Chemical analysis of acidic silicon etch solutions: I. Titrimetric determination of HNO3, HF, and H2SiF6

The chemical etching of silicon using HF-HNO₃ mixtures is a widely used process in the processing of silicon wafers for microelectronic or photovoltaic applications. The control of the etch bath composition is the necessary condition for an effective bath utilization, for the replenishment of the consumed acids, and to maintain a certain etch rate. The present paper describes two methods for the total analysis of the individual etch bath constituents HF, HNO₃, and H₂SiF₆. Both methods start with an aqueous acid-base titration determining the total acid concentration and the concentration of H₂SiF₆. The first method is an acid-base titration using a 0.1 mol L⁻¹ methanolic solution of cyclohexylamine (CHA) as non-aqueous titrant to determine the content of nitric acid. Then, the amount of hydrofluoric acid is calculated from the difference between the total acid and nitric acid content. The second method is based on the determination of the total fluoride concentration using a fluoride ion-selective electrode (F-ISE). The content of hydrofluoric acid is obtained from the difference between the total fluoride content and the amount of fluoride bound as H₂SiF₆. The amount of nitric acid results finally calculated as difference to the total acid content.