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.

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 development of smart nanomaterials has attracted great attention in several fields like nanoscience and nanotechnology due to their unique response to external stimuli. Many of them are based on polymers that can exhibit a shape-changes when submitted to environmental modifications. Poly(N-isopropylacrylamide), PNIPAM, is a thermo-responsive polymer. Linear chains are water soluble at room temperature but undergo a reversible coil-to-globule transition at a lower critical solution temperature (LCST) close to 32°C due to the dehydration and subsequent collapse of its chains into compact globules. [1] This phenomenon results in a volume phase transition (VPT) in PNIPAM based crosslinked microgels and can be used to promote original thermal effects.Hybrid nanocomposite microgels associating PNIPAM and gold nanoparticles (GNP) have thus been designed in order to take advantage of the outstanding plasmonic and photo-thermal properties of GNP to promote the VPT of the microgels through an efficient photo-thermal conversion. [2] With their strong diameter-dependent optical absorption in the near infrared (NIR) and their large surface area favoring photo-thermal transfer, semiconducting single-walled carbon nanotubes (s-SWNT) are also good candidates for photo-thermal conversion in the NIR (Figure 1a). However, to the best of our knowledge, no thorough studies of nanomaterials based on both SWNT and PNIPAM have been reported so far.Here we describe the preparation of SWNT/PNIPAM hybrid microgels through a non-covalent functionalization technique. These nanoparticles are stable in water and show a VPT, which can be promoted either by direct heating or by excitation of the resonant absorption of s-SWNT in the NIR (Figure 1b-c). The photoluminescence (PL) signal can be used to monitor the VPT by a redshift observed when crossing the LCST, while the Raman signatures remain essentially the same.

Poly[R-3-hydroxybutyrate-co-(R-3-hydroxyvalerate)] (PHBVs) are promising biopolymers, which could substitute petro-based plastics for packaging applications. To anticipate the behavior of PHBVs when transformed using conventional thermo-mechanical shaping processes, it is needed to better understand the effect of processing temperature on their crystallization behavior and final properties. The objectives of the present work were thus (1) to better understand the influence of the processing temperature on the PHBV macromolecular and crystalline structures, depending on its HV content, and (2) to define a processing window guaranteeing optimized mechanical properties of PHBV films. An innovative experimental strategy was proposed, enabling the study of melting and crystallization events, crystalline structure changes, and evolution of mechanical properties of PHBV according to processing temperature, using identical thermal cycles. A comprehensive dynamic monitoring of the studied PHBVs was achieved by coupling differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), step scan DSC (SDSC), observations of isothermal crystallization under polarized optical microscopy (POM), thermo-regulated wide angle X-ray analysis (WAXS), Nuclear Magnetic Resonance (NRM), and finally mechanical tests on PHBV films. The combination of these experiments revealed how inappropriate processing temperatures can result in irreversible changes in PHBVs’ macromolecular and crystalline structures, thermal behavior and mechanical performances. When increasing the HV content of the copolymer, adjusting the processing conditions according to these results revealed to be critical to match the functional properties targeted for a specific use.

Metal oxide aluminosilicate and aluminogermanate nanotubes, called imogolite nanotubes, are custom made nanotubes with controlled diameter, morphology and organization. These nanotubes undergo major structural changes at high temperatures. Here, we report a complete analysis of the structural transformation of single and double-walled aluminogermanate nanotubes, organized or not in bundles, up to 800 • C. Complementary X-ray scattering and spectroscopy experiments were performed. The evolution of both Al and Ge atoms coordination during the transformation process was studied in-situ. Quantitative analysis of X-ray absorption spectra reveals that the dehydroxylation of nanotubes leads to intermediate stages of 'metaimogolite', which differ in the coordination of the aluminium atoms. A mechanism explaining the major structural reorganization is proposed based on atomic jump processes.

The development of smart nanomaterials has attracted great attention in several fields like nanoscience, materials science,engineering and nanotechnology due to their unique response to external stimuli. Many of them are based on polymers thatcan exhibit great shape-changes when submitted to environmental modifications. Poly(N-isopropylacrylamide), PNIPAM, is sucha thermo-responsive polymer. It is water soluble at room temperature, forming gels by cross-linking but undergoes a reversiblecoil-to-globule volume phase transition (VPT) at a lower critical solution temperature (LCST) close to 32 °C due to thedehydration and subsequent collapse of its chains into compact globules.
Hybrid nanocomposite microgels associating PNIPAM and gold nanoparticles (GNP) have been designed in order to takeadvantage of the outstanding plasmonic and photo-thermal properties of GNP to promote the volume phase transition of themicrogels through an efficient photo-thermal conversion. With their strong diameter-dependent optical absorption in the nearinfrared (NIR) and their large surface area favoring photo-thermal transfer, semiconducting SWNT (s-SWNT) are goodcandidates for photo-thermal conversion in the NIR and may therefore be used to prepare multi-responsive hybrid microgels(Figure 1). However, to the best of our knowledge, no thorough studies of such nanomaterials have been reported so far.
Here we report the preparation of smart SWNT/PNIPAM nanocomposites through non-covalent functionalization techniques.These SWNT/PNIPAM hybrid microgels are stable in water and show a VPT, which can be promoted either by direct heating orby excitation of the resonant absorption of s-SWNT in the near infrared. Furthermore, the photoluminescence (PL) signal of s-SWNT is modulated at the phase transition and therefore, the PL signal can be used to monitor the VPT. This is illustrated inFigure 2, showing coupled Raman/PL measurements below and above the LCST, where a redshift of the PL bands is observedwhen crossing the LCST while the Raman signatures remain essentially the same.