Title: Investigations of the electronic, vibrational and structural properties of single and few-layer graphene
Description: Single and few-layer graphene (SLG and FLG) have stimulated great scientific interest because of their distinctive properties and potential for novel applications. In this dissertation, we investigate the mechanical, electronic and vibrational properties of these remarkable materials by various techniques, including atomic-force microscopy (AFM) and Raman, infrared (IR), and ultrafast optical spectroscopy. With respect to its mechanical properties, SLG is known to be capable of undergoing significant mechanical deformation. We have applied AFM to investigate how the morphology of SLG is influenced by the substrate on which it is deposited. We have found that SLG is strongly affected by the morphology of the underlying supporting surface. In particular, SLG deposited on atomically flat surfaces of mica substrates exhibits an ultraflat morphology, with height variation essentially indistinguishable from that observed for the surface of cleaved graphite. One of the most distinctive aspects of SLG is its spectrum of electronic excitations, with its characteristic linear energy-momentum dispersion relation.

We have examined the dynamics of the corresponding Dirac fermions by optical emission spectroscopy. By analyzing the spectra of light emission induced in the spectral visible range by 30-femtosecond laser pulses, we find that the charge carriers in graphene cool by the emission of strongly coupled optical phonons in a few 10's of femtoseconds and thermalize among themselves even more rapidly. The charge carriers and the strongly coupled optical phonons are thus essentially in thermal equilibrium with one another on the picosecond time scale, but can be driven strongly out of equilibrium with the other phonons in the system. Temperatures exceeding 3000 K are achieved for the subsystem of the charge carriers and optical phonons under femtosecond laser excitation. While SLG exhibits remarkable physical properties, its few-layer counterparts are also of great interest. In particular, FLG can exist in various crystallographic stacking sequences, which strongly influence the material's electronic properties.

We have developed an accurate and convenient method of characterizing stacking order in FLG using the lineshape of the Raman 2D-mode. Raman imaging allows us to visualize directly the spatial distribution of Bernal (ABA) and rhombohedral (ABC) stacking in trilayer and tetralayer graphene. We find that 15% of exfoliated graphene trilayers and tetralayers are comprised of micrometer-sized domains of rhombohedral stacking, rather than of usual Bernal stacking. The accurate identification of stacking domains in FLG allows us to investigate the influence of stacking order on the material's electronic properties. In particular, we have studied by means of IR spectroscopy the possibility of opening a band gap by the application of a strong perpendicular electric field in trilayer graphene. We observe an electrically tunable band gap exceeding 100 meV in ABC trilayers, while no band gap is found for ABA trilayers. We have also studied the influence of layer thickness and stacking order on the Raman response of the out-of-plane vibrations in FLG.

We observe a Raman combination mode that involves the layer-breathing vibrations in FLG. This Raman mode is absent in SLG and exhibits a lineshape that depends sensitively on both the material's layer thickness and stacking sequence.