We demonstrate that, in monolayers (MLs) of semiconducting transition metal dichalcogenides, the s-type Rydberg series of excitonic states follows a simple energy ladder: ǫn = −Ry * /(n + δ) 2 , n=1,2,. . . , in which Ry * is very close to the Rydberg energy scaled by the dielectric constant of the medium surrounding the ML and by the reduced effective electron-hole mass, whereas the ML polarizability is only accounted for by δ. This is justified by the analysis of experimental data on excitonic resonances, as extracted from magneto-optical measurements of a high-quality WSe2 ML encapsulated in hexagonal boron nitride (hBN), and well reproduced with an analytically solvable Schrödinger equation when approximating the electron-hole potential in the form of a modified Kratzer potential. Applying our convention to other, MoSe2, WS2, MoS2 MLs encapsulated in hBN, we estimate an apparent magnitude of δ for each of the studied structures. Intriguingly, δ is found to be close to zero for WSe2 as well as for MoS2 monolayers, what implies that the energy ladder of excitonic states in these two-dimensional structures resembles that of Rydberg states of a three-dimensional hydrogen atom.

Reflectance and magneto-reflectance experiments together with theoretical modelling based on the k · p approach have been employed to study the evolution of direct bandgap excitons in MoS2 layers with a thickness ranging from mono-to trilayer. The extra excitonic resonances observed in MoS2 multilayers emerge as a result of the hybridization of Bloch states of each sub-layer due to the interlayer coupling. The properties of such excitons in bi-and trilayers are classified by the symmetry of corresponding crystals. The inter-and intralayer character of the reported excitonic resonances is fingerprinted with the magneto-optical measurements: the excitonic g-factors of opposite sign and of different amplitude are revealed for these two types of resonances. The parameters describing the strength of the spin-orbit interaction are estimated for bi-and trilayer MoS2.

Temperature-dependent (5 K-300 K) Raman scattering study of A 1g /A′ 1 phonon modes in mono-layer (1L), bilayer (2L), trilayer (3L), and tetralayer (4L) MoTe 2 is reported. The temperature evolution of the modes' intensity critically depends on the flake thickness. In particular with λ = 632.8-nm light excitation, a strongly non-monotonic dependence of the A 1g mode intensity is observed in 2L MoTe 2 . The intensity decreases with decreasing temperature down to 220 K, and the A 1g mode almost completely vanishes from the Stokes scattering spectrum in the temperature range between 160 K and 220 K. The peak recovers at lower temperatures, and at T = 5 K, it becomes three times more intense that at room temperature. Similar non-monotonic intensity evolution is observed for the out-of-plane mode in 3L MoTe 2 in which tellurium atoms in all three layers vibrate in-phase. The intensity of the other out-of-plane Raman-active mode (with vibrations of tellurium atoms in the central layer shifted by 180° with respect to the vibrations in outer layers) only weakly depends on temperature. The observed quenching of the Raman scattering in 2L and 3L MoTe 2 is attributed to a destructive interference between the resonant and non-resonant contributions to the Raman scattering amplitude. The observed "antiresonance" is related to the electronic excitation at the M point of the Brillouin zone in few-layer MoTe 2 .

The effect of bis(trifluoromethane) sulfonimide (TFSI, superacid) treatment on the optical properties of MoS2 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 MoS2 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 MoS2 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 MoS2 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.

We present results of µ-Raman and µ-photoluminescence study of few-layer WS2 flakes that have been locally thinned down by a focused laser beam. The Raman spectroscopy measurements prove that the investigated flake was locally thinned down to a monolayer. Interestingly, µ-photoluminescence experiments allowed us to observe huge intensity fluctuations at the boundary of laser-thinned region. Similar effects were found at the edges of a WS2 bilayer flake, which has not been subjected to laser-thinning. The origin of the observed time evolution of the photoluminescence response is discussed in terms of potential fluctuations resulting from light-induced changes of the charge state of defects.