Surface phonon-polaritons propagating along interfaces of polar dielectrics coexist with excitons in many van der Waals heterostructures, so understanding their mutual interactions is of great interest. Here, we investigate the type I surface phonon polariton of hBN via low-temperature resonant-Raman spectroscopy in hBN/WSe2 heterostructures. The resonantly enhanced hBN surface phonon polariton (SPhP) Raman signal, when laser energy is such that the scattered photons have energy close to that of the WSe2 excitons, enables detailed characterization of type I SPhP in hBN even when hBN is one monolayer thick. We find that the measured bandwidth of the SPhP Raman signal depends on the thicknesses of the hBN layer. We are able explain the experimental data using transfer matrix method simulations of SPhP dispersions providing that we assume the Raman scattering to be momentum non-conserving, as could be the case if localized WSe2 exciton states participated in the process. We further show that resonant Raman scattering from SiO2 SPhP can also be mediated by WSe$_2$.
Monolayer transition metal dichalcogenides, known for exhibiting strong excitonic resonances, constitute a very interesting and versatile platform for 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 WS…
Due to high binding energy and oscillator strength, excitons in thin flakes of transition metal dichalcogenides constitute a perfect foundation for realizing a strongly coupled light-matter system. In this paper we investigate mono- and few-layer WSe$_2$ flakes encapsulated in hexagonal boron nitride and incorporated into a planar dielectric cavity. We use an open cavity design which provides tunability of the cavity mode energy by as much as 150 meV. We observe a strong coupling regime between the cavity photons and the neutral excitons in direct-bandgap monolayer WSe$_2$, as well as in few-l…
Hybridisation of electronic bands of two-dimensional materials, assembled into twistronic heterostructures, enables one to tune their optoelectronic properties by selecting conditions for resonant interlayer hybridisation. Resonant interlayer hybridisation qualitatively modifies the excitons in such heterostructures, transforming these optically active modes into superposition states of interlayer and intralayer excitons. For MoSe$_2$/WSe$_2$ heterostructures, strong hybridization occurs between the holes in the spin-split valence band of WSe$_2$ and in the top valence band of MoSe$_2$, especi…
Van der Waals (vdW) materials, weakly bound layered compounds, have received enormous interest as they offer a malleable playground for a wide range of physical properties in thermal, electronic and optical devices. In particular, owing to their inherent deep subwavelength light confinement, they support a variety of light-matter interactions phenomena such as plasmons, excitons and phonons conveyed as polaritonic modes. Specifically, semiconductor vdW materials such as WSe_2 are particularly attractive for photonic and quantum integrated technologies since they sustain VIS-NIR exciton-polarit…
Synthesis and characterization of high-quality single-crystal WSe2 films on highly-insulating substrate is presented. We demonstrate for the first time that the presence of gold nanoparticles in the basal plane of a WSe2 film can enhance its Raman scattering intensity. The experimentally observed enhancement ratio in the Raman signal correlates well with the simulated electric field intensity using a three-dimensional electromagnetic software and theoretical calculation. This work provides guidelines for the use of two-dimensional WSe2 films as a SERS substrate.
