Shriram Shivaraman

Measurement of ultrafast carrier dynamics in epitaxial graphene

Using ultrafast optical pump-probe spectroscopy, we have measured carrier relaxation times in epitaxial graphene layers grown on SiC wafers. We find two distinct time scales associated with the relaxation of nonequilibrium photogenerated carriers. An initial fast relaxation transient in the 70–120fs range is followed by a slower relaxation process in the 0.4–1.7ps range. The slower relaxation time is found to be inversely proportional to the degree of crystalline disorder in the graphene layers as measured by Raman spectroscopy. We relate the measured fast and slow time constants to carrier-carrier and carrier-phonon intraband and interband scattering processes in graphene.

Ultrafast Optical-Pump Terahertz-Probe Spectroscopy of the Carrier Relaxation and Recombination Dynamics in Epitaxial Graphene

The ultrafast relaxation and recombination dynamics of photogenerated electrons and holes in epitaxial graphene are studied using optical-pump terahertz-probe spectroscopy. The conductivity in graphene at terahertz frequencies depends on the carrier concentration as well as the carrier distribution in energy. Time-resolved studies of the conductivity can therefore be used to probe the dynamics associated with carrier intraband relaxation and interband recombination. We report the electron-hole recombination times in epitaxial graphene for the first time. Our results show that carrier cooling occurs on subpicosecond time scales and that interband recombination times are carrier density dependent.

Measurement of the optical absorption spectra of epitaxial graphene from terahertz to visible

We present experimental results on the optical absorption spectra of epitaxial graphene from the visible to the terahertz frequency range. In the terahertz range, the absorption is dominated by intraband processes with a frequency dependence similar to the Drude model. In the near-IR range, the absorption is due to interband processes and the measured optical conductivity is close to the theoretical value of e2/4ℏ. We extract values for the carrier densities, the number of carbon atom layers, and the intraband scattering times from the measurements.

Ultrafast relaxation dynamics of hot optical phonons in graphene

Using ultrafast optical pump-probe spectroscopy, we study the relaxation dynamics of hot optical phonons in few-layer and multilayer graphene films grown by epitaxy on silicon carbide substrates and by chemical vapor deposition on nickel substrates. In the first few hundred femtoseconds after photoexcitation, the hot carriers lose most of their energy to the generation of hot optical phonons which then present the main bottleneck to subsequent cooling. Optical phonon cooling on short time scales is found to be independent of the graphene growth technique, the number of layers, and the type of the substrate. We find average phonon lifetimes in the 2.5–2.55 ps range. We model the relaxation dynamics of the coupled carrier-phonon system with rate equations and find a good agreement between the experimental data and the theory. The extracted optical phonon lifetimes agree very well with the theory based on anharmonic phonon interactions.

Free-Standing Epitaxial Graphene

We report on a method to produce free-standing graphene sheets from epitaxial graphene on silicon carbide (SiC) substrate. Doubly clamped nanomechanical resonators with lengths up to 20 microm were patterned using this technique and their resonant motion was actuated and detected optically. Resonance frequencies of the order of tens of megahertz were measured for most devices, indicating that the resonators are much stiffer than expected for beams under no tension. Raman spectroscopy suggests that the graphene is not chemically modified during the release of the devices, demonstrating that the technique is a robust means of fabricating large-area suspended graphene structures.

Carrier recombination and generation rates for intravalley and intervalley phonon scattering in graphene

Electron-hole generation and recombination rates for intravalley and intervalley phonon scattering in graphene are presented. The transverse and the longitudinal optical phonon modes E2g modes near the zone center point contribute to intravalley interband carrier scattering. At the zone edge KK point, only the transverse optical phonon mode A 1 mode contributes significantly to intervalley interband scattering with recombination rates faster than those due to zone-center phonons. The calculated recombination times range from less than a picosecond to more than hundreds of picoseconds and are strong functions of temperature and electron and hole densities. The theoretical calculations agree well with experimental measurements of the recombination rates of photoexcited carriers in graphene.

van der Waals epitaxial growth of graphene on sapphire by chemical vapor deposition without a metal catalyst.

van der Waals epitaxial growth of graphene on c-plane (0001) sapphire by CVD without a metal catalyst is presented. The effects of CH(4) partial pressure, growth temperature, and H(2)/CH(4) ratio were investigated and growth conditions optimized. The formation of monolayer graphene was shown by Raman spectroscopy, optical transmission, grazing incidence X-ray diffraction (GIXRD), and low voltage transmission electron microscopy (LVTEM). Electrical analysis revealed that a room temperature Hall mobility above 2000 cm(2)/V·s was achieved, and the mobility and carrier type were correlated to growth conditions. Both GIXRD and LVTEM studies confirm a dominant crystal orientation (principally graphene [10-10] || sapphire [11-20]) for about 80-90% of the material concomitant with epitaxial growth. The initial phase of the nucleation and the lateral growth from the nucleation seeds were observed using atomic force microscopy. The initial nuclei density was ~24 μm(-2), and a lateral growth rate of ~82 nm/min was determined. Density functional theory calculations reveal that the binding between graphene and sapphire is dominated by weak dispersion interactions and indicate that the epitaxial relation as observed by GIXRD is due to preferential binding of small molecules on sapphire during early stages of graphene formation.

Very Slow Cooling Dynamics of Photoexcited Carriers in Graphene Observed by Optical-Pump Terahertz-Probe Spectroscopy

Using optical-pump terahertz-probe spectroscopy, we study the relaxation dynamics of photoexcited carriers in graphene at different substrate temperatures. We find that at lower temperatures the tail of the relaxation transients measured by the differential probe transmission become slower, extending beyond several hundred picoseconds below 50 K. We interpret the observed relaxation transients as resulting from the cooling of the photoexcited carriers via phonon emission. The slow cooling of the photoexcited carriers at low temperatures is attributed to the bulk of the electron and hole energy distributions moving close enough to the Dirac point that both intraband and interband scattering of carriers via optical phonon emission become inefficient for removing heat from the carriers. Our model, which includes intraband carrier scattering and interband carrier recombination and generation, agrees very well with the experimental observations.

Schottky barrier inhomogeneities at the interface of few layer epitaxial graphene and silicon carbide

In this work, we study electron transport across the heterojunction interface of epitaxial few-layer graphene grown on silicon carbide and the underlying substrate. The observed Schottky barrier is characterized using current-voltage, capacitance-voltage and photocurrent spectroscopy techniques. It is found that the graphene/SiC heterojunction cannot be characterized by a single unique barrier height because of lateral barrier inhomogeneities. A Gaussian distribution of barrier heights with a mean barrier height φBm=1.06eV and standard deviation σ=137±11meV explains the experimental data quite well.

Emission of terahertz radiation from SiC

We report the emission of strong coherent broadband terahertz radiation from 6H-silicon-carbide (SiC) excited with optical pulses. The measured terahertz spectral signal-to-noise ratio is better than one thousand. We determine that the terahertz radiation is generated via second order optical nonlinearity (optical rectification). We present a measurement of the ratio of nonlinear susceptibility tensor elements χzzz(2)/χzxx(2) and the complex index of refraction of silicon carbide at terahertz frequencies.