Defect and Diffusion Forum Vols. 237-240

Abstract: Diffusion of 6Li in the refractory metals Ta and W has been studied using the nondestructive neutron depth profiling technique. The preliminary results point out the complex behavior of 6Li atoms in W and Ta. The experiment showed that the Fickian diffusion is affected by the presence of traps and radiation defects in the sample surface layer. Further experiments and computer simulations of the diffusion process are in progress.

Abstract: Ag and Cu diffused into CdTe exhibit unusual shapes of their concentration profiles, especially if the diffusion was performed under Cd vapor pressure. The shapes of the concentration profiles at low concentrations of Ag or Cu are well described by a model based on the interaction with intrinsic defects. In that model the characteristic features of the profiles can be independently reproduced by appropriate parameters. It turns out that the resulting profiles are determined by the diffusion of interstitial Cd atoms and reflect the actual distribution of the intrinsic defects in the crystal, i.e. the deviation from stoichiometry.

Abstract: Diffusion of 64Cu, 59Fe, and 63Ni radiotracers has been measured in Cu–Fe–Ni alloys of different compositions at 1271 K. The measured penetration profiles reveal grain boundary-induced part along with the volume diffusion one. Correction on grain boundary diffusion was taken into account when determining the volume diffusivities of the components. When the Cu content in the alloys increases, the diffusivities increase by order of magnitude. This behaviour correlates well with decreasing of the melting temperature of corresponding alloys, as the Cu content increases. Modelling of interdiffusion in the Cu–Fe–Ni system based on Danielewski-Holly model of interdiffusion is presented. In this model (extended Darken method for multi-component systems) a postulate that the total mass flow is a sum of the diffusion and the drift flows was applied for the description of interdiffusion in the closed system. Nernst-Planck’s flux formula assuming a chemical potential gradient as a driving force for the mass transport was used for computing the diffusion flux in non-ideal multi-component systems. In computations of the diffusion profiles the measured tracer diffusion coefficients of Cu, Fe and Ni as well as the literature data on thermodynamic activities for the Cu–Fe–Ni system were used. The calculated interdiffusion concentration profiles (diffusion paths) reveal satisfactory agreement with the experimental results.

Abstract: Thermodynamic model is developed of which it follows that saturation value of solute segregated in grain boundary, provided all available sites occupied, must be close to the solute concentration, in the nearest in composition phase in grain as it follows from phase diagram. Based on the analysis of experimental data for three binary systems (Cu –Sb, Fe – P and Fe – Sn) it is shown that the surplus concentration of the solute atoms in GB as compared with a concentration in grain is distributed equally between two fracture surfaces but takes up more than one atomic layer. The thickness of the segregation region (with surplus concentration in grain boundary) averages usually from 3 to 6 interatomic distances. As a rule, solute distribution is symmetrical on each side of the fracture surface. It is shown that maximum of grain boundary concentration falls on the first layer on the fracture surface. The method is developed of the calculation of the first layer concentration. It is shown that this concentration is close to the solute concentration in the nearest in composition phase in grain.

Abstract: The self-diffusion of nitrogen is investigated in polycrystalline thin silicon nitride films using a gas-exchange method (14N2/Si3 15N4) in comparison to Si3 14N4/Si3 15N4/Si3 14N4 isotope heterostructures. The films are produced by reactive r. f. magnetron sputtering. Depth profile analysis is carried out with secondary ion mass spectrometry (SIMS), secondary neutral mass spectrometry (SNMS), and nuclear resonant reaction analysis (NRRA). The nitrogen diffusivities determined with the use of isotope heterostructures follow an Arrhenius law in the temperature range between 1200 and 1700 °C with an activation enthalpy of DH = 4.9 eV and a pre-exponential factor of D0 = 1 x 10-6 m2/s, indicating a conventional diffusion mechanism via localized point defects. Using the gas-exchange method, the nitrogen diffusivities could be obtained only in the temperature range between 1600 and 1700 °C. This is due to the fact that at temperatures below 1600 °C the surface exchange process with its high activation enthalpy (about 10 eV) is rate limiting, leading to non detectable diffusion profiles. The application of the different methods of depth profiling leads to the same diffusivities within estimated errors.

Abstract: Thin metal films react with silicon substrates to form various metal silicides. The sequence and kinetics of phase formation are still an area of intense research. Comparatively much less work has been done on the issue of stress development caused by the appearance of these new phases. A detailed review of the subject has been done ten years ago. We present here recent results obtained on Pd-Si, Co-Si, Ni-Si and discuss them in the light of what is known today on the elastic and plastic properties of thin films. A simple model published by S. - L. Zhang and F. M. d’Heurle takes into account the simultaneous stress formation due to the reaction and the relaxation of these stresses. It provides a qualitatively satisfying picture of stress evolution at least for the first phase which forms. The model relies on two basic elements: 1) stress formation due to the formation of a new phase, and 2) the stress relaxation mechanism at work in the growing silicide film. The sign of the stress can be understood from the variation in volume that occurs at the growing interface(s). The stress relaxation mechanisms at work in a growing film are complex. They are highly dependent on the microstructure (as we have shown when comparing Pd/Si(001) and Pd/Si (111)) but should be also highly size dependent (e.g. dislocation glide is more difficult in small scale structures). Inhomogeneous plastic relaxation in polycrystalline silicide films may be an important issue.

Abstract: We considered the flattening of perturbed surface of a thin stress-free polycrystalline film with columnar microstructure deposited on rigid substrate. We show that the mass transport along the film/substrate interface and along the grain boundaries significantly contributes to the overall rate of surface flattening of the film. The diffusion along the film/substrate interface and along the grain boundaries is driven by the capillary stresses in the film. Using the approximation of small surface slopes, we calculated the distribution of capillary stresses in the film, and derived an explicit expression for the temporal behavior of the film topography. The initial distribution of the capillary stresses rapidly relaxes to the steady-state one that does not allow the accumulation of bending strain in the film. For the films with passivated or contaminated surfaces exhibiting reduced surface diffusivity the interfacial and grain boundary diffusion play a leading role in kinetics of surface flattening. The flattening process can be accelerated in this case by several orders of magnitude. The results of our work can be helpful in design of thin films and coatings with enhanced selfhealing capabilities.