DOE OSTI2010
We report on the first observation of the macroscopic (long-range) Si-SiO{sub 2} phase separation in Si-rich oxide SiO{sub x}(x<2) obtained by continuous-wave laser annealing of free-standing SiO{sub x} films. The effect is analyzed by a unique combination of microscopic methods (Raman, transmission, photoluminescence, and infrared spectroscopy, transmission electron microscopy, electron energy loss spectroscopy, and x-ray photoelectron spectroscopy). Three regions can be distinguished on a SiO{sub x} free-standing film after 488 nm laser annealing at intensities above {approx}10{sup 4} W cm{sup -2}: central spot, ring around the central spot, and pristine film outside the irradiated area. In the pristine SiO{sub x} material, small Si nanocrystals (Si-nc) (diameters of a few nanometer) are surrounded by SiO{sub 2} with an addition of residual suboxides, the Si-nc being produced by annealing at 1100 deg. C in a furnace. The central spot of the laser-annealed area (up to {approx}30 {mu}m wide in these experiments) is practically free of Si excess and mainly consists of amorphous SiO{sub 2}. The ring around the central spot contains large spherical Si-nc (diameters up to {approx}100 nm) embedded in amorphous SiO{sub 2} without the presence of suboxides. Laser-induced temperatures in the structurally modified regions presumably exceed the Si melting temperature. The macroscopic Si-SiO{sub 2} phase separation is connected with extensive diffusion in temperature gradient leading to the Si concentration gradient. The present work demonstrates the advantages of high spatial resolution for analysis in materials research.