We report on the establishment of a new lab-scale experimental capability for Spin and Angular Resolved Photoemission Spectroscopy (SARPES) for the study of valleytronics related materials. The ARPES capabilities of the system were demonstrated by measurement on gold [Au(111)] and molybdenum disulphide (MoS2) single crystals and the full functionality of the spin detector was also verified. Experimental results are compared with theoretical modeling by ab-initio band structure calculations. We discuss the potential scope of measurement that this experimental setup affords for investigating spin-related properties (e.g. spin-orbit coupling, valley transport, etc.) in layered materials.

Molybdenum disulfide (MoS2) thin films were fabricated by two-step chemical vapor deposition (CVD) using (t-C4H9)2S2 and the effects of temperature, gas flow rate, and atmosphere on the formation were investigated in order to achieve high-speed low-temperature MoS2 film formation. From the results of X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) investigations, it was confirmed that c-axis orientation of the pre-deposited Mo film has a significant involvement in the crystal orientation after the reaction low temperature sulfurization annealing and we successfully obtained 3 nm c-axis oriented MoS2 thin film. From the S/Mo ratios in the films, it was revealed that the sulfurization reaction proceeds faster with increase in the sulfurization temperature and the gas flow rate. Moreover, the sulfurization under the H2 atmosphere promotes decomposition reaction of (t-C4H9)2S2, which were confirmed by XPS and density functional theory (DFT) simulation.

The effect of temperature (5K to 300K) on the Raman scattering due to A1g/A1’ modes associated with the out-of-plane vibrations in bilayer (2L) and trilayer (3L) MoTe2 is investigated. The temperature evolution of the modes critically depends on the flake thickness. The A1g mode intensity in 2L MoTe2 observed with λ=632.8 nm light excitation decreases with decreasing temperature down to 220K and the mode vanishes from the Stokes scattering spectrum in the temperature range between 160K and 220K. The peak recovers at lower temperatures and at T=5K it becomes three times more intense that at room temperature. Similar non-monotonic intensity evolution is observed for the A1’ mode in 3L MoTe2 in which tellurium atoms in all three layers vibrate in-phase. On the contrary, the intensity of the other out-of-plane Raman-active mode in which vibrations of tellurium atoms in the central layer of 3L MoTe2 are shifted by 180° with respect to vibrations in outer layers, only weakly depends on temperature.

The observed quenching of the out-of-plane modes in the Raman scattering in thin MoTe2 layers is related to the destructive interference of the resonant- and the non-resonant contributions to the Raman scattering. The resonance with the M point of the Brillouin zone in few-layers of MoTe2 is considered. Effects related to the resonant quenching of the in-phase out-of-plane mode are discussed.

Cubic boron nitride (cBN) is a synthetic wide band gap material that has attracted attention due to its high thermal conductivity, optical transparency and optical emission. In this work, defects in cBN have been investigated using experimental and theoretical X-ray absorption near edge structure (XANES). Vacancy and O substitutional defects were considered, with O substituted at the N site (ON) to be the most energetically favorable. All defects produce unique signatures in either the B or N K-edges and can thus be identified using XANES. The calculations coupled with electron-irradiation / annealing experiments strongly suggest that ON is the dominant defect in irradiated cBN and remains after annealing. This defect is a likely source of optical emission in cBN.

In this work we have investigated, by fully atomistic reactive (force field ReaxFF) molecular dynamics simulations, some aspects of impact dynamics of water nanodroplets on graphdiyne-like membranes. We simulated graphdiyne-supported membranes impacted by nanodroplets at different velocities (from 100 up to 1500 m/s). The results show that due to the graphdiyne porous and elastic structure, the droplets present an impact dynamics very complex in relation to the ones observed for graphene membranes. Under impact the droplets spread over the surface with a maximum contact radius proportional to the impact velocity. Depending on the energy impact value, a number of water molecules were able to percolate the nanopore sheets. However, even in these cases the droplet shape is preserved and the main differences between the different impact velocities cases reside on the splashing pattern at the maximum spreading.

