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Ultralow Adhesion and Friction of Fluoro-Hydro Alkyne-Derived Self-Assembled Monolayers on H‑Terminated Si(111)

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journal contribution
posted on 21.12.2012, 00:00 by Sidharam P. Pujari, Evan Spruijt, Martien A. Cohen Stuart, Cees J. M. van Rijn, Jos M. J. Paulusse, Han Zuilhof
New fluorine-containing terminal alkynes were synthesized and self-assembled onto Si(111) substrates to obtain fluorine-containing organic monolayers. The monolayers were analyzed in detail by ellipsometry, X-ray photoelectron spectroscopy (XPS), Fourier transform infrared reflection absorption spectroscopy (FT-IRRAS), static water contact angle measurements (CA), and atomic force microscopy (AFM). The SAMs exhibit excellent hydrophobicity, with static water contact angles of up to 119° and low critical surface tensions of 5–20 mN/m depending on the number of F atoms per molecule. IRRAS confirmed the formation of highly ordered monolayers, as indicated by the antisymmetric and symmetric stretching vibrations of the CH2 moieties at 2918–2920 and 2850–2851 cm–1, respectively. Upon increasing the number of fluorine atoms in the alkyne chains from 0 to 17, the adhesion of bare silica probes to the SAMs in air decreases from 11.6 ± 0.20 mJ/m2 for fluorine-free (F0) alkyne monolayers to as low as 3.2 ± 0.03 mJ/m2 for a heptadecafluoro-hexadecyne (F17)-based monolayer. Likewise, the friction coefficient decreases from 5.7 × 10–2 to 1.2 × 10–2. The combination of high ordering, excellent hydrophobicity, low adhesion, and low friction makes these fluoro-hydro alkyne-derived monolayers highly promising candidates for use in high-performance microelectronic devices.