Ultralyophobic Oxidized Aluminum Surfaces Exhibiting Negligible Contact Angle Hysteresis

Abstract

Ultralyophobic oxidized aluminum surfaces exhibiting negligible contact angle hysteresis for probe liquids were prepared by chemical vapor deposition (CVD) of bis((tridecafluoro-1,1,2,2,-tetrahydrooctyl)-dimethylsiloxy)methylsilane (CF(3)(CF(2))(5)CH(2)CH(2)Si(CH(3))(2)O)(2)SiCH(3)H, (R(F)Si(Me)(2)O)(2)SiMeH). Oxidized aluminum surfaces were prepared by photooxidation/cleaning of sputter-coated aluminum on silicon wafers (Si/Al(Al(2)(O(3)))) using oxygen plasma. X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) confirmed that this facile CVD method produces a monolayer with a thickness of 1.1 nm on the Si/Al(Al(2)(O(3))) surface without a discernible change in surface morphology. After monolayer deposition, the hydrophilic Si/Al(Al(2)(O(3))) surface became both hydrophobic and oleophobic and exhibited essentially no contact angle hysteresis for water and n-hexadecane (advancing/receding contact angles (theta(A)/theta(R)) = 110 degrees/109 degrees and 52 degrees/50 degrees, respectively). Droplets move very easily on this surface and roll off of slightly tilted surfaces, independently of the contact angle (which is a practical definition of ultralyophobic). A conventional fluoroalkylsilane monolayer was also prepared from 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (CF(3)(CF(2))(7)CH(2)CH(2)Si(OCH(3))(3), R(F)Si(OMe)(3)) for comparison. The theta(A)/theta(R) values for water and n-hexadecane are 121 degrees/106 degrees and 76 degrees/71 degrees, respectively. The larger hysteresis values indicate the "pinning" of probe liquids, even though advancing contact angles are larger than those of the (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers. The (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers have excellent hydrolytic stability in water. We propose that the (R(F)Si(Me)(2)O)(2)SiMeH-derived monolayers are flexible and liquidlike and that drops in contact with these surfaces experience very low energy barriers between metastable states, leading to the formation of nonhysteretic ultralyophobic surfaces.