We report the synthesis of MoS2(1-x)Te2x by co-sputtering deposition and effect of mixture on its bandgap. The deposition was carried out at room temperature, and the sputtering power on individual MoS2 and MoTe2 targets were varied to obtain films with different compositions. Investigation with X-ray photoelectron spectroscopy confirmed the formation of Mo-Te and Mo-S bonds after post-deposition annealing (PDA), and one of the samples exhibited composition ratio of Mo:S:Te = 1:1.2:0.8 and 1:1.9:0.1 achieving 1:2 ratio of metal to chalcogen. Bandgap of MoS1.2Te0.8 and MoS1.9Te0.1 was evaluated with Tauc plot analysis from the extinction coefficient obtained by spectroscopic ellipsometry measurements. The obtained bandgaps were 1.0 eV and 1.3 eV. The resulting bandgap was lower than that of bulk MoS2 and higher than that of bulk MoTe2 suggesting mixture of both materials was achieved by co-sputtering.

Two-dimensional group IV layers beyond graphene, as silicene, germanene and the Sn-based stanene, have been recently synthesized by molecular beam epitaxy. Density Functional Theyory (DFT) calculations predict low-buckled structures for these 2D nanosheets, with a hexagonal honeycomb conformation, typical of the graphene-like surfaces. The buckling parameter δ increases from Si to Sn-based layers, with a maximum predicted of 0.92 Å for stanene. High-buckled structures for these materials resulted to be unstable. We have previously shown that for silicene and germanene, the origin of the buckled structure resides on the pseudo Jahn-Teller puckering distortion, resulting from non-adiabatic effects. It has been shown that hexagermabenzene, the single hexagonal unit of germanene, is subject to a strong vibronic coupling whose origin is the pseudo Jahn-Teller effect. This coupling resulted to be around ten times larger than the one obtained for hexasilabenzene. For stanene, an additional effect needs to be considered to understand the origin of buckling: the spin-orbit coupling (SOC). This SOC contributes to open an electronic band gap, enabling the use of these layers as nanoelectronic components. In this work, we present an analysis based on DFT in the Zeroth-Order Regular Approximation (ZORA) for both scalar relativistic and spin-orbit versions that quantify the influence of the spin-orbit coupling in the puckering of Sn6H6. Also, under the linear vibronic coupling model between the ground and the lowest excited states, we present the pseudo Jahn-Teller contribution. The scalar ZORA approximation is used to perform time-dependent DFT calculations to incorporate the low-energy excitations contributions. Our model leads to the determination of the coupling constants and predicts simultaneously the Adiabatic Potential Energy Surface behavior for the ground and excited states around the maximum symmetry point. These values allow us to compare the Jahn-Teller relevance in buckling with the other group IV layers.

The advent of graphene created a revolution in materials science. Because of this there is a renewed interest in other carbon-based structures. Graphene is the ultimate (just one atom thick) membrane. It has been proposed that graphene can work as impermeable membrane to standard gases, such argon and helium. Graphene-like porous membranes, but presenting larger porosity and potential selectivity would have many technological applications. Biphenylene carbon (BPC), sometimes called graphenylene, is one of these structures. BPC is a porous two-dimensional (planar) allotrope carbon, with its pores resembling typical sieve cavities and/or some kind of zeolites. In this work, we have investigated the hydrogenation dynamics of BPC membranes under different conditions (hydrogenation plasma density, temperature, etc.). We have carried out an extensive study through fully atomistic molecular dynamics (MD) simulations using the reactive force field ReaxFF, as implemented in the well-known Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) code. Our results show that the BPC hydrogenation processes exhibit very complex patterns and the formation of correlated domains (hydrogenated islands) observed in the case of graphene hydrogenation was also observed here. MD results also show that under hydrogenation BPC structure undergoes a change in its topology, the pores undergoing structural transformations and extensive hydrogenation can produce significant structural damages, with the formation of large defective areas and large structural holes, leading to structural collapse.