Ionosilica ionogels have been lately introduced as emerging all-ionic designer materials. They consist of an ionic liquid (IL) guest trapped within a solid ionosilica support host. In this work, we investigate the influence of the (i) ionosilica nature and (ii) the ionosilica/IL ratio on the mobility of the confined IL. We report the elaboration of various ionosilica ionogels via a nonhydrolytic sol-gel process, using namely tris(3-(trimethoxysilyl)propyl)amine (TTA), Methyl-tris(3-(trimethoxysilyl)propyl)ammonium iodide (MTTA) and tetrakis(3-(trimethoxysilyl)-propyl)ammonium iodide (TKTA) as ionosilica precursors, with the IL butyl-methyl imidazolium bis-triflimide ([BMIM] TFSI). Various ionogels were prepared from different ratios between the ionosilica host and the IL guest. The host/guest interactions i.e. the change in the conformational contribution of the IL counter-anion were explored by means of Raman spectroscopy. In addition, the transport properties of the confined species were probed via spin echo solid-state NMR experiments and Complex Impedance Spectroscopy (CIS) measurements. Raman experiments revealed different conformational equilibrium for the TFSI anion in the various ionosilica ionogels, with an increase in the cisoid form compared to the bulk IL due to confinement effects. The TFSI anion seems to experience different degree of confinement and thus different interactions with the ionosilica scaffold as a function of the investigated parameters. Concomitantly, the 1H spin echo NMR and CIS measurements revealed a significantly higher ionic mobility in the materials synthesized in the presence of the tris-trialkoxysilylated ammonium precursor compared to the one synthesized in the presence of tetra-trialkoxysilylated ammonium precursor. These results may reflect stronger host-guest interactions in the latter case related to the higher degree of reticulation of the network. All these techniques give concordant results and highlight an effect of the chemical constitution of the ionosilica scaffold and the amount of confined IL on its dynamics within the network.

Hybrid van der Waals heterostructures made of 2D materials and organic molecules exploit the high sensitivity of 2D materials to all interfacial modifications and the inherent versatility of the organic compounds [1-2]. In this study, we are interested in the quinoïdal zwitterion/MoS2 hybrid system in which organic crystals are grown by epitaxy on the MoS2 surface and can reorganize in other forms after thermal annealing [3]. By means of field effect transistor measurements and atomic force microscopy, we demonstrate that the charge transfer between organic molecules and 2D materials strongly depends on the conformation of the molecular film. This work shows the great sensibility of MoS2 transistors for sensing molecular events occurring at the nanoscale providing a new experimental tool in addition to the usual microscopies and spectroscopies techniques.References :[1] Late, D. J.; Huang, Y.-K.; Liu, B.; Acharya, J.; Shirodkar, S. N.; Luo, J.; Yan, A.; Charles, D.; Waghmare, U. V.; Dravid, V. P.; Rao, C. N. R. Sensing Behavior of Atomically Thin-Layered MoS 2 Transistors. ACS Nano 2013, 7 (6), 4879–4891. [2] Li, N.; Wang, Q.; Shen, C.; Wei, Z.; Yu, H.; Zhao, J.; Lu, X.; Wang, G.; He, C.; Xie, L.; Zhu, J.; Du, L.; Yang, R.; Shi, D.; Zhang, G. Large-Scale Flexible and Transparent Electronics Based on Monolayer Molybdenum Disulfide Field-Effect Transistors. Nat. Electron. 2020, 3 (11), 711–717.[3] Lockhart de la Rosa, C. J.; Phillipson, R.; Teyssandier, J.; Adisoejoso, J.; Balaji, Y.; Huyghebaert, C.; Radu, I.; Heyns, M.; De Feyter, S.; De Gendt, S. Molecular Doping of MoS 2 Transistors by Self-Assembled Oleylamine Networks. Appl. Phys. Lett. 2016, 109 (25), 253112.

Hybrid van der Waals heterostructures made of 2D materials and organic molecules exploit the high sensitivity of 2D materials to all interfacial modifications and the inherent versatility of the organic compounds [1-2]. In this study, we are interested in the quinoïdal zwitterion/MoS2 hybrid system in which organic crystals are grown by epitaxy on the MoS2 surface and can reorganize in other forms after thermal annealing [3]. By means of field effect transistor measurements and atomic force microscopy, we demonstrate that the charge transfer between organic molecules and 2D materials strongly depends on the conformation of the molecular film. This work shows the great sensibility of MoS2 transistors for sensing molecular events occurring at the nanoscale providing a new experimental tool in addition to the usual microscopies and spectroscopies techniques.[1] Late, D. J.; Huang, Y.-K.; Liu, B.; Acharya, J.; Shirodkar, S. N.; Luo, J.; Yan, A.; Charles, D.; Waghmare, U. V.; Dravid, V. P.; Rao, C. N. R. Sensing Behavior of Atomically Thin-Layered MoS 2 Transistors. ACS Nano 2013, 7 (6), 4879–4891.[2] Li, N.; Wang, Q.; Shen, C.; Wei, Z.; Yu, H.; Zhao, J.; Lu, X.; Wang, G.; He, C.; Xie, L.; Zhu, J.; Du, L.; Yang, R.; Shi, D.; Zhang, G. Large-Scale Flexible and Transparent Electronics Based on Monolayer Molybdenum Disulfide Field-Effect Transistors. Nat. Electron. 2020, 3 (11), 711–717. [3] Lockhart de la Rosa, C. J.; Phillipson, R.; Teyssandier, J.; Adisoejoso, J.; Balaji, Y.; Huyghebaert, C.; Radu, I.; Heyns, M.; De Feyter, S.; De Gendt, S. Molecular Doping of MoS 2 Transistors by Self-Assembled Oleylamine Networks. Appl. Phys. Lett. 2016, 109 (25), 253112.

