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The excitonic insulator is an elusive electronic phase exhibiting a correlated excitonic ground state. Materials with such a phase are expected to have intriguing properties such as excitonic high-temperature superconductivity. However, compelling evidence on the experimental realization is still missing. Here, we theoretically propose hybrids of two-dimensional semiconductors functionalized by organic molecules as prototypes of excitonic insulators, with the exemplary candidate WS2-F6TCNNQ. This material system exhibits an excitonic insulating phase at room temperature with a ground state formed by a condensate of interlayer excitons. To address an experimentally relevant situation, we calculate the corresponding phase diagram for the important parameters: temperature, gap energy, and dielectric environment. Further, to guide future experimental detection, we show how to optically characterize the different excitonic phases via far-infrared to terahertz spectroscopy valid also for monolayer materials.

Interfaces of dye molecules and two-dimensional transition metal dichalcogenides (TMDCs) combine strong molecular dipole excitations with high carrier mobilities in semiconductors. F\"orster type energy transfer is one key mechanism for the coupling between both constituents. We report microscopic calculations of a spectrally resolved F\"orster induced transition rate from dye molecules to a TMDC layer. Our approach is based on microscopic Bloch equations which are solved self-consistently together with Maxwells equations. This approach allows to incorporate the dielectric environment of a TMDC semiconductor, sandwiched between donor molecules and a substrate. Our analysis reveals transfer rates in the meV range for typical dye molecules in closely stacked structures, with a non-trivial dependence of the F\"orster rate on the molecular transition energy resulting from unique signatures of dark, momentum forbidden TMDC excitons.

Vertical heterostructures (HS) of transition metal dichalcogenides (TMDs) host interlayer excitons (ILX), with electrons and holes residing in different layers. With respect to their intralayer counterparts, ILX feature much longer lifetimes and diffusion lengths, paving the way to excitonic optoelectronic devices operating at room temperature. While the recombination dynamics of ILX has been intensively studied, the formation process and its underlying physical mechanisms are still largely unexplored. Here we use ultrafast transient absorption spectroscopy with a white-light probe, spanning both intralayer and interlayer exciton resonances, to simultaneously capture and time-resolve interlayer charge transfer and ILX formation dynamics in a MoSe$_2$/WSe$_2$ HS. We find that the ILX formation timescale is nearly an order of magnitude (~1 ps) longer than the interlayer charge transfer time (~100 fs). Microscopic calculations attribute the relative delay to an interplay between a phonon-assisted interlayer exciton cascade and subsequent cooling processes, and excitonic wave-function overlap. Our results provide an explanation to the efficient photocurrent generation observed in optoelectronic devices based on TMD HS, as the ILX have an opportunity to dissociate during their thermalization process., Comment: 18 pages, 4 figures

The equilibrium and non-equilibrium optical properties of single-layer transition metal dichalcogenides (TMDs) are determined by strongly bound excitons. Exciton relaxation dynamics in TMDs have been extensively studied by time-domain optical spectroscopies. However, the formation dynamics of excitons following non-resonant photoexcitation of free electron-hole pairs have been challenging to directly probe because of their inherently fast timescales. Here, we use extremely short optical pulses to non-resonantly excite an electron-hole plasma and show the formation of two-dimensional excitons in single-layer MoS2 on the timescale of 30 fs via the induced changes to photo-absorption. These formation dynamics are significantly faster than in conventional 2D quantum wells and are attributed to the intense Coulombic interactions present in 2D TMDs. A theoretical model of a coherent polarization that dephases and relaxes to an incoherent exciton population reproduces the experimental dynamics on the sub-100-fs timescale and sheds light into the underlying mechanism of how the lowest-energy excitons, which are the most important for optoelectronic applications, form from higher-energy excitations. Importantly, a phonon-mediated exciton cascade from higher energy states to the ground excitonic state is found to be the rate-limiting process. These results set an ultimate timescale of the exciton formation in TMDs and elucidate the exceptionally fast physical mechanism behind this process., The formation dynamics of excitons in 2D transition metal dichalcogenides are challenging to probe directly because of their inherently fast timescales. Here, the authors use extremely short optical pulses to excite an electron-hole plasma, and show the formation of 2D excitons in MoS2 on the timescale of 30 fs.

