Defect and Diffusion Forum Vols. 289-292

Abstract: The formation of hollow metal oxide nanoparticles through oxidation process has been studied by transmission electron microscopy for Cu, Zn, Al, Pb and Ni in order to clarify the detailed formation mechanism of hollow oxide nanoparticles and their governing factors. For Cu, Zn, Al and Ni nanoparticles, hollow oxide nanoparticles are obtained as a result of vacancy aggregation in the oxidation processes. These results arise from faster outward diffusion of metal ions through the oxide layer in the oxidation processes. On the other hand, Pb nanoparticles turn to solid PbO, because the diffusivity difference DPb < DO in PbO leads to no formation of vacancy clusters.

Abstract: By molecular dynamics simulation it is shown that interdiffusion in the initial f.c.c. Ag-core ( 28 at. %) – Ni-shell ( 72 at. %) and Ni-core ( 34 at. %) – Pd-shell ( 66 at. %) nanoparticles can lead to surface–sandwich segregation. It is observed that there is a separation of the initial Ag-Ni core-shell structure into Ag-core – Ni-intermediate shell – Ag-disperse surface monolayer. The initial crystal Ni-Pd core-shell structure transforms to the core of a non-crystalline Pd-rich solid solution with quite strongly developed icosahedral short-range order, which is covered by a surface–sandwich shell, where Ni atoms are located in the centres of interpenetrating icosahedra of a subsurface Kagomé net layer while the Pd atoms occupy the vertices of the icosahedra and cover this Ni layer from inside and outside. We demonstrate that under certain conditions a surface–sandwich segregation phenomenon at the nanoscale can be observed in systems with completely different phase diagrams in the bulk states: in systems displaying the extremely low mutual solubility as in the Ag-Ni system, or in systems exhibiting a continuous mutual solid solubility like the Pd-Ni system.

Abstract: In this paper, a hollow random binary alloy nanosphere and initially homogeneous is considered under the approximation that the radial dependence of the vacancy formation free energy can be neglected. On the basis of a theoretical description and kinetic Monte Carlo simulations it is shown that the steady-state condition for the atomic components is not achievable during its shrinkage at any composition when the ratio of the tracer diffusion coefficients is not greater than two orders of magnitude. In the theoretical description, the dependence of the collapse time of the hollow random binary alloy nanosphere on the atomic fraction of the faster diffusing species at can be estimated by using the geometric mean of the ratios of the atomic fluxes at self-diffusion and steady-state. At the ratio of the atomic fluxes approaches the self-diffusion ratio as increases.

Abstract: The structural stability of hollow Cu2O and NiO nanoparticles, which were obtained via oxidation of Cu and Ni nanoparticles in air, was studied by transmission electron microscopy (TEM). Hollow Cu2O and NiO were observed to have shrunk at 473 and 623 K in annealing under 5.0×10-5 Pa, respectively, where the reduction reactions from oxides to metals started. As a result of shrinking associated with reduction, hollow oxides turned into solid metal nanoparticles after annealing at higher temperatures for a long time. In addition, hollow oxides shrunk and collapsed through high-temperature oxidation. It was found that shrinking of hollow oxides during oxidation occurs at temperature where the diffusion coefficients of slower diffusing species reach around 10-22 m2s-1. It seems that the hollow oxide nanoparticles tend to shrink and collapse at high temperatures because the hollow structures are energetically unstable.

Abstract: An annotated analytical essay of possible nanofabrication and nanotechnology applications is presented with respect to: (1) some techniques and original results [1-4] concerning the regularities and micromechanisms (physics) of the hydrogen fluoride gas activator influence on the diffusion-controlled oxidation processes of titanium, zirconium and zirconium-based alloys with niobium, and also – on nitriding, boriding and carbiding a series of refractory metals (Ti, Zr, Nb, Mo, W, Ta); (2) some techniques, original results and physics of the diffusion-controlled formation processes of the compound-like nanosegregation [5-13] and the results [13-23] on the liquid-like phase at grain boundary regions in metals and alloys. In the scope of this review, a constructive analysis, the Arrhenius-type treatment, and the original data interpretation [16-21] has been carried out for the first time; (3) some techniques, original analytical results, and physics [24, 25] of the diffusion-controlled processes of the hydrogen multilayer intercalation (physisorption of a condensation or clustering type) with carbonaceous nanostructures. The main objective of the given analytical essay is to attract the researchers’ attention to the expediency of such a non-conventional data analysis and interpretation.

