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The nonlinear optical response of a material is a sensitive probe of electronic and structural dynamics under strong light fields. The induced microscopic polarizations are usually detected via their far-field light emission, thus limiting spatial resolution. Several powerful near-field techniques circumvent this limitation by employing local nanoscale scatterers; however, their signal strength scales unfavorably as the probe volume decreases. Here, we demonstrate that time-resolved atomic force microscopy is capable of temporally and spatially resolving the microscopic, electrostatic forces arising from a nonlinear optical polarization in an insulating dielectric driven by femtosecond optical fields. The measured forces can be qualitatively explained by a second-order nonlinear interaction in the sample. The force resulting from this nonlinear interaction has frequency components below the mechanical resonance frequency of the cantilever and is thus detectable by regular atomic force microscopy methods. The capability to measure a nonlinear polarization through its electrostatic force is a powerful means to revisit nonlinear optical effects at the nanoscale, without the need for emitted photons or electrons from the surface. © 2020 National Academy of Sciences. All rights reserved., Proceedings of the National Academy of Sciences of the United States of America, 117 (33), ISSN:0027-8424, ISSN:1091-6490

Heterobilayers consisting of MoSe$_2$ and WSe$_2$ monolayers can host optically bright interlayer excitons with intriguing properties such as ultralong lifetimes and pronounced circular polarization of their photoluminescence due to valley polarization, which can be induced by circularly polarized excitation or applied magnetic fields. Here, we report on the observation of an intrinsic valley-magnetophonon resonance for localized interlayer excitons promoted by invervalley hole scattering. It leads to a resonant increase of the photoluminescence polarization degree at the same field of 24.2 Tesla for H-type and R-type stacking configurations despite their vastly different excitonic energy splittings. As a microscopic mechanism of the hole intervalley scattering we identify the scattering with chiral TA phonons of MoSe$_2$ between excitonic states mixed by the long-range electron hole exchange interaction., Comment: 7+5 pages, 2+0 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.

Two-dimensional transition metal dichalcogenides offer a fascinating platform for creating van der Waals heterojunctions with exciting physical properties. Because of their typical type-II band alignment, photoexcited electrons and holes can separate

We report about the investigation of twisted MoSe2 homo- and MoSe2–WSe2 heterobilayers by means of low-frequency Raman spectroscopy (LFRS) and low-temperature micro photoluminescence (µPL). In room-temperature LFRS experiments on both, twisted MoSe2 homobilayers and twisted MoSe2–WSe2 heterobilayers, we observe moiré phonons, i.e. folded acoustic phonon modes due to the moiré superlattice. In the heterobilayers, we can identify moiré phonons of both materials, MoSe2 and WSe2. While the twist angles for the homobilayers are relatively precisely known from the applied tear-and-stack preparation method, the twist angles of the heterobilayers have to be determined via second-harmonic-generation microscopy on monolayer regions of the samples, which has significant uncertainties. We show that by the moiré phonons of the heterobilayers, the relative twist angles can be determined on a local scale with much higher precision. We apply our technique for the investigation of a large area H-type (twist angle θ = 60∘ + δ) MoSe2–WSe2 heterobilayer. These investigations show that spatial regions, which can be identified to be atomically reconstructed (i.e. δ = 0∘) by the observation of an interlayer shear mode in LFRS experiments, exhibit a strong, momentum-allowed interlayer-exciton signal in low-temperature µPL. On the contrary, regions, where moiré phonons are observed, i.e. which can be identified to be rigidly twisted by a misalignment angle in the range of 5 ° ≲ | δ | ≲ 6 ° , exhibit no significant interlayer-exciton signals.

We investigate WSe$_2$-MoSe$_2$ heterobilayers with different twist angles $\theta \pm \delta$ between the two layers, by low-frequency Raman scattering. In sufficiently aligned samples with $\theta=0^\circ$, or $\theta=60^\circ$, and $\delta \lesssim 3^\circ$, 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 $\theta\pm \delta$. Our findings are corroborated by the fact that the ISM is not observed in samples with twist angles, which deviate by $\delta > 3^\circ$ from $0^\circ$ or $60^\circ$. This is expected, since in such incommensurate structures, with the possibility of Moir$\acute{\text{e}}$-lattice formation, there is no restoring force for an ISM. Furthermore, we observe the ISM even in sufficiently aligned heterobilayers, which are encapsulated in hexagonal Boron nitride. This is particularly relevant for the characterization of high-quality heterostructure devices., Comment: 5 pages, 4 figures

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.