We provide a microscopic approach to describe the onset of radial oscillation of a silver nanoparticle. Using the Heisenberg equation of motion framework, we find that the coupled ultrafast dynamics of coherently excited electron occupation and the coherent phonon amplitude initiate periodic size oscillations of the nanoparticle. Compared to the established interpretation of experiments, our results show a more direct coupling mechanism between the field intensity and coherent phonons. This interaction triggers a size oscillation via an optically induced electron density gradient occurring directly with the optical excitation. This source is more efficient than the incoherent heating process currently discussed in the literature and well-describes the early onset of the oscillations in recent experiments., 13 pages, 3 figures

In van der Waals heterostructures (HS) consisting of stacked MoSe$_2$ and WSe$_2$ monolayers, optically bright interlayer excitons (ILE) can be observed when the constituent layers are crystallographically aligned. The symmetry of the monolayers allows for two different types of alignment, in which the momentum-direct interlayer transitions are either valley-conserving (R-type alignment) or changing the valley index (H-type anti-alignment). Here, we study the valley polarization dynamics of ILE in magnetic fields up to 30~Tesla by time-resolved photoluminescence (PL). For all ILE types, we find a finite initial PL circular degree of polarization ($DoP$) after unpolarized excitation in applied magnetic fields. For ILE in H-type HS, we observe a systematic increase of the PL $DoP$ with time in applied magnetic fields, which saturates at values close to unity for the largest fields. By contrast, for ILE in R-type HS, the PL $DoP$ shows a decrease and a zero crossing before saturating with opposite polarization. This unintuitive behavior can be explained by a model considering the different ILE states in H- and R-type HS and their selection rules coupling PL helicity and valley polarization.

We present a rigorous quasinormal mode approach to describe the strong coupling behavior between a monolayer of ${\mathrm{MoSe}}_{2}$ and a single gold nanoparticle. The onset of strong coupling, described through a classical spectral mode splitting (analog of vacuum Rabi splitting) is quantified by computing the full three-dimensional hybrid quasinormal modes of the combined structure, allowing one to accurately model light-matter interactions without invoking the usual phenomenological theories of strong coupling. We explore the hybrid quasinormal modes as a function of gap size and temperature, and find spectral splittings in the range of around 80--110 meV, with no fitting parameters for the material models. We also show how the hybrid modes exhibit Fano-like resonances and quantify the complex poles of the hybrid modes as well as the Purcell factor resonances from embedded dipole emitters. The Rabi splitting is found to be larger at elevated temperatures for very small gap separations between the metal nanoparticle and the monolayer, but smaller at elevated temperatures for larger gaps. We also show how these spectral splittings can differ qualitatively from the actual complex poles of the hybrid quasinormal modes.

Here we report a pronounced redshift of the trion resonance in MoSe 2 monolayer induced by picosecond THz pulses. The kinetic energy gained by hot carriers due to absorption of THz radiation is transferred during the formation of the trion, leading to an effective redshift of its optical transition. By performing time resolved measurements, we have determined the electron cooling time (τ = 70 ps) and estimated the absorption at 7.7 THz (α = 0.3%). A quantitative model based on the Heisenberg equation of motion explains the experimental observations and reproduces the data with good accuracy.

van der Waals heterostructures composed of transition metal dichalcogenide monolayers (TMDCs) are characterized by their truly rich excitonic properties which are determined by their structural, geometric, and electronic properties: In contrast to pure monolayers, electrons and holes can be hosted in different materials, resulting in highly tunable dipolar many-particle complexes. However, for genuine spatially indirect excitons, the dipolar nature is usually accompanied by a notable quenching of the exciton oscillator strength. Via electric and magnetic field dependent measurements, we demonstrate that a slightly biased pristine bilayer ${\mathrm{MoS}}_{2}$ hosts strongly dipolar excitons, which preserve a strong oscillator strength. We scrutinize their giant dipole moment, and shed further light on their orbital and valley physics via bias-dependent magnetic field measurements.

