Gunnar Berghäuser

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.

Analytical approach to excitonic properties of MoS2

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.

Excitonic linewidth and coherence lifetime 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.

Trion formation dynamics in monolayer transition metal dichalcogenides

We report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond time scale through exciton-electron interaction. As the pump energy is tuned from the high energy to low energy side of the inhomogeneously broadened exciton resonance, the trion formation time increases by ∼50%. This feature can be explained by the existence of both localized and delocalized excitons in a disordered potential and suggests the existence of an exciton mobility edge in transition metal dichalcogenides.

Ultrafast Coulomb-Induced Intervalley Coupling in Atomically Thin WS2

Monolayers of semiconducting transition metal dichalcogenides hold the promise for a new paradigm in electronics by exploiting the valley degree of freedom in addition to charge and spin. For MoS2, WS2, and WSe2, valley polarization can be conveniently initialized and read out by circularly polarized light. However, the underlying microscopic processes governing valley polarization in these atomically thin equivalents of graphene are still not fully understood. Here, we present a joint experiment-theory study on the ultrafast time-resolved intervalley dynamics in monolayer WS2. Based on a microscopic theory, we reveal the many-particle mechanisms behind the observed spectral features. We show that Coulomb-induced intervalley coupling explains the immediate and prominent pump-probe signal in the unpumped valley and the seemingly low valley polarization degrees typically observed in pump-probe measurements compared to photoluminescence studies. The gained insights are also applicable to other light-emitting monolayer transition metal dichalcogenides, such as MoS2 and WSe2, where the Coulomb-induced intervalley coupling also determines the initial carrier dynamics.

Proposal for dark exciton based chemical sensors

The rapidly increasing use of sensors throughout different research disciplines and the demand for more efficient devices with less power consumption depends critically on the emergence of new sensor materials and novel sensor concepts. Atomically thin transition metal dichalcogenides have a huge potential for sensor development within a wide range of applications. Their optimal surface-to-volume ratio combined with strong light–matter interaction results in a high sensitivity to changes in their surroundings. Here, we present a highly efficient sensing mechanism to detect molecules based on dark excitons in these materials. We show that the presence of molecules with a dipole moment transforms dark states into bright excitons, resulting in an additional pronounced peak in easy accessible optical spectra. This effect exhibits a huge potential for sensor applications, since it offers an unambiguous optical fingerprint for the detection of molecules—in contrast to common sensing schemes relying on small peak shifts and intensity changes.

Optical fingerprint of dark 2p-states in transition metal dichalcogenides

We present a microscopic study on higher excitonic states in transition metal dichalcogenides in the presence of disorder. We show that the geometric phase cancels the degeneration of 2s and 2p states and that a significant disorder-induced coupling of bright and dark states offers a strategy to circumvent optical selection rules. As a prove, we show a direct fingerprint of dark 2p states in absorption spectra of WS

Strain Control of Exciton–Phonon Coupling in Atomically Thin Semiconductors

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Phonon Sidebands in Monolayer Transition Metal Dichalcogenides

. The predicted softening of optical selection rules through exciton-disorder coupling is of general nature and therefore applicable to related two-dimensional semiconductors.

Impact of strain on the optical fingerprint of monolayer transition-metal dichalcogenides

Semiconducting transition metal dichalcogenide (TMDC) monolayers have exceptional physical properties. They show bright photoluminescence due to their unique band structure and absorb more than 10% of the light at their excitonic resonances despite their atomic thickness. At room temperature, the width of the exciton transitions is governed by the exciton-phonon interaction leading to strongly asymmetric line shapes. TMDC monolayers are also extremely flexible, sustaining mechanical strain of about 10% without breaking. The excitonic properties strongly depend on strain. For example, exciton energies of TMDC monolayers significantly redshift under uniaxial tensile strain. Here, we demonstrate that the width and the asymmetric line shape of excitonic resonances in TMDC monolayers can be controlled with applied strain. We measure photoluminescence and absorption spectra of the A exciton in monolayer MoSe2, WSe2, WS2, and MoS2 under uniaxial tensile strain. We find that the A exciton substantially narrows and becomes more symmetric for the selenium-based monolayer materials, while no change is observed for atomically thin WS2. For MoS2 monolayers, the line width increases. These effects are due to a modified exciton-phonon coupling at increasing strain levels because of changes in the electronic band structure of the respective monolayer materials. This interpretation based on steady-state experiments is corroborated by time-resolved photoluminescence measurements. Our results demonstrate that moderate strain values on the order of only 1% are already sufficient to globally tune the exciton-phonon interaction in TMDC monolayers and hold the promise for controlling the coupling on the nanoscale.