Determining by Raman spectroscopy the average thickness and N-layer-specific surface coverages of MoS2 thin films with domains much smaller than the laser spot size.

Raman spectroscopy is a widely used technique to characterize nanomaterials because of its convenience, non-destructiveness, and sensitivity to materials change. The primary purpose of this work is to determine via Raman spectroscopy the average thickness of MoS2 thin films synthesized by direct liquid injection pulsed-pressure chemical vapor deposition (DLI-PP-CVD). Such samples are constituted of nanoflakes (with a lateral size of typically 50 nm, i.e., well below the laser spot size), with possibly a distribution of thicknesses and twist angles between stacked layers. As an essential preliminary, we first reassess the applicability of different Raman criteria to determine the thicknesses (or layer number, N) of MoS2 flakes from measurements performed on reference samples, namely well-characterized mechanically exfoliated or standard chemical vapor deposition MoS2 large flakes deposited on 90 ± 6 nm SiO2 on Si substrates. Then, we discuss the applicability of the same criteria for significantly different DLI-PP-CVD MoS2 samples with average thicknesses ranging from sub-monolayer up to three layers. Finally, an original procedure based on the measurement of the intensity of the layer breathing modes is proposed to evaluate the surface coverage for each N (i.e., the ratio between the surface covered by exactly N layers and the total surface) in DLI-PP-CVD MoS2 samples.

Electrical monitoring of organic crystal phase transition using MoS2 field effect transistor.

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. In this study, we are interested in the quinoidal zwitterion/MoS2 hybrid system in which organic crystals are grown by epitaxy on the MoS2 surface and reorganize in another polymorph after thermal annealing. By means of field-effect transistor measurements recorded in situ all along the process, atomic force microscopy and density functional theory calculations we demonstrate that the charge transfer between quinoidal zwitterions and MoS2 strongly depends on the conformation of the molecular film. Remarkably, both the field effect mobility and the current modulation depth of the transistors remain unchanged which opens up promising prospects for efficient devices based on this hybrid system. We also show that MoS2 transistors enable fast and accurate detection of structural modifications that occur during phases transitions of the organic layer. This work highlights that MoS2 transistors are remarkable tools for on-chip detection of molecular events occurring at the nanoscale, which paves the way for the investigation of other dynamical systems.

Restoring self-limited growth of single-layer graphene on copper foil via backside coating.

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.

In situ Raman probing of graphene over a broad doping range upon rubidium vapor exposure.

We report in situ Raman scattering experiments on single-layer graphene (SLG) and Bernal bilayer graphene (BLG) during exposure to rubidium vapor. The G- and 2D-band evolutions with doping time are presented and analyzed. On SLG, the extended doping range scanned (up to about 10(14) electrons/cm(2)) allows the observation of three regimes in the evolution of the G-band frequency: a continuous upshift followed by a plateau and a downshift. Overall the measured evolution is interpreted as the signature of the competition between dynamic and adiabatic effects upon n-doping. Comparison of the obtained results with theoretical predictions indicates however that a substrate pinning effect occurs and inhibits charge-induced lattice expansion of SLG. At low doping, a direct link between electrostatic gating and Rb doping results is presented. For BLG, the added electrons are shown to be first confined in the top layer, but the system evolves with time toward a more symmetric repartition of the added electrons in both layers. The results obtained on BLG also confirm that the slope of the phonon dispersion close to the K point tends to be slightly reduced at low doping but suggest the occurrence of an unexpected increase of the phonon dispersion slope at higher electron concentration.

Multiscale investigation of graphene layers on 6H-SiC(000-1).

In this article, a multiscale investigation of few graphene layers grown on 6H-SiC(000-1) under ultrahigh vacuum (UHV) conditions is presented. At 100-µm scale, the authors show that the UHV growth yields few layer graphene (FLG) with an average thickness given by Auger spectroscopy between 1 and 2 graphene planes. At the same scale, electron diffraction reveals a significant rotational disorder between the first graphene layer and the SiC surface, although well-defined preferred orientations exist. This is confirmed at the nanometer scale by scanning tunneling microscopy (STM). Finally, STM (at the nm scale) and Raman spectroscopy (at the µm scale) show that the FLG stacking is turbostratic, and that the domain size of the crystallites ranges from 10 to 100 nm. The most striking result is that the FLGs experience a strong compressive stress that is seldom observed for graphene grown on the C face of SiC substrates.