While valleys (energy extrema) are present in all band structures of solids, their preeminent role in determining exciton resonances and dynamics in atomically thin transition metal dichalcogenides (TMDC) is unique. Using two-dimensional coherent electronic spectroscopy, we find that exciton decoherence occurs on a much faster time scale in MoSe$_2$ bilayers than that in the monolayers. We further identify two population relaxation channels in the bilayer, a coherent and an incoherent one. Our microscopic model reveals that phonon-emission processes facilitate scattering events from the $K$ valley to other lower energy $\Gamma$ and $\Lambda$ valleys in the bilayer. Our combined experimental and theoretical studies unequivocally establish different microscopic mechanisms that determine exciton quantum dynamics in TMDC monolayers and bilayers. Understanding exciton quantum dynamics provides critical guidance to manipulation of spin/valley degrees of freedom in TMDC bilayers., Comment: 6 pages, 4 figures

Enhanced Coulomb interactions in monolayer transition metal dichalcogenides cause tightly bound electron-hole pairs (excitons) that dominate their linear and nonlinear optical response. The latter includes bleaching, energy renormalizations, and higher-order Coulomb correlation effects like biexcitons and excitation-induced dephasing. While the first three are extensively studied, no theoretical footing for excitation-induced dephasing in exciton-dominated semiconductors is available so far. In this Letter, we present microscopic calculations based on excitonic Heisenberg equations of motion and identify the coupling of optically pumped excitons to exciton-exciton scattering continua as the leading mechanism responsible for an optical-power-dependent linewidth broadening (excitation-induced dephasing) and sideband formation. Performing time-, momentum-, and energy-resolved simulations, we quantitatively evaluate the exciton-induced dephasing for the most common monolayer transition metal dichalcogenides and find an excellent agreement with recent experiments.

van der Waals heterostructures composed of transition metal dichalcogenide monolayers (TMDCs) are characterized by their truly rich excitonic properties which are determined by their structural, geometric, and electronic properties: In contrast to pure monolayers, electrons and holes can be hosted in different materials, resulting in highly tunable dipolar many-particle complexes. However, for genuine spatially indirect excitons, the dipolar nature is usually accompanied by a notable quenching of the exciton oscillator strength. Via electric and magnetic field dependent measurements, we demonstrate that a slightly biased pristine bilayer MoS_{2} hosts strongly dipolar excitons, which preserve a strong oscillator strength. We scrutinize their giant dipole moment, and shed further light on their orbital and valley physics via bias-dependent magnetic field measurements.

Excitons, Coulomb-bound electron-hole pairs, are the fundamental excitations governing the optoelectronic properties of semiconductors. While optical signatures of excitons have been studied extensively, experimental access to the excitonic wave function itself has been elusive. Using multidimensional photoemission spectroscopy, we present a momentum-, energy- and time-resolved perspective on excitons in the layered semiconductor WSe2. By tuning the excitation wavelength, we determine the energy-momentum signature of bright exciton formation and its difference from conventional single-particle excited states. The multidimensional data allows to retrieve fundamental exciton properties like the binding energy and the exciton-lattice coupling and to reconstruct the real-space excitonic distribution function via Fourier transform. All quantities are in excellent agreement with microscopic calculations. Our approach provides a full characterization of the exciton properties and is applicable to bright and dark excitons in semiconducting materials, heterostructures and devices. The data we uploaded here is the four-dimensional trARPES data used in this paper., This work was funded by the Max Planck Society, the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation and the H2020-EU.1.2.1. FET Open programs (Grant Nos. ERC-2015-CoG-682843, ERC-2015-AdG-694097, and OPTOlogic 899794), the Max Planck Society's Research Network BiGmax on Big-Data-Driven Materials-Science, and the German Research Foundation (DFG) within the Emmy Noether program (Grant No. RE 3977/1), through SFB 951 "Hybrid Inorganic/Organic Systems for Opto-Electronics (HIOS)" (Project No. 182087777, projects B12 and B17), the SFB/TRR 227 "Ultrafast Spin Dynamics" (projects A09 and B07), the Research Unit FOR 1700 "Atomic Wires" (project E5), and the Priority Program SPP 2244 (project 443366970). D.C.thanks the graduate school Advanced Materials (SFB 951) for support. S.B. acknowledges financial support from the NSERC-Banting Postdoctoral Fellowships Program. T.P. acknowledges financial support from the Alexander von Humboldt Foundation.