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.

There is a pressing need for reliable, reproducible and accurate measurements of graphene’s properties, through international standards, to facilitate industrial growth. However, trustworthy and verified standards require rigorous metrological studies, determining, quantifying and reducing the sources of measurement uncertainty. Towards this effort, we report the procedure and the results of an international interlaboratory comparison (ILC) study, conducted under Versailles Project on Advanced Materials and Standards. This ILC focusses on the comparability of Raman spectroscopy measurements of chemical vapour deposition (CVD) grown graphene using the same measurement protocol across different institutes and laboratories. With data gathered from 17 participants across academia, industry (including instrument manufacturers) and national metrology institutes, this study investigates the measurement uncertainty contributions from both Raman spectroscopy measurements and data analysis procedures, as well as provides solutions for improved accuracy and precision. While many of the reported Raman metrics were relatively consistent, significant and meaningful outliers occurred due to differences in the instruments and data analysis. These variations resulted in inconsistent reports of peak intensity ratios, peak widths and the coverage of graphene. Due to a lack of relative intensity calibration, the relative difference reported in the 2D- and G peak intensity ratios ( I 2 D / I G ) was up to 200%. It was also shown that the standard deviation for Γ 2 D values reported by different software packages, was 15× larger for Lorentzian fit functions than for pseudo-Voigt functions. This study has shown that by adopting a relative intensity calibration and consistent peak fitting and data analysis methodologies, these large, and previously unquantified, variations can be significantly reduced, allowing more reproducible and comparable measurements for the graphene community, supporting fundamental research through to the growing graphene industry worldwide. This project and its findings directly underpin the development of the ISO/IEC standard ‘ DTS 21356-2—Nanotechnologies—Structural Characterisation of CVD-grown Graphene ’.

The functionalization of carbon nanotubes by polymers necessitates two steps, first their modification by oxidizing them or by covalently attaching small compounds to them, then the growth of the polymer chains from these anchors or their grafting onto them. In order to better control the process and the rate of functionalization, we develop polymers able to covalently react with the carbon nanotubes by their side chains in one step. We describe the synthesis of a copolymer of dodecylthiophene and its analogue bearing an aniline group at the end of the dodecyl side chain. This copolymer can functionalize single-walled carbon nanotubes (SWNTs) non-covalently and disperse more SWNTs than its hexyl analogues. UV-Vis and fluorescence spectroscopies show that in these non-covalent hybrids, the polymer forms p-stacked aggregates on the SWNTs. The non-covalent hybrids can be transformed into covalent ones by diazonium coupling. In these covalent hybrids the polymer is no longer p-stacked. According to Raman spectroscopy, the conformation of the poly(3-hexylthiophene) backbone is more ordered in the non-covalent hybrids than in the covalent ones.

Twisted bilayer graphene is a fascinating system due to the possibility of tuning the electronic and optical properties by controlling the twisting angle θ between the layers. The coupling between the Dirac cones of the two graphene layers gives rise to van Hove singularities (vHs) in the density of electronic states, whose energies vary with θ. Raman spectroscopy is a fundamental tool to study twisted bilayer graphene (TBG) systems since the Raman response is hugely enhanced when the photons are in resonance with transition between vHs and new peaks appear in the Raman spectra due to phonons within the interior of the Brillouin zone of graphene that are activated by the Moiré superlattice. It was recently shown that these new peaks can be activated by the intralayer and the interlayer electron–phonon processes. In this work we study how each one of these processes enhances the intensities of the peaks coming from the acoustic and optical phonon branches of graphene. Resonance Raman measurements, performed in many different TBG samples with θ between 4∘ and 16∘ and using several different laser excitation energies in the near-infrared (NIR) and visible ranges (1.39–2.71 eV), reveal the distinct enhancement of the different phonons of graphene by the intralayer and interlayer processes. Experimental results are nicely explained by theoretical calculations of the double-resonance Raman intensity in graphene by imposing the momentum conservation rules for the intralayer and the interlayer electron–phonon resonant conditions in TBGs. Our results show that the resonant enhancement of the Raman response in all cases is affected by the quantum interference effect and the symmetry requirements of the double resonance Raman process in graphene.