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Van der Waals stacking has provided unprecedented flexibility in shaping many-body interactions by controlling electronic quantum confinement and orbital overlap. Theory has predicted that also electron-phonon coupling critically influences the quantum ground state of low-dimensional systems. Here we introduce proximity-controlled strong-coupling between Coulomb correlations and lattice dynamics in neighbouring van der Waals materials, creating new electrically neutral hybrid eigenmodes. Specifically, we explore how the internal orbital 1s-2p transition of Coulomb-bound electron-hole pairs in monolayer tungsten diselenide resonantly hybridizes with lattice vibrations of a polar capping layer of gypsum, giving rise to exciton-phonon mixed eigenmodes, called excitonic Lyman polarons. Tuning orbital exciton resonances across the vibrational resonances, we observe distinct anticrossing and polarons with adjustable exciton and phonon compositions. Such proximity-induced hybridization can be further controlled by quantum designing the spatial wavefunction overlap of excitons and phonons, providing a promising new strategy to engineer novel ground states of two-dimensional systems., Here, the authors demonstrate proximity-controlled strong-coupling between Coulomb correlations and lattice dynamics in neighbouring van der Waals materials (WSe2 and a gypsum layer), creating electrically neutral hybrid exciton-phonon eigenmodes called excitonic Lyman polarons.

Layered transition metal dichalcogenides exhibit the emergence of a direct bandgap at the monolayer limit along with pronounced excitonic effects. In these materials, interaction with phonons is the dominant mechanism that limits the exciton coherence lifetime. Exciton-phonon interaction also facilitates energy and momentum relaxation, and influences exciton diffusion under most experimental conditions. However, the fundamental changes in the exciton-phonon interaction are not well understood as the material undergoes the transition from a direct to an indirect bandgap semiconductor. Here, we address this question through optical spectroscopy and microscopic theory. In the experiment, we study room-temperature statistics of the exciton line width for a large number of mono- and bilayer WS2 samples. We observe a systematic increase in the room-temperature line width of the bilayer compared to the monolayer of 50 meV, corresponding to an additional scattering rate of ∼0.1 fs-1. We further address both phonon emission and absorption processes by examining the temperature dependence of the width of the exciton resonances. Using a theoretical approach based on many-body formalism, we are able to explain the experimental results and establish a microscopic framework for exciton-phonon interactions that can be applied to naturally occurring and artificially prepared multilayer structures.

Heterostructures of van der Waals bonded layered materials offer unique means to tailor dielectric screening with atomic-layer precision, opening a fertile field of fundamental research. The optical analyses used so far have relied on interband spectroscopy. Here we demonstrate how a capping layer of hexagonal boron nitride (hBN) renormalizes the internal structure of excitons in a WSe$_2$ monolayer using intraband transitions. Ultrabroadband terahertz probes sensitively map out the full complex-valued mid-infrared conductivity of the heterostructure after optical injection of $1s$ A excitons. This approach allows us to trace the energies and linewidths of the atom-like $1s$-$2p$ transition of optically bright and dark excitons as well as the densities of these quasiparticles. The fundamental excitonic resonance red shifts and narrows in the WSe$_2$/hBN heterostructure compared to the bare monolayer. Furthermore, the ultrafast temporal evolution of the mid-infrared response function evidences the formation of optically dark excitons from an initial bright population. Our results provide key insight into the effect of non local screening on electron-hole correlations and open new possibilities of dielectric engineering of van der Waals heterostructures.

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., Two-dimensional materials have shown great promise as efficient chemical sensors. Here, the authors present a sensing mechanism to allow the detection of molecules based on dark excitons in atomically thin transition metal dichalcogenides.

