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Heterostructures (HSs) formed by the transition-metal dichalcogenides (TMDCs) materials have shown great promise in next-generation optoelectronic and photonic applications. An artificially twisted HS, allows us to manipulate the optical, and electronic properties. With this work, we introduce the understanding of the complex energy transfer (ET) process governed by the dipolar interaction in a twisted molybdenum diselenide (MoSe2) homobilayer without any charge-blocking interlayer. We fabricated an unconventional homobilayer (i.e., HS) with a large twist angle by combining the chemical vapor deposition (CVD) and mechanical exfoliation (Exf.) techniques to fully exploit the lattice parameters mismatch and indirect/direct (CVD/Exf.) bandgap nature. This effectively weaken the charge transfer (CT) process and allows the ET process to take over the carrier recombination channels. We utilize a series of optical and electron spectroscopy techniques complementing by the density functional theory calculations, to describe a massive photoluminescence enhancement from the HS area due to an efficient ET process. Our results show that the electronically decoupled MoSe2 homobilayer is coupled by the ET process, mimicking a 'true' heterobilayer nature., Comment: 4 figures

The effect of pressure on Raman scattering (RS) in the bulk HfS$_2$ is investigated under hydrostatic and non-hydrostatic conditions. The RS lineshape does not change significantly in the hydrostatic regime, showing a systematic blueshift of the spectral features. In a non-hydrostatic environment, seven peaks emerge in the spectrum ($P$=7 GPa) dominating the lineshape up to $P$=10.5 GPa. The change in the RS lineshape manifests a pressure-induced phase transition in HfS$_2$. The simultaneous observation of both low-pressure (LP) and high-pressure (HP) related RS peaks suggests the corresponding coexistence of two different phases over a large pressure range. We found that the HP-related phase is metastable, persisting during the decompression cycle down to $P$=1.2 GPa with the LP-related features finally recovering at even lower pressures. The angle-resolved polarized RS (ARPRS) performed under $P$=7.4 GPa revealed a strong in-plane anisotropy of both the LP-related A$_{1g}$ mode and the HP peaks. The anisotropy is related to the possible distortion of the structure induced by the non-hydrostatic component of the pressure. We describe the obtained results by the influence of the non-hydrostatic pressure on the observed phase transition. We interpret our results in terms of a distorted $Pnma$ phase as a possible HP induced structure of HfS$_2$.

We investigate the vibrational and magnetic properties of thin layers of chromium tribromide (CrBr$_3$) with a thickness ranging from three to twenty layers (3~L to 20~L) revealed by the Raman scattering (RS) technique. Systematic dependence of the RS process efficiency on the energy of the laser excitation is explored for four different excitation energies: 1.96 eV, 2.21 eV, 2.41 eV, and 3.06 eV. Our characterization demonstrates that for 12 L CrBr$_3$, 3.06~eV excitation could be considered resonant with interband electronic transitions due to the enhanced intensity of the Raman-active scattering resonances and the qualitative change in the Raman spectra. Polarization-resolved RS measurements for 12 L CrBr$_3$ and first-principles calculations allow us to identify five observable phonon modes characterized by distinct symmetries, classified as the A$_\textrm{g}$ and E$_\textrm{g}$ modes. The evolution of phonon modes with temperature for a 20 L CrBr$_3$ encapsulated in hexagonal boron nitride flakes demonstrates alterations of phonon energies and/or linewidths of resonances indicative of a transition between the paramagnetic and ferromagnetic state at Curie temperature ($T_\textrm{C} \approx 50$ K). The exploration of the effects of thickness on the phonon energies demonstrated small variations pronounces exclusively for the thinnest layers in the vicinity of 3 - 5 L. This observation is attributed to strong localization in the real space of interband electronic excitations, limiting the effects of confinement for resonantly excited Raman modes to atomically thin layers., Comment: 12 pages, 5 figures