As conventional electronic is approaching its fundamental limits, huge efforts have been taken to explore new concepts of ultrafast control at the quantum level. Lightwave electronics — the foundation of attosecond science [1] — has opened a spectacular perspective by utilizing the carrier wave of an intense light pulse to steer the translational motion of charges faster than a single cycle of light [1–4]. Despite their promising potential as future information carrier, the electron's internal quantum attributes such as the spin and the valley pseudospin [5] have not been switchable at optical clock rates.

The weak spin-orbit interaction in graphene was predicted to be increased, e.g., by hydrogenation. This should result in a sizable spin Hall effect (SHE). We employ two different methods to examine the spin Hall effect in weakly hydrogenated graphene. For hydrogenation we expose graphene to a hydrogen plasma and use Raman spectroscopy to characterize this method. We then investigate the SHE of hydrogenated graphene in the H-bar method and by direct measurements of the inverse SHE. Although a large nonlocal resistance can be observed in the H-bar structure, comparison with the results of the other method indicate that this nonlocal resistance is caused by a non-spin-related origin.

Heterostructures of atomically thin van der Waals bonded monolayers have opened a unique platform to engineer Coulomb correlations, shaping excitonic, Mott insulating, or superconducting phases. In transition metal dichalcogenide heterostructures, electrons and holes residing in different monolayers can bind into spatially indirect excitons with a strong potential for optoelectronics, valleytronics, Bose condensation, superfluidity, and moir\'e-induced nanodot lattices. Yet these ideas require a microscopic understanding of the formation, dissociation, and thermalization dynamics of correlations including ultrafast phase transitions. Here we introduce a direct ultrafast access to Coulomb correlations between monolayers; phase-locked mid-infrared pulses allow us to measure the binding energy of interlayer excitons in WSe2/WS2 hetero-bilayers by revealing a novel 1s-2p resonance, explained by a fully quantum mechanical model. Furthermore, we trace, with subcycle time resolution, the transformation of an exciton gas photogenerated in the WSe2 layer directly into interlayer excitons. Depending on the stacking angle, intra- and interlayer species coexist on picosecond scales and the 1s-2p resonance becomes renormalized. Our work provides a direct measurement of the binding energy of interlayer excitons and opens the possibility to trace and control correlations in novel artificial materials., Comment: This is a post-peer-review, pre-copyedit version of an article published in Nature Materials. The final authenticated version is available online at https://doi.org/10.1038/s41563-019-0337-0

In heterobilayers consisting of different transition-metal dichalcogenide (TMDC) monolayers, optically excited electron-hole pairs can be spatially separated into the adjacent layers due to a type-II band alignment. However, they remain Coulomb correlated and form interlayer excitons (ILEs), which recombine radiatively. While these ILEs are observed in several TMDC material combinations, their characters and properties depend on the specific system. Herein, some of these peculiarities are demonstrated by comparing studies performed on two different heterobilayer combinations: MoS2-WSe2 and MoSe2-WSe2.

We control the linear polarization of emission from the coherently emitting ${K}^{+}$ and ${K}^{\ensuremath{-}}$ valleys (valley coherence) in monolayer ${\mathrm{WS}}_{2}$ with an out-of-plane magnetic field of up to 25 T. The magnetic-field-induced valley Zeeman splitting causes a rotation of the emission polarization with respect to the excitation by up to 35\ifmmode^\circ\else\textdegree\fi{} and reduces the polarization degree by up to 16%. We explain both of these phenomena with a model based on two noninteracting coherent two-level systems. We deduce that the coherent light emission from the valleys decays with a time constant of ${\ensuremath{\tau}}_{c}=260\text{ }\text{ }\mathrm{fs}$.

Intense lightwaves can accelerate quasiparticles inside solids. This strong-field light-matter interaction results in the emission of high-harmonic or high-order sideband radiation. While the former process relies on a complex coupling between simultaneously driven interband polarization and intraband currents, high-order sidebands originate from a ballistic acceleration of the quasiparticles within the bands. This mechanism allows for the implementation of a quasiparticle collider in order to study those entities in close analogy to conventional collision experiments. Accelerating electrons and holes in a monolayer of transition metal dichalcogenides extends this scheme to internal quantum degrees of freedom. Our experiments show a lightwave-indu-ced switching of the valley pseudospin, paving the way to ultimately fast valleytronics.