Here we exploit transient reflectivity with sub-20fs temporal resolution to extract the exciton formation timescale from the build up of A/B exciton dynamics of 1L-MoS2. The timescale for this process ranges from ~15fs to ~35fs. © 2020 The Author(s)

Low-temperature photoluminescence (PL) of hBN-encapsulated monolayer tungsten diselenide (WSe2) shows a multitude of sharp emission peaks below the bright exciton. Some of them have been recently i...

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.

Locally adapted trees and shrubs are suggested to show higher fitness at their site of origin than non-locally adapted ones. The production in tree nurseries could take this into account to improve outplanting performance. However, separate production of specific ecotypes in nurseries increases the costs of production and may reduce the availability of a specific species. In this study, we investigated drought stress reactions of 2 year-old container-grown seedlings of Quercus robur L. and Tilia cordata Mill. from four and three different populations, respectively, each from a different site of origin. Slow- and fast-developing drought stress treatments were applied in a greenhouse study to determine any difference in drought tolerance. Control plants were well irrigated. Depending on the species and stress development, only marginal interpopulation differences in particular physiological (pre-dawn water potential, stomatal conductance, relative water content) and/or biochemical (glucose, fructose, sucrose, starch, proline) reactions to drought existed. These differences did not consistently reflect precipitation conditions at the population sites of origin, indicating only low level of local adaptation for populations of the target species. Index words: adaptation, carbohydrates, pedunculate oak, provenances, proline, small-leaved lime. Species used in this study: pedunculate oak (Quercus robur L.); small-leaved linden (Tilia cordata Mill.).

Single layers of transition metal dichalcogenides exhibit tightly bound excitons with large oscillator strength making them to promising materials for future optoelectronic applications. Despite that the linear response of these ultrathin materials is extensively studied, a profound understanding of the excitonic second-order nonlinear optical response, including trigonal warping and Berry curvature effects, is lacking so far. To bridge this gap, in this paper we report a microscopic model for the second-order nonlinear susceptibility tensor of these materials. Based on a $kp$ description of the underlying many-particle Hamiltonian we are able to address excitonic features as well as trigonal warping effects, spin-valley coupling, and also Berry curvature to the susceptibility tensor. We present explicit calculation of the latter for the exemplary materials ${\mathrm{MoS}}_{2}$ and ${\mathrm{WS}}_{2}$ on silicon substrate and encapsulated in hBN. For instance we predict resonant susceptibility for second-harmonic generation $0.5--1.3\phantom{\rule{4pt}{0ex}}\mathrm{nm}/\mathrm{V}$ and double-resonant susceptibility $10--30\phantom{\rule{4pt}{0ex}}\mathrm{n}\mathrm{m}/\mathrm{V}$ for the difference and sum-frequency generation processes. Our results are in good agreement with available experimental findings in the literature.

The reduced dielectric screening in atomically thin transition metal dichalcogenides allows to study the hydrogen-like series of higher exciton states in optical spectra even at room temperature. The width of excitonic peaks provides information about the radiative decay and phonon-assisted scattering channels limiting the lifetime of these quasi-particles. While linewidth studies so far have been limited to the exciton ground state, encapsulation with hBN has recently enabled quantitative measurements of the broadening of excited exciton resonances. Here, we present a joint experiment-theory study combining microscopic calculations with spectroscopic measurements on the intrinsic linewidth and lifetime of higher exciton states in hBN-encapsulated WSe$_2$ monolayers. Surprisingly, despite the increased number of scattering channels, we find both in theory and experiment that the linewidth of higher excitonic states is similar or even smaller compared to the ground state. Our microscopic calculations ascribe this behavior to a reduced exciton-phonon scattering efficiency for higher excitons due to spatially extended orbital functions.

Atomically thin Transition-metal dichalcogenides (TMDs) have come into the spotlight in optoelectronics thanks to their outstanding physical properties [1,2]. In single-layer (1L) TMDs strong quantum confinement effects cause a weak screening of Coulomb, so that the excitons created by photo-excitation have large binding energy, up to several hundred meVs [3]. While the steady-state properties of TMDCs have been studied in detail by linear optical techniques, the recent application of time-resolved nonlinear spectroscopy (mainly ultrafast pump-probe) has enabled the study of excited-state dynamics on femtosecond timescales [4] opening up questions about the mechanisms of exciton relaxations and exciton-exciton interactions.

