Microscopic Understanding of Ultrafast Charge Transfer in van der Waals Heterostructures.

Van der Waals heterostructures show many intriguing phenomena including ultrafast charge separation following strong excitonic absorption in the visible spectral range. However, despite the enormous potential for future applications in the field of optoelectronics, the underlying microscopic mechanism remains controversial. Here we use time- and angle-resolved photoemission spectroscopy combined with microscopic many-particle theory to reveal the relevant microscopic charge transfer channels in epitaxial WS_{2}/graphene heterostructures. We find that the timescale for efficient ultrafast charge separation in the material is determined by direct tunneling at those points in the Brillouin zone where WS_{2} and graphene bands cross, while the lifetime of the charge separated transient state is set by defect-assisted tunneling through localized sulphur vacancies. The subtle interplay of intrinsic and defect-related charge transfer channels revealed in the present work can be exploited for the design of highly efficient light harvesting and detecting devices.

Ultrafast transition between exciton phases in van der Waals heterostructures.

Heterostructures of atomically thin van der Waals bonded monolayers have opened a unique platform to engineer Coulomb correlations, shaping excitonic1-3, Mott insulating4 or superconducting phases5,6. In transition metal dichalcogenide heterostructures7, electrons and holes residing in different monolayers can bind into spatially indirect excitons1,3,8-11 with a strong potential for optoelectronics11,12, valleytronics1,3,13, Bose condensation14, superfluidity14,15 and moiré-induced nanodot lattices16. Yet these ideas require a microscopic understanding of the formation, dissociation and thermalization dynamics of correlations including ultrafast phase transitions. Here we introduce a direct ultrafast access to Coulomb correlations between monolayers, where phase-locked mid-infrared pulses allow us to measure the binding energy of interlayer excitons in WSe2/WS2 hetero-bilayers by revealing a novel 1s-2p resonance, explained by a fully quantum mechanical model. Furthermore, we trace, with subcycle time resolution, the transformation of an exciton gas photogenerated in the WSe2 layer directly into interlayer excitons. Depending on the stacking angle, intra- and interlayer species coexist on picosecond scales and the 1s-2p resonance becomes renormalized. Our work provides a direct measurement of the binding energy of interlayer excitons and opens the possibility to trace and control correlations in novel artificial materials.

Slow Noncollinear Coulomb Scattering in the Vicinity of the Dirac Point in Graphene.

The Coulomb scattering dynamics in graphene in energetic proximity to the Dirac point is investigated by polarization resolved pump-probe spectroscopy and microscopic theory. Collinear Coulomb scattering rapidly thermalizes the carrier distribution in k directions pointing radially away from the Dirac point. Our study reveals, however, that, in almost intrinsic graphene, full thermalization in all directions relying on noncollinear scattering is much slower. For low photon energies, carrier-optical-phonon processes are strongly suppressed and Coulomb mediated noncollinear scattering is remarkably slow, namely on a ps time scale. This effect is very promising for infrared and THz devices based on hot carrier effects.

Experimental verification of carrier multiplication in graphene.

We report on the first direct experimental observation of carrier multiplication in graphene reaching a multiplication factor of up to 2 and persisting on a picoseconds time scale. Exploiting multicolor pump-probe measurement techniques, the excited nonequilibrium carrier distribution is retrieved on an ultrafast time scale. This provides access to the temporal evolution of the optically excited carrier density and thus allows quantitative conclusions on possible carrier multiplication. Microscopic time- and momentum-resolved calculations on the ultrafast relaxation dynamics of optically excited carriers confirm the observation of carrier multiplication under corresponding experimental conditions, suggesting graphene as a promising material for novel high-efficiency photodetection devices.

Microscopic model of the optical absorption of carbon nanotubes functionalized with molecular spiropyran photoswitches.

The adsorption of molecules to the surface of carbon nanostructures opens a new field of hybrid systems with distinct and controllable properties. We present a microscopic study of the optical absorption in carbon nanotubes functionalized with molecular spiropyran photoswitches. The switching process induces a change in the dipole moment leading to a significant coupling to the charge carriers in the nanotube. As a result, the absorption spectra of functionalized tubes reveal a considerable redshift of transition energies depending on the switching state of the spiropyran molecule. Our results suggest that carbon nanotubes are excellent substrates for the optical readout of spiropyran-based molecular switches. The gained insights can be applied to other noncovalently functionalized one-dimensional nanostructures in an externally induced dipole field.

