Reduced graphene oxide (rGO) is added in the [6,6]‐Phenyl‐C61‐butyric acid methyl ester (PCBM) electron transport layer (ETL) of planar inverted perovskite solar cells (PSCs), resulting in a power conversion efficiency (PCE) improvement of ≈12%, with a hysteresis‐free PCE of 14.5%, compared to 12.9% for the pristine PCBM based device. The universality of the method is demonstrated in PSCs based on CH3NH3PbI3−xClx and CH3NH3PbI3 perovskites, deposited through one step and two step spin coating process, respectively. After a comprehensive spectroscopic characterization of both devices, it is clear that the introduction of rGO in PCBM ETL results in an important increase of the ETL conductivity, together with reduced series resistance and surface roughness. As a result, a significant photoluminescence quenching of such perovskite/ETL is observed, confirming the increased measured short circuit current density. Transient absorption measurements reveal that in the rGO‐based device, the relaxation process of the excited electrons is significantly faster compared to the reference, which implies that the charge injection rate is significantly faster for the first. Furthermore, the light soaking effect is significantly reduced. Finally, aging measurements reveal that the rGO stabilizes the ELT/perovskite interface, which results in the stabilization of perovskite crystal structure after prolonged illumination.

Solution‐processed organic–inorganic lead halide perovskite solar cells (PSCs) are considered as one of the most promising photovoltaic technologies thanks to both high performance and low manufacturing cost. However, a key challenge of this technology is the lack of ambient stability over prolonged solar irradiation under continuous operating conditions. In fact, only a few studies (carried out in inert atmosphere) already approach the industrial standards. Here, it is shown how the introduction of MoS2 flakes as a hole transport interlayer in inverted planar PSCs results in a power conversion efficiency (PCE) of ≈17%, overcoming the one of the standard reference devices. Furthermore, this approach allows the realization of ultrastable PSCs, stressed in ambient conditions and working at continuous maximum power point. In particular, the photovoltaic performances of the proposed PSCs represent the current state‐of‐the‐art in terms of lifetime, retaining 80% of their initial performance after 568 h of continuous stress test, thus approaching the industrial stability standards. Moreover, it is further demonstrated the feasibility of this approach by fabricating large‐area PSCs (0.5 cm2 active area) with MoS2 as the interlayer. These large‐area PSCs show improved performance (i.e., PCE = 13.17%) when compared with the standard devices (PCE = 10.64%).

Combining MoS2 monolayers to form multilayers allows to access new functionalities. Deterministic assembly of large area van der Waals structures requires concrete indicators of successful interlayer coupling in bilayers grown by chemical vapor deposition. In this work, we examine the correlation between the stacking order and the interlayer coupling of valence states in both as-grown MoS2 homobilayer samples and in artificially stacked bilayers from monolayers, all grown by chemical vapor deposition. We show that hole delocalization over the bilayer is only allowed in 2H stacking and results in strong interlayer exciton absorption and also in a larger A-B exciton separation as compared to 3R bilayers. Comparing 2H and 3R reflectivity spectra allows to extract an interlayer coupling energy of about t⊥ = 49 meV. Beyond DFT calculations including excitonic effects confirm signatures of efficient interlayer coupling for 2H stacking in agreement with our experiments.