The recent emergence of atomically thin two-dimensional (2D) materials has opened up possibilities for the design of ultrathin and flexible nanoelectronic devices. As truly 2D materials, they exhibit an optimal surface-to-volume ratio, which results in an extremely high sensitivity to external changes which can not be achieved by conventional semiconductors. This makes these materials optimal candidates for sensing applications. Here, we propose a dark exciton based concept for ultrasensitive strain sensors. By investigating both dark and bright excitons in tungsten-based monolayer transition metal dichalcogenides, we demonstrate that the dark-bright-exciton separation can be controlled by strain, which has a crucial impact on the activation of dark excitonic states. The predicted opposite strain-induced shifts for dark and bright excitons result in a pronounced change in photoluminescence stemming from dark excitons even at very small strain values. The predicted high optical gauge factors of up to 8000 are promising for the design of optical strain sensors.

Large spin–orbit coupling in combination with circular dichroism allows access to spin-polarized and valley-polarized states in a controlled way in transition metal dichalcogenides. The promising application in spin-valleytronics devices requires a thorough understanding of intervalley coupling mechanisms, which determine the lifetime of spin and valley polarizations. Here we present a joint theory–experiment study shedding light on the Dexter-like intervalley coupling. We reveal that this mechanism couples A and B excitonic states in different valleys, giving rise to an efficient intervalley transfer of coherent exciton populations. We demonstrate that the valley polarization vanishes and is even inverted for A excitons, when the B exciton is resonantly excited and vice versa. Our theoretical findings are supported by energy-resolved and valley-resolved pump-probe experiments and also provide an explanation for the recently measured up-conversion in photoluminescence. The gained insights might help to develop strategies to overcome the intrinsic limit for spin and valley polarizations., In atomically thin transition metal dichalcogenides, spin- and valley-polarised states can be addressed thanks to large spin–orbit coupling and circular dichroism. Here, the authors investigate theoretically and experimentally the decay dynamics of spin and valley polarisation in transition metal dichalcogenide monolayers.

Niehues, Iris et al., 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., A.K., M.S., and D.C. acknowledge support by the Deutsche Forschungsgemeinschaft (DFG) through SFB 951 (to A.K.) and SFB 910 (to D.C.) and the School of Nanophotonics SFB 787 (to M.S.). E.M. and G.B. were supported by funding from the European Unions Horizon 2020 research and innovation program under grant agreement No. 696656 (Graphene Flagship) and the Swedish Research Council (VR).

Monolayer transition metal dichalcogenides (TMDs) exhibit a remarkably strong Coulomb interaction that manifests in tightly bound excitons. Due to the complex electronic band structure exhibiting several spin-split valleys in the conduction and valence band, dark excitonic states can be formed. They are inaccessibly by light due to the required spin-flip and/or momentum transfer. The relative position of these dark states with respect to the optically accessible bright excitons has a crucial impact on the emission efficiency of these materials and thus on their technological potential. Based on the solution of the Wannier equation, we present the excitonic landscape of the most studied TMD materials including the spectral position of momentum- and spin-forbidden excitonic states. We show that the knowledge of the electronic dispersion does not allow to conclude about the nature of the material's band gap, since excitonic effects can give rise to significant changes. Furthermore, we reveal that an exponentially reduced photoluminescence yield does not necessarily reflect a transition from a direct to a non-direct gap material, but can be ascribed in most cases to a change of the relative spectral distance between bright and dark excitonic states.

Monolayer transition metal dichalcogenides (TMDs) undergo substantial changes in the single-particle band structure and excitonic optical response upon the addition of just one layer. As opposed to the single-layer limit, the bandgap of bilayer (BL) TMD semiconductors is indirect which results in reduced photoluminescence with richly structured spectra that have eluded a detailed understanding to date. Here, we provide a closed interpretation of cryogenic emission from BL WSe2 as a representative material for the wider class of TMD semiconductors. By combining theoretical calculations with comprehensive spectroscopy experiments, we identify the crucial role of momentum-indirect excitons for the understanding of BL TMD emission. Our results shed light on the origin of quantum dot formation in BL crystals and will facilitate further advances directed at opto-electronic applications of layered TMD semiconductors in van der Waals heterostructures and devices., The electronic band structure of atomically thin transition metal dichalcogenides is strongly sensitive to the number of layers, resulting in modified light emission. Here, the authors investigate the cryogenic emission from bilayer WSe2 to identify the role of momentum-indirect excitons for its optical response.

