Suchergebnisse

The structural, electronic, and magnetic properties of pristine, defective, and oxidized monolayer TiS3 are investigated using first-principles calculations in the framework of density functional theory. We found that a single layer of TiS3 is a direct band gap semiconductor, and the bonding nature of the crystal is fundamentally different from other transition metal chalcogenides. The negatively charged surfaces of single layer TiS3 makes this crystal a promising material for lubrication applications. The formation energies of possible vacancies, i.e. S, Ti, TiS, and double S, are investigated via total energy optimization calculations. We found that the formation of a single S vacancy was the most likely one among the considered vacancy types. While a single S vacancy results in a nonmagnetic, semiconducting character with an enhanced band gap, other vacancy types induce metallic behavior with spin polarization of 0.3-0.8 μB. The reactivity of pristine and defective TiS3 crystals against oxidation was investigated using conjugate gradient calculations where we considered the interaction with atomic O, O2, and O3. While O2 has the lowest binding energy with 0.05-0.07 eV, O3 forms strong bonds stable even at moderate temperatures. The strong interaction (3.9-4.0 eV) between atomic O and TiS3 results in dissociative adsorption of some O-containing molecules. In addition, the presence of S-vacancies enhances the reactivity of the surface with atomic O, whereas it had a negative effect on the reactivity with O2 and O3 molecules. ; Flemish Science Foundation (FWO-Vl); Methusalem foundation of the Flemish government; Hercules foundation; FWO Pegasus Marie Curie Fellowship; TUBITAK (114F397)

The diffusive motion of metal nanoparticles Au and Ag on monolayer and between bilayer heterostructures of transition metal dichalcogenides and graphene are investigated in the framework of density functional theory. We found that the minimum energy barriers for diffusion and the possibility of cluster formation depend strongly on both the type of nanoparticle and the type of monolayers and bilayers. Moreover, the tendency to form clusters of Ag and Au can be tuned by creating various bilayers. Tunability of the diffusion characteristics of adatoms in van der Waals heterostructures holds promise for controllable growth of nanostructures. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License. ; Flemish Science Foundation (FWO-Vl)FWO; Methusalem foundation of the Flemish government; Hercules foundation; FWO Pegasus Marie Curie Fellowship; TUBITAKTurkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [111T318] ; This work was supported by the Flemish Science Foundation (FWO-Vl) and the Methusalem foundation of the Flemish government. Computational resources were provided by TUBITAK ULAKBIM, High Performance and Grid Computing Center (TR-Grid e-Infrastructure), and HPC infrastructure of the University of Antwerp (CalcUA) a division of the Flemish Supercomputer Center (VSC), which is funded by the Hercules foundation. H.S. is supported by a FWO Pegasus Marie Curie Fellowship. F.I. and R.T.S. acknowledge the support from TUBITAK Project No. 111T318.

Ca(OH)2 crystals, well known as portlandite, are grown in layered form, and we found that they can be exfoliated on different substrates. We performed first principles calculations to investigate the structural, electronic, vibrational, and mechanical properties of bulk, bilayer, and monolayer structures of this material. Different from other lamellar structures such as graphite and transition-metal dichalcogenides, intralayer bonding in Ca(OH)2 is mainly ionic, while the interlayer interaction remains a weak dispersion-type force. Unlike well-known transition-metal dichalcogenides that exhibit an indirect-to-direct band gap crossover when going from bulk to a single layer, Ca(OH)2 is a direct band gap semiconductor independent of the number layers. The in-plane Young's modulus and the in-plane shear modulus of monolayer Ca(OH)2 are predicted to be quite low while the in-plane Poisson ratio is larger in comparison to those in the monolayer of ionic crystal BN. We measured the Raman spectrum of bulk Ca(OH)2 and identified the high-frequency OH stretching mode A1g at 3620cm-1. In this study, bilayer and monolayer portlandite [Ca(OH)2] are predicted to be stable and their characteristics are analyzed in detail. Our results can guide further research on ultrathin hydroxites. ; Flemish Science Foundation (FWO-Vl); Methusalem foundation of the Flemish government; FWO Pegasus Long Marie Curie Fellowship