Strong optical nonlinearities play a central role in realizing quantum photonic technologies. In solid state systems, exciton-polaritons, which result from the hybridization of material excitations and cavity photons, are an attractive candidate to realize such nonlinearities. Here, the interaction between excitons forms the basis of the polaritonic nonlinearity. While the interaction between ground state excitons generates a notable optical nonlinearity, the strength of such ground state interactions is generally not sufficient to reach the regime of quantum nonlinear optics and strong single…
Few-layer tungsten diselenide (WSe2) is investigated using circularly polarized Raman spectroscopy with up to eight excitation energies. The main E2g1 and A1g modes near 250 cm-1 appear as a single peak in the Raman spectrum taken without consideration of polarization but are resolved by using circularly polarized Raman scattering. The resonance behaviors of the E2g1 and A1g modes are examined. Firstly, both the E2g1 and A1g modes are enhanced near resonances with the exciton states. The A1g mode exhibits Davydov splitting for trilayers or thicker near some of the exciton resonances. The low-f…
Solid state cavity quantum electrodynamics is a rapidly advancing field which explores the frontiers of light-matter coupling. Plasmonic approaches are of particular interest in this field, since they carry the potential to squeeze optical modes to spaces significantly below the diffraction limit1,2, enhancing light-matter coupling. They further serve as an architecture to design ultra-fast, non-linear integrated circuits with smallest footprints3. Transition metal dichalcogenides are ideally suited as the active material in such circuits as they interact strongly with light at the ultimate mo…
We investigate WSe$_2$-MoSe$_2$ heterobilayers with different twist angles $θ\pm δ$ between the two layers, by low-frequency Raman scattering. In sufficiently aligned samples with $θ=0^\circ$, or $θ=60^\circ$, and $δ\lesssim 3^\circ$, we observe an interlayer shear mode (ISM), which is a clear sign of a commensurate bilayer structure, i.e., the layers must undergo an atomic reconstruction to form R-type or H-type stacking orders. We find slightly different ISM energies of about 18~cm$^{-1}$ and 17~cm$^{-1}$ for H-type and R-type reconstructions, respectively, independent of the exact value of …
We present a high-resolution resonance Raman study of hBN encapsulated MoSe$_2$ and WSe$_2$ monolayers at 4 K using excitation energies from 1.6 eV to 2.25 eV. We report resonances with the WSe$_2$ A2s and MoSe$_2$ A2s and B2s excited Rydberg states despite their low oscillator strength. When resonant with the 2s states we identify new Raman peaks which are associated with intravalley scattering between different Rydberg states via optical phonons. By calibrating the Raman scattering efficiency and separately constraining the electric dipole matrix elements, we reveal that the scattering rates…
New techniques for probing hyperbolic phonon polaritons (HPP) in 2D materials will support the development of the emerging technologies in this field. Previous reports have shown that it is possible for WSe2 monolayers in contact with the hexagonal boron nitride (hBN) to generate HPP in the hBN via Raman scattering. In this paper, we set out new results on HPP Raman scattering induced in hBN by WSe2 and MoSe2 monolayers including new resonances at which the Raman scattering is enhanced. Analysis of the observed Raman lineshapes demonstrates that Raman scattering allows HPP with wavevectors wit…
Semiconducting transition-metal dichalcogenides (TMDCs) provide a fascinating discovery platform for strong light-matter interaction effects in the visible spectrum at ambient conditions. While most of the work has focused on hybridizing excitons with resonant photonic modes of external mirrors, cavities, or nanostructures, intriguingly, TMDC flakes of sub-wavelength thickness can themselves act as nanocavities. Here, we determine the optical response of such freestanding planar waveguides of WSe$_2$, by means of cathodoluminescence spectroscopy. We reveal strong exciton-photon interaction eff…
The emergence of spatial and temporal coherence of light emitted from solid-state systems is a fundamental phenomenon, rooting in a plethora of microscopic processes. It is intrinsically aligned with the control of light-matter coupling, and canonical for laser oscillation. However, it also emerges in the superradiance of multiple, phase-locked emitters, and more recently, coherence and long-range order have been investigated in bosonic condensates of thermalized light, as well as in exciton-polaritons driven to a ground state via stimulated scattering. Here, we experimentally show that the in…
Plexciton-mediated Raman scattering in strongly coupled systems