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., The interplay between dark and bright excitons has a significant impact on the optical properties of semiconducting transition metal dichalcogenides. Here, the authors perform computational and experimental studies which unveil the microscopic origin of the excitonic coherence lifetime in WS2 and MoSe2.

Excitons dominate the optical properties of monolayer transition metal dichalcogenides (TMDs). Besides optically accessible bright exciton states, TMDs exhibit also a multitude of optically forbidden dark excitons. Here, we show that efficient exciton-phonon scattering couples bright and dark states and gives rise to an asymmetric excitonic line shape. The observed asymmetry can be traced back to phonon-induced sidebands that are accompanied by a polaron redshift. We present a joint theory-experiment study investigating the microscopic origin of these sidebands in different TMD materials taking into account intra- and intervalley scattering channels opened by optical and acoustic phonons. The gained insights contribute to a better understanding of the optical fingerprint of these technologically promising nanomaterials.

The remarkably strong Coulomb interaction in atomically thin transition metal dichalcogenides (TMDs) results in an extraordinarily rich many-particle physics including the formation of tightly bound excitons. Besides optically accessible bright excitonic states, these materials also exhibit a variety of dark excitons. Since they can even lie below the bright states, they have a strong influence on the exciton dynamics, lifetimes, and photoluminescence. While very recently, the presence of dark excitonic states has been experimentally demonstrated, the origin of these states, their formation, and dynamics have not been revealed yet. Here, we present a microscopic study shedding light on time- and energy-resolved formation and thermalization of bright and dark intra- and intervalley excitons as well as their impact on the photoluminescence in different TMD materials. We demonstrate that intervalley dark excitons, so far widely overlooked in current literature, play a crucial role in tungsten-based TMDs giving rise to an enhanced photoluminescence and reduced exciton lifetimes at elevated temperatures.

Transition metal dichalcogenides (TMDs) have garnered considerable interest in recent years owing to their layer thickness-dependent optoelectronic properties. In monolayer TMDs, the large carrier effective masses, strong quantum confinement, and reduced dielectric screening lead to pronounced exciton resonances with remarkably large binding energies and coupled spin and valley degrees of freedom (valley excitons). Coherent control of valley excitons for atomically thin optoelectronics and valleytronics requires understanding and quantifying sources of exciton decoherence. In this work, we reveal how exciton-exciton and exciton-phonon scattering influence the coherent quantum dynamics of valley excitons in monolayer TMDs, specifically tungsten diselenide (WSe2), using two-dimensional coherent spectroscopy. Excitation-density and temperature dependent measurements of the homogeneous linewidth (inversely proportional to the optical coherence time) reveal that exciton-exciton and exciton-phonon interactions are significantly stronger compared to quasi-2D quantum wells and 3D bulk materials. The residual homogeneous linewidth extrapolated to zero excitation density and temperature is 1:6 meV (equivalent to a coherence time of 0.4 ps), which is limited only by the population recombination lifetime in this sample. (c) (2016) COPYRIGHT Society of Photo-Optical Instrumentation Engineers (SPIE). Downloading of the abstract is permitted for personal use only

We report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides (TMDs), specifically molybdenum diselenide (MoSe2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond timescale 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 TMDs. The quasiparticle formation and conversion processes are important for interpreting photoluminescence and photoconductivity in TMDs., 6 pages, 4 figures; accepted to PRB rapid

A remarkable property of atomically thin transition metal dichalcogenides (TMDs) is the possibility to selectively address single valleys by circularly polarized light. In the context of technological applications, it is very important to understand possible intervalley coupling mechanisms. Here, we show how the Dexter-like intervalley coupling mixes A and B states from opposite valleys leading to a significant broadening γB 1s of the B 1s exciton. The effect is much more pronounced in tungsten-based TMDs, where the coupling excitonic states are quasi-resonant. We calculate a ratio γB B 1s /γA B 1s ≈ 4.0, which is in good agreement with the experimentally measured value of 3.9 ± 0.7. In addition to the broadening effect, the Dexter-like intervalley coupling also leads to a considerable energy renormalization resulting in an increased energetic distance between A 1s and B 1s states.

