Homoepitaxy of Boron Nitride on Exfoliated Hexagonal Boron Nitride Flakes.

Although large efforts have been made to improve the growth of hexagonal boron nitride (hBN) by heteroepitaxy, the non-native substrates remain a fundamental factor that limits the quality. This problem can be solved by homoepitaxy, which is the growth of hBN on hBN substrates. In this report, we demonstrate the homoepitaxial growth of triangular BN grains on exfoliated hBN flakes by Metal-Organic Vapor Phase Epitaxy and show by atomic force microscopy and photoluminescence that the stacking of these triangular islands can deviate from the AA' stacking of hBN. We show that the stacking order is enforced by the crystallographic direction of the edge of the exfoliated hBN flakes, with armchair edges allowing for centrosymmetric stacking, whereas zigzag edges lead to the growth of noncentrosymmetric BN polytypes. Our results indicate pathways to grow homoepitaxial BN with tunable layer stacking, which is required to induce piezoelectricity or ferroelectricity.

Destructive Photon Echo Formation in Six-Wave Mixing Signals of a MoSe2 Monolayer.

Monolayers of transition metal dichalcogenides display a strong excitonic optical response. Additionally encapsulating the monolayer with hexagonal boron nitride allows to reach the limit of a purely homogeneously broadened exciton system. On such a MoSe2 -based system, ultrafast six-wave mixing spectroscopy is performed and a novel destructive photon echo effect is found. This process manifests as a characteristic depression of the nonlinear signal dynamics when scanning the delay between the applied laser pulses. By theoretically describing the process within a local field model, an excellent agreement with the experiment is reached. An effective Bloch vector representation is developed and thereby it is demonstrated that the destructive photon echo stems from a destructive interference of successive repetitions of the heterodyning experiment.

Exposing the trion's fine structure by controlling the carrier concentration in hBN-encapsulated MoS2.

Atomically thin materials, like semiconducting transition metal dichalcogenides, are highly sensitive to the environment. This opens up an opportunity to externally control their properties by changing their surroundings. In this work, high-quality van der Waals heterostructures assembled from hBN-encapsulated monolayer MoS2 are studied with the aid of photoluminescence, photoluminescence excitation, and reflectance contrast experiments. We demonstrate that carrier concentration in MoS2 monolayers, arising from charge transfer from impurities in the substrate, can be significantly tuned within one order of magnitude by the modification of the bottom hBN flake thickness. The studied structures, characterized by spectral lines with linewidths approaching the narrow homogeneously broadened limit enabled observations of subtle optical and spin-valley properties of excitonic complexes. Our results allowed us to resolve three optically-active negatively charged excitons in MoS2 monolayers, which are assigned to the intravalley singlet, intervalley singlet, and intervalley triplet states.

Excitonic Complexes in n-Doped WS2 Monolayer.

We investigate the origin of emission lines apparent in the low-temperature photoluminescence spectra of n-doped WS2 monolayer embedded in hexagonal BN layers using external magnetic fields and first-principles calculations. Apart from the neutral A exciton line, all observed emission lines are related to the negatively charged excitons. Consequently, we identify emissions due to both the bright (singlet and triplet) and dark (spin- and momentum-forbidden) negative trions as well as the phonon replicas of the latter optically inactive complexes. The semidark trions and negative biexcitons are distinguished. On the basis of their experimentally extracted and theoretically calculated g-factors, we identify three distinct families of emissions due to exciton complexes in WS2: bright, intravalley, and intervalley dark. The g-factors of the spin-split subbands in both the conduction and valence bands are also determined.

Valley polarization of singlet and triplet trions in a WS2 monolayer in magnetic fields.

The spectral signatures associated with different negatively charged exciton complexes (trions) in a WS2 monolayer encapsulated in hBN are analyzed from low temperature and polarization resolved reflectance contrast (RC) and photoluminescence (PL) experiments, with an applied magnetic field. Based on results obtained from the RC experiment, we show that the valley Zeeman effect affects the optical response of both the singlet and the triplet trion species through the evolution of their energy and of their relative intensity, when applying an external magnetic field. Our analysis allows us to estimate a free electron concentration of ∼1.3 × 1011 cm-2. The observed evolutions based on PL experiments on the same sample are different and can hardly be understood within the same simple frame, highlighting the complexity of relaxation processes involved in the PL response.

