Transparent proton transport through a two-dimensional nanomesh material.

Molecular sieving is of great importance to proton exchange in fuel cells, water desalination, and gas separation. Two-dimensional crystals emerge as superior materials showing desirable molecular permeability and selectivity. Here we demonstrate that a graphdiyne membrane, an experimentally fabricated member in the graphyne family, shows superior proton conductivity and perfect selectivity thanks to its intrinsic nanomesh structure. The trans-membrane hydrogen bonds across graphdiyne serve as ideal channels for proton transport in Grotthuss mechanism. The free energy barrier for proton transfer across graphdiyne is ~2.4 kJ mol-1, nearly identical to that in bulk water (2.1 kJ mol-1), enabling "transparent" proton transport at room temperature. This results in a proton conductivity of 0.6 S cm-1 for graphdiyne, four orders of magnitude greater than graphene. Considering its ultimate pore size of 0.55 nm, graphdiyne membrane blocks soluble fuel molecules and exhibits superior proton selectivity. These advantages endow graphdiyne a great potential as proton exchange material.

Microscopic origin for the orientation dependence of NV centers in chemical-vapor-deposited diamond.

First-principles calculation reveals that hydrogen, which is abundant in chemical vapor deposition (CVD), can significantly improve the uniformity of nitrogen-vacancy (NV) centers in diamond. It shows that the formation of NV centers can be described as a multi-step process: first, a substitutional N (NC) is preferentially formed at the surface layer over that of either a carbon vacancy (VC) or an in-pane nitrogen-vacancy-hydrogen (NVH) complex. Second, with the help of H, a VC is preferentially incorporated in the newly formed topmost layer as a nearest neighbor to the NC (now buried in the first sublayer). This NVH complex is even more stable than NC on the same layer. Third, H protects the already formed NV centers by forming low-energy NVHX complexes. These NV centers with their axes pointing along the directions of surface C-H bonds during their incorporation explain the experimental observations by CVD growth on (1 0 0) and (1 1 0) surfaces. Based on the model, we predict that CVD growth on (1 1 1) surface could eliminate the orientation domains to significantly improve the performance of NV centers.

Quantized water transport: ideal desalination through graphyne-4 membrane.

Graphyne sheet exhibits promising potential for nanoscale desalination to achieve both high water permeability and salt rejection rate. Extensive molecular dynamics simulations on pore-size effects suggest that γ-graphyne-4, with 4 acetylene bonds between two adjacent phenyl rings, has the best performance with 100% salt rejection and an unprecedented water permeability, to our knowledge, of ~13 L/cm(2)/day/MPa, 3 orders of magnitude higher than prevailing commercial membranes based on reverse osmosis, and ~10 times higher than the state-of-the-art nanoporous graphene. Strikingly, water permeability across graphyne exhibits unexpected nonlinear dependence on the pore size. This counter-intuitive behavior is attributed to the quantized nature of water flow at the nanoscale, which has wide implications in controlling nanoscale water transport and designing highly effective membranes.

Dimerization of boron dopant in diamond (100) epitaxy induced by strong pair correlation on the surface.

Experiments have shown that boron incorporation in diamond epitaxies is orientation dependent. Our first-principles calculations reveal that at a (100) surface, the formation of the boron dimer is more favored than that of the monomer, indicating a high density of ineffective boron formed under heavy doping. The reconstructed surface layer of carbon dimers in which the electrons are strongly pair correlated provides the mechanism. Hydrogen adsorption affects the correlation and thus the favorability of boron dimer formation, while at a (111) surface, the formation of boron monomer is more favored due to the less correlated surface electrons and hydrogen adsorption has no effect on the favorability.

Electronically nonalloyed state of a statistical single atomic layer semiconductor alloy.

Using atomically and momentum resolved scanning tunneling microscopy and spectroscopy, we demonstrate that a two-dimensional (2D) √3 × âˆš3 semiconducting Ga-Si single atomic alloy layer exhibits an electronic structure with atomic localization and which is different at the Si and Ga atom sites. No indication of an interaction or an electronic intermixing and formation of a new alloy band structure is present, as if no alloying happened. The electronic localization is traced back to the lack of intra alloy bonds due to the 2D atomically confined structure of the alloy overlayer.

Acetone adsorption on ice investigated by X-ray spectroscopy and density functional theory.

Using a combination of X-ray photoemission and near-edge X-ray absorption spectroscopy (NEXAFS) as well as density-functional theory (DFT), we have investigated the adsorption of acetone on ice in the temperature range from 218 to 245 K. The adsorption enthalpy determined from experiment (45 kJ mol(-1)) agrees well with the adsorption energy predicted by theory (41 to 44 kJ mol(-1)). Oxygen K-edge NEXAFS spectra indicate that the presence of acetone at the ice surface does not induce the formation of a pre-melted layer at temperatures up to 243 K. DFT calculations show that the energetically most favored adsorption geometry for acetone on ice is with the molecular plane almost parallel to the surface.

Large variation of vacancy formation energies in the surface of crystalline ice.