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., The band-edge optical response of transition metal dichalcogenides is dominated by tightly bound valley excitons. Here, the authors use optical two-dimensional Fourier transform spectroscopy to determine the exciton homogeneous linewidth in monolayer tungsten diselenide.

We reveal the ultrafast intervalley dynamics in monolayer WS 2 with a spectrally-resolved ultrafast pump-probe experiment and a microscopic theory. We find strong intervalley Coulomb coupling in the atomically thin semiconductor.

Chemical functionalization of atomically thin nanostructures presents a promising strategy to create new hybrid nanomaterials with remarkable and externally controllable properties. Here, we review our research in the field of theoretical modeling of carbon nanotubes, graphene, and transition metal dichalcogenides located in molecular dipole fields. In particular, we provide a microscopic view on the change of the optical response of these technologically promising nanomaterials due to the presence of photo-active spiropyran molecules. The feature article presents a review of recent theoretical work providing microscopic view on the optical response of chemically functionalized carbon nanotubes, graphene, and monolayered transition metal dichalcogenides. In particular, we propose a novel sensor mechanism based on the molecule-induced activation of dark excitons. This results in a pronounced additional peak presenting an unambiguous optical fingerprint for the attached molecules.

We present an analytical investigation of the optical absorption spectrum of monolayer molybdenum-disulfide. 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 describes well the valley-selective polarization in ${\mathrm{MoS}}_{2}$. 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 MoS${}_{2}$ features two pronounced peaks corresponding to the A and B exciton. For MoS${}_{2}$ on a SiO${}_{2}$ substrate, these are characterized by binding energies of 455 meV and 465 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.

Atomically thin transition metal dichalcogenides (TMDs) hold promising potential for applications in optoelectronics. Due to their direct band gap and the extraordinarily strong Coulomb interaction, TMDs exhibit efficient light-matter coupling and tightly bound excitons. Moreover, large spin orbit coupling in combination with circular dichroism allows for spin and valley selective optical excitation. As atomically thin materials, they are very sensitive to changes in the surrounding environment. This motivates a functionalization approach, where external molecules are adsorbed to the materials surface to tailor its optical properties. Here, we apply the density matrix theory to investigate the potential of non-covalently functionalized TMDs. Considering exemplary spiropyran molecules with a strong dipole moment, we predict spectral redshifts and the appearance of an additional side peak in the absorption spectrum of functionalized TMDs. We show that the molecular characteristics, e.g. coverage, orientation and dipole moment, crucially influence the optical properties of TMDs, leaving a unique optical fingerprint in the absorption spectrum. Furthermore, we find that the molecular dipole moments open a channel for coherent intervalley coupling between the high-symmetry K and K' points which may open new possibilities for spin-valleytronics application., 6 pages, 5 figures

Atomically thin transition metal dichalcogenides exhibit a remarkably strong Coulomb interaction. This results in a fascinating many-particle physics including a variety of bright and dark excitonic states that determine optical and electronic properties of these materials. So far, the impact of dark states has remained literally in the dark to a large extent, since a measurement of these optically forbidden states is very challenging. Here we demonstrate a strategy to measure a direct fingerprint of dark states even in standard linear absorption spectroscopy. We present a microscopic study on bright and dark higher excitonic states in the presence of disorder for the exemplary material of tungsten disulfide (WS2). We show that the geometric phase cancels the degeneration of 2s and 2p states and that a significant disorder-induced coupling of these bright and dark states offers a strategy to circumvent optical selection rules. As a proof, we show a clear fingerprint of dark 2p states in the absorption spectrum of WS2. The predicted softening of optical selection rules through exciton-disorder coupling is of general nature and therefore applicable to related two-dimensional semiconductors.