High-performance ULSI devices require ultraclean silicon surfaces, the complete removal of native oxides, and atomic level flatness and stabilization of the cleaned surfaces against molecular contaminants. Dry cleaning techniques are an attractive alternative to conventional wet processing for future ULSI production using cluster chambers or multi-process cham-bers. Organic contaminants, including photoresist polymers, are effectively removed by photo-excited ozone cleaning. We have found photo-excited halogen radicals to be useful for removing trace metals and native oxides from silicon surfaces without damaging on silicon and silicon-dioxide surfaces. We success-fully terminated hydrogen on (100) silicon surfaces by annealing in pure hydrogen ambient. A dry cleaning system with these sequential processes will be useful in constructing fully-integrated mass-production lines of high-performance ULSI devices.

Hydrogen termination of HF-treated Si surfaces and the oxidation kinetics have been studied by x-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FT-IR) Attenuated Total Reflection (ATR). The oxidation of hydrogen-terminated Si in air or in pure water proceeds parallel to the surface presumably from step edges, resulting in the layer-by-layer oxidation. The oxide gryowth rate on an Si(100) surface is faster than (110) and (111) when the wafer is stored in pure water. This is interpreted in terms of the steric hindrance against molecular oxygen penetration throughth the (110) and (111) surfaces where the atom void size is equal to or smaller than O2 molecule. The oxide growth rate in pure water for heavily doped n-type Si is significantly high compared to that of heavily doped p-type Si. This is explained by the conduction electron tunneling from Si to absorbed O2 molecule to form the O2- state. O2- ions easily decompose and induce the surface electric field, enhancing the oxidation rate. It is found that the oxidation of heavily doped n-type Si in pure water is effectively suppressed by adding a small amount (1003600 ppm) of HCl.