Ermin Malic

Carrier Multiplication in Graphene

Graphene as a zero-bandgap semiconductor is an ideal model structure to study the carrier relaxation channels, which are inefficient in conventional semiconductors. In particular, it is of fundamental interest to address the question whether Auger-type processes significantly influence the carrier dynamics in graphene. These scattering channels bridge the valence and conduction band allowing carrier multiplication, a process that generates multiple charge carriers from the absorption of a single photon. This has been suggested in literature for improving the efficiency of solar cells. Here we show, based on microscopic calculations within the density matrix formalism, that Auger processes do play an unusually strong role for the relaxation dynamics of photoexcited charge carriers in graphene. We predict that a considerable carrier multiplication takes place, confirming the potential of graphene as a new material for high-efficiency photodevices.

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.

Intrinsic homogeneous linewidth and broadening mechanisms of excitons in monolayer transition metal dichalcogenides

The band-edge optical response of transition metal dichalcogenides, an emerging class of atomically thin semiconductors, is dominated by tightly bound excitons localized at the corners of the Brillouin zone (valley excitons). A fundamental yet unknown property of valley excitons in these materials is the intrinsic homogeneous linewidth, which reflects irreversible quantum dissipation arising from system (exciton) and bath (vacuum and other quasiparticles) interactions and determines the timescale during which excitons can be coherently manipulated. Here we use optical two-dimensional Fourier transform spectroscopy to measure the exciton homogeneous linewidth in monolayer tungsten diselenide (WSe2). The homogeneous linewidth is found to be nearly two orders of magnitude narrower than the inhomogeneous width at low temperatures. We evaluate quantitatively the role of exciton–exciton and exciton–phonon interactions and population relaxation as linewidth broadening mechanisms. The key insights reported here—strong many-body effects and intrinsically rapid radiative recombination—are expected to be ubiquitous in atomically thin semiconductors.Monolayer transition metal dichalcogenides feature Coulomb-bound electron-hole pairs (excitons) with exceptionally large binding energy and coupled spin and valley degrees of freedom. These unique attributes have been leveraged for electrical and optical control of excitons for atomically-thin optoelectronics and valleytronics. The development of such technologies relies on understanding and quantifying the fundamental properties of the exciton. A key parameter is the intrinsic exciton homogeneous linewidth, which reflects irreversible quantum dissipation arising from system (exciton) and bath (vacuum and other quasiparticles) interactions. Using optical coherent two-dimensional spectroscopy, we provide the first experimental determination of the exciton homogeneous linewidth in monolayer transition metal dichalcogenides, specifically tungsten diselenide (WSe2). The role of exciton-exciton and exciton-phonon interactions in quantum decoherence is revealed through excitation density and temperature dependent linewidth measurements. The residual homogeneous linewidth extrapolated to zero density and temperature is ~1.5 meV, placing a lower bound of approximately 0.2 ps on the exciton radiative lifetime. The exciton quantum decoherence mechanisms presented in this work are expected to be ubiquitous in atomically-thin semiconductors.

Hot electron relaxation and phonon dynamics in graphene

Using density-matrix theory, we microscopically calculate the relaxation dynamics of photoexcited electrons in graphene. Electron-phonon coupling leads to an initially ultrafast energy dissipation and to a nonthermal phonon occupation of the highest optical phonon modes. We also calculate the temporal evolution of the electronic temperature and find good agreement with recent experimental work.

Impact of Auger processes on carrier dynamics in graphene

Auger processes are of great importance for both fundamental research and technological applications, since they change the number of charge carriers in a system. Here, we present a microscopic study on the influence of Auger relaxation channels on the carrier dynamics in graphene. The presented time-, momentum-, and angle-resolved calculations reveal the importance of the impact excitation giving rise to a significant multiplication of optically excited carriers and a remarkable Coulomb-induced carrier cooling effect. We propose low pump fluence, high excitation energy, and low ambient temperature as optimal conditions for an efficient carrier multiplication reaching values of up to

Analytical approach to excitonic properties of MoS2

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Excitonic linewidth and coherence lifetime in monolayer transition metal dichalcogenides

even in the presence of phonons. The optimal regime is confirmed by an analytic expression for the carrier multiplication, which gives further insights into the role of Auger processes for a Dirac-like carrier system. Our results can help to guide future experiments to demonstrate the carrier multiplication in graphene and related structures.

Experimental verification of carrier multiplication in graphene.

We present an analytical investigation of the optical absorption spectrum of monolayer molybdenumdisulfide. Based on the density matrix formalism, our approach gives insights into the microscopic origin of excitonic transitions, their relative oscillator strength, and binding energy. We show analytical expressions for the carrier-light coupling element, which contains the optical selection rules and well describes the valleyselective polarization in MoS2. In agreement with experimental results, we find the formation of strongly bound electron-hole pairs due to the efficient Coulomb interaction. The absorption spectrum of MoS2 on a silicon substrate features two pronounced peaks at 1.91 eV and 2.05 eV corresponding to the A and B exciton, which are characterized by binding energies of 420 meV and 440 meV, respectively. Our calculations reveal their relative oscillator strength and predict the appearance of further low-intensity excitonic transitions at higher energies. The presented approach is applicable to other transition metal dichalcogenides and can be extended to investigations of trion and biexcitonic effects.

Trion formation dynamics in monolayer transition metal dichalcogenides

Atomically thin transition metal dichalcogenides are direct-gap semiconductors with strong light–matter and Coulomb interactions. The latter accounts for tightly bound excitons, which dominate their optical properties. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in the optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emission from bright exciton states. Here, we investigate the microscopic origin of the excitonic coherence lifetime in two representative materials (WS2 and MoSe2) through a study combining microscopic theory with spectroscopic measurements. We show that the excitonic coherence lifetime is determined by phonon-induced intravalley scattering and intervalley scattering into dark excitonic states. In particular, in WS2, we identify exciton relaxation processes involving phonon emission into lower-lying dark states that are operative at all temperatures.

Absorption saturation in optically excited 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.