Resolving the atomic structure of the surface of ice particles within clouds, over the temperature range encountered in the atmosphere and relevant to understanding heterogeneous catalysis on ice, remains an experimental challenge. By using first-principles calculations, we show that the surface of crystalline ice exhibits a remarkable variance in vacancy formation energies, akin to an amorphous material. We find vacancy formation energies as low as ~0.1-0.2 eV, which leads to a higher than expected vacancy concentration. Because a vacancy's reactivity correlates with its formation energy, ice particles may be more reactive than previously thought. We also show that vacancies significantly reduce the formation energy of neighbouring vacancies, thus facilitating pitting and contributing to pre-melting and quasi-liquid layer formation. These surface properties arise from proton disorder and the relaxation of geometric constraints, which suggests that other frustrated materials may possess unusual surface characteristics.

Two-bit ferroelectric field-effect transistor memories assembled on individual nanotubes.

Carbon nanotube (CNT) ferroelectric field-effect transistors (FeFETs) with well-defined memory switch behaviors are promising for nonvolatile, nondestructive read-out (NDRO) memory operation and ultralow power consumption. Here, we report two-bit CNT-FeFET memories by assembling two top gates on individual nanotubes coated with ferroelectric thin films. Each bit of the nanotube transistor memory exhibits a controllable memory switching behavior induced by the reversible remnant polarization of the ferroelectric films, and its NDRO operation is demonstrated. The low driving voltage of 2 V, high carrier mobility over 1000 cm2 V(-1) s(-1), and potential ultrahigh integration density over 200 Gbit inch(-2) of the two-bit FeFET memory are highlighted in this paper.

On thin ice: surface order and disorder during pre-melting.

The effect of temperature on the structure of the ice Ih (0001) surface is considered through a series of molecular dynamics simulations on an ice slab. At relatively low temperatures (200 K) a small fraction of surface self-interstitials (i.e. admolecules) appear that are formed exclusively from molecules leaving the outermost bilayer. At higher temperatures (ca. 250 K), vacancies start to appear in the inner part of the outermost bilayer exposing the underlying bilayer and providing sites with a high concentration of dangling hydrogen bonds. Around 250-260 K aggregates of molecules formed on top of the outermost bilayer from self-interstitials become more mobile and have diffusivities approaching that of liquid water. At approximately 270-280 K the inner bilayer of one surface noticeably destructures and it appears that at above 285 K both surfaces are melting. The observed disparity in the onset of melting between the two sides of the slab is rationalised by considering the relationship between surface energy and the spatial distribution of protons at the surface; thermodynamic stability is conferred on the surface by maximising separations between dangling protons at the crystal exterior. Local hotspots associated with a high dangling proton density are suggested to be susceptible to pre-melting and may be more efficient at trapping species at the external surface than regions with low concentrations of protons thus potentially helping ice particles to catalyse reactions. A preliminary conclusion of this work is that only about 10-20 K below the melting temperature of the particular water potential employed is major disruption of the crystalline lattice noted which could be interpreted as being "liquid", the thickness of this film being about a nanometre.

Field emission of GaN-filled carbon nanotubes: high and stable emission current.

Field electron emission of GaN-filled carbon nanotubes, grown by microwave plasma enhanced chemical vapor deposition, was investigated. The detailed structural characterization shows that the filled nanotube has a GaN-core/C-shell structure, in which the GaN wire corresponds to a wurtzite structure. The field emission properties of the GaN-filled carbon nanotubes have been achieved with high and stable emission current. It is attributed to the unique cable-like structure, which makes the GaN-core/C-shell composite mechanically solid and chemically stable. This study suggests the GaN-filled carbon nanotube as an ideal candidate for future high-current and high-power field emitter applications.

Generalized electron counting in determination of metal-induced reconstruction of compound semiconductor surfaces.

Based on theoretical analysis, first-principles calculations, and experimental observations, we establish a generic guiding principle, embodied in generalized electron counting (GEC), that governs the surface reconstruction of compound semiconductors induced by different metal adsorbates. Within the GEC model, the adsorbates serve as an electron bath, donating or accepting the right number of electrons as the host surface chooses a specific reconstruction that obeys the classic electron-counting model. The predictive power of the GEC model is illustrated for a wide range of metal adsorbates.

Two-stage rotation mechanism for group-V precursor dissociation on Si(001).

We report ab initio identification of initial dissociation pathways for Sb4 and Bi4 tetramer precursors on Si(001). We reveal a two-stage double piecewise rotation mechanism for the tetramer to ad-dimer conversion involving two distinct pathways: one along the surface dimer row via a rhombus intermediate state and the other across the surface dimer row via a rotated rhombus intermediate state. These two-stage double piecewise rotation processes play a key role in lowering the kinetic barrier by establishing and maintaining energetically favorable bonding between adatoms and substrate atoms. These results provide an excellent account for experimental observations and elucidate their underlying atomistic origin that may offer useful insights for other surface reaction processes.

Direct synthesis of B-C-N single-walled nanotubes by bias-assisted hot filament chemical vapor deposition.