We experimentally study the radii of excitons in hBN-encapsulated WS2 monolayers by means of magneto-optical reflectance spectroscopy at cryogenic temperatures in magnetic fields up to 29 T. We observe field-induced energy shifts of the exciton ground and excited states due to valley Zeeman and diamagnetic effects. We find the g factor of the first excited state of $-4.2(+/-0.1) to be essentially equal to that of the ground state of -4.35(+/-0.1). From diamagnetic shifts we determine the root mean square radii of the excitons. The radius of the first excited state is found to be 5-8 nm and that of the ground state around 2 nm. Our results further confirm the Wannier-Mott nature of the exciton quasiparticles in monolayer semiconductors and the assignment of the optical resonances in absorption-type measurements. They also provide additional support for the applicability of the effective mass hydrogenlike models in these systems., accepted for publication in Phys. Rev. B

As conventional electronics approaches its limits 1 , nanoscience has urgently sought methods of fast control of electrons at the fundamental quantum level 2 . Lightwave electronics 3 —the foundation of attosecond science 4 —uses the oscillating carrier wave of intense light pulses to control the translational motion of the electron’s charge faster than a single cycle of light5–15. Despite being particularly promising information carriers, the internal quantum attributes of spin 16 and valley pseudospin17–21 have not been switchable on the subcycle scale. Here we demonstrate lightwave-driven changes of the valley pseudospin and introduce distinct signatures in the optical readout. Photogenerated electron–hole pairs in a monolayer of tungsten diselenide are accelerated and collided by a strong lightwave. The emergence of high-odd-order sidebands and anomalous changes in their polarization direction directly attest to the ultrafast pseudospin dynamics. Quantitative computations combining density functional theory with a non-perturbative quantum many-body approach assign the polarization of the sidebands to a lightwave-induced change of the valley pseudospin and confirm that the process is coherent and adiabatic. Our work opens the door to systematic valleytronic logic at optical clock rates.

Monolayers of transition metal dichalcogenides (TMDCs) feature exceptional optical properties that are dominated by excitons, tightly bound electron-hole pairs. Forming van der Waals heterostructures by deterministically stacking individual monolayers allows to tune various properties via choice of materials and relative orientation of the layers. In these structures, a new type of exciton emerges, where electron and hole are spatially separated. These interlayer excitons allow exploration of many-body quantum phenomena and are ideally suited for valleytronic applications. Mostly, a basic model of fully spatially-separated electron and hole stemming from the $K$ valleys of the monolayer Brillouin zones is applied to describe such excitons. Here, we combine photoluminescence spectroscopy and first principle calculations to expand the concept of interlayer excitons. We identify a partially charge-separated electron-hole pair in MoS$_2$/WSe$_2$ heterostructures residing at the $\Gamma$ and $K$ valleys. We control the emission energy of this new type of momentum-space indirect, yet strongly-bound exciton by variation of the relative orientation of the layers. These findings represent a crucial step towards the understanding and control of excitonic effects in TMDC heterostructures and devices., Comment: Nature Physics (2018), in press [main article (letter) and Supporting Information]

Two-dimensional transition-metal dichalcogenides (TMDCs) have recently emerged as a promising class of materials. A fascinating aspect of these atomically thin crystals is the possibility of combining different TMDCs into heterostructures. For several TMDC combinations, a staggered band alignment occurs, so that optically excited electron-hole pairs are spatially separated into different layers and form interlayer excitons (IEX). Here, we report on time-resolved, low-temperature photoluminescence (PL) of these IEX in a MoSe2-WSe2 heterostructure. In the time-resolved measurements, we observe indications of IEX diffusion in an inhomogeneous potential landscape. Excitation-density-dependent measurements reveal a dipolar, repulsive exciton-exciton interaction. PL measurements in applied magnetic fields show a giant valley-selective splitting of the IEX luminescence, with an effective g factor of about -15. This large value stems from the alignment of K+ and K- valleys of the constituent monolayers in our heterostructure, making intervalley transitions optically bright, so that contributions to the field-induced splitting arising from electron and hole valley magnetic moments add up. This giant splitting enables us to generate a near-unity valley polarization of interlayer excitons even under linearly polarized excitation by applying sufficiently large magnetic fields.

Localized surface-plasmon resonances enable efficient coupling to proximal resonant dipole transitions. By exploiting energy transfer from metal nanoparticles to monolayers of 2D crystals we point a way to generate single photons at room temperature.

