The structural ordering of thin silicon films at the amorphous to nano-crystalline phase transition by GISAXS and Raman spectroscopy

Thin silicon films were deposited by the plasma-enhanced chemical vapour deposition method using microwave (MW) and standard radio frequency (RF) gas discharge in silane gas diluted by hydrogen in the range that produces a mixture of amorphous and crystalline phases. The samples were analysed by Raman spectroscopy and grazing incidence small-angle X-ray scattering (GISAXS), while the threshold for the transition between the amorphous and crystalline phase was checked by the change in electrical conductivity. The crystalline fraction, estimated by Raman spectroscopy, varied between 0% and 70% while the individual crystal sizes were between 3 and 9 nm. However, the size distribution was broad suggesting also the existence of smaller and larger crystals.The “particles” observed by GISAXS, most probably voids, were in the range between 2 and 12 nm. The voids in samples deposited by MW plasma were larger when closer to the surface. Their shape indicated the formation of a columnar structure perpendicular to the surface, more pronounced at higher temperature. The samples deposited by RF plasma and low power had spherically symmetric “particles” with uniform size across the depth of the samples. An increase of the RF power resulted in the formation of a columnar structure parallel to the surface. The observed differences are discussed in relation to the difference in growing kinetics of the used deposition methods.