Moir\'{e} excitons (MXs) are electron-hole pairs localised by the periodic (moir\'{e}) potential forming in two-dimensional heterostructures (HSs). MXs can be exploited, $e.g.$, for creating nanoscale-ordered quantum emitters and achieving or probing strongly correlated electronic phases at relatively high temperatures. Here, we studied the exciton properties of a WSe$_2$/MoSe$_2$ HS from $T$=6 K to room temperature using time-resolved and continuous-wave micro-photoluminescence, also under magnetic field. The exciton dynamics and emission lineshape evolution with temperature show clear signatures that MXs de-trap from the moir\'{e} potential and turn into free interlayer excitons (IXs) at $T\gtrsim$120 K. The MX-to-IX transition is also apparent from the exciton magnetic moment reversing its sign when the moir\'{e} potential is not capable to localise excitons at elevated temperatures. Concomitantly, the exciton formation and decay times reduce drastically. Thus, our findings establish the conditions for a truly confined nature of the exciton states in a moir\'{e} superlattice with increasing temperature.

To fully explore exciton-based applications and improve their performance, it is essential to understand the exciton behavior in anisotropic materials. Here, we investigate the optical properties of anisotropic excitons in GeS encapsulated by h-BN, using different approaches that combine polarization- and temperature-dependent photoluminescence (PL) measurements, \textit{ab initio} calculations, and effective mass approximation (EMA). Using the Bethe-Salpeter Equation (BSE) method, we found that the optical absorption spectra in GeS are significantly affected by the Coulomb interaction included in the BSE method, which shows the importance of excitonic effects besides it exhibits a significant dependence on the direction of polarization, revealing the anisotropic nature of bulk GeS. Combining \textit{ab initio} calculations and EMA methods, we investigate the quasi-hydrogenic exciton states and oscillator strength (OS) of GeS along the zigzag and armchair axes. We found that the anisotropy induces lifting of the degeneracy and mixing of the excitonic states in GeS, which results in highly nonhydrogenic features. Very good agreement with the experiment is observed., Comment: 15 pages, 7 figures + SI

Quantum phenomena at interfaces create functionalities at the level of materials. Ferromagnetism in van der Waals systems with diverse arrangements of spins opened a pathway for utilizing proximity magnetic fields to activate properties of materials which would otherwise require external stimuli. Herewith, we realize this notion via creating heterostructures comprising bulk CrCl$_3$ ferromagnet with in-plane easy-axis magnetization and monolayer WSe$_2$ semiconductor. We demonstrate that the in-plane component of the proximity field activates the dark excitons within WSe$_2$. Zero-external-field emission from the dark states allowed us to establish the in-plane and out-of-plane components of the proximity field via inspection of the emission intensity and Zeeman effect, yielding canted orientations at the degree range of $10^{\circ}$ $-$ $30^{\circ}$ at different locations of the heterostructures, attributed to the features of interfacial topography. Our findings are relevant for the development of spintronics and valleytronics with long-lived dark states in technological timescales and sensing applications of local magnetic fields realized simultaneously in multiple dimensions., Comment: 7 pages, 5 figures + SI

High light absorption (~15%) and strong photoluminescence (PL) emission in monolayer (1L) transition metal dichalcogenide (TMD) make it an ideal candidate for optoelectronic applications. Competing interlayer charge (CT) and energy transfer (ET) processes control the photocarrier relaxation pathways in TMD heterostructures (HSs). In TMDs, long-distance ET can survive up to several tens of nm, unlike the CT process. Our experiment shows that an efficient ET occurs from the 1Ls WSe2-to-MoS2 with an interlayer hBN, due to the resonant overlapping of the high-lying excitonic states between the two TMDs, resulting in enhanced HS MoS2 PL emission. This type of unconventional ET from the lower-to-higher optical bandgap material is not typical in the TMD HSs. With increasing temperature, the ET process becomes weaker due to the increased electron-phonon scattering, destroying the enhanced MoS2 emission. Our work provides new insight into the long-distance ET process and its effect on the photocarrier relaxation pathways., Comment: 5 figures and SI included

