Elasticity, band-gap bowing, and polarization of AlxGa1-xN alloys

Elastic constants, the bulk modulus, Young's modulus, band-gap bowing coefficients, spontaneous and piezoelectric polarizations, and piezoelectric coefficients of hexagonal AlxGa1-xN ternary alloys are calculated using first-principles methods. The fully relaxed structures and the structures subjected to homogeneous biaxial and uniaxial tension are investigated. We show that the biaxial tension in the plane perpendicular to the c axis and the uniaxial tension along the c axis all reduce the bulk modulus, whereas they reduce and enhance Young's modulus, respectively. We find that the biaxial and uniaxial tension can enhance the bowing coefficients. We also find that the biaxial tension can enhance the total polarization, while the uniaxial tension will suppress the total polarization. (C) 2008 American Institute of Physics.

Electronic Properties of Nonstoichiometric PbSe Quantum Dots from First Principles

One-Hundred Talent Plan of the Chinese Academy of Sciences；National Science Fund for Distinguished Young Scholars 60925016；National High Technology Research and Development program of China 2009AA034101

Ab initio study on the electronic, magnetic, and mechanical properties of CaCu3V4O12

The electronic, magnetic, and mechanical properties of CaCu3V4O12 are investigated by use of the density functional theory method. The calculated results indicate that CaCu3V4O12 is a half-metallic and ferrimagnetic compound. The magnetic coupling for Cu-V is antiferromagnetic, while those for Cu-Cu and V-V are ferromagnetic. The obtained elastic constants suggest that the compound is mechanically stable. The calculated oxidation states and density of states reveal the existence of a mixed valence for Cu and V. This supports the experimental observation of the mixed valence in Ca2+Cu2+Cu2+(V25+V24+)O-12.

Structural stability and magnetic coupling in CaCu3Co4O12 from first principles

The structural, electronic and magnetic properties of CaCu3Co4O12 were studied by use of the full-potential linearized augmented plane wave method. The calculated results indicate that CaCu3Co4O12 is stable both thermodynamically and mechanically. Both GGA (generalized gradient approximation) and GGA + U methods predict that CaCu3Co4O12 is metallic. The ferromagnetic configuration is only slightly more stable in energy compared with the non-magnetic configuration (3.7 meV), suggesting that they are competitive for being the ground state. Co is in the low spin state (S = 1/2).

Universal tight binding model for chemical reactions in solution and at surfaces. II. Water

A revised water model intended for use in condensed phase simulations in the framework of the self consistent polarizable ion tight binding theory is constructed. The model is applied to water monomer, dimer, hexamers, ice, and liquid, where it demonstrates good agreement with theoretical results obtained by more accurate methods, such as DFT and CCSD(T), and with experiment. In particular, the temperature dependence of the self diffusion coefficient in liquid water predicted by the model, closely reproduces experimental curves in the temperature interval between 230 K and 350 K. In addition, and in contrast to standard DFT, the model properly orders the relative densities of liquid water and ice. A notable, but inevitable, shortcoming of the model is underestimation of the static dielectric constant by a factor of two. We demonstrate that the description of inter and intramolecular forces embodied in the tight binding approximation in quantum mechanics leads to a number of valuable insights which can be missing from ab initio quantum chemistry and classical force fields. These include a discussion of the origin of the enhanced molecular electric dipole moment in the condensed phases, and a detailed explanation for the increase of coordination number in liquid water as a function of temperature and compared with ice-leading to insights into the anomalous expansion on freezing. The theory holds out the prospect of an understanding of the currently unexplained density maximum of water near the freezing point. 

Electronic and magnetic properties of Ti and Fe on graphene

The structural, electronic and magnetic properties of Fe and Ti atomic wires and the complete covering when adsorbed on graphene are presented through ab initio calculations based on density functional theory. The most stable configurations are investigated for Fe and Ti in different concentrations adsorbed on the graphene surface, and the corresponding binding energies are calculated. The results show a tendency of the Ti atoms to cover uniformly the graphene surface, whereas the Fe atoms form clusters. The adsorption of the transition metal on the graphene surface changes significantly the electronic density of states near the graphene Fermi region. In all arrangements studied, a charge transfer is observed from the adsorbed species to the graphene surface due to the high hybridizations between the systems.

Driving forces for the adsorption of cyclopentene on InP(001)

In this work the interaction of cyclopentene with a set of InP(001) surfaces is investigated by means of the density functional theory. We propose a simple approach for evaluating the surface strain and based on it we have found a linear relation between bond and strain energies and the adsorption energy. Our results also indicate that the higher the bond energy, the more disperse the charge distribution is around the adsorption site associated to the high occupied state, a key feature that characterizes the adsorption process. Different adsorption coverages are used to evaluate the proposed equation. Our results suggest that the proposed approach might be extended to other systems where the interaction of the semiconductor surface and the molecule is restricted to first neighbor sites. (C) 2011 Elsevier B.V. All rights reserved.