Institute of Light Resources and Environmental Science, Henan Academy of Sciences（河南省科学院光资源与环境科学研究所）；School of Physics, Xi’an Jiaotong University（西安交通大学物理学院）
The electronic states at the direct band gap of monolayer WSe2 at the $K^+$ and $K^-$ valleys are related by time reversal and may be viewed as pseudo-spins. The corresponding optical interband transitions are governed by robust excitons. In double resonant Raman spectroscopy, we uncover that the 2s exciton state energy differs from the 1s state energy by exactly the energy of the combination of several prominent phonons. Superimposed on the exciton photoluminescence (PL) we observe the double resonant Raman signal. This spectrally narrow peak shifts with the excitation laser energy as incomin…
The two-fold valley degeneracy in two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs) (Mo,W)(S,Se)2 is suitable for "valleytronics", the storage and manupulation of information utilizing the valley degree of freedom. The conservation of luminescent photon helicity in these 2D crystal monolayers has been widely regarded as a benchmark indicator for charge carrier valley polarization. Here we perform helicity-resolved Raman scattering of the TMDC atomic layers. In drastic contrast to luminescence, the dominant first-order zone-center Raman bands, including the low energy…
We report on nano-optical imaging study of WSe2 thin flakes with the scanning near-field optical microscopy (NSOM). The NSOM technique allows us to visualize in real space various waveguide photon modes inside WSe2. By tuning the excitation laser energy, we are able to map the entire dispersion of these waveguide modes both above and below the A exciton energy of WSe2. We found that all the modes interact strongly with WSe2 excitons. The outcome of the interaction is that the observed waveguide modes shift to higher momenta right below the A exciton energy. At higher energies, on the other han…
The large oscillator strength of excitons in transition metal dichalcogenide layers facilitates the formation of exciton-polariton resonances for monolayers and van-der-Waals heterostructures embedded in optical microcavities. Here, we show, that locally changing the number of layers in a WSe2/hBN/WSe2 van-der-Waals heterostructure embedded in a monolithic, high-quality-factor cavity gives rise to a local variation of the coupling strength. This effect yields a polaritonic stair case potential, which we demonstrate at room temperature. Our result paves the way towards engineering local polarit…
Spontaneous Raman Scattering under Vibrational Strong Coupling: The Critical Role of Polariton Spatial Mode Coherence
Université de Strasbourg, CNRS, Institut de Physique et Chimie des Matériaux de Strasbourg（斯特拉斯堡大学）；Université Claude Bernard Lyon 1, CNRS, Institut Lumière Matière（里昂第一大学）
Strong coupling between cavity photons and molecular vibrations can lead to the formation of vibron-polaritons. In a recent experiment with PVAc molecules in a metal-metal microcavity [A.Shalabney et al., Ang.Chem.Int.Ed. 54 7971 (2015)], such a coupling was observed to enhance the Raman scattering probability by several orders of magnitude. Inspired by this, we theoretically analyze the effect of strong photon-vibron coupling on the Raman scattering amplitude of organic molecules. This problem has recently been addressed in [J.del Pino, J.Feist and F.J.Garcia-Vidal; J.Phys.Chem.C 119 29132 (2…
Raman scattering is a ubiquitous phenomenon in light-matter interactions which reveals a material's electronic, structural and thermal properties. Controlling this process would enable new ways of studying and manipulating fundamental material properties. Here, we report a novel Raman scattering process at the interface between different van der Waals (vdW) materials as well as between a monolayer semiconductor and 3D crystalline substrates. We find that interfacing a WSe2 monolayer with materials such as SiO2, sapphire, and hexagonal boron nitride (hBN) enables Raman transitions with phonons …
The optical responses of semiconducting transition metal dichalcogenides are dominated by excitons. Being able to strongly interact with light and other materials excitations, excitons in semiconductors are prototypes for investigating many-particle and strong-field physics, including exciton-exciton, exciton-photon, and exciton-phonon interactions. Strong exciton-photon interactions, in particular, can lead to the emergence of exciton-polariton hybrid quasiparticles with peculiar characteristics, and a tendency toward macroscopic and spontaneous coherence. Normally, far-field and near-field o…