Raman scattering (RS) in bulk hafnium disulfide (HfS$_2$) is investigated as a function of temperature (5 K $-$ 350 K) with polarization resolution and excitation of several laser energies. An unexpected temperature dependence of the energies of the main Raman-active (A$_{\textrm{1g}}$ and E$_{\textrm{g}}$) modes with the temperature-induced blueshift in the low-temperature limit is observed. The low-temperature quenching of a mode $\omega_1$ (134 cm$^{-1}$) and the emergence of a new mode at approx. 184 cm$^{-1}$, labeled Z, is reported. The optical anisotropy of the RS in HfS$_2$ is also reported, which is highly susceptible to the excitation energy. The apparent quenching of the A$_{\textrm{1g}}$ mode at $T$=5 K and of the E$_{\textrm{g}}$ mode at $T$=300 K in the RS spectrum excited with 3.06~eV excitation is also observed. We discuss the results in the context of possible resonant character of light-phonon interactions. Analyzed is also a possible effect of the iodine molecules intercalated in the van der Waals gaps between neighboring HfS$_2$ layers, which inevitably result from the growth procedure., Comment: 9 pages, 7 figures +SI

Excitons in thin layers of semiconducting transition metal dichalcogenides are highly subject to the strongly modified Coulomb electron-hole interaction in these materials. Therefore, they do not follow the model system of a two-dimensional hydrogen atom. We investigate experimentally and theoretically excitonic properties in both the monolayer (ML) and the bilayer (BL) of MoSe$_2$ encapsulated in hexagonal BN. The measured magnetic field evolutions of the reflectance contrast spectra of the MoSe$_2$ ML and BL allow us to determine $g$-factors of intralayer A and B excitons, as well as the $g$-factor of the interlayer exciton. We explain the dependence of $g$-factors on the number of layers and excitation state using first principles calculations. Furthermore, we demonstrate that the experimentally measured ladder of excitonic $s$ states in the ML can be reproduced using the $\mathbf{k\cdot p}$ approach with the Rytova-Keldysh potential that describes the electron-hole interaction. In contrast, the analogous calculation for the BL case requires taking into account the out-of-plane dielectric response of the MoSe$_2$ BL., Comment: 10 pages, 4 figures, + SM

The possibility of almost linear tuning of the band gap and of the electrical and optical properties in monolayers (MLs) of semiconducting transition metal dichalcogenide (S-TMD) alloys opens up the way to fabricate materials with on-demand characteristics. By making use of photoluminescence spectroscopy, we investigate optical properties of WSSe MLs with a S/Se ratio of 57/43 deposited on SiO$_2$/Si substrate and encapsulated in hexagonal BN flakes. Similarly to the $"parent"$ WS$_2$ and WSe$_2$ MLs, we assign the WSSe MLs to the ML family with the dark ground exciton state. We find that, in addition to the neutral bright A exciton line, three observed emission lines are associated with negatively charged excitons. The application of in-plane and out-of-plane magnetic fields allows us to assign undeniably the bright and dark (spin- and momentum-forbidden) negative trions as well as the phonon replica of the dark spin-forbidden complex. Furthermore, the existence of the single photon emitters in the WSSe ML is also demonstrated, thus prompting the opportunity to enlarge the wavelength range for potential future quantum applications of S-TMDs., Comment: 6 pages, 5 figures, +ESI

The temperature evolution of the resonant Raman scattering from high-quality bilayer 2H-MoS$_{2}$ encapsulated in hexagonal BN flakes is presented. The observed resonant Raman scattering spectrum as initiated by the laser energy of 1.96 eV, close to the A excitonic resonance, shows rich and distinct vibrational features that are otherwise not observed in non-resonant scattering. The appearance of 1$^{st}$ and 2$^{nd}$ order phonon modes is unambiguously observed in a broad range of temperatures from 5 K to 320 K. The spectrum includes the Raman-active modes, $i.e.$ E$_\textrm{1g}^{2}$($\Gamma$) and A$_\textrm{1g}$($\Gamma$) along with their Davydov-split counterparts, $i.e.$ E$_\textrm{1u}$($\Gamma$) and B$_\textrm{1u}$($\Gamma$). The temperature evolution of the Raman scattering spectrum brings forward key observations, as the integrated intensity profiles of different phonon modes show diverse trends. The Raman-active A$_{1g}$($\Gamma$) mode, which dominates the Raman scattering spectrum at $T$=5~K quenches with increasing temperature. Surprisingly, at room temperature the B$_\textrm{1u}$($\Gamma$) mode, which is infrared-active in the bilayer, is substantially stronger than its nominally Raman-active A$_\textrm{1g}$($\Gamma$) counterpart., Comment: 7 pages, 3 figures

