[30] for Si nanoparticles synthesized by pulsed laser ablation, where the determined crystallization temperatures were in the
range of 800 to 1,300 K (depending on the nanoparticle AZD3965 size). These temperatures are far below the melting point of bulk Si (1,683 K). In our case, the annealing temperature of 1,373 K is also well below the melting point of bulk Si and only slightly below the melting point of a-Si (1,420 K for relaxed a-Si [31]). However, it is well known that the melting temperature of a nanoparticle decreases significantly with size, as a consequence of the additional free energy contribution of the surface to the overall Gibbs free energy [32]. For example, it has been shown that free-standing Si nanoparticles with a size of 20 nm melt at around 1,000 K [32]. On the other hand, nanoparticles embedded in a matrix can exhibit both melting-point depression and enhancement [33], and the actual melting behavior depends on the nature of the interface between the nanoparticle and the matrix. It has been found that when the interface between the nanoparticle and the matrix is coherent, the thermal vibration of the surface (interface) atoms selleck screening library of the nanoparticle is suppressed. This suppression may prevent the melting of the nanocrystals’
surface and lead to an increase of the melting temperature. This kind of behavior has been found for lead nanocrystals in an aluminum matrix and was attributed to the lattice structures of the two crystals ‘locking up’, suppressing the vibration of the nanoparticles’ surface atoms [34]. Contrary to this, irregularly shaped and FDA-approved Drug Library incoherent interfaces can be directly correlated with lowering of melting temperature of a nanoparticle [35]. In the investigated case, we expect
that directly after deposition we deal with amorphous pentoxifylline Si nanoparticles embedded in a disordered oxide matrix. Moreover, it is improbable that the sputtering technique allows deposit of coherent (epitaxial) interfaces between the amorphous nanoparticles and the matrix. Due to a large density gradient of the Si nanoparticles and the oxide host, when merged at their interface, the network topologies in either side deform in order to accommodate the transition [36]. Therefore, we expect the interfaces between Si nanoparticles and the matrix to be incoherent. This can be further supported by the latest findings of molecular dynamics simulations which have shown that the interface structure between Si-NCs and the matrix is generally highly porous on the silica side, making the contact with the Si-NCs discontinuous [37]. Taking this into account, we expect that the melting temperature of small, amorphous Si nanoparticles embedded in SRSO matrix might be depressed below the melting point of a-Si. If this is the case, melting of the nanoparticles may be possible at 1,100°C. Having this in mind, we suggest the following origin of the compressive stress observed in our experiment.