Monolayers of a series of 1-alkynes, from 1-dodecyne to 1-octadecyne, have been prepared on the hydrogen-terminated Si(100) surface via a thermal reaction of the organic compound with this Si surface. An efficient procedure is presented for the synthesis of 1-alkynes from the corresponding 1-alkenes. The resulting monolayeres were characterized by water contact angle measurements, ATR infrared spectroscopy, and X-ray reflectivity. The results show that these 1-alkynes give well-ordered, covalently bonded monolayers, which are at least as ordered as those of the corresponding 1-alkenes. The exact binding geometry of the 1-alkyne to the Si surface was investigated. The results from the IR spectroscopy and X-ray reflectivity measurements indicate that the 1-alkynes form two Si-C bonds to the surface per reacting molecule. Quantum mechanical calculations conform that this formation of two Si-C bonds is not only chemically possible but also energetically much more favorable than formation of only one Si-C bond per reacting molecule.

Sieval, A. B., Opitz, R., Maas, H. P. A., Schoeman, M. G., Meijer, G., Vergeldt, F. J., … Sudhölter, E. J. R. (2000). Monolayers of 1-alkynes on the H-terminated Si(100) surface. Langmuir, 16, 10359–10368. doi:10.1021/la001109n