Among the most common few-layers transition metal dichalcogenides (TMDs), WSe2 is the most challenging material from the lattice dynamics point of view. Indeed, for a long time the main two phonon modes (A1g and E12g) have been wrongly assigned. In the last few years, these two modes have been properly interpreted, and their quasi-degeneracy in the monolayer has been used for its identification. In this work, we show that this approach has a limited validity and we propose an alternative, more general approach, based on multi-phonon bands. Moreover, we show and interpret all the peaks (about 4…
While conventional semiconductor technology relies on the manipulation of electrical charge for the implementation of computational logic, additional degrees of freedom such as spin and valley offer alternative avenues for the encoding of information. In transition metal dichalcogenide (TMD) monolayers, where spin-valley locking is present, strong retention of valley chirality has been reported for MoS$_2$, WSe$_2$ and WS$_2$ while MoSe$_2$ shows anomalously low valley polarisation retention. In this work, chiral selectivity of MoSe$_2$ cavity polaritons under helical excitation is reported wi…
Using angle-resolved Raman spectroscopy, we show that a resonantly excited ground-state exciton-polariton fluid behaves like a nonequilibrium coolant for its host solid-state semiconductor microcavity. With this optical technique, we obtain a detailed measurement of the thermal fluxes generated by the pumped polaritons. We thus find a maximum cooling power for a cryostat temperature of $50$K and below where optical cooling is usually suppressed, and we identify the participation of an ultrafast cooling mechanism. We also show that the nonequilibrium character of polaritons constitutes an unexp…
Two-dimensional transition metal dichalcogenide (TMD) semiconductors provide a unique possibility to access the electronic valley degree of freedom using polarized light, opening the way to valley information transfer between distant systems. Excitons with a well-defined valley index (or valley pseudospin) as well as superpositions of the exciton valley states can be created with light having circular and linear polarization, respectively. However, the generated excitons have short lifetimes (ps) and are also subject to the electron-hole exchange interaction leading to fast relaxation of the v…
Transition metal dichalcogenide (TMD) monolayers are direct bandgap semiconductors that feature tightly bound excitons, strong spin-orbit coupling, and spin-valley degrees of freedom. Depending on the spin configuration of the electron-hole pairs, intra-valley excitons of TMD monolayers can be either optically bright or dark. Dark excitons involve nominally spin-forbidden optical transitions with zero in-plane transition dipole moment, making their detection with conventional far-field optical techniques challenging. Here, we introduce a new method for probing the optical properties of two-dim…
Monolayer (ML) transition metal dichalcogenides (TMDs) integrated in optical microcavities host exciton-polaritons as a hallmark of the strong light-matter coupling regime. Analogous concepts for hybrid light-matter systems employing spatially indirect excitons with a permanent electric dipole moment in heterobilayer (HBL) crystals promise realizations of exciton-polariton gases and condensates with immanent dipolar interactions. Here, we identify optical signatures of spatially indirect momentum-bright and momentum-dark interlayer excitons in vertical MoSe$_2$-WSe$_2$ heterostructures and imp…
Surface Plasmon Polaritons (SPP) are exploited due to their intriguing properties for photonic circuits fabrication and miniaturization, for surface enhanced spectroscopies and imaging beyond the diffraction limit. However, the excitation of these plasmonic modes by direct illumination is forbidden by energy/momentum conservation rules. One strategy to overcome this limitation relies on diffraction gratings to match the wavevector of the incoming photons with that of propagating SPP excitations. The main limit of the approaches so far reported in literature is that they rely on highly ordered …
Coupling single photon emitters to surface plasmons provides a versatile ground for on chip quantum photonics. However, achieving good coupling efficiency requires precise alignment of both the position and dipole orientation of the emitter relative to the plasmonic mode. We demonstrate coupling of single emitters in the 2-D semiconductor, WSe2 self-aligned with propagating surface plasmon polaritons in silver-air-silver, metal-insulator-metal waveguides. The waveguide produces strain induced defects in the monolayer which are close to the surface plasmon mode with favorable dipole orientation…
