The ultimate surface exposure provided by graphene monolayer makes it the ideal sensor platform but also exposes its intrinsic properties to any nvironmental perturbations. We show in this work that structural and electronic characterization of graphene in air by Raman spectroscopy is significantly affected by the substrate surface cleaning method and moderate laser power conditions. In particular, we demonstrate that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between electron and hole doping with visible photons. The amplitude of this photo-induced doping is found to require hydrophilic substrates and to vanish in suspended graphene. These findings suggest that optically gated graphene devices operating with a sub-second time scale can be envisioned but also that Raman spectroscopy might not be as non-invasive as generally assumed.

In this communication, we report data recorded by in situ Raman experiments on single-layer (SLG) and bilayer (BLG) graphene during exposure to rubidium vapor. By this way, we have been able to follow continuously the changes of the G and 2D bands features over a broad doping range (up to about 1014 electrons/cm2). From the comparison with theoretical predictions, we state that the evolution of the G-mode in SLG is understood as resulting of the competition between adiabatic and non-adiabatic effects in presence of a substrate pinning effect which inhibits the charge-induced lattice expansion of graphene layer [1]. For BLG, the added electrons are shown to be first confined in the top layer before a more symmetric charge repartition at high level doping. The evolution of the 2D band of BLG suggests an unexpected increase of the phonon dispersion upon doping [1]. On the other hand, the ultimate surface exposure provided by graphene monolayer makes it the ideal sensor platform but also exposes its intrinsic properties to any environmental perturbations. In this work, we demonstrate that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between electron and hole doping with visible photons. This photo-induced doping happens under moderate laser power conditions but is significantly affected by the substrate cleaning method. In particular, it requires hydrophilic substrates and vanishes for suspended graphene. These findings also suggest that Raman spectroscopy is not always as non-invasive as generally assumed [2]. [1] R. Parret et al., ACS Nano 7, 165 (2013) [2] A. Tiberj et al., Scientific Reports 3:2355 (2013)

The ultimate surface exposure provided by graphene monolayer makes it the ideal sensor platform but also exposes its intrinsic properties to any environmental perturbations. We show in this work that structural and electronic characterization of graphene in air by Raman spectroscopy is significantly affected by the substrate surface cleaning method and moderate laser power conditions. In particular, we demonstrate that the charge carrier density of graphene exfoliated on a SiO2/Si substrate can be finely and reversibly tuned between electron and hole doping with visible photons. The amplitude of this photo-induced doping is found to require hydrophilic substrates and to vanish in suspended graphene. These findings suggest that optically gated graphene devices operating with a sub-second time scale can be envisioned but also that Raman spectroscopy might not be as non-invasive as generally assumed.

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 1014 electrons/cm2) 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.

A powerful imaging technique based on femtosecond time-resolved measurements with a high dynamic range, commercial CCD camera is presented. Ultrafast phenomena induced by a femtosecond laser pump are visualized through the lock-in type acquisition of images recorded by a femtosecond laser probe. This technique allows time-resolved measurements of laser excited phenomena at multiple probe wavelengths (spectrometer mode) or conventional imaging of the sample surface (imaging mode). Two examples based on time-resolved imaging of the sample surface are presented. First, we follow the non-linear reshaping of an acoustic strain pulse in a hybrid gold/cobalt layer at ambient temperature in a sequence of images. Second, we examine time-resolved images of transient thermal heating in graphene samples where we observe heat dissipation as fast as one picosecond which neither depends on the number of layers nor the shape of the graphene sample. A wealth of adaptations of the presented technique can be considered such as imaging of ultrasonic echoes in biological samples (ultrasonic microscopy with resolution down to tens of nanometer).

The Raman bands intensities, frequencies, widths and profiles of few layer graphene (FLG) are extremely sensitive to doping, strain, stacking order, number of graphene sheets, crystalline quality and laser wavelength. For samples of epitaxial graphene grown on silicon carbide, the laser wavelength is basically the only factor known a priori. Furthermore, the concomitance of second order SiC Raman modes in the graphene G and D bands region complicates the extraction of the graphene signal. Developing a robust characterization tool enabling to disentangle all these effects and to provide reliable information is thus highly needed and challenging. We propose an approach where micro-Raman spectroscopy is combined with reflectivity and transmission measurements to discriminate between the different contributions in the measured Raman signatures and to access to the detailed characteristics of the samples. Here, we demonstrate the efficiency of this method in order to determine the number of graphene layers. We address then the question of using the 2D band width or ratio of the 2D and G bands intensities as a criteria to distinguish between mono and multi layer(s) graphene.