Etching of hexagonal SiC surfaces in chlorine-containing gas media at ambient pressure

The modification of the silicon carbide (4H-SiC) single-crystal surface in a chlorine-containing gas mixture at high temperature (800-1000 °C) and ambient pressure was investigated. The results of silicon carbide chlorination are found to strongly depend on the hexagonal surface orientation. Due to the thermodynamically more favorable reaction of chlorine with silicon rather than carbon, the C-terminated side (0001¯) clearly undergoes considerable changes, resulting in coverage by a black-colored carbon film, whereas the Si-side (0 0 0 1) surprisingly remains visually untouched. With using X-ray photoelectron spectroscopy (XPS), angle-resolved XPS and SEM it is shown that this drastic change in behavior is associated with a different structure of oxicarbide/silicate adlayer formed on the C- and Si-terminated sides of silicon carbide surface during experimental pre-treatment and air exposure. The presence of oxygen bridges connecting the silicate adlayer with the bulk SiC in the case of Si-side inhibits the chlorination reaction and makes this surface strongly resistant to chlorine attack. Only some places on the Si-terminated side demonstrate traces of chlorine etching in the form of hexagonal-shaped voids, which are possibly initiated by distortion of the initial crystalline structure by micropipes. In contrast, a thin carbon layer resulted on the C-terminated side as a consequence of the chlorination process. XPS, ARXPS, SEM and Raman spectroscopy study of created film allows us to argue that it consists mainly of sp2-bonded carbon, mostly in the form of nanoscale graphene sheets. The absence of a protective oxygen bridge between the silicate adlayer and the bulk silicon carbide crystal leads to unlimited growth of carbon film on the SiC(0001¯) side.