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.

Chirality manifestation in elastic coupling between the layers of double-walled carbon nanotubes.

The search for new relatively easy physicochemical methods for the structural identification of carbon nanotubes represents a key challenge. Here, analyzing the experimental data on double-walled carbon nanotubes (DWCNTs) obtained by us and taken from the literature, we have expressed the magnitude of elastic coupling between two tubular walls forming a DWCNT as a simple function dependent not only on DWCNT diameters but also on the difference between the chirality angles of the constituent nanotubes. To get this quite unexpected result, which allows us to relate more precisely the structural parameters of a DWCNT with frequencies of its radial breathing-like modes (RBLM), we have developed a new model for the RBLM dynamics that takes into account a possible deposition of water molecules from ambient air onto the DWCNT surface. The model constructed allows us to predict the higher prevalence of DWCNTs comprising two walls with identical handedness. The application of the results obtained for the identification of DWCNTs is also considered.

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.

Growth of low doped monolayer graphene on SiC(0001) via sublimation at low argon pressure.

Silicon carbide (SiC) sublimation is the most promising option to achieve transfer-free graphene at the wafer-scale. We investigated the initial growth stages from the buffer layer to monolayer graphene on SiC(0001) as a function of annealing temperature at low argon pressure (10 mbar). A buffer layer, fully covering the SiC substrate, forms when the substrate is annealed at 1600 °C. Graphene formation starts from the step edges of the SiC substrate at higher temperature (1700 °C). The spatial homogeneity of the monolayer graphene was observed at 1750 °C, as characterized by Raman spectroscopy and magneto-transport. Raman spectroscopy mapping indicated an AG-graphene/AG-HOPG ratio of around 3.3%, which is very close to the experimental value reported for a graphene monolayer. Transport measurements from room temperature down to 1.7 K indicated slightly p-doped samples (p ≃ 1010 cm-2) and confirmed both continuity and thickness of the monolayer graphene film. Successive growth processes have confirmed the reproducibility and homogeneity of these monolayer films.

Direct measurement of the absolute absorption spectrum of individual semiconducting single-wall carbon nanotubes.

The optical properties of single-wall carbon nanotubes are very promising for developing novel opto-electronic components and sensors with applications in many fields. Despite numerous studies performed using photoluminescence or Raman and Rayleigh scattering, knowledge of their optical response is still partial. Here we determine using spatial modulation spectroscopy, over a broad optical spectral range, the spectrum and amplitude of the absorption cross-section of individual semiconducting single-wall carbon nanotubes. These quantitative measurements permit determination of the oscillator strength of the different excitonic resonances and their dependencies on the excitonic transition and type of semiconducting nanotube. A non-resonant background is also identified and its cross-section comparable to the ideal graphene optical absorbance. Furthermore, investigation of the same single-wall nanotube either free standing or lying on a substrate shows large broadening of the excitonic resonances with increase of oscillator strength, as well as stark weakening of polarization-dependent antenna effects, due to nanotube-substrate interaction.

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.

Wall-selective probing of double-walled carbon nanotubes using covalent functionalization.

Double-walled carbon nanotubes (DWNTs) present an original coaxial geometry in which the inner wall is naturally protected from the environment by the outer wall. Covalent functionalization is introduced here as an effective approach to investigate DWNT devices. Performed using an aryldiazonium salt, the functionalization is reversible upon thermal annealing and occurs strictly at the surface of the outer wall, leaving the inner wall essentially unaltered by the chemical bonding. Measurements on functionalized DWNT transistors show that the electrical current is carried by the inner wall and provide unambiguous identification of the metallic or semiconducting character of both walls. New insights about current saturation at high bias in DWNTs are also presented as an illustration of new experiments unlocked by the method. The wall-selectivity of the functionalization not only enables selective optical and electrical probing of the DWNTs, but it also paves the way to designing novel electronic devices in which the inner wall is used for electrical transport while the outer wall chemically interacts with the environment.

High performance resonance Raman spectroscopy using volume Bragg gratings as tunable light filters.

