This study investigates the effect of mask material and thickness on the silicon etching profile using a high-density plasma (HDP) etching system, aiming to reduce optical loss in silicon-based optical waveguides. As the mask thickness increased, the etching sidewall angle became steeper. An etching profile angle of 87° was obtained when tetraethyl orthosilicate (TEOS) was used as the mask material, while 80° was obtained for photoresist (PR). This is attributed to electron charging on the mask surface in the plasma. The charged mask modifies the distribution and strength of the electric field depending on its thickness, thereby affecting the trajectory of positive ions accelerated toward the substrate by the bias voltage. Furthermore, Plasma diagnostics using optical emission spectroscopy (OES) and surface composition analysis using field emission Auger electron spectroscopy (FE-AES) revealed that changes in the mask material also alter the reaction pathways and formation characteristics of active species and silicon by-products in the plasma. These results suggest that the mask material influences the overall plasma characteristics, including electron density and ion energy, and plays a critical role in the precise control of silicon etching profiles for high-performance optical device fabrication.