Biexciton and Singlet Trion Upconvert Exciton Photoluminescence in a MoSe2 Monolayer Supported by Acoustic and Optical K-Valley Phonons.

Transition metal dichalcogenide monolayers represent unique platforms for studying both electronic and phononic interactions as well as intra- and intervalley exciton complexes. Here, we investigate the upconversion of exciton photoluminescence in MoSe2 monolayers. Within the nominal transparency window of MoSe2 the exciton emission is enhanced for resonantly addressing the spin-singlet negative trion and neutral biexciton at a few tens of meV below the neutral exciton transition. We identify that the A'1 optical phonon at the K valley provides the energy gain in the upconversion process at the trion resonance, while ZA(K) phonons with their spin- and valley-switching properties support the biexciton driven upconversion of the exciton emission. Interestingly, the latter upconversion process yields unpolarized exciton photoluminescence, while the former also leads to circularly polarized emission. Our study highlights high-order exciton complexes interacting with optical and acoustic K-valley phonons and upconverting light into the bright exciton.

Resonant Exciton Scattering Reveals Raman Forbidden Phonon Modes in Layered GeS.

Germanium monosulfide with an anisotropic puckered crystalline structure has recently attracted much attention due to its unique optical and electronic properties; however, exciton-phonon interactions were only superficially elucidated. We study the resonant Raman scattering and the photoluminescence of the optically active Γ-exciton in layered GeS flakes and evaluate the exciton and phonon responses on variations in the excitation energy, laser-light and emission polarizations, temperature, and laser power. A double-resonance mechanism allows for observing Raman forbidden (dark) first- and second-order longitudinal-optical phonon modes whose symmetries and energies are moreover calculated by density functional perturbation theory. For (quasi)-resonant exciton excitation, the selection rules become relaxed so that a fourth-order Fröhlich intraband process is mediated by the scattering of the electron with a longitudinal-optical and an acoustic phonon. Our results demonstrate considerable coupling between phonons and photogenerated carriers in GeS flakes and the high efficiency of multiorder scattering in optical processes.

Upconversion photoluminescence excitation reveals exciton-trion and exciton-biexciton coupling in hBN/WS[Formula: see text]/hBN van der Waals heterostructures.

Monolayers of transition-metal dichalcogenides with direct band gap located at the binary [Formula: see text] points of the Brillouin zone are promising materials for applications in opto- and spin-electronics due to strongly enhanced Coulomb interactions and specific spin-valley properties. They furthermore represent a unique platform to study electron-electron and electron-phonon interactions in diverse exciton complexes. Here, we demonstrate processes in which the neutral biexciton and two negative trions, namely the spin-triplet and spin-singlet trions, upconvert light into a bright intravalley exciton in an hBN-encapsulated WS[Formula: see text] monolayer. We propose that the energy gains required in the polarized upconversion photoluminescence originate from different interactions including resonant optical phonons, a cooling of resident electrons and a non-local and an anisotropic electron-hole exchange, respectively. The temperature dependence (7-120 K) of the excitonic upconversion intensity obtained at excitation energies corresponding to the biexciton and trions provides insight into an increasing phonon population as well as a thermally enhanced electron scattering. Our study sheds new light on the understanding of excitonic spin and valley properties of van der Waals heterostructures and improves the understanding of photonic upconversion mechanisms in two-dimensional quantum materials.

Upconversion of Light into Bright Intravalley Excitons via Dark Intervalley Excitons in hBN-Encapsulated WSe2 Monolayers.

Semiconducting monolayers of transition-metal dichalcogenides are outstanding platforms to study both electronic and phononic interactions as well as intra- and intervalley excitons and trions. These excitonic complexes are optically either active (bright) or inactive (dark) due to selection rules from spin or momentum conservation. Exploring ways of brightening dark excitons and trions has strongly been pursued in semiconductor physics. Here, we report on a mechanism in which a dark intervalley exciton upconverts light into a bright intravalley exciton in hBN-encapsulated WSe2 monolayers. Excitation spectra of upconverted photoluminescence reveals resonances at energies 34.5 and 46.0 meV below the neutral exciton in the nominal WSe2 transparency range. The required energy gains are theoretically explained by cooling of resident electrons or by exciton scattering with Λ- or K-valley phonons. Accordingly, an elevated temperature and a moderate concentration of resident electrons are necessary for observing the upconversion resonances. The interaction process observed between the inter- and intravalley excitons elucidates the importance of dark excitons for the optics of two-dimensional materials.

Investigations of Electron-Electron and Interlayer Electron-Phonon Coupling in van der Waals hBN/WSe2/hBN Heterostructures by Photoluminescence Excitation Experiments.

Monolayers of transition metal dichalcogenides (TMDs) with their unique physical properties are very promising for future applications in novel electronic devices. In TMDs monolayers, strong and opposite spin splittings of the energy gaps at the K points allow for exciting carriers with various combinations of valley and spin indices using circularly polarized light, which can further be used in spintronics and valleytronics. The physical properties of van der Waals heterostructures composed of TMDs monolayers and hexagonal boron nitride (hBN) layers significantly depend on different kinds of interactions. Here, we report on observing both a strong increase in the emission intensity as well as a preservation of the helicity of the excitation light in the emission from hBN/WSe2/hBN heterostructures related to interlayer electron-phonon coupling. In combined low-temperature (T = 7 K) reflectivity contrast and photoluminescence excitation experiments, we find that the increase in the emission intensity is attributed to a double resonance, where the laser excitation and the combined Raman mode A'1 (WSe2) + ZO (hBN) are in resonance with the excited (2s) and ground (1s) states of the A exciton in a WSe2 monolayer. In reference to the 2s state, our interpretation is in contrast with previous reports, in which this state has been attributed to the hybrid exciton state existing only in the hBN-encapsulated WSe2 monolayer. Moreover, we observe that the electron-phonon coupling also enhances the helicity preservation of the exciting light in the emission of all observed excitonic complexes. The highest helicity preservation of more than 60% is obtained in the emission of the neutral biexciton and negatively charged exciton (trion) in its triplet state. Additionally, to the best of our knowledge, the strongly intensified emission of the neutral biexciton XX0 at double resonance condition is observed for the first time.

Layer number dependence of the work function and optical properties of single and few layers MoS2: effect of substrate.

We have examined the influence of flake-substrate effects that affect one and few layers of MoS2 in terms of their electrical and optical properties. In the measurements, we used SiO2/Si substrates with etched cavities and aluminum electrodes. Suspended areas are easily identifiable both on images depicting the topography and on the surface potential maps measured with the Kelvin probe force microscopy. Compared to the SiO2/Si supported material, surface potential decrease is observable at the membrane. The surface potential value of the flakes located on the electrodes is the lowest. PL measurements prove that single MoS2 monolayer was obtained. Suspended regions are also correlated with maps obtained as a result of Raman spectroscopy.