Kinetic studies on acidic wet chemical etching of silicon in binary and ternary mixtures of HF, HNO3 and H2SiF6

The etching of silicon with mixtures of hydrofluoric acid (HF), nitric acid (HNO3) and hexafluorosilicic acid (H2SiF6) proceeds in a complex reaction scenario consisting of interacting side reactions. Almost no other dissolution reaction is so massively dependent on the reaction conditions that influence the etching rate and the mechanism of the individual reactions. Extensive studies of the reaction rate of silicon etching in binary and ternary acid mixtures have allowed the transition point between the reaction-controlled and diffusion-controlled reaction regimes to be determined as a function of the composition of the etching mixture. It was verified that the reaction mechanism for binary and ternary mixtures does not differ and only the lower water content in ternary mixtures favours an enhanced formation of the reactive N(III) intermediate HNO2 in side reactions. Based on the exact knowledge of the point of mechanism change, determination of the reaction rate under quasi-isothermal conditions in the bulk etching range allows, for the first time, deriving formal kinetic terms from the kinetic data to describe the dissolution rate in both the reaction-controlled and diffusion-controlled regimes. The formal kinetic terms were designed both for the kinetically correct quasi-isothermal approach to the dissolution rate in the Si bulk and for the application-oriented approach that includes induction phases and temperature increases in the considered dissolution period as well as influences of the surface properties. Moreover, by using the water content of the etching mixtures as a proxy variable, uniform calculation of the etching rates in HF/HNO3 as well as in HF/HNO3/H2SiF6 mixtures in the entire composition range of the application can be formulated.