Kinetics and coverage dependent reaction mechanisms of the copper atomic layer deposition from copper dimethylamino-2-propoxide and diethylzinc

Atomic layer deposition (ALD) has been recognized as a promising method to deposit conformal and uniform thin film of copper for future electronic devices. However, many aspects of the reaction mechanism and the surface chemistry of copper ALD remain unclear. In this paper, we employ plane wave density functional theory (DFT) to study the transmetalation ALD reaction of copper dimethylamino-2-propoxide [Cu(dmap)2] and diethylzinc [Et2Zn] that was realized experimentally by Lee et al. [ Angew. Chem., Int. Ed. 2009, 48, 4536−4539]. We find that the Cu(dmap)2 molecule adsorbs and dissociates through the scission of one or two Cu–O bonds into surface-bound dmap and Cu(dmap) fragments during the copper pulse. As Et2Zn adsorbs on the surface covered with Cu(dmap) and dmap fragments, butane formation and desorption was found to be facilitated by the surrounding ligands, which leads to one reaction mechanism, while the migration of ethyl groups to the surface leads to another reaction mechanism. During both reaction mechanisms, ligand diffusion and reordering are generally endothermic processes, which may result in residual ligands blocking the surface sites at the end of the Et2Zn pulse, and in residual Zn being reduced and incorporated as an impurity. We also find that the nearby ligands play a cooperative role in lowering the activation energy for formation and desorption of byproducts, which explains the advantage of using organometallic precursors and reducing agents in Cu ALD. The ALD growth rate estimated for the mechanism is consistent with the experimental value of 0.2 Å/cycle. The proposed reaction mechanisms provide insight into ALD processes for copper and other transition metals.

Role of lithium vacancies in accelerating the dehydrogenation kinetics on a LiBH4(010) surface : an Ab initio study

In this work, ab initio density functional calculations were performed to explore the effect of surface lithium vacancies on the initial dehydrogenation kinetics of lithium borohydride. We found that some B−H bonds in neighboring BH4-1 complexes around the vacancy became elongated (weakened). The activation barriers for the recombination of H atoms to form H2 were decreased from 3.64 eV for the stoichiometrically complete LiBH4(010) surface to 1.53 and 0.23 eV in the presence of mono- and di-vacancies, respectively. Our results indicate that the creation of Li vacancies may play a critical role in accelerating the dehydrogenation kinetics of LiBH4.

Muon-spin rotation spectra in the mixed phase of high-T-c superconductors: Thermal fluctuations and disorder effects

We study muon-spin rotation (mu SR) spectra in the mixed phase of highly anisotropic layered superconductors, specifically Bi2+xSr2-xCaCu2O8+delta (BSCCO), by modeling the fluid and solid phases of pancake Vortices using liquid-state and density functional methods. The role of thermal fluctuations in causing motional narrowing of mu SR line shapes is quantified in terms of a first-principles theory of the flux-lattice melting transition. The effects of random point pinning are investigated using a replica treatment of liquid-state correlations and a replicated density functional theory. Our results indicate that motional narrowing in the pure system, although substantial, cannot account for the remarkably small linewidths obtained experimentally at relatively high fields and low temperatures. We find that satisfactory agreement with the mu SR data for BSCCO in this regime can be obtained through the ansatz that this ''phase'' is characterized by frozen short-range positional correlations reflecting the structure of the liquid just above the melting transition. This proposal is consistent with recent suggestions of a ''pinned liquid'' or ''glassy'' state of pancake Vortices in the presence of pinning disorder. Our results for the high-temperature liquid phase indicate that measurable linewidths may be obtained in this phase as a consequence of density inhomogeneities induced by the pinning disorder. The results presented here comprise a unified, first-principles theoretical treatment of mu SR spectra in highly anisotropic layered superconductors in terms of a controlled set of approximations. [S0163-1829(99)08033-9].

Decisões judiciais no campo da biotecnociência: a bioética como fonte de legitimação

A tese analisa decisões judiciais prolatadas em casos da bioética clínica, especificamente: requerimento de autorização para interrupção de gestação de feto anencéfalo, liberdade de recusa à imposição de procedimento de transfusão de sangue em razão de crença religiosa em paciente Testemunha de Jeová e a mudança de nome e sexo de transexual com ou sem realização de cirurgia de transgenitalismo. A escolha dos três tipos de casos levados a julgamento ao Poder Judiciário se deu em virtude de serem questões características ao direito existencial, de repercussão no Ser do indivíduo, em seus direitos personalíssimos. Para isso foram analisadas 84 decisões judiciais, mediante a aplicação da teoria Principiológica de Beauchamp & Childress e análise de cada decisão quanto à aplicação dos quatro Princípios que desenvolve: do respeito à autonomia, da não maleficência, da beneficência e da justiça. O resultado da análise demonstrou que ao utilizar os quatro Princípios, com especificação e ponderação dos mesmos, o julgador profere decisões de cunho liberal. Quando não utiliza os Princípios ou extrapola os limites de sua aplicação, o julgador profere decisões de cunho conservador. As decisões judiciais de caráter liberal são despidas de preconceitos e moralismos e permitem o respeito aos direitos individuais sem descuidar dos direitos dos demais membros da sociedade. As decisões conservadoras se baseiam na literalidade da lei e violam direitos individuais, sem acrescentar segurança à sociedade. A apropriação desta teoria da ética biomédica pelo biodireito, se apresenta como método seguro e eficaz na prolação de decisão judicial em casos da bioética clínica e conduz o julgador a decisões mais justas por serem apoiadas em boas razões.

