X-ray-diffraction study of crystalline Si nanocluster formation in annealed silicon-rich silicon oxides

The formation and subsequent growth of crystalline silicon nanoclusters (Si-ncs) in annealed silicon-rich silicon oxides (SRSOs) were studied by glancing angle x-ray diffraction. SRSO samples with Si concentrations (y) of 0.40, 0.42, and 0.45 were grown by inductively coupled plasma-enhanced chemical-vapor deposition (PECVD). Samples with y=0.42 grown by electron-cyclotron-resonance PECVD were also studied. Annealing treatments were performed at temperatures (T) of 900, 1000, and 1100 °C for times (t) between 0.5 and 3 h in flowing Ar. As-grown SRSO films did not present signs of Si clusters (amorphous or crystalline); however, (111), (220), and (311) Bragg peaks corresponding to c-Si were clearly seen after annealing at 900 °C for the y=0.45 sample, but only barely seen for the y=0.42 and undetected for the y=0.40 samples. For T=1000°C, all studied SRSO samples clearly showed the c-Si diffraction peaks, which became narrower with increasing t and T. From the width of the Si (111) peaks, the mean size of Si-ncs and their dependence on T and t was determined. Activation energies were deduced from the T dependence by fitting the results to two growth models of Si precipitates in an a-SiO2 matrix reported in the literature. The activation energies qualitatively agree with values deduced from transmission electron microscopy studies of annealed SRSO reported in the literature. However, they are significantly lower than Si diffusion activation energies available in the literature for SiO2 with low excess Si. A broad feature is also observed in the x-ray diffractograms for as-grown samples with low y, which shifts to the peak position corresponding to a-SiO2 with increasing T. This behavior is explained by the formation of a well-defined a-SiO2 phase with increasing T, where mixed Si–O4−nSin (n=1,2,3) tetrahedra in the as-grown alloy are gradually converted into Si–O4 and Si–Si4 as phase separation of Si and SiO2 proceeds. From the measured Si (111) peak positions, small Si-ncs are found to be tensilely strained by as much as ∼0.8%. This effect becomes insignificant as Si-ncs become larger with increasing y or T.