Ultra-long-working-distance spectroscopy of single nanostructures with aspherical solid immersion microlenses.

In light science and applications, equally important roles are played by efficient light emitters/detectors and by the optical elements responsible for light extraction and delivery. The latter should be simple, cost effective, broadband, versatile and compatible with other components of widely desired micro-optical systems. Ideally, they should also operate without high-numerical-aperture optics. Here, we demonstrate that all these requirements can be met with elliptical microlenses 3D printed on top of light emitters. Importantly, the microlenses we propose readily form the collected light into an ultra-low divergence beam (half-angle divergence below 1°) perfectly suited for ultra-long-working-distance optical measurements (600 mm with a 1-inch collection lens), which are not accessible to date with other spectroscopic techniques. Our microlenses can be fabricated on a wide variety of samples, including semiconductor quantum dots and fragile van der Waals heterostructures made of novel two-dimensional materials, such as monolayer and few-layer transition metal dichalcogenides.

Narrow Excitonic Lines and Large-Scale Homogeneity of Transition-Metal Dichalcogenide Monolayers Grown by Molecular Beam Epitaxy on Hexagonal Boron Nitride.

Monolayer transition-metal dichalcogenides (TMDs) manifest exceptional optical properties related to narrow excitonic resonances. However, these properties have been so far explored only for structures produced by techniques inducing considerable large-scale inhomogeneity. In contrast, techniques which are essentially free from this disadvantage, such as molecular beam epitaxy (MBE), have to date yielded only structures characterized by considerable spectral broadening, which hinders most of the interesting optical effects. Here, we report for the first time on the MBE-grown TMD exhibiting narrow and resolved spectral lines of neutral and charged exciton. Moreover, our material exhibits unprecedented high homogeneity of optical properties, with variation of the exciton energy as small as ±0.16 meV over a distance of tens of micrometers. Our recipe for MBE growth is presented for MoSe2 and includes the use of atomically flat hexagonal boron nitride substrate. This recipe opens a possibility of producing TMD heterostructures with optical quality, dimensions, and homogeneity required for optoelectronic applications.

Valley polarization of exciton-polaritons in monolayer WSe2 in a tunable microcavity.

Monolayer transition metal dichalcogenides, known for exhibiting strong excitonic resonances, constitute a very interesting and versatile platform for the investigation of light-matter interactions. In this work, we report on a strong coupling regime between excitons in monolayer WSe2 and photons confined in an open, voltage-tunable dielectric microcavity. The tunability of our system allows us to extend the exciton-polariton state over a wide energy range and, in particular, to bring the excitonic component of the lower polariton mode into resonance with other excitonic transitions in monolayer WSe2. We can retain up to 40% of initial circular polarization of the laser or loose it completely if polariton modes are brought into resonances with low energy excitonic modes.

The lifetime of interlayer breathing modes of few-layer 2H-MoSe2 membranes.

A time-resolved observation of coherent interlayer longitudinal acoustic phonons in thin layers of 2H-MoSe2 is reported. A femtosecond pump-probe technique is used to investigate the evolution of the energy loss of these vibrational modes in a wide selection of MoSe2 flakes with different thicknesses ranging from bilayer up to the bulk limit. By directly analysing the temporal decay of the modes, we can clearly distinguish an abrupt crossover related to the acoustic mean free path of the phonons in a layered system, and the constraints imposed on the acoustic decay channels when reducing the dimensionality. For thicker samples, the main acoustic attenuation mechanism is attributed to the scattering of the acoustic modes with thermal phonons. For samples thinner than ∼20 molecular layers, the predominant damping mechanism is ascribed to the effects of surface asperity. Losses intrinsic to the low dimensionality of single or few layer materials impose critical limitations for their use in optomechanical and optoelectronic devices.

