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International audience; 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.

International audience; 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)

International audience; T he main obstacle to the use of graphene on the industrial scale is the growth of a large and homogenous monolayer graphene Concerning this issue, it is worthnoting that our group has recently developed a reproducible and controlled growth process of a monolayer graphene on SiC 0001 by sublimation at low Ar pressure i e 10 mbar Still, the control of the electronic properties of the obtained graphene by this process is very challenging E g the mobility on our graphene on 4 H SiC (0001) is around 2000 cm 2 v 1 s 1 at RT which is in the range of the measured mobilities on similar substrates Yet, it is still very low when compared with the mobilities reported for suspended graphene. It is well acceptedthat the electronic properties of graphene on SiC are highly sensitive to the substrate underneath It was reported that the mobility of graphene on SiC 0001 increases with increasing SiC steps width, and its resistance increases with increasing SiC steps height. This means that the electronic properties of graphene on SiC 0001 can be tuned by controlling the height and width of the terraces that results from the surface reconstruction of SiC before the growth i e Step bunching phenomenon

The growth of single-layer graphene (SLG) by chemical vapor deposition (CVD) on copper surfaces is very popular because of the self-limiting effect that, in principle, prevents the growth of few-layer graphene (FLG). However, the reproducibility of the CVD growth of homogeneous SLG remains a major challenge, especially if one wants to avoid heavy surface treatments, monocrystalline substrates and expensive equipment to control the atmosphere inside the growth system. We demonstrate here that backside tungsten coating of copper foils allows for the exclusive growth of SLG with full coverage by atmospheric pressure CVD implemented in a vacuum-free furnace. We show that the absence of FLG patches is related to the suppression of carbon diffusion through copper. In the perspective of large-scale production of graphene, this approach constitutes a significant improvement to the traditional CVD growth process since (1) a tight control of the hydrocarbon flow is no longer required to avoid FLG formation and, consequently, (2) the growth duration necessary to reach full coverage can be drastically shortened.

International audience; 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].

International audience; 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.

National audience; Raman spectroscopy (RS) of graphene-related materials (GRM) is being considered as a fast, versatile, powerful and non-destructive characterization technique. RS is sensitive to the number of layers, their stacking order, the nature and density of defects, the charge carrier density and in-plane strain variations. However, the positions, linewidths, profiles, intensities of the graphene/multilayer graphene (MLG) Raman bands are not only affected by all these perturbations but also depend on the uniformity across the probed area and on the substrate (through optical interference effects, dielectric screening…). An accurate interpretation of Raman spectra becomes then extremely complex and deserves the combined use of complementary diagnosis. We recently developed a RS set-up allowing to monitor simultaneously the laser power, transmission, reflection and Raman signal.In this contribution, we discuss the application of this tool for counting the number of layers of different kind of graphene/MLG samples with the aim to define standard procedures for GRM characterization on different substrates.

International audience; Une introduction à la spectroscopie Raman de résonance

International audience; 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

International audience; We report the direct and unambiguous evidence of the existence of inner semiconducting tube (iSCT) photoluminescence (PL) from measurements performed on four individual free-standing index-identified double-walled carbon nanotubes (DWNTs). Based on thorough Rayleigh scattering, Raman scattering and PL experiments, we are able to demonstrate that the iSCT PL is observed with a quantum yield estimated as a few 10-6 independently of the semiconducting or metallic nature of the outer tube. This result is mainly attributed to ultrafast exciton transfer from inner to outer tube. Furthermore, by carrying out PL excitation experiments on the (14,1)@(15,12) DWNT, we show that the iSCT PL can be detected through the optical excitation of the outer tube (Figure 1) indicating that the exciton transfer can also occur in the opposite way.References[1] D.I. Levshov et al., Phys Rev. B 96 (2017), pp. 195410

International audience; Since 2008, epitaxial graphene growth has been developed in terms of homogeneity and scale by using a 1 ATM argon pressure at high temperature (>1650°C). Until now, it still remains challenging to obtain films with different and controlled characteristics such as the thickness or the doping by tuning the growth parameters. Here, we optimized the epitaxial growth of monolayer graphene (1LG) on 4H-SiC (0001) under a low argon pressure of 10 mbar. This intermediate pressure allows growing a continued 1LG in a short process ~1h30.First, we discuss the initial growth stages from buffer layer to 1LG as a function of annealing temperature (same heating rate). The combined Raman spectroscopy and atomic force microscopy analyses show that a buffer layer, fully covering the Si-face of SiC, forms as the first step of growth. Subsequently, 1LG starts to grow at step edges and continue to cover the buffer layer on terraces with a step-flow growth mechanism. Eventually, reproducible syntheses of 1LG films were achieved by this temperature-controlled growth process. Then, we investigate the structural and electronic properties of the 1LG films. The integrated intensity of G-band in Raman spectra normalized with respect to a HOPG reference, AG/AG-HOPG, of each spectrum in Raman map of our continued graphene film is very close to the experimental value reported for a 1LG, demonstrating the good homogeneity. Atomically resolved scanning tunnellingmicroscopy (STM) evidences a (6x6) superstructure, indicative of 1LG covering a reconstructed interface layer[7]. Regarding the transport measurement, quantum Hall plateau values observed in our graphene layers confirmed both continuity and thickness of the1LG film. Moreover, we estimated a hole concentration of p~10^10 - 10^11 /(cm^2) at 1.7 K in helium atmosphere. We ascribe this unusual doping type to an atmosphere contamination effect since we regain the typical n-doped graphene under vacuum by transport measurement and STM analysis.

International audience; Introduction to Raman spectroscopy of carbon nanostructures

International audience; A After a brief overview of the discovery and the Raman study of new forms of carbons (intercalated graphite, carbon fiber, fullerenes, carbon nanotubes), the invaluable contribution of late Professor M. Dresselhaus is noted and the 10 reviews and 10 contributions collected to present a picture of the present Raman investigations of graphene and related 2D materials (such as black phosphorus, MoS2) are presented. Methods for numbering the graphene layers, the effects of external perturbations (temperature, pressure, doping and magnetic field) on the phonons of graphene, characterization of the chemical and structural properties of graphene at the nanoscale level by tip-enhanced Raman spectroscopy (TERS), surface enhanced Raman spectroscopy (SERS) and hyperspectral imaging, and applications combining graphene and Raman spectroscopy are addressed.