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 ’.

Today, most of electronic devices are based on heterostructures made by molecular beam epitaxy. The impact of van der Waals heterostructures made of 2D materials, already significant at the academic level [1], could generate a technological breakthrough in this field of electronics. Indeed, due to the weak van der Waals interlayer interactions, several materials can be assembled with a precise control of their thicknesses or their twist angles and with high quality interfaces.Recently, hybrid van der waals heterostructures, obtained by combining 2D materials and self-organized organic layers has been developed [2]. Such approach is promising to push further the versatility in terms of materials and thus a wide range of properties are expected.In this poster, we present recent results obtained on field effect transistor based on an hybrid van der Waals heterostructure made of molybdenum disulfide (MoS2) for the inorganic part and quinoidal zwitterions (QZ) for the organic part. The organic layer deposition is achieved under high vacuum, on top of the MoS2 channel of the transistor and the evolution of the transfer characteristic of the transistor is measured in situ.We observed a n-type doping and an increase of the charge carrier density of two orders of magnitudes which is comparable to the doping obtained with optimized charge transfer molecules [3][4]. These results which demonstrate the high compatibility of the QZ with MoS2 open the way for future investigations on functionalized hybrid QZ-2D materials heterostructures[1] A. K. Geim & I. V. Grigorieva Nature 499, 419–425 (2013)[2] Gobbi, M., Orgiu, E., Samorì, P., Adv. Mater. 2018, 30, 1706103.[3] Kiriya, D., Tosun, M., Zhao, P., Kang, J. S., & Javey, A. (2014). Air-Stable Surface Charge TransferDoping of MoS2 by Benzyl Viologen. Journal of the American Chemical Society, 136(22)[4] Dey, S., Matte, H. S. S. R., Shirodkar, S. N., Waghmare, U. V., & Rao, C. N. R. (2013). Charge-Transfer Interaction between Few-Layer MoS2and Tetrathiafulvalene. Chemistry - An Asian Journal,8(8)

The so-called buffer layer (BL) is a carbon rich reconstructed layer formed during SiC (0001) sublimation.The covalent bonds between some carbon atoms in this layer and underlying silicon atoms makes itdifferent from epitaxial graphene. We report a systematical and statistical investigation of the BLsignature and its coupling with epitaxial graphene by Raman spectroscopy. Three different BLs arestudied: bare buffer layer obtained by direct growth (BL0), interfacial buffer layer between graphene andSiC (c-BL1) and the interfacial buffer layer without graphene above (u-BL1). To obtain the latter, wedevelop a mechanical exfoliation of graphene by removing an epoxy-based resin or nickel layer. The BLsare ordered-like on the whole BL growth temperature range. BL0 Raman signature may vary from sampleto sample but forms patches on the same terrace. u-BL1 share similar properties with BL0, albeit withmore variability. These BLs have a strikingly larger overall intensity than BL with graphene on top. Thesignal high frequency side onset upshifts upon graphene coverage, unexplainable by a simple straineffect. Two fine peaks (1235, 1360 cm1), present for epitaxial monolayer and absent for BL and transferred graphene. These findings point to a coupling between graphene and BL.

L’obtention de films de graphène aux caractéristiques contrôlées, comme le nombre de couches ou le dopage, anime toujours une partie de la communauté. La décomposition thermique contrôlée du carbure de silicium (SiC) permet d’envisager la croissance homogène de graphène directement sur des substrats de grande surface. Ce mode de croissance du graphène a initialement été développé à des pressions proches de la pression atmosphérique sous argon et à haute température. Dans l’étude présentée, les croissances par sublimation ont été réalisées à basse pression d’argon (10 mbar). Dans tous les cas, lors de la sublimation du SiC du côté dit « face silicium », il se forme une première couche, dite tampon, qui deviendra, par la suite, la couche de graphène sous laquelle se formera une nouvelle couche tampon. Nous discuterons de la présence et des caractéristiques de cette couche tampon. Nous mettrons notamment en évidence l’inhomogénéité de sa signature Raman, et la nécessité d’une procédure du traitement des données robuste. Puis, nous discuterons, à partir d’une étude complémentaire Raman et AFM, les premiers instants de croissance de la monocouche de graphène, par un mécanisme en bord de marches du SiC. Enfin, des mesures électriques à basse température (1.7 K) et sous champ magnétique (jusqu’à 13 T) complèteront les études menées en confirmant la continuité et la qualité de la monocouche de graphène.