Noboru Takeuchi

First principles calculations of the ground state properties and structural phase transformation in YN

We have studied the structural and electronic properties of YN in rock salt (sodium chloride), caesium chloride, zinc blende and wurtzite structures using first-principles total energy calculations. Rock salt is the calculated ground state structure with a = 4.93 A, B0 = 157 GPa. The experimental lattice constant is a = 4.877 A. There is an additional local minimum in the wurtzite structure with total energy 0.28 eV/unit cell higher. At high pressure (~ 138 GPa), our calculations predict a phase transformation from a NaCl to a CsCl structure.

Yttrium nitride thin films grown by reactive laser ablation

Abstract Yttrium nitride thin films were grown on silicon substrates by laser ablating an yttrium target in molecular nitrogen environments. The composition and chemical state were determined with Auger electron, X-Ray photoelectron, and energy loss spectroscopies. The reaction between yttrium and nitrogen is very effective using this method. Ellipsometry measurements indicate that the films are metallic. We attribute this behavior to a small oxygen contamination. Each oxygen atom introduces two additional electrons to the unit cell, resulting in a complex semiconductor–ionic–metallic system. These results are corroborated by first principles total energy calculations of clean and oxygen doped YN.

Density functional theory study of the organic functionalization of hydrogenated silicene

Silicene, the silicon analogous of graphene, is a newly synthesized two-dimensional nanomaterial, with unique features and promising potential applications. In this paper we present density functional theory calculations of the organic functionalization of hydrogenated silicene with acetylene, ethylene, and styrene. The results are compared with previous works of the adsorption on H-Si[111]. For styrene, binding energies for the intermediate and final states as well as the energy barrier for hydrogen abstraction are rather similar for the two systems. On the other hand, results for acetylene and ethylene are surprisingly different in H-silicene: the abstraction barrier is much smaller in H-silicene than in H-Si[111]. These differences can be understood by the different electrostatic potentials due to the presence of the H atoms at the bottom of the silicene bilayer that allows the delocalization of the spin density at the reaction intermediate state.

Toward accurate reaction energetics for molecular line growth at surface: Quantum Monte Carlo and density functional theory calculations.

We revisit the molecular line growth mechanism of styrene on the hydrogenated Si(001)2x1 surface. In particular, we investigate the energetics of the radical chain reaction mechanism by means of diffusion quantum Monte Carlo (QMC) and density functional theory (DFT) calculations. For the exchange correlation (XC) functional we use the nonempirical generalized-gradient approximation (GGA) and meta-GGA. We find that the QMC result also predicts the intra-dimer-row growth of the molecular line over the inter-dimer-row growth, supporting the conclusion based on DFT results. However, the absolute magnitudes of the adsorption/reaction energies and the heights of the energy barriers differ considerably between the QMC and DFT with the GGA/meta-GGA XC functionals.

Electronic superstructures on the graphite surface studied by first-principles calculations

Abstract We present results of a first-principles study of the graphite surface in the presence of defects. Our calculations, based on density functional theory, show superstructures of periodicity ( 3 × 3 ) in the electronic structure of the surface. In good agreement with STM experiments, these superstructures show a variety of patterns with their intensity decaying away from the defect. Two kind of defects were considered: metallic adatoms absorbed on graphite, and vacancies in the surface lattice. Similar results were found in both cases. Our results give strong support to the idea that these superstructures are due to purely electronic effects, and do not correspond to any atomic reconstruction of the graphite surface.

Density functional theory studies of the adsorption of hydrogen sulfide on aluminum doped silicane.

First principles total energy calculations have been performed to study the hydrogen sulfide (H2S) adsorption on silicane, an unusual one monolayer of Si(111) surface hydrogenated on both sides. The H2S adsorption may take place in dissociative or non-dissociative forms. Silicane has been considered as: (A) non-doped with a hydrogen vacancy, and doped in two main configurations; (B) with an aluminum replacing a hydrogen atom and (C-n; n = 1, 2, 3) with an aluminum replacing a silicon atom at a lattice site. In addition, three supercells; 4x4, 3x3 and 2x2 have been explored for both non-doped and doped silicane. The non-dissociative adsorption takes place in geometries (A), (C-1), (C-2) and (C-3) while the dissociative in (B). Adsorption energies of the dissociative case are larger than those corresponding to the non-dissociated cases. In the dissociative adsorption, the molecule is fragmented in a HS structure and a H atom which are bonded to the aluminum to form a H-S-Al-H structure. The presence of the doping produces some electronic changes as the periodicity varies. Calculations of the total density of states (DOS) indicate that in most cases the energy gap decreases as the periodicity changes from 4x4 to 2x2. The features of the total DOS are explained in terms of the partial DOS. The reported charge density plots explain quite well the chemisorptions and physisorptions of the molecule on silicane in agreement with adsorption energies.