We directly monitor exciton propagation in freestanding and SiO_{2}-supported WS_{2} monolayers through spatially and time-resolved microphotoluminescence under ambient conditions. We find a highly nonlinear behavior with characteristic, qualitative changes in the spatial profiles of the exciton emission and an effective diffusion coefficient increasing from 0.3 to more than 30 cm^{2}/s, depending on the injected exciton density. Solving the diffusion equation while accounting for Auger recombination allows us to identify and quantitatively understand the main origin of the increase in the observed diffusion coefficient. At elevated excitation densities, the initial Gaussian distribution of the excitons evolves into long-lived halo shapes with μm-scale diameter, indicating additional memory effects in the exciton dynamics.

Atomically thin semiconductors provide an ideal testbed to investigate the physics of Coulomb-bound many-body states. We shed light on the intricate structure of such complexes by studying the magnetic-field-induced splitting of biexcitons in monolayer ${\mathrm{WS}}_{2}$ using polarization-resolved photoluminescence spectroscopy in out-of-plane magnetic fields up to 30 T. The observed $g$ factor of the biexciton amounts to about $\ensuremath{-}3.9$, closely matching the $g$ factor of the neutral exciton. The biexciton emission shows an inverted circular field-induced polarization upon linearly polarized excitation; i.e., it exhibits preferential emission from the high-energy peak in a magnetic field. This phenomenon is explained by taking into account the hybrid configuration of the biexciton constituents in momentum space and their respective energetic behavior in magnetic fields. Our findings reveal the critical role of dark excitons in the composition of this many-body state.

Single-layer WS2 is a direct-gap semiconductor showing strong excitonic photoluminescence features in the visible spectral range. Here, we present temperature-dependent photoluminescence measurements on mechanically exfoliated single-layer WS2, revealing the existence of neutral and charged excitons at low temperatures as well as at room temperature. By applying a gate voltage, we can electrically control the ratio of excitons and trions and assert a residual n-type doping of our samples. At high excitation densities and low temperatures, an additional peak at energies below the trion dominates the photoluminescence, which we identify as biexciton emission. (© 2015 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

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In atomically thin transition metal dichalcogenides (TMDs), reduced dielectric screening of the Coulomb interaction leads to strongly correlated many-body states, including excitons and trions, that dominate the optical properties. Higher-order states, such as bound biexcitons, are possible but are difficult to identify unambiguously using linear optical spectroscopy methods. Here, we implement polarization-resolved two-dimensional coherent spectroscopy (2DCS) to unravel the complex optical response of monolayer MoSe2 and identify multiple higher-order correlated states. Decisive signatures of neutral and charged inter-valley biexcitons appear in cross-polarized two-dimensional spectra as distinct resonances with respective ∼20 and ∼5 meV binding energies—similar to recent calculations using variational and Monte Carlo methods. A theoretical model considering the valley-dependent optical selection rules reveals the quantum pathways that give rise to these states. Inter-valley biexcitons identified here, comprising of neutral and charged excitons from different valleys, offer new opportunities for developing ultrathin biexciton lasers and polarization-entangled photon sources. Atomically thin transition metal dichalcogenides host excitons and trions, however higher-order states, although possible, are difficult to identify experimentally. Here, the authors perform polarization-resolved coherent spectroscopy to unveil the signature of neutral and charged inter-valley biexcitons in monolayer MoSe2.

Monolayers of the transition metal dichalcogenides (TMDCs) MoS 2 , MoSe 2 , WS 2 , WSe 2 and MoTe 2 are a new class of atomically thin, direct band gap semiconductors with extraordinary optical and electronic properties. Due to their unique electronic structure the spin and valley (K+ or K−) of the excitons are locked, which allows for selective, optical addressing of the valleys. These properties render atomically thin TMDCs promising materials for applications in the field of “valleytronics”, where the valley index is used as a carrier for quantum information.

In heterostructures consisting of different transition-metal dichalcogenide monolayers, a staggered band alignment can occur, leading to rapid charge separation of optically generated electron-hole pairs into opposite monolayers. These spatially separated electron-hole pairs are Coulomb-coupled and form interlayer excitons. Here, we study these interlayer excitons in a heterostructure consisting of MoSe$_2$ and WSe$_2$ monolayers using photoluminescence spectroscopy. We observe a non-trivial temperature dependence of the linewidth and the peak energy of the interlayer exciton, including an unusually strong initial redshift of the transition with temperature, as well as a pronounced blueshift of the emission energy with increasing excitation power. By combining these observations with time-resolved photoluminescence measurements, we are able to explain the observed behavior as a combination of interlayer exciton diffusion and dipolar, repulsive exciton-exciton interaction.