We designed a near infrared tunable resonance Raman spectroscopy system based on a tandem of thick volume Bragg gratings (VBGs). VBGs are here the constituents of two light filtering units: a tunable laser line filter (LLF) and a tunable notch filter (NF). When adapted in a micro-Raman setup with a single stage monochromator (1800 gr/mm grating), the tandem of LLF and NF allowed measurements of Raman signals down to +/-20 cm(-1). The good performance and fast tunability of the VBG Raman system was demonstrated on a sulfur powder and on a bulk single-walled carbon nanotube sample through a series of 22 Stokes and anti-Stokes spectra recorded at excitation wavelengths between 800 and 990 nm. The main drawbacks of the setup are the limited spectral range to the near infrared and the small angular acceptance of the filters (approximately 1 mrad), which causes mainly attenuation problems with the NF. The impact of the main limitations is discussed and solutions are provided.

Directed assembly of SWNTs by electrostatic interactions and its application for making network transistors.

Single-wall carbon nanotubes (SWNTs) are promising building blocks for the fabrication of nanoelectronic devices. However, achieving control over their assembly on substrates has been challenging and is still a bottleneck to their utilization. Herein, we present a general method for directing the chemical assembly of SWNTs on substrates through electrostatic interactions. By covalently functionalizing both the nanotube sidewalls and the SiO(2) substrate with charged groups, dense networks of SWNTs were produced. The method is selective and highly efficient to process network field-effect transistors.

Periodic inclusion of room-temperature-ferromagnetic metal phosphide nanoparticles in carbon nanotubes.

We demonstrate the use of sequential catalytic growth to encapsulate iron, nickel-iron, and iron-cobalt phosphide catalyst nanoparticles periodically along the entire lengths of carbon nanotubes. Investigations by local electron spectroscopies and electron diffraction reveal the compositions and crystal structures of the encapsulated particles. Significantly, high spatial resolution magnetic characterization using magnetic force microscopy and off-axis electron holography demonstrates that encapsulated iron-cobalt phosphide nanoparticles are ferromagnetic at room temperature, in accordance with the properties of bulk metal phosphides of the same structure and composition.

Electron diffraction analysis of individual single-walled carbon nanotubes.

We present a detailed electron diffraction study of individual single-walled carbon nanotubes. A novel sample preparation procedure provides well-separated, long and straight individual single-shell nanotubes. Diffraction experiments are carried out at 60 kV, below the threshold for knock-on damage in carbon nanotubes. We describe experimental parameters that allow single-tube electron diffraction experiments with widely available thermal emission transmission electron microscopes. Further, we review the simulation of diffraction patterns for these objects.

Raman modes of index-identified freestanding single-walled carbon nanotubes.

Using electron diffraction on freestanding single-walled carbon nanotubes, we have determined the structural indices (n,m) of tubes in the diameter range from 1.4 to 3 nm. On the same freestanding tubes, we have recorded Raman spectra of the tangential modes and the radial breathing mode. For the smaller diameters (1.4-1.7 nm), these measurements confirm previously established radial breathing mode frequency versus diameter relations and would be consistent with the theoretically predicted proportionality to the inverse diameter. However, for extending the relation to larger diameters, either a yet unexplained environmental constant has to be assumed, or the linear relation has to be abandoned.

Single-molecule torsional pendulum.

We have built a torsional pendulum based on an individual single-walled carbon nanotube, which is used as a torsional spring and mechanical support for the moving part. The moving part can be rotated by an electric field, resulting in large but fully elastic torsional deformations of the nanotube. As a result of the extremely small restoring force associated with the torsional deformation of a single molecule, unusually large oscillations are excited by the thermal energy of the pendulum. By diffraction analysis, we are able to determine the handedness of the molecule in our device. Mechanical devices with molecular-scale components are potential building blocks for nanoelectromechanical systems and may also serve as sensors or actuators.

Relevant synthesis parameters for the sequential catalytic growth of carbon nanotubes.

Sequential catalytic growth provides an efficient tool for the synthesis of carbon nanotubes periodically inserted with catalyst nanoparticles. Several synthesis parameters were found crucial in order to induce this particular growth mechanism. The presence of phosphorus is required to form metal phosphide particles active for the formation of carbon nanotubes with a matchstick morphology. The metal composition (Ni/Fe ratio) and the carbon supply have no influence on the nanofilament type but strongly affect the nanotube yield. The synthesis temperature induces important changes on both the nanofilament type and yield, which are correlated with important transformations of the catalyst layer in terms of composition, particle size, and physical state.