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Single layers of WS2 are direct gap semiconductors with high photoluminescence (PL) yield holding great promise for emerging applications in optoelectronics. The spatial confinement in a 2D monolayer together with the weak dielectric screening lead to huge binding energies for the neutral excitons as well as other excitonic complexes, such as trions and biexcitons whose binding energies scale accordingly. Here, we report on the existence of biexcitons in mechanically exfoliated WS2 flakes from 78 K up to room temperature. Performing temperature and power dependent PL measurements, we identify the biexciton emission channel through the superlinear behavior of the integrated PL intensity as a function of the excitation power density. On the contrary, neutral and charged excitons show a linear to sublinear dependence in the whole temperature range. From the energy difference between the emission channels of the biexciton and neutral exciton, a biexciton binding energy of 65-70 meV is determined. *Corresponding authors: gnk@materials.uoc.gr ; stratak@iesl.forth.gr 2 The interest on two-dimensional (2D) materials has been steadily increasing since the discovery of graphene, a material with fascinating properties and great potential for various applications 1 . Transition metal dichalcogenides (TMDs) with the form MX2 (M = Mo, W, Ti, etc and X = S, Se, Te) exhibit a structure very similar to that of graphene and have attracted significant attention of the scientific community 2-5 for a number of reasons. Among the most attractive features of TMD compounds is that their electronic properties can vary from metallic to those of a wide band gap semiconductor depending on the structure, composition and dimensionality, while their band structure can be easily tuned by applying stress 6 . Owing to such layer-dependent electronic structure, TMDs exhibit extraordinary optoelectronic properties 7,8 as well as potential for enhanced performance in applications such as photodetectors 9 , photovoltaics 10,11 and non-linear optical components 12 .Among their prominent optical properties, TMD monolayers show strong PL in the visible and near-infrared spectral range, due to the transition from indirect band gap semiconductors in their bulk and few-layer forms, to direct band gap semiconductors in the monolayer limit 13 . Besides this, the spatial confinement of carriers in a 2D monolayer lattice and the weak dielectric screening, give rise to unusually strong excitonic effects and high binding energies [14][15][16] . These properties favor the stability of a variety of excitonic quasiparticles with extremely large binding energies, including neutral excitons with binding energies of several hundred meV 17,18 , charged excitons (trions) was shown that the biexciton emission in WS2 can be electrically tuned 27 , which is of great importance for TMDs-based photonic devices.The unusually strong excitonic effects in TMDs strongly suggest an enhanced thermal stability of biexciton emission. While neutral and charged excitons have...

The effect of femtosecond laser irradiation on bulk and single-layer MoS2 on silicon oxide is studied. Optical, Field Emission Scanning Electron Microscopy (FESEM) and Raman microscopies were used to quantify the damage. The intensity of A1g and E2g1 vibrational modes was recorded as a function of the number of irradiation pulses. The observed behavior was attributed to laser-induced bond breaking and subsequent atoms removal due to electronic excitations. The single-pulse optical damage threshold was determined for the monolayer and bulk under 800nm and 1030nm pulsed laser irradiation and the role of two-photon versus one photon absorption effects is discussed.Comment: 14 pages, 4 figures, 24 references, PD

We used nonlinear laser scanning optical microscopy to study atomically thin transition metal dichalcogenides (TMDs) and revealed, with unprecedented resolution, the orientational distribution of armchair directions and their degree of organization in the two-dimensional (2D) crystal lattice. In particular, we carried out polarization-resolved second-harmonic generation (PSHG) imaging for monolayer WS2 and obtained, with high-precision, the orientation of the main crystallographic axis (armchair orientation) for each individual 120 × 120 nm2 pixel of the 2D crystal area. Such nanoscale resolution was realized by fitting the experimental PSHG images, obtained with sub-micron precision, to a new generalized theoretical model that accounts for the nonlinear optical properties of TMDs. This enabled us to distinguish between different crystallographic domains, locate boundaries and reveal fine structure. As a consequence, we can calculate the mean orientational average of armchair angle distributions in specific regions of interest and define the corresponding standard deviation as a figure-of-merit for the 2D crystal quality.

Stacked atomically thin transition metal dichalcogenides (TMDs) exhibit fundamentally new physical properties compared to those of the individual layers. The twist angle between the layers plays a crucial role in tuning these properties. Having a tool that provides high-resolution, large area mapping of the twist angle, would be of great importance in the characterization of such 2D structures. Here we use polarization-resolved second harmonic generation (P-SHG) imaging microscopy to rapidly map the twist angle in large areas of overlapping WS2 stacked layers. The robustness of our methodology lies in the combination of both intensity and polarization measurements of SHG in the overlapping region. This allows the accurate measurement and consequent pixel-by-pixel mapping of the twist angle in this area. For the specific case of 30° twist angle, P-SHG enables imaging of individual layers.