Abstract
We have used infrared spectroscopy, ellipsometry, and contact angle measurements to study self-assembled monolayer (SAM) formation on aluminum native oxide from three alkanephosphonic acids: CF3(CF2)7(CH2)11PO3H2 (F8H11PA), and CH3(CH2)nPO3H2 (n = 15 (H16PA); n = 21 (H22PA)). These compounds show significant differences in film structure and film formation kinetics. Strikingly, the methylene segment of the semifluorinated F8H11PA SAM never reaches an ordered state even at long assembly times. This contrasts with the ordered chains in equilibrium films from H16PA and H22PA. We attribute this behavior to steric effects of the fluorocarbon segment and the phosphonic acid headgroup. F8H11PA represents an amphiphile in which bulky head and tail groups prevent an interposed hydrocarbon segment from ordering. For all three phosphonic acids, negative peaks attributed to loss of Al−OH groups in the infrared spectra of the monolayers are consistent with a condensation reaction between the acids and surface hydroxy...
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