Non Parabolic Shift of Interfaces and Effect of Diffusion Asymmetry on Nanoscale Solid State Reactions

In a set of recent papers we have shown that the diffusion asymmetry in diffusion couples (the diffusion coefficient is orders of magnitude larger in one of the parent materials) leads to interesting phenomena: i) sharp interface remains sharp and shifts with non Fickian (anomalous) kinetics [1-5], ii) originally diffuse interface sharpens even in ideal (completely miscible) systems [6,7], iii) an initially existing thin AB phase in A/AB/B diffusion couple can be dissolved [8], iv) there exists a crossover thickness (typically between few nanometers and 1m) above which the interface shift turns back to the Fickian behaviour [9], v) the growth rate of a product of solid state reaction can be linear even if there is no any extra potential barrier present (which is the classical interpretation of the “interface reaction control” for linear kinetics) [10]. These latter results will be summarized and reformulated according to the usual expression for linear-parabolic law containing the interdiffusion coefficient, D, and interface transfer coefficient, K. Relation between the activation energies of D and K will be analyzed and compared with available experimental data.

Silicide Formation Reactions in a-Si/Co Multilayered Samples

Solid state reactions between amorpous Si and crystalline Co have been investigated by synchrotron radiation at Bessy (Berlin, Germany). The multilayered samples (with 10 periods of a-Si(15 nm)/Co(15 nm) layers) were produced by magnetron sputtering and isothermally heat treated at temperatures between 523 and 593 K. From the time evolution of the XRD spectra first the growth rate of the CoSi phase as well as the decay rate of the Co layer we determined (at 523 and 543 K). The kinetics were described by a power law; tk, and for the growth of CoSi k=0.65 while for the loss of the Co the k=0.77 was obtained, respectively. At higher temperatures (at 573 and 593 K) the formation and growth of the Co2Si layer, at the expense of the Co and already existing CoSi layers, was observed with exponents of about 1 for all the above kinetics. These results, together with the results of resistance kinetics measurements, in similar multilayered as well as bi-layered samples at similar temperatures, providing similar exponents will be presented. Possibility of the interface reaction control and/or the effect of the diffusion asymmetry (which was recently published for the interpretation of solid state reactions with non-parabolic kinetics on the nanoscale) will be discussed.

Co Anomalous Growth Kinetics of the CoSi Reaction Layer in a Si/System

Solid state reactions between amorphous Si and crystalline Co have been investigated by 4W electrical resistance and TEM. Multilayered (with 10 periods of 5nm a-Si/5nm Co and 10 nma- Si/10nm Co layers) as well as tri-layered samples (20nm a-Si/3nmCoSi/6nm Co) were produced by magnetron sputtering and isothermally heat treated at different temperatures between 473 and 523K. From the time evolution of the normalized resistance the kinetics of the process were determined by fitting a power law, tk, and k was between 0.8 and 1. Possibility of the interface reaction control and/or the effect of the diffusion asymmetry (which was recently published for the non-parabolic interface shifts on the nanoscale) will be discussed.

Growth Kinetics on Nanoscale: Finite Diffusion Permeability of Interfaces

Growth kinetic is either diffusion or interface reaction controlled process, characterized by parabolic or linear relationships, respectively. The well known diffusion paradox, predicting infinitely fast diffusion kinetics at short times (distances) for diffusion control will be discussed and resolved, by showing that the diffusion permeability across the interface should be finite at the very beginning of the process. Thus one can arrive at an atomistic interpretation of the interface transfer coefficient, K, and at linear growth kinetics even if there is no extra potential barrier present at the interface, usually assumed in the interpretation of interface reaction control. It is also shown that this phenomenon is a typical nanoeffect: after a certain diffusion distance (lying between 0.01 and 300 nm, depending on the composition dependence of the diffusion coefficient) the finite permeability of the interface will not restrict the growth and normal diffusion control will be observed.