Tuning carrier concentration in a superacid treated MoS2 monolayer.

The effect of bis(trifluoromethane) sulfonimide (TFSI, superacid) treatment on the optical properties of MoS2 monolayers is investigated by means of photoluminescence, reflectance contrast and Raman scattering spectroscopy employed in a broad temperature range. It is shown that when applied multiple times, the treatment results in progressive quenching of the trion emission/absorption and in the redshift of the neutral exciton emission/absorption associated with both the A and B excitonic resonances. Based on this evolution, a trion complex related to the B exciton in monolayer MoS2 is unambiguously identified. A defect-related emission observed at low temperatures also disappears from the spectrum as a result of the treatment. Our observations are attributed to effective passivation of defects on the MoS2 monolayer surface. The passivation reduces the carrier density, which in turn affects the out-of-plane electric field in the sample. The observed tuning of the carrier concentration strongly influences also the Raman scattering in the MoS2 monolayer. An enhancement of Raman scattering at resonant excitation in the vicinity of the A neutral exciton is clearly seen for both the out-of-plane A'1 and in-plane E' modes. On the contrary, when the excitation is in resonance with a corresponding trion, the Raman scattering features become hardly visible. These results confirm the role of the excitonic charge state plays in the resonance effect of the excitation energy on the Raman scattering in transition metal dichalcogenides.

The optical response of monolayer, few-layer and bulk tungsten disulfide.

We present a comprehensive optical study of thin flakes of tungsten disulfide (WS2) with thickness ranging from mono- to octalayer and in the bulk limit. It is shown that the optical band-gap absorption of monolayer WS2 is governed by competing resonances arising from one neutral and two distinct negatively charged excitons whose contributions to the overall absorption of light vary as a function of temperature and carrier concentration. The photoluminescence response of monolayer WS2 is found to be largely dominated by disorder/impurity- and/or phonon-assisted recombination processes. The indirect band-gap luminescence in multilayer WS2 turns out to be a phonon-mediated process whose energy evolution with the number of layers surprisingly follows a simple model of a two-dimensional confinement. The energy position of the direct band-gap response (A and B resonances) is only weakly dependent on the layer thickness, which underlines an approximate compensation of the effect of the reduction of the exciton binding energy by the shrinkage of the apparent band gap. The A-exciton absorption-type spectra in multilayer WS2 display a non-trivial fine structure which results from the specific hybridization of the electronic states in the vicinity of the K-point of the Brillouin zone. The effects of temperature on the absorption-like and photoluminescence spectra of various WS2 layers are also quantified.

Raman scattering excitation spectroscopy of monolayer WS2.

Resonant Raman scattering is investigated in monolayer WS2 at low temperature with the aid of an unconventional technique, i.e., Raman scattering excitation (RSE) spectroscopy. The RSE spectrum is made up by sweeping the excitation energy, when the detection energy is fixed in resonance with excitonic transitions related to either neutral or charged excitons. We demonstrate that the shape of the RSE spectrum strongly depends on the selected detection energy. The resonance of outgoing light with the neutral exciton leads to an extremely rich RSE spectrum, which displays several Raman scattering features not reported so far, while no clear effect on the associated background photoluminescence is observed. Instead, when the outgoing photons resonate with the negatively charged exciton, a strong enhancement of the related emission occurs. Presented results show that the RSE spectroscopy can be a useful technique to study electron-phonon interactions in thin layers of transition metal dichalcogenides.

Sub-bandgap Voltage Electroluminescence and Magneto-oscillations in a WSe2 Light-Emitting van der Waals Heterostructure.

We report on experimental investigations of an electrically driven WSe2 based light-emitting van der Waals heterostructure. We observe a threshold voltage for electroluminescence significantly lower than the corresponding single particle band gap of monolayer WSe2. This observation can be interpreted by considering the Coulomb interaction and a tunneling process involving excitons, well beyond the picture of independent charge carriers. An applied magnetic field reveals pronounced magneto-oscillations in the electroluminescence of the free exciton emission intensity with a 1/B periodicity. This effect is ascribed to a modulation of the tunneling probability resulting from the Landau quantization in the graphene electrodes. A sharp feature in the differential conductance indicates that the Fermi level is pinned and allows for an estimation of the acceptor binding energy.