Two-dimensional boron nitride structures functionalization: first principles studies

Density functional theory calculations have been performed to investigate two-dimensional hexagonal boron nitride (2D hBN) structures functionalization with organic molecules. 2x2, 4x4 and 6x6 periodic 2D hBN layers have been considered to interact with acetylene. To deal with the exchange-correlation energy the generalized gradient approximation (GGA) is invoked. The electron-ion interaction is treated with the pseudopotential method. The GGA with the Perdew-Burke-Ernzerhoff (PBE) functionals together with van der Waals interactions are considered to deal with the composed systems. To investigate the functionalization two main configurations have been explored; in one case the molecule interacts with the boron atom and in the other with the nitrogen atom. Results of the adsorption energies indicate chemisorption in both cases. The total density of states (DOS) displays an energy gap in both cases. The projected DOS indicate that the B-p and N-p orbitals are those that make the most important contribution in the valence band and the H-s and C-p orbitals provide an important contribution in the conduction band to the DOS. Provided that the interactions of the acetylene with the 2D layer modify the structural and electronic properties of the hBN the possibility of structural functionalization using organic molecules may be concluded.

Van der Waals molecular interactions in the organic functionalization of graphane, silicane, and germanane with alkene and alkyne molecules: a DFT-D2 study

Density functional theory with the addition of a semi-empirical dispersion potential was applied to the conventional Kohn–Sham energy to study the adsorption of alkene and alkyne molecules on hydrogen-terminated two-dimensional group IV systems (graphane, silicane, and germanane) by means of a radical-initiated reaction. In particular, we investigated the interactions of acetylene, ethylene, and styrene with those surfaces. Although we had studied these systems previously, we included van der Waals interactions in all of the cases examined in the present work. These forces, which are noncovalent interactions, can heavily influence different processes in molecular chemistry, such as the adsorption of organic molecules on semiconductor surfaces. This unified approach allowed us to perform a comparative study of the relative reactivities of the various organic molecule/surface systems. The results showed that the degree of covalency of the surface, the lattice size, and the partial charge distribution (caused by differences in electronegativity) are all key elements that determine the reactivity between the molecules and the surfaces tested in this work. The covalent nature of graphane gives rise to energetically favorable intermediate states, while the opposite polarities of the charge distributions of silicane and germanane with the organic molecules favor subsequent steps of the radical-initiated reaction. Finally, the lattice size is a factor that has important consequences due to steric effects present in the systems and the possibility of chain reaction continuation. The results obtained in this work show that careful selection of the substrate is very important. Calculated energy barriers, heats of adsorption, and optimized atomic structures show that the silicane system offers the best reactivity in organic functionalization.

First principles calculations of the growth of Si on Ge(001) using As as surfactant

We have performed first principles total energy calculations to investigate the role of As as surfactant in the growth of Si on Ge(001). Ge has a lower surface free energy than Si and, therefore, the preferred growth mode of Si on a Ge surface is to form islands. However, it has been shown experimentally that the deposit of one layer of As on the Ge(001) surface can help in the fabrication of thick, low-defect films of Si. Our calculations show that indeed the presence of a terminating As layer modifies the growth mode, promoting epitaxial growth of Si on Ge(001). We also found that another advantage of the capping As layer is to reduce greatly the possibility of Si and Ge intermixing.

Ab initio molecular dynamics study of amorphous Ge

We present results of a first-principles molecular dynamics study of amorphous Ge. The calculations are performed at the density of crystal Ge (c-Ge). Our computer generated network describes the structural and electronic properties of amorphous Ge in good agreement with experiments and previous calculations.