Non-volatile resistive switching mechanism in single-layer MoS2 memristors: insights from ab initio modelling of Au and MoS2 interfaces.

Non-volatile memristive devices based on two-dimensional (2D) layered materials provide an attractive alternative to conventional flash memory chips. Single-layer semiconductors, such as monolayer molybdenum disulphide (ML-MoS2), enable the aggressive downscaling of devices towards greater system integration density. The "atomristor", the most compact device to date, has been shown to undergo a resistive switching between its high-resistance (HRS) and low-resistance (LRS) states of several orders of magnitude. The main hypothesis behind its working mechanism relies on the migration of sulphur vacancies in the proximity of the metal contact during device operation, thus inducing the variation of the Schottky barrier at the metal-semiconductor interface. However, the interface physics is not yet fully understood: other hypotheses were proposed, involving the migration of metal atoms from the electrode. In this work, we aim to elucidate the mechanism of the resistive switching in the atomristor. We carry out density functional theory (DFT) simulations on model Au and ML-MoS2 interfaces with and without the presence of point defects, either vacancies or substitutions. To construct realistic interfaces, we combine DFT with Green's function surface simulations. Our findings reveal that it is not the mere presence of S vacancies but rather the migration of Au atoms from the electrode to MoS2 that modulate the interface barrier. Indeed, Au atoms act as conductive "bridges", thus facilitating the flow of charge between the two materials.

Capillary-force-driven self-assembly of carbon nanotubes: from ab initio calculations to modeling of self-assembly.

In elasto-capillary driven self-assembly of arrays of carbon nanotubes (CNTs) different factors play a role, from the mechanical properties of CNTs to the array geometry. In this work, we provide a multi-scale investigation where we first use density functional theory (DFT) to predict fully ab initio relevant mechanical properties such as Young's modulus, Poisson's ratio, and surface energy. To the best of our knowledge, we are the first to report DFT calculations of the surface energy of CNTs. Then, we feed the computed DFT parameters into a model for capillary-force-driven self-assembly of CNTs. By doing so, we are able to derive and predict cross-correlation between material parameters and array architecture.

Assessing doping strategies for monolayer MoS2 towards non-enzymatic detection of cortisol: a first-principles study.

In this work, we investigate by means of atomistic density functional theory simulations the interaction between cortisol (the target molecule) and monolayer MoS2 (the substrate). The aim is to assess viable strategies for the non-enzymatic chemical sensing of cortisol. Metal doping of the sensing material could offer a way to improve the device response upon analyte adsorption, and could also enable novel and alternative detection mechanisms. For such reasons, we explore metal doping of MoS2 with Ni, Pd, and Pt, as these are metal elements commonly used in experiments. Then, we study the material response from the structural, electronic, and charge-transfer points of view. Based on our results, we propose two possible sensing mechanisms and device architectures: (i) a field-effect transistor, and (ii) an electrochemical sensor. In the former, Ni-doped MoS2 would act as the FET channel, and the sensing mechanism involves the variation of the surface electrostatic charge upon the adsorption of cortisol. In the latter, MoS2 decorated with Pt nanoparticles could act as the working electrode, and the sensing mechanism would involve the reduction of cortisol. In addition, our findings may suggest the suitability of both doped and metal-doped MoS2 as sensing layers in an optical sensor.

Linear-scaling density functional simulations of the effect of crystallographic structure on the electronic and optical properties of fullerene solvates.

In this work, the crystal properties, HOMO and LUMO energies, band gaps, density of states, as well as the optical absorption spectra of fullerene C60 and its derivative phenyl-C61-butyric-acid-methyl-ester (PCBM) co-crystallised with various solvents such as benzene, biphenyl, cyclohexane, and chlorobenzene were investigated computationally using linear-scaling density functional theory with plane waves as implemented in the ONETEP program. Such solvates are useful materials as electron acceptors for organic photovoltaic (OPV) devices. We found that the fullerene parts contained in the solvates are unstable without solvents, and the interactions between fullerene and solvent molecules in C60 and PCBM solvates make a significant contribution to the cohesive energies of solvates, indicating that solvent molecules are essential to keep C60 and PCBM solvates stable. Both the band gap (Eg) and the HOMO and LUMO states of C60 and PCBM solvates are mainly determined by the fullerene parts contained in solvates. Chlorobenzene- and ortho-dichlorobenzene-solvated PCBM are the most promising electron-accepting materials among these solvates for increasing the driving force for charge separation in OPVs due to their relatively high LUMO energies. The UV-Vis absorption spectra of solvent-free C60 and PCBM crystals in the present work are similar to those of C60 and PCBM thin films shown in the literature. Changes in the absorption spectra of C60 solvates relative to the solvent-free C60 crystal are more significant than those of PCBM solvates due to the weaker effect of solvents on the π-stacking interactions between fullerene molecules in the latter solvates. The main absorptions for all C60 and PCBM crystals are located in the ultraviolet (UV) region.

Ab initio modeling of 2D layered organohalide lead perovskites.

A number of 2D layered perovskites A2PbI4 and BPbI4, with A and B mono- and divalent ammonium and imidazolium cations, have been modeled with different theoretical methods. The periodic structures have been optimized (both in monoclinic and in triclinic systems, corresponding to eclipsed and staggered arrangements of the inorganic layers) at the DFT level, with hybrid functionals, Gaussian-type orbitals and dispersion energy corrections. With the same methods, the various contributions to the solid stabilization energy have been discussed, separating electrostatic and dispersion energies, organic-organic intralayer interactions and H-bonding effects, when applicable. Then the electronic band gaps have been computed with plane waves, at the DFT level with scalar and full relativistic potentials, and including the correlation energy through the GW approximation. Spin orbit coupling and GW effects have been combined in an additive scheme, validated by comparing the computed gap with well known experimental and theoretical results for a model system. Finally, various contributions to the computed band gaps have been discussed on some of the studied systems, by varying some geometrical parameters and by substituting one cation in another's place.