Recently reported large values of exciton-polariton nonlinearity of transition metal dichalcogenide (TMD) monolayers coupled to optically resonant structures approach the values characteristic for GaAs-based systems in the regime of strong light-matter coupling. Contrary to the latter, TMD-based polaritonic devices remain operational at ambient conditions and therefore have greater potential for practical nanophotonic applications. Here we present the study of the nonlinear properties of Ta$_2$O$_5$ slab waveguide coupled to a WSe$_2$ monolayer. We first confirm that the hybridization between …
The Raman 2D line of graphene is widely used for device characterization and during device fabrication as it contains valuable information on e.g. the direction and magnitude of mechanical strain and doping. Here we present systematic asymmetries in the 2D line shape of exfoliated graphene and graphene grown by chemical vapor deposition. Both graphene crystals are fully encapsulated in van der Waals heterostructures, where hexagonal boron nitride and tungsten diselenide are used as substrate materials. In both material stacks, we find very low doping values and extremely homogeneous strain dis…
Hyperbolic crystals like α-MoO$_3$ can support large wavevectors and photon density as compared to the commonly used dielectric crystals, which makes them a highly desirable platform for compact photonic devices. The extreme anisotropy of the dielectric constant in these crystals is intricately linked with the anisotropic character of the phonons, which along with photon confinement leads to the rich physics of phonon polaritons. However, the chiral nature of phonons in these hyperbolic crystals have not been studied in detail. In this study, we report our observations of helicity selective Ra…
Suspended graphene waveguides were deposited on micron-scale periodic metal (plasmonic) structures. Raman scattering of test molecules (B. Megaterium), deposited on the waveguides' surface, exhibited azimuthal cycles upon rotation: at these micron scales, spontaneous Raman ought to be independent of phase matching conditions. In addition, we observed angular-selective quadratic intensity dependence contrary to the typical linear behavior of spontaneous Raman. The effects were observed at very modest pump laser intensities (<10 MW/cm2 at the sample surface, oftenly used in Raman experiments). W…
Several theoretical predictions have claimed that the neutral exciton of TMDCs splits into a transversal and longitudinal exciton branch, with the longitudinal one, which is the upper branch, exhibiting an extraordinary strong dispersion in the meV range within the light cone. Historically, this was linked for semiconductor quantum wells to strong far-field optical dipole coupling, or strong electronic long-range exchange interactions, describing two sides of the same coin. Recently, experiments utilizing Fourier-space spectroscopy have shown that the exciton (exciton-polariton) dispersion can…
Layer-Dependent Interfacial Coupling and Exciton Pinning in WSe2/Graphene Heterostructures
Empa – Swiss Federal Laboratories for Materials Science and Technology（瑞士联邦材料科技研究所）；University of Basel（巴塞尔大学）；Swiss Nanoscience Institute, University of Basel（巴塞尔大学瑞士纳米科学研究所）；The Pennsylvania State University（宾夕法尼亚州立大学）
We have investigated the vibrational properties of van der Waals heterostructures of monolayer transition metal dichalcogenides (TMDs), specifically MoS2/WSe2 and MoSe2/MoS2 heterobilayers as well as twisted MoS2 bilayers, by means of ultralow-frequency Raman spectroscopy. We discovered Raman features (at 30 ~ 40 cm-1) that arise from the layer-breathing mode (LBM) vibrations between the two incommensurate TMD monolayers in these structures. The LBM Raman intensity correlates strongly with the suppression of photoluminescence that arises from interlayer charge transfer. The LBM is generated on…
We report on the resonant coupling between localized surface plasmon resonances (LSPRs) in nanostructured Ag films, and an adsorbed monolayer of Rhodamine 6G dye. Hybridization of the plasmons and molecular excitons creates new coupled polaritonic modes, which have been tuned by varying the LSPR wavelength. The resulting polariton dispersion curve shows an anticrossing behavior which is very well fit by a simple coupled-oscillator Hamiltonian, giving a giant Rabi-splitting energy of ~400 meV. The strength of this coupling is shown to be proportional to the square root of the molecular density.…
In this Letter we analyze theoretically how the emergence of collective strong coupling between vibrational excitations and confined cavity modes affects Raman scattering processes. This work is motivated by recent experiments [Shalabney et al., Angew. Chemie 54, 7971 (2015)], which reported enhancements of up to three orders of magnitude in the Raman signal. By using different models within linear response theory, we show that the total Raman cross section is maintained constant when the system evolves from the weak-coupling limit to the strong-coupling regime. A redistribution of the Raman s…