Carrier relaxation in epitaxial graphene photoexcited near the Dirac point.

We study the carrier dynamics in epitaxially grown graphene in the range of photon energies from 10 to 250 meV. The experiments complemented by microscopic modeling reveal that the carrier relaxation is significantly slowed down as the photon energy is tuned to values below the optical-phonon frequency; however, owing to the presence of hot carriers, optical-phonon emission is still the predominant relaxation process. For photon energies about twice the value of the Fermi energy, a transition from pump-induced transmission to pump-induced absorption occurs due to the interplay of interband and intraband processes.

The impact of pump fluence on carrier relaxation dynamics in optically excited graphene.

The carrier dynamics in optically excited graphene is determined by an interplay between the Coulomb- and phonon-induced scattering processes. The pump fluence of the excitation pulse plays a crucial role: for high fluences the ultrafast relaxation dynamics is determined by carrier­carrier scattering, whereas for low fluences the carrier­phonon relaxation channels are predominant. On the basis of a microscopic approach, we shed light on the influence of the pump fluence on the temporal evolution of carrier and phonon occupations as well as on the many-particle dephasing of the microscopic polarization. The new insights obtained contribute to a better understanding of the ultrafast carrier dynamics in graphene and can guide future pump­probe experiments.

Time-resolved spectroscopy on epitaxial graphene in the infrared spectral range: relaxation dynamics and saturation behavior.

We present the results of pump­probe experiments on multilayer graphene samples performed in a wide spectral range, namely from the near infrared (photon energy 1.5 eV) to the terahertz (photon energy 8 meV) spectral range. In the near infrared, exciting carriers and probing at higher photon energies provides direct evidence for a hot carrier distribution. Furthermore, spectroscopic signatures of the highly doped graphene layers at the interface to SiC are observed in the near-infrared range. In the mid-infrared range, the various relaxation mechanisms, in particular scattering via optical phonons and Auger-type processes, are identified by comparing the experimental results to microscopic modeling. Changes from induced transmission to induced absorption are attributed to probing above or below the Fermi edge of the graphene layers. This effect occurs for certain photon energies in the near-infrared range, where it is related to highly doped graphene layers at the interface to SiC, and in the far-infrared range for the quasi-intrinsic graphene layers. In addition to the relaxation dynamics, the saturation of pump-induced bleaching of graphene is studied. Here a quadratic dependence of the saturation fluence on the pump photon energy in the infrared spectral range is revealed.

Carbon nanotubes as substrates for molecular spiropyran-based switches.

We present a joint theory-experiment study investigating the excitonic absorption of spiropyran-functionalized carbon nanotubes. The functionalization is promising for engineering switches on a molecular level, since spiropyrans can be reversibly switched between two different conformations, inducing a distinguishable and measurable change of optical transition energies in the substrate nanotube. Here, we address the question of whether an optical read-out of such a molecular switch is possible. Combining density matrix and density functional theory, we first calculate the excitonic absorption of pristine and functionalized nanotubes. Depending on the switching state of the attached molecule, we observe a red-shift of transition energies by about 15 meV due to the coupling of excitons with the molecular dipole moment. Then we perform experiments measuring the absorption spectrum of functionalized carbon nanotubes for both conformations of the spiropyran molecule. We find good qualitative agreement between the theoretically predicted and experimentally measured red-shift, confirming the possibility for an optical read-out of the nanotube-based molecular switch.

Impact of Coulomb scattering on the ultrafast gain recovery in InGaAs quantum dots.

The application of quantum dot (QD) semiconductor optical amplifiers (SOAs) in above 100-Gbit Ethernet networks demands an ultrafast gain recovery on time scales similar to that of the input pulse approximately 100 GHz repetition frequency. Microscopic scattering processes have to act at shortest possible time scales and mechanisms speeding up the Coulomb scattering have to be explored, controlled, and exploited. We present a microscopic description of the gain recovery by coupled polarization- and population dynamics in a thermal nonequilibrium situation going beyond rate-equation models and discuss the limitations of Coulomb scattering between 0D and 2D-confined quantum states. An experiment is designed which demonstrates the control of gain recovery for THz pulse trains in InGaAs QD-based SOAs under powerful electrical injection.