In this work, the orientation-dependent adsorption of surfactant molecules on the silicon surface during etching in surfactant-added tetramethylammonium hydroxide (TMAH) is investigated. Triton X-100 (C14H22O(C2H4O)n, n = 9–10) and 25 wt% TMAH are used as surfactant and main etchant, respectively. The crystallographic planes affected by the surfactant molecules are determined by analyzing the etching behavior of different mask patterns on Si{1 0 0} wafers and silicon hemispheres in pure and surfactant-added TMAH. Taken together, the shapes of the etched profiles and the analysis of the hemispherical etch rates confirm that thick and dense adsorbed surfactant layers are typically formed on both the exact and vicinal Si{1 1 0} surfaces. In addition, the results indicate that the adsorbed surfactant layer behaves as a permeable mask, partially slowing down the etch rate of the affected surface orientation/s and thus enforcing their appearance on the etching front. The peculiar etching properties of surfactant-added and surfactant-free TMAH are then utilized for the fabrication of advanced micromechanical structures with new shapes on Si{1 0 0} wafers and polydimethylsiloxane based on complex Si{1 0 0} molds.

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