Role of Sulfur in Catalyzing Fluorine Atom Fast Etching of Silicon with Smooth Surface Morphology

Chemical reaction probabilities, defined as the number of silicon atoms removed per incident fluorine atom, have been investigated in mixtures of NF3 and SF6 plasmas in an inductively-coupled plasma reactor. Fluorine atom densities were measured by optical emission actinometry, and isotropic etching rates were measured by the degree of undercutting of SiO2-masked silicon by cross-sectional scanning electron microscopy. In addition, atomic force microscopy was used to examine surface morphology of etched Si surfaces. The F atom reaction probabilities derived from isotropic etching rates indicate an ∼30-fold higher reaction probability in SF6 plasmas compared with values in NF3 plasmas. Surfaces etched in SF6 plasmas were much smoother than those etched in NF3 plasmas. The addition of only 10% SF6 to an NF3 plasma produced a much higher reaction probability (∼5-fold) than in a pure NF3 plasma. This surprising enhancement of reaction probabilities for F with Si in SF6 plasmas is further investigated, based on the mechanism of adsorbed sulfur acting as a catalyst to greatly enhance the etching rate of Si. Dilute sulfur solutions in isopropyl alcohol were allowed to evaporate on the masked Si samples, depositing sulfur in relatively high concentrations near mask edges in ∼2 μm diameter periodic “strings of beads.” The sulfur-dosed sample etched several times faster at the center of each bead than a sample not exposed to sulfur that was placed side by side. The catalytic effect of sulfur is ascribed to an enhanced F sticking coefficient and/or decreased desorption rate on a surface covered with sulfur.