Abstract: We report experiments on the diffusion of n-type dopants in isotopically controlled Ge multilayer structures doped with carbon. The diffusion profiles reveal a strong aggregation of the dopants within the carbon-doped layers and a retarded penetration depth compared to dopant diffusion in high purity natural Ge. Dopant aggregation and diffusion retardation is strongest for Sb and similar for P and As. Successful modeling of the simultaneous self- and dopant diffusion is performed on the basis of the vacancy mechanism and additional reactions that take into account the formation of carbon-vacancy-dopant and dopant-vacancy complexes. The stability of these complexes is confirmed by density functional theory calculations. The overall consistency between experimental and theoretical results supports the stabilization of donor-vacancy complexes in Ge by the presence of carbon and the dopant deactivation via the formation of dopant-vacancy complexes. These results help to develop concepts to suppress the enhanced diffusion of n-type dopants and the donor deactivation in Ge. Both issues hamper the formation of ultra shallow donor profiles with high active dopant concentrations that are required for the fabrication of Ge-based n-type metal oxide semiconductor field effect transistors.

Abstract: Studies of self-diffusion in solids are presented, which are based on neutron reflectometry. For the application of this technique the samples under investigation are prepared in form of isotope heterostructures. These are nanometer sized thin films, which are chemically completely homogenous, but isotope modulated. Using this method, diffusion lengths in the order of 1 nm and below can be detected which allows to determine ultra low diffusivities in the order of 10-25 m2/s. For the model system amorphous silicon nitride we demonstrate how the structure of the isotope hetrostructures (triple layers or multilayers) influences the efficiency of diffusivity determination.

Abstract: We make use of a novel X-ray radiography method to measure chemical diffusion in capillaries in binary Al-Ni melts. Data are compared to self diffusion coefficients of Ni obtained by quasielastic neutron scattering as well as diffusion and thermodynamic data obtained by molecular dynamic simulations. Interdiffusion compared to self diffusion is enhanced with a maximum at Al40Ni60. We show that this enhancement is caused by thermodynamic forces as described by the Darken-Manning equation. In liquid Al-Ni alloys the Manning factor that is smaller than one can be attributed to collective cross correlations.

Abstract: Thermodynamic and kinetic models are developed for grain boundary segregation and diffusion with regards to the possible complexes formation in grain boundary. The equilibrium state for ideal solutions can be described by the equilibrium constants b and K. The first corresponds to the pure segregation, i.e. the exchange A and B atoms between grain boundary and the bulk. The second represents the equilibrium of the reaction of the complexes formation in grain boundary. The segregation isotherm and diffusion profiles are calculated. It is shown that both b and K equilibrium constants define completely dependence of the total grain boundary concentration of B atoms on the bulk concentration and distribution of B atoms between two states: free (pure exchange) and tied (in the complexes). Segregation in both forms (free B atoms and tied B atoms) decreases grain boundary diffusivity in comparison with the absence of segregation.

Abstract: Diffusion-induced recrystallization (DIR) is investigated in Au/Cu and Ag/Pd thin-film interdiffusion couples. It is experimentally demonstrated that several generations of new grains are formed inside the diffusion zone by a cascade-like process. Each generation is distinguished by a characteristic composition level. In order to understand the observed composition levels quantitatively, a thermo-mechanic model has been derived, which determines the thermo-elastic driving force to the grain boundary. By the model, it is shown that those grains dominate the diffusion zone, which develop the maximum possible stress in front of the moving boundary.