Spin-valley Rashba monolayer laser.

Direct-bandgap transition metal dichalcogenide monolayers are appealing candidates to construct atomic-scale spin-optical light sources owing to their valley-contrasting optical selection rules. Here we report on a spin-optical monolayer laser by incorporating a WS2 monolayer into a heterostructure microcavity supporting high-Q photonic spin-valley resonances. Inspired by the creation of valley pseudo-spins in monolayers, the spin-valley modes are generated from a photonic Rashba-type spin splitting of a bound state in the continuum, which gives rise to opposite spin-polarized ±K valleys due to emergent photonic spin-orbit interaction under inversion symmetry breaking. The Rashba monolayer laser shows intrinsic spin polarizations, high spatial and temporal coherence, and inherent symmetry-enabled robustness features, enabling valley coherence in the WS2 monolayer upon arbitrary pump polarizations at room temperature. Our monolayer-integrated spin-valley microcavities open avenues for further classical and non-classical coherent spin-optical light sources exploring both electron and photon spins.

Tungsten Oxide Mediated Quasi-van der Waals Epitaxy of WS2 on Sapphire.

Conventional epitaxy plays a crucial role in current state-of-the art semiconductor technology, as it provides a path for accurate control at the atomic scale of thin films and nanostructures, to be used as the building blocks in nanoelectronics, optoelectronics, sensors, etc. Four decades ago, the terms "van der Waals" (vdW) and "quasi-vdW (Q-vdW) epitaxy" were coined to explain the oriented growth of vdW layers on 2D and 3D substrates, respectively. The major difference with conventional epitaxy is the weaker interaction between the epi-layer and the epi-substrates. Indeed, research on Q-vdW epitaxial growth of transition metal dichalcogenides (TMDCs) has been intense, with oriented growth of atomically thin semiconductors on sapphire being one of the most studied systems. Nonetheless, there are some striking and not yet understood differences in the literature regarding the orientation registry between the epi-layers and epi-substrate and the interface chemistry. Here we study the growth of WS2 via a sequential exposure of the metal and the chalcogen precursors in a metal-organic chemical vapor deposition (MOCVD) system, introducing a metal-seeding step prior to the growth. The ability to control the delivery of the precursor made it possible to study the formation of a continuous and apparently ordered WO3 mono- or few-layer at the surface of a c-plane sapphire. Such an interfacial layer is shown to strongly influence the subsequent quasi-vdW epitaxial growth of the atomically thin semiconductor layers on sapphire. Hence, here we elucidate an epitaxial growth mechanism and demonstrate the robustness of the metal-seeding approach for the oriented formation of other TMDC layers. This work may enable the rational design of vdW and quasi-vdW epitaxial growth on different material systems.

Bright excitonic multiplexing mediated by dark exciton transition in two-dimensional TMDCs at room temperature.

2D-semiconductors with strong light-matter interaction are attractive materials for integrated and tunable optical devices. Here, we demonstrate room-temperature wavelength multiplexing of the two-primary bright excitonic channels (Ab-, Bb-) in monolayer transition metal dichalcogenides (TMDs) arising from a dark exciton mediated transition. We present how tuning dark excitons via an out-of-plane electric field cedes the system equilibrium from one excitonic channel to the other, encoding the field polarization into wavelength information. In addition, we demonstrate how such exciton multiplexing is dictated by thermal-scattering by performing temperature dependent photoluminescence measurements. Finally, we demonstrate experimentally and theoretically how excitonic mixing can explain preferable decay through dark states in MoX2 in comparison with WX2 monolayers. Such field polarization-based manipulation of excitonic transitions can pave the way for novel photonic device architectures.

Growth-Etch Metal-Organic Chemical Vapor Deposition Approach of WS2 Atomic Layers.

Metal-organic chemical vapor deposition (MOCVD) is one of the main methodologies used for thin-film fabrication in the semiconductor industry today and is considered one of the most promising routes to achieve large-scale and high-quality 2D transition metal dichalcogenides (TMDCs). However, if special measures are not taken, MOCVD suffers from some serious drawbacks, such as small domain size and carbon contamination, resulting in poor optical and crystal quality, which may inhibit its implementation for the large-scale fabrication of atomic-thin semiconductors. Here we present a growth-etch MOCVD (GE-MOCVD) methodology, in which a small amount of water vapor is introduced during the growth, while the precursors are delivered in pulses. The evolution of the growth as a function of the amount of water vapor, the number and type of cycles, and the gas composition is described. We show a significant domain size increase is achieved relative to our conventional process. The improved crystal quality of WS2 (and WSe2) domains wasis demonstrated by means of Raman spectroscopy, photoluminescence (PL) spectroscopy, and HRTEM studies. Moreover, time-resolved PL studies show very long exciton lifetimes, comparable to those observed in mechanically exfoliated flakes. Thus, the GE-MOCVD approach presented here may facilitate their integration into a wide range of applications.

Seeded-growth of WS2 atomic layers: the effect on chemical and optical properties.

The growth of high quality materials from well-defined seeds is a well-established and beneficial procedure, as it enables the control of the crystal orientation, domain size, phase and chemical composition of nanocrystals, thin films and 3D crystals. The seeded-growth approach for 2D transition metal dichalcogenides (TMDs) is investigated, envisaging that seeds have a great impact on the chemical composition of the grown layers and thus, on their chemical and optical properties. The controlled nucleation and narrow domain size distribution of single crystalline WS2 atomic layers are demonstrated by employing the seeded-growth approach. The growth of single layer WS2 domains from well-defined Au seeds leads to nanoparticle (NP) decoration over the domain in a very peculiar way that might be related to the growth mechanism of such atomic-layers. The segmentation in Raman enhancement and photoluminescence maps of exciton and trion emissions well correlate with the presence of Au NPs observed in electron microscopy and chemical maps obtained by time-of-flight secondary ion mass spectroscopic imaging. This work emphasizes the importance of the seed material and its effect on the grown 2D material and may lead to novel methodologies for controlled growth, doping and the formation of hybrid materials to be used in catalysis, sensors and optoelectronics.

Size-Dependent Localized Phonon Population in Semiconducting Si Nanowires.

The optical phonons in semiconductor nanostructures play an indispensable role in fundamental phenomenon and device applications based on these nanostructures. We study the Raman spectroscopy of optical phonons in Si nanowires (NWs) whose sizes are beyond the phonon confinement regime. The peak shift and unusual asymmetric broadening by one-phonon mode in Si NWs is observed during far-field Raman studies. Using an appropriate thermal anchoring and localized Raman measurements on single NWs by near-field tip-enhanced Raman spectroscopy (TERS), we demonstrate the decoupling of multiple origins responsible for the peak shift accompanied by asymmetric broadening of the one-phonon mode and the appearance of multiple phonon peaks from a single measurement area. A model based on the localized phonon population induced by NW size-dependent charge depletion is proposed to explain the observed dependence of phonon characteristics on NW size. The scanning Kelvin probe force microscopy measurements confirm the size-dependent intrinsic semiconductor surface and interface states-induced charge depletions in single Si NWs. The study clearly suggests the size-dependent phonon characteristics of Si NWs which are crucial for several NW-based photovoltaic and thermoelectric devices.