intertube coupling, originating from the van der Waals interaction between the inner and outer tubes, plays an important role in determining the features/characteristics of the collectiveradial breathing-like modes and G modes.