Direct synthesis of large-scale ternary boron carbonitride single-walled nanotubes (BCN-SWNTs) via a bias-assisted HFCVD process was presented. The BCN-SWNTs were grown over the powdery Fe-Mo/MgO catalyst by using CH4, B2H6, and ethylenediamine vapor as the reactant gases. As high as 16 atom % nitrogen can be incorporated within the nanotube shells, with the boron content in the range of 2-4 atom %. The ternary covalent bonding nature of the BCN-SWNTs was well characterized, and the B, C, and N elemental maps were clearly imaged by energy-filtered transmission electron microscopy.

Dissolution dynamics of NaCl nanocrystal in liquid water.

The dissolution dynamics of a NaCl nanocrystal in liquid water was studied using molecular dynamics simulations. The dissolution process was found to start with a Cl(-) ion at a corner site, followed by a Na(+) ion nearby. Both show directional preference in the dissolution path. An ion sequence with alternating charge, i.e., Cl(-), Na(+), Cl(-), Na(+), etc. was found to dominate the dissolution process. This image can be understood from the ionic hydration structures and the Coulomb interaction between the ions.

Dynamic ad-dimer twisting assisted nanowire self-assembly on Si(001).

Based on ab initio total energy calculation, we show that a dynamic ad-dimer twisting assisted (DATA) process plays a crucial role in facilitating a novel structural reconstruction involving surface and subsurface atoms on Si(001). It leads to self-assembly of long nanowires of group-V elements (Bi, Sb) in the trenches of surface dimer vacancy lines (DVLs) with a characteristic double-dimer configuration. The key to this is the lowering of the kinetic barrier by the DATA process in conjunction with a favorable interaction between ad-dimers and step edges in DVLs. The present results provide an excellent account for experimental observations and reveal the atomistic origin and the dynamic transformation path for nanowire self-assembly on Si(001).

Initial stages of Ti growth on diamond (100) surfaces: from single adatom diffusion to quantum wire formation.

Using first-principles total energy calculations within density functional theory, we investigate the energetics, kinetics, and transport properties of Ti on clean and hydrogen-terminated diamond (100)-2x1 surfaces at increasing Ti coverages. On a clean surface, an isolated Ti adatom prefers to adsorb on top of a C-C dimer row, and also diffuses faster along the dimer row direction. As the Ti coverage increases, the preferred adsorption site converts from an atop site to a site located between the dimer rows. Passivation of the surface at the monohydride coverage not only greatly enhances the Ti mobility, but also weakens the diffusion isotropy. Based on these energetic and kinetic characteristics, we propose a viable approach to fabricate ideal Ti quantum wires on hydrogen-terminated diamond substrates.

Ultrathin chromium oxide films on the W(100) surface.

Ultrathin chromium oxide films were prepared on a W(100) surface under ultrahigh-vacuum conditions and investigated in situ by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and low-energy electron diffraction. The results show that, at Cr coverage of less than 1 monolayer, CrO2 is formed by oxidizing pre-deposited Cr at 300-320 K in approximately 10(-7) mbar oxygen. However, an increase of temperature causes formation of Cr2O3. At Cr coverage above 1 monolayer, only Cr2O3 is detected.

Synthesis and oxidation of CeN film: an in situ investigation by electron spectroscopies.

Nearly stoichiometric CeN film is synthesized on a Re(0001) substrate in an ultrahigh vacuum system involving highly active N atoms in the growth process, generated by thermal decomposition of NH3 by use of a hot tungsten filament. The electronic structure of the CeN film as prepared is equivalent to that of a single crystal observed by in situ Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). AES and XPS investigations show that CeN film is directly oxidized to CeO2 after exposure to O2 at room temperature. However, CeN changes into Ce2O3 after annealing in approximately 10(-6) mbar of O2 atmosphere at elevated temperature.

Superconductivity modulated by quantum size effects.

We have fabricated ultrathin lead films on silicon substrates with atomic-scale control of the thickness over a macroscopic area. We observed oscillatory behavior of the superconducting transition temperature when the film thickness was increased by one atomic layer at a time. This oscillating behavior was shown to be a manifestation of the Fabry-Perot interference modes of electron de Broglie waves (quantum well states) in the films, which modulate the electron density of states near the Fermi level and the electron-phonon coupling, which are the two factors that control superconductivity transitions. This result suggests the possibility of modifying superconductivity and other physical properties of a thin film by exploiting well-controlled and thickness-dependent quantum size effects.

Contrasting growth modes of Mn on Ge(100) and Ge(111) surfaces: subsurface segregation versus intermixing.

Based on first-principles total energy calculations within density functional theory, we show that a low dose of Mn on Ge(100) initiates in a novel subsurface growth mode, characterized by easy access to, and strong preference for, interstitial sites located between the two topmost Ge layers. Strikingly, such a "subsurfactant action" is preserved even during epitaxial growth of additional Ge layers, analogous to the well-known phenomenon of surfactant action. In contrast, along the [111] orientation, Mn can easily diffuse into the bulk via interstitial sites. These results are discussed within the context of dopant control in dilute magnetic semiconductors.