ZnPSe3_3 as ultrabright indirect bandgap system with microsecond excitonic lifetimes

We report an optical characterization of ZnPSe$_3$ crystals that demonstrates indirect band gap characteristics in combination with unusually strong photoluminescence. We found evidence of interband recombination from excitonic states with microsecond lifetimes. Through optical characterization, we reconstructed the electronic band scheme relevant for fundamental processes of light absorption, carrier relaxation and radiative recombination. The investigation of the radiative processes in the presence of magnetic field revealed spin polarization of fundamental electronic states. This observation opens a pathway towards controlling the spin of excitonic states in technologically relevant microsecond timescales

Breathing modes in few-layer MoTe2_2 activated by h-BN encapsulation

The encapsulation of few-layer transition metal dichalcogenides (TMDs) in hexagonal boron nitride (h-BN) is known to improve significantly their optical and electronic properties. However, it may be expected that the h-BN encapsulation may affect also vibration properties of TMDs due to an atomically flat surface of h-BN layers. In order to study its effect on interlayer interactions in few-layer TMDs, we investigate low-energy Raman scattering spectra of bi- and trilayer MoTe$_2$. Surprisingly, three breathing modes are observed in the Raman spectra of the structures deposited on or encapsulated in h-BN as compared to a single breathing mode for the flakes deposited on a SiO$_2$/Si substrate. The shear mode is not affected by changing the MoTe$_2$ environment. The emerged structure of breathing modes is ascribed to the apparent interaction between the MoTe$_2$ layer and the bottom h-BN flake. The structure becomes visible due to a high-quality surface of the former flake. Consequently, the observed triple structure of breathing modes originates from the combination modes due to interlayer and layer-substrate interactions. Our results confirm that the h-BN encapsulation affects substantially vibration properties of layered materials.Comment: 10 pages, 9 figure

Neutral and charged dark excitons in monolayer WS2_2

Low temperature and polarization resolved magneto-photoluminescence experiments are used to investigate the properties of dark excitons and dark trions in a monolayer of WS$_2$ encapsulated in hexagonal BN (hBN). We find that this system is an $n$-type doped semiconductor and that dark trions dominate the emission spectrum. In line with previous studies on WSe$_2$, we identify the Coulomb exchange interaction coupled neutral dark and grey excitons through their polarization properties, while an analogous effect is not observed for dark trions. Applying the magnetic field in both perpendicular and parallel configurations with respect to the monolayer plane, we determine the g-factor of dark trions to be $g\sim$-8.6. Their decay rate is close to 0.5 ns, more than 2 orders of magnitude longer than that of bright excitons.Comment: 6 pages, 6 figures, supplemental materia

Raman scattering from the bulk inactive out-of-plane B2g1^{1}_{2\text{g}} mode in few-layer MoTe2_{2}

Raman scattering from the out-of-plane vibrational modes (A$_{1\text{g}}$/A'$_{1}$), which originate from the bulk-inactive out-of-plane B$^{1}_{2\text{g}}$ mode, are studied in few-layer MoTe$_{2}$. Temperature-dependent measurements reveal a doublet structure of the corresponding peaks in the Raman scattering spectra of tetralayer and pentalayer samples. A strong enhancement of their lower energy components is recorded at low temperature for 1.91 eV and 1.96 eV laser excitation. We discuss the attribution of the peaks to the inner modes of the respective Raman-active vibrations. The temperature evolution of their intensity strongly suggests a resonant character of the employed excitation, which leads to the mode enhancement at low temperature. The resonance of the laser light with the singularity of the electronic density of states at the $M$ point of the Brillouin zone in MoTe$_{2}$ is proposed to be responsible for the observed effects.Comment: 10 pages, 5 figure

Pressure-driven phase transitions in bulk HfS2_2

The effect of hydrostatic pressure up to 27 GPa on the Raman scattering (RS) in bulk HfS$_2$ is investigated. There are two transformations of RS spectra, which take place during compression at pressure between 5.7 GPa and 9.8 GPa as well as between 12.8 GPa and 15.2 GPa. Seven vibrational modes can be observed after the transformation, as compared to four modes before the transformation. The observed change suggests structural change in the material of yet unknown nature. The frequencies of the RS modes observed above the transformation change linearly with pressure and corresponding pressure coefficients have been determined. The other transition manifests itself as a change in the RS lineshape. While a series of well-defined RS modes are observed under pressure below the transition, broad spectral bands can be seen at higher pressure. The overall lineshape of the spectra resembles that of disordered materials. The lineshape does not change during decompression, which suggests permanent nature of the high-pressure transition.Comment: 4 pages, 4 figure

Raman scattering excitation in monolayers of semiconducting transition metal dichalcogenides

Raman scattering excitation (RSE) is an experimental technique in which the spectrum is made up by sweeping the excitation energy when the detection energy is fixed. We study the low-temperature ($T$=5~K) RSE spectra measured on four high quality monolayers (ML) of semiconducting transition metal dichalcogenides (S-TMDs), $i.e.$ MoS$_2$, MoSe$_2$, WS$_2$, and WSe$_2$, encapsulated in hexagonal BN. The outgoing resonant conditions of Raman scattering reveal an extraordinary intensity enhancement of the phonon modes, which results in extremely rich RSE spectra. The obtained spectra are composed not only of Raman-active peaks, $i.e.$ in-plane E$'$ and out-of-plane A$'_1$, but the appearance of 1$^{st}$, 2$^{nd}$, and higher-order phonon modes is recognised. The intensity profiles of the A$'_1$ modes in the investigated MLs resemble the emissions due to neutral excitons measured in the corresponding PL spectra for the outgoing type of resonant Raman scattering conditions. Furthermore, for the WSe$_2$ ML, the A$'_1$ mode was observed when the incoming light was in resonance with the neutral exciton line. The strength of the exciton-phonon coupling (EPC) in S-TMD MLs strongly depends on the type of their ground excitonic state, $i.e.$ bright or dark, resulting in different shapes of the RSE spectra. Our results demonstrate that RSE spectroscopy is a powerful technique for studying EPC in S-TMD MLs.Comment: 9 pages, 6 figures, ES

Valley polarization of singlet and triplet trions in WS2_2 monolayer in magnetic fields

The spectral signatures associated with different negatively charged exciton complexes (trions) in a WS$_2$ monolayer encapsulated in hBN, are analyzed from low temperature and polarization resolved reflectance contrast (RC) and photoluminescence (PL) experiments, with an applied magnetic field. Based on results obtained from the RC experiment, we show that the valley Zeeman effect affects the optical response of both the singlet and the triplet trion species through the evolution of their energy and of their relative intensity, when applying an external magnetic field. Our analysis allows us to estimate a free electron concentration of $\sim 1.3 \cdot 10^{11}$ cm$^{-2}$. The observed evolutions based on PL experiments on the same sample are different and can hardly be understood within the same simple frame highlighting the complexity of relaxation processes involved in the PL response.Comment: 7 pages, 4 figures; source file correcte