The dielectric environment of atomically-thin monolayer (ML) of semiconducting transition metal dichalcogenides affects both the electronic band gap and the excitonic binding energy in the ML. We investigate the effect of the environment on the in-plane magnetic field brightening of neutral and charged dark exciton emissions in the WSe$_2$ ML. The monolayers placed in three dielectric environments are studied, in particular, the ML encapsulated in hexagonal BN (hBN) flakes, the ML deposited on a hBN layer, and the ML embedded between the hBN flake and SiO$_2$/Si substrate. We observe that the brightening rates of the neutral and charged dark excitons depend on the dielectric environment, which may be related to the variation of the level of carrier concentration in the ML. Moreover, the surrounding media, characterized by different dielectric constants, influences weakly the relative energies of the neutral and charged dark excitons in reference to the bright ones., Comment: 5 pages, 4 figures

The optical response of bulk germanium sulfide (GeS) is investigated systematically using different polarization-resolved experimental techniques, such as photoluminescence (PL), reflectance contrast (RC), and Raman scattering (RS). It is shown that while the low-temperature ($T$=5 K) optical band-gap absorption is governed by a single resonance related to the neutral exciton, the corresponding emission is dominated by the disorder/impurity- and/or phonon-assisted recombination processes. Both the RC and PL spectra are found to be linearly polarized along the armchair direction. The low and room ($T$=300 K) temperature RS spectra consist of six Raman peaks identified with the help of Density Fuctional Theory (DFT) calculations: A$^1_{\textrm{g}}$, A$^2_{\textrm{g}}$, A$^3_{\textrm{g}}$, A$^4_{\textrm{g}}$, B$^1_{\textrm{1g}}$, and B$^2_{\textrm{1g}}$, which polarization properties are studied under four different excitation energies. We found that the polarization orientations of the A$^2_{\textrm{g}}$ and A$^4_{\textrm{g}}$ modes under specific excitation energy can be useful tools to determine the GeS crystallographic directions: armchair and zigzag., Comment: 7 pages, 7 figures

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 MoS$_2$ are studied with the aid of photoluminescence, photoluminescence excitation, and reflectance contrast experiments. We demonstrate that carrier concentration in MoS$_2$ 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 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 MoS$_2$ monolayers, which are assigned to the intravalley singlet, intervalley singlet, and intervalley triplet states., Comment: 9 pages, 4 figures

III-VI post-transition metal chalcogenides (InSe and GaSe) are a new class of layered semiconductors, which feature a strong variation of size and type of their band gaps as a function of number of layers (N). Here, we investigate exfoliated layers of InSe and GaSe ranging from bulk crystals down to monolayer, encapsulated in hexagonal boron nitride, using Raman spectroscopy. We present the N-dependence of both intralayer vibrations within each atomic layer, as well as of the interlayer shear and layer breathing modes. A linear chain model can be used to describe the evolution of the peak positions as a function of N, consistent with first principles calculations., Comment: 6 pages, 5 figures

The effect of bis(trifluoromethane) sulfonimide (TFSI, superacid) treatment on the optical properties of MoS$_2$ 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 MoS$_2$ 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 MoS$_{2}$ 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 MoS$_2$ 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., Comment: 8 pages, 4 figures

Resonant Raman scattering is investigated in monolayer WS$_2$ at low temperature with the aid of an unconventional spectroscopy technique, $i.e.$, Raman scattering excitation (RSE). The RSE spectrum is made up by sweeping the excitation energy, when the detection energy is fixed in resonance with excitonic transitions related to neutral and/or charged excitons. We demonstrate that the shape of the RSE spectrum strongly depends on a selected detection energy. The out-going resonance with the neutral exciton leads to an extremely rich RSE spectrum displaying several Raman scattering features not reported so far, while no clear effect on the associated background photoluminescence is observed. Instead, a strong enhancement of the emission due to the negatively charged exciton is apparent when the out-going photons resonate with this exciton. Presented results show that the RSE spectroscopy can be a useful technique to study electron-phonon interactions in thin layers of transition metal dichalcogenides., Comment: 9 pages, 5 figures