Atomically thin transition metal dichalcogenides can be stacked to van der Waals heterostructures enabling the design of new materials with tailored properties. The strong Coulomb interaction gives rise to interlayer excitons, where electrons and holes are spatially separated in different layers. In this work, we reveal the time- and momentum-dependent elementary processes behind the formation, thermalization and photoemission of interlayer excitons for the exemplary MoSe2–WSe2 heterostructure. We identify tunneling of holes from MoSe2 to WSe2 on a ps timescale as the crucial process for interlayer exciton formation. We also predict a drastic reduction of the formation time as a function of the interlayer energy offset suggesting that interlayer excitons can be externally tuned. Finally, we explain the experimental observation of a dominant photoluminescence from interlayer excitons despite the vanishingly small oscillator strength as a consequence of huge interlayer exciton occupations at low temperatures. Single layers of transition metal dichalcogenides are expected to be suitable for a number of applications and by stacking layers of different materials on top of each other (heterostructures) an even richer variety of properties can be explored. To this end the authors theoretically investigate cross material exciton states in a heterostructures of MoSe2 and WSe2 layers.

Time- and angle-resolved photoemission spectroscopy (trARPES) is a powerful spectroscopic method to measure the ultrafast electron dynamics directly in momentum space. However, band gap materials with exceptionally strong Coulomb interaction such as monolayer transition-metal dichalcogenides exhibit tightly bound excitons, which dominate their optical properties. This raises the question of whether excitons, in particular their formation and relaxation dynamics, can be detected in photoemissions. Here, we develop a fully microscopic theory of the temporal dynamics of excitonic time- and angle-resolved photoemission with a particular focus on the phonon-mediated thermalization of optically excited excitons to momentum-forbidden dark exciton states. We find that trARPES is able to probe the ultrafast exciton formation and relaxation throughout the Brillouin zone.

We investigate the impact of optically induced F\"orster coupling in van der Waals heterostructures consisting of graphene and a monolayer transition metal dichalcogenide (TMD). In particular, we predict the corresponding dephasing rates and a fast energy transfer between the TMD layer and graphene being in the picosecond range. Exemplary we find a transition rate of thermalized excitons of about 4 ps$^{-1}$ in a MoSe$_2$-graphene stack at room temperature. This timescale is in good agreement with the recently measured exciton lifetime in this heterostructure.

The photoluminescence (PL) spectrum of transition-metal dichalcogenides (TMDs) shows a multitude of emission peaks below the bright exciton line, and not all of them have been explained yet. Here, we study the emission traces of phonon-assisted recombinations of indirect excitons. To this end, we develop a microscopic theory describing simultaneous exciton, phonon, and photon interaction and including consistent many-particle dephasing. We explain the drastically different PL below the bright exciton in tungsten- and molybdenum-based materials as the result of different configurations of bright and momentum-dark states. In good agreement with experiments, our calculations predict that WSe2 exhibits clearly visible low-temperature PL signals stemming from the phonon-assisted recombination of momentum-dark K–K′ excitons.

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 WS

Monolayer transition metal dichalcogenides (TMDs) are known to be highly sensitive to externally applied tensile or compressive strain. In particular, strain can be exploited as a tool to control the optical response of TMDs. However, the role of excitonic effects under strain has not been fully understood yet. Utilizing the strain-induced modification of electron and phonon dispersion obtained by first principle calculations, we present in this work microscopic insights into the strain-dependent optical response of various TMD materials. In particular, we explain recent experiments on the change of excitonic linewidths in strained TMDs and predict their behavior for tensile and compressive strain at low temperatures., 7 pages, 7 figures

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.

Monolayer transition metal dichalcogenides (TMDs) show an optimal surface-to-volume ratio and are thus promising candidates for novel molecule sensor devices. It was recently predicted that a certain class of molecules exhibiting a large dipole moment can be detected through the activation of optically inaccessible (dark) excitonic states in absorption spectra of tungsten-based TMDs. In this paper, we investigate the molecule signatures in photoluminescence spectra in dependence of a number of different experimentally accessible quantities, such as excitation density, temperature, as well as molecular characteristics including the dipole moment and its orientation, molecule-TMD distance, molecular coverage, and distribution. We show that under certain optimal conditions even room-temperature detection of molecules can be achieved.

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.