Being motivated by recent achievements in the rapidly developing fields of optical bound states in the continuum (BICs) and excitons in monolayers of transition metal dichalcogenides, we analyze strong coupling between BICs in $\rm Ta_2O_5$ periodic photonic structures and excitons in $\rm WSe_2$ monolayers. We demonstrate that giant radiative lifetime of BICs allow to engineer the exciton-polariton lifetime enhancing it three orders of magnitude compared to a bare exciton. We show that maximal lifetime of hybrid light-matter state can be achieved at any point of $\mathbf{k}$-space by shaping …
Coupling of an atom-like emitter to surface plasmons provides a path toward significant optical nonlinearity, which is essential in quantum information processing and quantum networks. A large coupling strength requires nanometer-scale positioning accuracy of the emitter near the surface of the plasmonic structure, which is challenging. We demonstrate the coupling of single localized defects in a tungsten diselenide (WSe2) monolayer self-aligned to the surface plasmon mode of a silver nanowire. The silver nanowire induces a strain gradient on the monolayer at the overlapping area, leading to t…
Energy relaxation of photo-excited charge carriers is of significant fundamental interest and crucial for the performance of monolayer (1L) transition metal dichaclogenides (TMDs) in optoelectronics. We measure light scattering and emission in 1L-WSe$_2$ close to the laser excitation energy (down to~$\sim$0.6meV). We detect a series of periodic maxima in the hot photoluminescence intensity, stemming from energy states higher than the A-exciton state, in addition to sharp, non-periodic Raman lines related to the phonon modes. We find a period $\sim$15meV for peaks both below (Stokes) and above …
Strong spin-orbit coupling and inversion symmetry breaking in transition metal dichalcogenide monolayers yield the intriguing effects of valley-dependent optical selection rules. As such, it is possible to substantially polarize valley excitons with chiral light and furthermore create coherent superpositions of K and K- polarized states. Yet, at ambient conditions dephasing usually becomes too dominant, and valley coherence typically is not observable. Here, we demonstrate that valley coherence is, however, clearly observable for a single monolayer of WSe2, if it is strongly coupled to the opt…
Two-dimensional transition metal dichalcogenides (TMDCs) have recently become attractive semiconductor materials for several optoelectronic applications, such as photodetection, light harvesting, phototransistors, light-emitting diodes, and lasers. They are particularly appealing because their bandgap lies in the visible and near-IR range, and they possess strong excitonic resonances, high oscillator strengths, and valley-selective response. Coupling these materials to optical nanocavities enhances the quantum yield of exciton emission, enabling advanced quantum optics and nanophotonic devices…
Polaritons in metals, semimetals, semiconductors, and polar insulators, with their extreme confinement of electromagnetic energy, provide many promising opportunities for enhancing typically weak light-matter interactions such as multipolar radiation, multiphoton spontaneous emission, Raman scattering, and material nonlinearities. These highly confined polaritons are quasi-electrostatic in nature, with most of their energy residing in the electric field. As a result, these "electric" polaritons are far from optimized for enhancing emission of a magnetic nature, such as spin relaxation, which i…
The functional form of Coulomb interactions in the transition metal dichalcogenides and other van der Waals solids is critical to many of their unique properties, e.g. strongly-correlated electron states, superconductivity and emergent ferromagnetism. This paper presents measurements of key excitonic energy levels in MoSe2/WSe2 heterostructures. These measurements are obtained from resonance Raman experiments on specific Raman peaks only observed at excited states of the excitons. This data is used to validate a model of the Coulomb potential in these structures which predicts the exciton ener…
We propose a scheme to perform single-shot quantum non-demolition (QND) readout of the spin of an electron trapped in a semiconductor quantum dot (QD). Our proposal relies on the interaction of the QD electron spin with optically excited, quantum well (QW) microcavity exciton-polaritons. The spin-dependent Coulomb exchange interaction between the QD electron and cavity polaritons causes the phase and intensity response of left circularly polarized light to be different to that of the right circularly polarized light, in such a way that the QD electron's spin can be inferred from the response t…