Radiatively Limited Dephasing and Exciton Dynamics in MoSe2 Monolayers Revealed with Four-Wave Mixing Microscopy.

By implementing four-wave mixing (FWM) microspectroscopy, we measure coherence and population dynamics of the exciton transitions in monolayers of MoSe2. We reveal their dephasing times T2 and radiative lifetime T1 in a subpicosecond (ps) range, approaching T2 = 2T1 and thus indicating radiatively limited dephasing at a temperature of 6 K. We elucidate the dephasing mechanisms by varying the temperature and by probing various locations on the flake exhibiting a different local disorder. At the nanosecond range, we observe the residual FWM produced by the incoherent excitons, which initially disperse toward the dark states but then relax back to the optically active states within the light cone. By introducing polarization-resolved excitation, we infer intervalley exciton dynamics, revealing an initial polarization degree of around 30%, constant during the initial subpicosecond decay, followed by the depolarization on a picosecond time scale. The FWM hyperspectral imaging reveals the doped and undoped areas of the sample, allowing us to investigate the neutral exciton, the charged one, or both transitions at the same time. In the latter, we observe the exciton-trion beating in the coherence evolution indicating their coherent coupling.

Rhombohedral Multilayer Graphene: A Magneto-Raman Scattering Study.

Graphene layers are known to stack in two stable configurations, namely, ABA or ABC stacking, with drastically distinct electronic properties. Unlike the ABA stacking, little has been done to experimentally investigate the electronic properties of ABC graphene multilayers. Here, we report on the first magneto optical study of a large ABC domain in a graphene multilayer flake, with ABC sequences exceeding 17 graphene sheets. ABC-stacked multilayers can be fingerprinted with a characteristic electronic Raman scattering response, which persists even at room temperatures. Tracing the magnetic field evolution of the inter Landau level excitations from this domain gives strong evidence for the existence of a dispersionless electronic band near the Fermi level, characteristic of such stacking. Our findings present a simple yet powerful approach to probe ABC stacking in graphene multilayer flakes, where this highly degenerated band appears as an appealing candidate to host strongly correlated states.

Exciton band structure in layered MoSe2: from a monolayer to the bulk limit.

We present the micro-photoluminescence (µPL) and micro-reflectance contrast (µRC) spectroscopy studies on thin films of MoSe(2) with layer thicknesses ranging from a monolayer (1L) up to 5L. The thickness dependent evolution of the ground and excited state excitonic transitions taking place at various points of the Brillouin zone is determined. Temperature activated energy shifts and linewidth broadenings of the excitonic resonances in 1L, 2L and 3L flakes are accounted for by using standard formalisms previously developed for semiconductors. A peculiar shape of the optical response of the ground state (A) exciton in monolayer MoSe(2) is tentatively attributed to the appearance of a Fano-type resonance. Rather trivial and clearly decaying PL spectra of monolayer MoSe(2) with temperature confirm that the ground state exciton in this material is optically bright in contrast to a dark exciton ground state in monolayer WSe(2).

Excitonic resonances in thin films of WSe2: from monolayer to bulk material.

We present optical spectroscopy (photoluminescence and reflectance) studies of thin layers of the transition metal dichalcogenide WSe2, with thickness ranging from mono- to tetra-layer and in the bulk limit. The investigated spectra show the evolution of excitonic resonances as a function of layer thickness, due to changes in the band structure and, importantly, due to modifications of the strength of Coulomb interactions as well. The observed temperature-activated energy shift and broadening of the fundamental direct exciton are well accounted for by standard formalisms used for conventional semiconductors. A large increase of the photoluminescence yield with temperature is observed in a WSe2 monolayer, indicating the existence of competing radiative channels. The observation of absorption-type resonances due to both neutral and charged excitons in the WSe2 monolayer is reported and the effect of the transfer of oscillator strength from charged to neutral excitons upon an increase of temperature is demonstrated.