The bipolar doping of ZnS via native defects and external dopants

By employing first-principle total-energy calculations, a systematic study of the dopability of ZnS to be both n- and p-types compared with that of ZnO is carried out. We find that all the attempted acceptor dopants, group V substituting on the S lattice site and group I and IB on the Zn sites in ZnS, have lower ionization energies than the corresponding ones in ZnO. This can be accounted for by the fact that ZnS has relative higher valence band maximum than ZnO. Native ZnS is weak p-type under S-rich condition, as the abundant acceptor V-Zn has rather large ionization energy. Self-compensations by the formation of interstitial donors in group I and IB-doped p-type ZnS can be avoided when sample is prepared under S-rich condition. In terms of ionization energies, Li-Zn and N-S are the preferred acceptors in ZnS. Native n- type doping of ZnS is limited by the spontaneous formation of intrinsic V-Zn(2-); high efficient n-type doping with dopants is harder to achieve than in ZnO because of the readiness of forming native compensating centers and higher ionization energy of donors in ZnS. (C) 2009 American Institute of Physics. [DOI 10.1063/1.3103585]

Aluminium doping induced enhancement of p-d coupling in ZnO

Valence-band type Auger lines in Al doped and undoped ZnO were comparatively studied with the corresponding core level x-ray photoelectron spectrography (XPS) spectra as references. Then the shift trend of energy levels in the valence band was that p and p-s-d states move upwards but e and p-d states downwards with increasing Al concentration. The decreased energy of the Zn 3d state is larger than the increased energy of the 0 2p state, indicating the lowering of total energy. This may indicate that Al doping could induce the enhancement of p-d coupling in ZnO, which originates from stronger Al-O hybridization. The shifts of these states and the mechanism were confirmed by valence band XPS spectra and 0 K-edge x-ray absorption spectrography (XAS) spectra. Finally, some previously reported phenomena are explained based on the Al doping induced enhancement of p-d coupling.

Quantum confinement effect in thin quantum wires

The electronic states and optical transition properties of three semiconductor wires Si? GaAs, and ZnSe are studied by the empirical pseudopotential homojunction model. The energy levels, wave functions, optical transition matrix elements, and lifetimes are obtained for wires of square cross section with width from 2 to 5 (root 2a/2), where a is the lattice constant. It is found that these three kinds of wires have different quantum confinement properties. For Si wires, the energy gap is pseudodirect, and the wave function of the electronic ground state consists mainly of four bulk Delta states. The optical transition matrix elements are much smaller than that of a direct transition, and increase with decreasing wire width. Where the width of wire is 7.7 Angstrom, the Si wire changes from an indirect energy gap to a direct energy gap due to mixing of the bulk Gamma(15) state. For GaAs wires. the energy gap is also pseudodirect in the width range considered, but the optical transition matrix elements are larger than those of Si wires by two orders of magnitude for the same width. However, there is no transfer to a direct energy gap as the wire width decreases. For ZnSe wires, the energy gap is always direct, and the optical transition matrix elements are comparable to those of the direct energy gap bulk semiconductors. They decrease with decreasing wire width due to mixing of the bulk Gamma(1) state with other states. All quantum confinement properties are discussed and explained by our theoretical model and the semiconductor energy band structures derived. The calculated lifetimes of the Si wire, and the positions of photoluminescence peaks, are in good agreement with experimental results.

Tunable photoluminescent and cathodoluminescent properties of ZnO and ZnO : Zn phosphors

ZnO and ZnO: Zn powder phosphors were prepared by the polyol-method followed by annealing in air and reducing gas, respectively. The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), X-ray photoelectron spectra (XPS), electron paramagnetic resonance (EPR), and photoluminescence (PL) and cathodoluminescence ( CL) spectra, respectively. The results indicate that all samples are in agreement with the hexagonal structure of the ZnO phase and the particle sizes are in the range of 1-2 mu m. The PL and CL spectra of ZnO powders annealed at 950 degrees C in air consist of a weak ultraviolet emission band ( similar to 390 nm) and a broad emission band centered at about 527 nm, exhibiting yellow emission color to the naked eyes. When the sample was reduced at the temperatures from 500 to 1050 degrees C, the yellow emission decreased gradually and disappeared completely at 800 degrees C, whereas the ultraviolet emission band became the strongest. Above this temperature, the green emission ( similar to 500 nm) appeared and increased with increasing of reducing temperatures.