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.

ReS2 is considered as a promising candidate for novel electronic and sensor applications. The low crystal symmetry of this van der Waals compound leads to a highly anisotropic optical, vibrational, and transport behavior. However, the details of the electronic band structure of this fascinating material are still largely unexplored. We present a momentum-resolved study of the electronic structure of monolayer, bilayer, and bulk ReS2 using k-space photoemission microscopy in combination with first-principles calculations. We demonstrate that the valence electrons in bulk ReS2 are—contrary to assumptions in recent literature—significantly delocalized across the van der Waals gap. Furthermore, we directly observe the evolution of the valence band dispersion as a function of the number of layers, revealing the transition from an indirect band gap in bulk ReS2 to a direct gap in the bilayer and the monolayer. We also find a significantly increased effective hole mass in single-layer crystals. Our results establish bilayer ReS2 as an advantageous building block for two-dimensional devices and van der Waals heterostructures.

Many of the fundamental optical and electronic properties of atomically thin transition metal dichalcogenides are dominated by strong Coulomb interactions between electrons and holes, forming tightly bound atom-like states called excitons. Here, we directly trace the ultrafast formation of excitons by monitoring the absolute densities of bound and unbound electron-hole pairs in single monolayers of WSe

Transition metal dichalcogenides represent an ideal testbed to study excitonic effects, spin-related phenomena and fundamental light-matter coupling in nanoscopic condensed matter systems. In particular, the valley degree of freedom, which is unique to such direct band gap monolayers with broken inversion symmetry, adds fundamental interest in these materials. Here, we implement a Tamm-plasmon structure with an embedded MoSe2 monolayer and study the formation of polaritonic quasi-particles. Strong coupling conditions between the Tamm-mode and the trion resonance of MoSe2 are established, yielding bright luminescence from the polaritonic ground state under non-resonant optical excitation. We demonstrate, that tailoring the electrodynamic environment of the monolayer results in a significantly increased valley polarization. This enhancement can be related to change in recombination dynamics shown in time-resolved photoluminescence measurements. We furthermore observe strong upconversion luminescence from resonantly excited polariton states in the lower polariton branch. This upconverted polariton luminescence is shown to preserve the valley polarization of the trion-polariton, which paves the way towards combining spin-valley physics and exciton scattering experiments., Comment: 15 pages, 4 figures

Many of the fundamental optical and electronic properties of atomically thin transition metal dichalcogenides are dominated by strong Coulomb interactions between electrons and holes, forming tightly bound atom-like states called excitons. Here, we directly trace the ultrafast formation of excitons by monitoring the absolute densities of bound and unbound electron hole pairs in single monolayers of WSe2 on a diamond substrate following femtosecond nonresonant optical excitation. To this end, phase locked mid-infrared probe pulses and field-sensitive electro-optic sampling are used to map out the full complex-valued optical conductivity of the nonequilibrium system and to discern the hallmark low-energy responses of bound and unbound pairs. While the spectral shape of the infrared response immediately after above-bandgap injection is dominated by free charge carriers, up to 60% of the electron-hole pairs are bound into excitons already on a subpicosecond time scale, evidencing extremely fast and efficient exciton formation. During the subsequent recombination phase, we still find a large density of free carriers in addition to excitons, indicating a nonequilibrium state of the photoexcited electron-hole system.

Two-dimensional semiconducting materials are particularly appealing for many applications. Although theory predicts a large number of two-dimensional materials, experimentally only a few of these materials have been identified and characterized comprehensively in the ultrathin limit. Lead iodide, which belongs to the transition metal halides family and has a direct bandgap in the visible spectrum, has been known for a long time and has been well characterized in its bulk form. Nevertheless, studies of this material in the nanometer thickness regime are rather scarce. In this article we demonstrate an easy way to synthesize ultrathin, highly crystalline flakes of PbI2 by precipitation from a solution in water. We thoroughly characterize the produced thin flakes with different techniques ranging from optical and Raman spectros-copy to temperature-dependent photoluminescence and electron microscopy. We compare the results to ab initio calculations of the band structure of the material. Finally, we fabricate photodetectors based on PbI2 and study their optoelectronic properties., main text 20 pages + 10 figures, supporting information 16 pages + 17 figures

