Silicon nanocluster crystallization in SiOx films studied by Raman scattering

Abstract

Precipitation and crystallization of Si nanocrystals have been monitored by means of Raman spectroscopy. SiOx films with different compositions have been deposited by low-pressure chemical-vapor deposition technique onto silica substrates and treated to temperatures exceeding 800 °C. The evolution of the Raman signal with the thermal budget reveals that the silicon transition from amorphous to crystalline state shifts to higher temperatures as the Si content in the layers is lowered. A rather complete crystallization of the nanoparticles is achieved after annealing at 1250 °C for a Si excess lower than 20%, while for higher excesses the crystalline fraction reaches only 40%, suggesting the formation of a crystalline core surrounded by an amorphous shell. The Raman spectra have been analyzed by a phonon confinement model that takes into account stress effects. An increasing nanocrystal size, from 2.5 to 3.4 nm, has been estimated when the Si excess varies from 16 to 29 at. %. For small Si nanocrystals a strong hydrostatic stress has been observed, induced by a very abrupt transition with the surrounding SiO2. Its magnitude correlates with the increase in thermal budget required for the crystallization of the amorphous clusters. This study underlines the fundamental role of hydrostatic stress in retarding the crystallization of Si nanoclusters.