Point defects, local strain or impurities can crucially impact the optical response of atomically thin two-dimensional materials as they offer trapping potentials for excitons. These trapped excitons appear in photoluminescence spectra as new resonances below the bright exciton that can even be exploited for single photon emission. While large progress has been made in deterministically introducing defects, only little is known about their impact on the optical fingerprint of 2D materials. Here, based on a microscopic approach we reveal direct signatures of localized bright excitonic states as well as indirect phonon-assisted side bands of localized momentum-dark excitons. The visibility of localized excitons strongly depends on temperature and disorder potential width. This results in different regimes, where either the bright or dark localized states are dominant in optical spectra. We trace back this behavior to an interplay between disorder-induced exciton capture and intervalley exciton-phonon scattering processes.
We report ultrafast pump-probe spectroscopy examining exciton dynamics in atomically thin MoS2. Spectrally- and temporally-resolved measurements are performed to investigate the interaction dynamics of two important direct-gap excitons (A and B) and their associated broadening kinetics. The two excitons show strongly correlated inter-excitonic dynamic, in which the transient blue-shifted excitonic absorption originates from the internal A-B excitonic interaction. The observed complex spectral response is determined by the exciton collision-induced linewidth broadening; the broadening of the B …
The effect of anisotropy in the energy spectrum on the binding energy and structural properties of excitons, trions, and biexcitons is investigated. To this end we employ the stochastic variational method with a correlated Gaussian basis. We present results for the binding energy of different excitonic complexes in black phosphorus (bP) and TiS$_3$ and compare them with recent results in the literature when available, for which we find good agreement. The binding energies of excitonic complexes in bP are larger than those in TiS$_3$. We calculate the different average interparticle distances i…
The interaction of optically excited excitons in atomically thin semiconductors with residual doping densities leads to many-body effects which are continuously tunable by external gate voltages. Here, we develop a fully microscopic theory to describe the doping-dependent manipulation of the excitonic properties in atomically thin transition metal dichalcogenides. In particular, we establish a diagonalization approach for the Schrödinger equation which characterizes the interaction of a virtual exciton with the Fermi sea of dopants. Solving this many-body Schrödinger equation provides access t…
Bottom-up approaches allow the production of ultra-narrow and atomically precise graphene nanoribbons (GNRs), with electronic and optical properties controlled by the specific atomic structure. Combining Raman spectroscopy and ab-initio simulations, we show that GNR width, edge geometry and functional groups all influence their Raman spectra. The low-energy spectral region below 1000 cm-1 is particularly sensitive to edge morphology and functionalization, while the D peak dispersion can be used to uniquely fingerprint the presence of GNRs, and differentiates them from other sp2 carbon nanostru…
We systematically measure the dielectric function of atomically thin MoS2 films with different layer numbers and demonstrate that excitonic effects play a dominant role in the dielectric function when the films are less than 5-7 layers thick. The dielectric function shows an anomalous dependence on the layer number. It decreases with the layer number increasing when the films are less than 5-7 layers thick but turns to increase with the layer number for thicker films. We show that this is because the excitonic effect is very strong in the thin MoS2 films and its contribution to the dielectric …
Strong Coulomb interactions in atomically thin semiconductors like monolayer WSe$_2$ induce not only tightly bound excitons, but also make their optical properties very sensible to doping. By utilizing a microscopic theory based on the excitonic Heisenberg equations of motion, we systematically determine the influence of doping on the excitonic linewidth, lineshift, and oscillator strength. We calculate trion resonances and demonstrate that the Coulomb coupling of excitons to the trionic continuum generates a non-Markovian interference, which, due to a time retardation, builds up a phase respo…
Fingerprints of Excitonic Collective Modes in the Two-Dimensional Electron Gas
Friedrich-Schiller-Universät Jena（耶拿弗里德里希·席勒大学）；Ruhr University Bochum（波鸿鲁尔大学）；École Polytechnique, Institut Polytechnique de Paris（巴黎综合理工学院，巴黎理工学院）；Synchrotron SOLEIL（SOLEIL同步辐射中心）
We present a systematic investigation of the electronic properties of bulk and few layer ReS$_2$ van der Waals crystals using low temperature optical spectroscopy. Weak photoluminescence emission is observed from two non-degenerate band edge excitonic transitions separated by $\sim$ 20 meV. The comparable emission intensity of both excitonic transitions is incompatible with a fully thermalized (Boltzmann) distribution of excitons, indicating the hot nature of the emission. While DFT calculations predict bilayer ReS$_2$ to have a direct fundamental band gap, our optical data suggests that the f…
