Nanoasperity Adhesion of the Silicon Surface in Humid Air: The Roles of Surface Chemistry and Oxidized Layer Structures

The interfacial adhesion between silicon oxide surfaces is normally believed to be governed by the surface chemistry of the topmost surface affecting the water contact angle and hydrogen bonding interactions. In the case of a silicon wafer, the physical structure of the native oxide at the surface can vary drastically depending on the aging process; thus, not only the surface chemistry but also the history of surface treatment can also have a profound impact on nanoasperity adhesion. This study reports the effect of aging conditions (ambient air, liquid water, and liquid ethanol) on the nanoasperity adhesion behaviors of a silicon surface. When the silicon surface is kept in liquid alcohol, the surface remains hydrophobic, and adhesion in ambient air can be explained with the capillary effect of the liquid meniscus condensed around the annulus of the nanoasperity contact. When the silicon surface is oxidized in ambient air, the surface gradually becomes hydrophilic, and the strongly hydrogen-bonded water network of adsorbed water plays a dominant role in the nanoasperity interfacial adhesion force. When the silicon surface is aged in liquid water, the interfacial adhesion force measured in ambient air is significantly larger than the value predicted from the theoretical model based on the water contact angle and the hydrogen bonding interaction at the topmost surface. This is because the surface layer oxidized in liquid water is gel-like and thus can swell upon uptake of water from the humid air. To fully encompass all these behaviors, a solid-adsorbate-solid model predicting the adhesion force is developed by introducing a fitting parameter β, which can be adjusted depending on the adsorbed water structure and the swelling capacity of the oxidized surface layer.