The demonstration of energy transfer from hotspots of electroluminescent silver nanoparticles to a two-dimensional crystal overlayer of a transition-metal dichalcogenide provides a tunable, sub-diffraction, electrically driven light source. Few inventions have shaped the world like the incandescent bulb. Edison used thermal radiation from ohmically heated conductors, but some noble metals also exhibit ‘cold’ electroluminescence in percolation films1,2, tunnel diodes3, electromigrated nanoparticle aggregates4,5, optical antennas6 or scanning tunnelling microscopy7,8,9. The origin of this radiation, which is spectrally broad and depends on applied bias, is controversial given the low radiative yields of electronic transitions. Nanoparticle electroluminescence is particularly intriguing because it involves localized surface-plasmon resonances with large dipole moments. Such plasmons enable very efficient non-radiative fluorescence resonance energy transfer (FRET) coupling to proximal resonant dipole transitions. Here, we demonstrate nanoscopic FRET–light-emitting diodes which exploit the opposite process, energy transfer from silver nanoparticles to exfoliated monolayers of transition-metal dichalcogenides10. In diffraction-limited hotspots showing pronounced photon bunching, broadband silver electroluminescence is focused into the narrow excitonic resonance of the atomically thin overlayer. Such devices may offer alternatives to conventional nano-light-emitting diodes11 in on-chip optical interconnects.

We use two-dimensional Fourier transform spectroscopy to measure coherence between the trions in the opposite valleys in monolayer MoSe 2 . The trion valley coherence time ∼230fs is limited by pure dephasing of the trion resonance.

As conventional electronic is approaching its ultimate limits, tremendous efforts have been taken to explore novel concepts of ultrafast quantum control. Lightwave electronics - the foundation of attosecond science - has opened a spectacular perspective by utilizing the oscillating carrier wave of an intense light pulse to control the translational motion of the electron’s charge faster than a single cycle of light [1-7]. Despite their promising potential as future information carriers [8,10], the internal quantum attributes such as spins and valley pseudospins have not been switchable at optical clock rates. Here we demonstrate a novel subcycle control scheme of the electron’s pseudospin in a monolayer of tungsten diselenide using strong mid-infrared lightwaves [9]. Our work opens the door towards systematic valleytronic protocols at optical clock rates.

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 disulfide 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 shift of the exciton and trion resonances gives us insight into the real-space extension of these quasiparticles, magnetic field-induced valley polarization effects shed light onto the exciton and trion dispersion relations in reciprocal space. The field dependence of the trion valley polarizations is in line with the predicted trion splitting into singlet and triplet configurations.

In atomically thin transition metal dichalcogenides (TMDs), reduced dielectric screening of the Coulomb interaction leads to strongly correlated many-body states, including excitons and trions, that dominate the optical properties. Higher-order states, such as bound biexcitons, are possible but are difficult to identify unambiguously using linear optical spectroscopy methods. Here, we implement polarization-resolved two-dimensional coherent spectroscopy (2DCS) to unravel the complex optical response of monolayer MoSe2 and identify multiple higher-order correlated states. Decisive signatures of neutral and charged inter-valley biexcitons appear in cross-polarized two-dimensional spectra as distinct resonances with respective ∼20 and ∼5 meV binding energies—similar to recent calculations using variational and Monte Carlo methods. A theoretical model considering the valley-dependent optical selection rules reveals the quantum pathways that give rise to these states. Inter-valley biexcitons identified here, comprising of neutral and charged excitons from different valleys, offer new opportunities for developing ultrathin biexciton lasers and polarization-entangled photon sources., Atomically thin transition metal dichalcogenides host excitons and trions, however higher-order states, although possible, are difficult to identify experimentally. Here, the authors perform polarization-resolved coherent spectroscopy to unveil the signature of neutral and charged inter-valley biexcitons in monolayer MoSe2.