Strain presents a straightforward tool to tune electronic properties of atomically thin nanomaterials that are highly sensitive to lattice deformations. While the influence of strain on the electronic band structure has been intensively studied, there are only few works on its impact on optical properties of monolayer transition metal dichalcogenides (TMDs). Combining microscopic theory based on Wannier and Bloch equations with nearestneighbor tight-binding approximation, we present an analytical view on how uni- and biaxial strain influences the optical fingerprint of TMDs including their exc…
Two-dimensional transition metal di-chalcogenide semiconductors provide unique possibilities to investigate strongly confined excitonic physics and a plasmonic platform integrable to such materials constitutes a hybrid system that can be of interest to enable manipulation of their cumulative optical properties. Here we report tuning of excitonic emission from monolayer WSe2, mechanically exfoliated on top of a periodic two dimensional plasmonic array of elliptical gold (Au) nanodiscs. By exploiting the polarization-dependent nature of plasmonic resonance of the nano plasmonic array (NPA), the …
The recent discovery of magnetism in atomically thin layers of van der Waals crystals has created great opportunities for exploring light-matter interactions and magneto-optical phenomena in the two-dimensional limit. Optical and magneto-optical experiments have provided insights into these topics, revealing strong magnetic circular dichroism and giant Kerr signals in atomically thin ferromagnetic insulators. However, the nature of the giant magneto-optical responses and their microscopic mechanism remain unclear. Here, by performing first-principles GW and Bethe-Salpeter equation calculations…
Mott transition has been realized in atomically thin monolayer (ML) of two dimensional semiconductors (WS$_2$) via optically excited carriers above a critical carrier density through many body interactions. The above nonlinear optical transition occurs when excited electron hole pairs in ML WS2 continuum heavily interact with each other followed by transformation into a collective electron hole plasma phase (EHP), by losing their identity as individual quasiparticles. This is manifested by the alluring red-shift-blue-shift crossover (RBC) phenomena of the excitonic peaks in the emission spectr…
Understanding and controlling the nanoscale transport of excitonic quasiparticles in atomically thin 2D semiconductors is crucial to produce highly efficient nano-excitonic devices. Here, we present a nano-gap device to selectively confine excitons or trions of 2D transition metal dichalcogenides at the nanoscale, facilitated by the drift-dominant exciton funnelling into the strain-induced local spot. We investigate the spatio-spectral characteristics of the funnelled excitons in a WSe2 monolayer (ML) and converted trions in a MoS2 ML using hyperspectral tip-enhanced photoluminescence (TEPL) i…
We demonstrate a new approach for dynamically manipulating the optical response of an atomically thin semiconductor, a monolayer of MoSe2, by suspending it over a metallic mirror. First, we show that suspended van der Waals heterostructures incorporating a MoSe2 monolayer host spatially homogeneous, lifetime-broadened excitons. Then, we interface this nearly ideal excitonic system with a metallic mirror and demonstrate control over the exciton-photon coupling. Specifically, by electromechanically changing the distance between the heterostructure and the mirror, thereby changing the local photo…
We have experimentally determined the energies of the ground and first four excited excitonic states of the fundamental optical transition in monolayer WS2, a model system for the growing class of atomically thin two-dimensional semiconductor crystals. From the spectra, we establish a large exciton binding energy of 0.32 eV and a pronounced deviation from the usual hydrogenic Rydberg series of energy levels of the excitonic states. We explain both of these results using a microscopic theory in which the non-local nature of the effective dielectric screening modifies the functional form of the …
Transition metal dichalcogenide monolayers are promising candidates for exploring new electronic and optical phenomena and for realizing atomically thin optoelectronic devices. They host tightly bound electron-hole pairs (excitons) that can be efficiently excited by resonant light fields. Here, we demonstrate that a single monolayer of molybdenum diselenide (MoSe2) can dramatically modify light transmission near the excitonic resonance, acting as an electrically switchable mirror that reflects up to 85% of incident light at cryogenic temperatures. This high reflectance is a direct consequence …
Raman scattering and photoluminescence spectroscopy are used to investigate the optical properties of single layer black phosphorus obtained by mechanical exfoliation of bulk crystals under an argon atmosphere. The Raman spectroscopy, performed in situ on the same flake as the photoluminescence measurements, demonstrates the single layer character of the investigated samples. The emission spectra, dominated by excitonic effects, display the expected in plane anisotropy. The emission energy depends on the type of substrate on which the flake is placed due to the different dielectric screening. …
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$_2$. The predicted softening of optical selection rules through exciton-disorder coupling is of general nature and therefore applicable to related two-dimensional semiconductors.
