A 27 MHz/2 MHz Ar/CO/CFx rf capacitive discharge was used to selectively etch submicron SiO2/Si, SiO2/TiSi2 and SiO2/TiN structures. The borophosphosilicate glass etch rate (∼1.0 μm/min) was observed to decrease with bottom electrode temperature, whereas etch selectivity to TiSi2 (≳50:1) was found to increase with temperature, with a photoresist selectivity ≳50:1. Plasma emission of the dual frequency discharge indicated the presence of an abundant concentration of the CF2 radical (249 nm) as compared to a lower frequency (400 kHz) rf discharge with low etch selectivity (<20:1). Langmuir probe measurement indicated an enhancement of ion density of an order of magnitude (∼5×1010 cm−3) as compared to the low frequency (400 kHz) rf discharge. Particle‐in‐cell simulation was used to calculate plasma density as a function of excitation frequency. Plasma density scales with the square of the source frequency while it remains relatively independent of the substrate frequency.