The optical properties of semiconducting transition metal dichalcogenides are dominated by both neutral excitons (electron-hole pairs) and charged excitons (trions) that are stable even at room temperature. While trions directly influence charge transport properties in optoelectronic devices, excitons may be relevant through exciton-trion coupling and conversion phenomena. In this work, we reveal the coherent and incoherent nature of exciton-trion coupling and the relevant timescales in monolayer MoSe2 using optical two-dimensional coherent spectroscopy. Coherent interaction between excitons and trions is definitively identified as quantum beating of cross-coupling peaks that persists for a few hundred femtoseconds. For longer times up to 10 ps, surprisingly, the relative intensity of the cross-coupling peaks increases, which is attributed to incoherent energy transfer likely due to phonon-assisted up-conversion and down-conversion processes that are efficient even at cryogenic temperature.

Monolayer transition-metal dichalcogenides have recently emerged as possible candidates for valleytronic applications, as the spin and valley pseudospin are directly coupled and stabilized by a large spin splitting. The optical properties of these two-dimensional crystals are dominated by tightly bound electron–hole pairs (excitons) and more complex quasiparticles such as charged excitons (trions). Here we investigate monolayer WS2 samples via photoluminescence and time-resolved Kerr rotation. In photoluminescence and in energy-dependent Kerr rotation measurements, we are able to resolve two different trion states, which we interpret as intravalley and intervalley trions. Using time-resolved Kerr rotation, we observe a rapid initial valley polarization decay for the A exciton and the trion states. Subsequently, we observe a crossover towards exciton–exciton interaction-related dynamics, consistent with the formation and decay of optically dark A excitons. By contrast, resonant excitation of the B exciton transition leads to a very slow decay of the Kerr signal., Monolayer transition metal dichalcogenides are promising materials for valleytronics applications. Here, the authors study WS2 samples using photoluminescence spectroscopy and time-resolved Kerr-rotation measurements at low temperatures, gaining insight into the valley dynamics of excitons.

Ever since Ernest Rutherford scattered α-particles from gold foils1, collision experiments have revealed insights into atoms, nuclei and elementary particles2. In solids, many-body correlations lead to characteristic resonances3—called quasiparticles—such as excitons, dropletons4, polarons and Cooper pairs. The structure and dynamics of quasiparticles are important because they define macroscopic phenomena such as Mott insulating states, spontaneous spin- and charge-order, and high-temperature superconductivity5. However, the extremely short lifetimes of these entities6 make practical implementations of a suitable collider challenging. Here we exploit lightwave-driven charge transport7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, the foundation of attosecond science9, 10, 11, 12, 13, to explore ultrafast quasiparticle collisions directly in the time domain: a femtosecond optical pulse creates excitonic electron–hole pairs in the layered dichalcogenide tungsten diselenide while a strong terahertz field accelerates and collides the electrons with the holes. The underlying dynamics of the wave packets, including collision, pair annihilation, quantum interference and dephasing, are detected as light emission in high-order spectral sidebands17, 18, 19 of the optical excitation. A full quantum theory explains our observations microscopically. This approach enables collision experiments with various complex quasiparticles and suggests a promising new way of generating sub-femtosecond pulses.

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 shift of the exciton and trion resonances gives us insight into the real-space extension of these quasiparticles, magnetic field induced valley polarization effects shed light onto the exciton and trion dispersion relations in reciprocal space. The field dependence of the trion valley polarizations is in line with the predicted trion splitting into singlet and triplet configurations.

ReS2 has recently emerged as a new member in the rapidly growing family of two-dimensional materials. Unlike MoS2 or WSe2, the optical and electrical properties of ReS2 are not isotropic due to the reduced symmetry of the crystal. Here, we present layer-dependent Raman measurements of ReS2 samples ranging from monolayers to ten layers in the ultralow frequency regime. We observe layer breathing and shear modes which allow for easy assignment of the number of layers. Polarization-dependent measurements give further insight into the crystal structure and reveal an energetic shift of the shear mode which stems from the in-plane anisotropy of the shear modulus in this material. ((c) 2016 WILEY-VCH Verlag GmbH &Co. KGaA, Weinheim)

We demonstrate the exfoliation of large-area monolayer flakes prepared from bulk MoS 2 crystals. The flakes are first characterized using Raman and photoluminescence measurements. We then utilize time-resolved Kerr rotation (TRKR) measurements to probe the valley dynamics in the monolayer flakes at low temperatures. This technique allows resonant excitation of the excitonic transitions and yields sub-picosecond resolution. We find valley lifetimes of about 40 ps at a temperature of 4 K in monolayer MoS 2 for resonant excitation. With increasing temperatures, we observe a dramatic decrease of the valley lifetimes, indicating that valley dephasing is mediated by phonon-related scattering processes.