Atomically thin semiconductors made from transition metal dichalcogenides (TMDs) are model systems for investigations of strong light-matter interactions and applications in nanophotonics, opto-electronics and valley-tronics. However, the photoluminescence spectra of TMD monolayers display a large number of features that are particularly challenging to decipher. On a practical level, monochromatic TMD-based emitters would be beneficial for low-dimensional devices but this challenge is yet to be resolved. Here, we show that graphene, directly stacked onto TMD monolayers enables single and narro…
The p-n diodes represent the most fundamental device building block for diverse optoelectronic functions, but are difficult to achieve in atomically thin transition metal dichalcogenides (TMDs) due to the inability to selectively dope them into p- or n-type semiconductors. Here we report the first demonstration of an atomically thin and atomically sharp heterojunction p-n diode by vertically stacking p-type monolayer tungsten diselenide (WSe2) and n-type few-layer molybdenum disulfide (MoS2). Electrical measurement demonstrates excellent diode characteristics with well-defined current rectific…
Excitons in two-dimensional semiconductors provide a novel platform for fundamental studies of many-body interactions. In particular, dipolar interactions between spatially indirect excitons may give rise to strongly correlated phases of matter that so far have been out of reach of experiments. Here, we show that excitonic few-body systems in atomically thin transition-metal dichalcogenides undergo a crossover from a Tonks-Girardeau to a charge-density-wave regime. To this end, we take into account realistic system parameters and predict the effective exciton-exciton interaction potential. We …
Recently, atomically well-defined cove-shaped graphene nanoribbons have been obtained using bottom-up synthesis. These nanoribbons have an optical gap in the visible range of the spectrum which make them candidates for donor materials in photovoltaic devices. From the atomistic point of view, their electronic and optical properties are not clearly understood. Therefore, in this work we carry out ab-initio density functional theory calculations combine with many-body perturbation formalism to study their electronic and optical properties. Through the comparison with experimental measurements, w…
Transition-metal dichalcogenides can be easily produced as atomically thin sheets, exhibiting the possibility to optically polarize and read out the valley pseudospin of extremely stable excitonic quasiparticles present in these 2D semiconductors. Here, we investigate a monolayer of tungsten disulphide in high magnetic fields up to 30\,T via photoluminescence spectroscopy at low temperatures. The valley degeneracy is lifted for all optical features, particularly for excitons, singlet and triplet trions, for which we determine the g factor separately. While the observation of a diamagnetic shif…
Antiferromagnets display enormous potential in spintronics owing to its intrinsic nature, including terahertz resonance, multilevel states, and absence of stray fields. Combining with the layered nature, van der Waals (vdW) antiferromagnets hold the promise in providing new insights and new designs in two-dimensional (2D) spintronics. The zero net magnetic moments of vdW antiferromagnets strengthens the spin stability, however, impedes the correlation between spin and other excitation elements, like excitons. Such coupling is urgently anticipated for fundamental magneto-optical studies and pot…
Electronic states in two-dimensional layered materials can exhibit a remarkable variety of correlated phases including Wigner-crystals, Mott insulators, charge density waves, and superconductivity. Recent experimental and theoretical research has indicated that ferromagnetic phases can exist in electronically-doped transition metal dichalcogenide (TMD) semiconductors, but a stable magnetic state at zero magnetic field has eluded detection. Here, we experimentally demonstrate that mesoscopic ferromagnetic order can be generated and controlled by local optical pumping in monolayer WSe2 at zero a…
Excitons dominate the optics of atomically-thin transition metal dichalcogenides and 2D van der Waals heterostructures. Interlayer 2D excitons, with an electron and a hole residing in different layers, form rapidly in heterostructures either via direct charge transfer or via Coulomb interactions that exchange energy between layers. Here, we report prominent intertube excitonic effects in quasi-1D van der Waals heterostructures consisting of C/BN/MoS$_2$ core/shell/skin nanotubes. Remarkably, under pulsed infrared excitation of excitons in the semiconducting CNTs we observed a rapid (sub-picose…
Atomically thin transition metal dichalcogenides (TMDs) are direct-gap semiconductors with strong light-matter and Coulomb interaction. The latter accounts for tightly bound excitons, which dominate the optical properties of these technologically promising materials. Besides the optically accessible bright excitons, these systems exhibit a variety of dark excitonic states. They are not visible in optical spectra, but can strongly influence the coherence lifetime and the linewidth of the emission from bright exciton states. In a recent study, an experimental evidence for the existence of such d…
Twisted atomically thin semiconductors are characterized by moiré excitons. Their optical signatures and selection rules are well understood. However, their hybridization with photons in the strong coupling regime for heterostructures integrated in an optical cavity has not been in the focus of research yet. Here, we combine an excitonic density matrix formalism with a Hopfield approach to provide microscopic insights into moiré exciton polaritons. In particular, we show that exciton-light coupling, polariton energy, and even the number of polariton branches can be controlled via the twist ang…
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 …
Long-range and fast transport of coherent excitons is important for development of high-speed excitonic circuits and quantum computing applications. However, most of these coherent excitons have only been observed in some low-dimensional semiconductors when coupled with cavities, as there are large inhomogeneous broadening and dephasing effects on the exciton transport in their native states of the materials. Here, by confining coherent excitons at the 2D quantum limit, we firstly observed molecular aggregation enabled super-transport of excitons in atomically thin two-dimensional (2D) organic…
In many atomically thin materials their optical absorption is dominated by excitonic transitions. It was recently found that optical selection rules in these materials are influenced by the band topology near the valleys. We propose that gate-controlled band ordering in a single atomic monolayer, through changes in the valley winding number and excitonic transitions, can be probed in helicity-resolved absorption and photoluminescence. This predicted tunable band topology is confirmed by combining an effective Hamiltonian and a Bethe-Salpeter equation for an accurate description of excitons, wi…
We demonstrate the reduction of the inhomogeneous linewidth of the free excitons in atomically thin transition metal dichalcogenides (TMDCs) MoSe$_{2}$, WSe$_{2}$ and MoS$_{2}$ by encapsulation within few nanometer thick hBN. Encapsulation is shown to result in a significant reduction of the 10K excitonic linewidths down to $\sim3.5 \text{ meV}$ for n-MoSe$_{2}$, $\sim5.0 \text{ meV}$ for p-WSe$_{2}$ and $\sim4.8 \text{ meV}$ for n-MoS$_{2}$. Evidence is obtained that the hBN environment effectively lowers the Fermi level since the relative spectral weight shifts towards the neutral exciton em…
We examine excitons formed in the bulk of a topological insulator as the system is tuned via a parameter between topological and trivial insulating phases, arguing that nontrivial topology has fingerprints in the spectrum of these excitons. The closely related hydrogen atom problem is well known to have a degeneracy due to a hidden symmetry, and the changes to the excitonic spectrum that we find can be understood as a result of breaking of this underlying symmetry due to the Berry phase. Furthermore, this phase is found to affect the spectrum in the topological parameter regime much more stron…
Excitons are composite bosons that can feature spin singlet and triplet states. In usual semiconductors, without an additional spin-flip mechanism, triplet excitons are extremely inefficient optical emitters. Large spin-orbit coupling in transition metal dichalcogenides (TMDs) couples circularly polarized light to excitons with selective valley and spin. Here, we demonstrate electrically controlled brightening of spin-triplet interlayer excitons in a MoSe$_2$/WSe$_2$ TMD van der Waals (vdW) heterostructure. The atomic registry of vdW layers in TMD heterostructures provides a quasi-angular mome…
Monolayer transition metal dichalcogenides (TMDs) possess superior optical properties, including the valley degree of freedom that can be accessed through the excitation light of certain helicity. While WS2 and WSe2 are known for their excellent valley polarization due to the strong spin-orbit coupling, the optical bandgap is limited by the ability to choose from only these two materials. This limitation can be overcome through the monolayer alloy semiconductor, WS2xSe2(1-x), which promises an atomically thin semiconductor with tunable bandgap. In this work, we show that the high-quality BN en…
Monolayers of transition metal dichalcogenides (TMDCs) exhibit an exceptionally strong Coulomb interaction between charge carriers due to the two-dimensional carrier confinement in connection with weak dielectric screening. High densities of excited charge carriers in the various band-structure valleys cause strong many-body renormalizations that influence both the electronic properties and the optical response of the material. We investigate electronic and optical properties of the typical monolayer TMDCs MoS$_2$, MoSe$_2$, WS$_2$ and WSe$_2$ in the presence of excited carriers by solving sem…
The dynamics of a mobile quantum impurity in a degenerate Fermi system is a fundamental problem in many-body physics. The interest in this field has been renewed due to recent ground-breaking experiments with ultra-cold Fermi gases. Optical creation of an exciton or a polariton in a two-dimensional electron system embedded in a microcavity constitutes a new frontier for this field due to an interplay between cavity-coupling favoring ultra-low mass polariton formation and exciton-electron interactions leading to polaron or trion formation. Here, we present cavity spectroscopy of gate-tunable mo…
Excitonic emission from atomically precise graphene nanoribbons (GNRs) synthesised on a metal surface is probed with atomic-scale spatial resolution using a scanning tunneling microscopy (STM) approach. A STM-based strategy to transfer the GNRs to a partially insulating surface is used to prevent light emission quenching of the ribbons by the metal substrate. Sub-nanometer resolved STM-induced fluorescence spectra reveal emission from localized dark excitons build upon the topological end states of the GNRs. A low frequency vibronic emission comb whose characteristics change with the GNR lengt…
Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) are attractive materials for next generation nanoscale optoelectronic applications. Understanding nanoscale optical behavior of the edges and grain boundaries of synthetically grown TMDCs is vital for optimizing their optoelectronic properties. Elucidating the nanoscale optical properties of 2D materials through far-field optical microscopy requires a diffraction-limited optical beam diameter sub-micron in size. Here we present our experimental work on spatial photoluminescence (PL) scanning of large size ( $\geq 50$…
