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Nanoscale. 2017 May 18;9(19):6291-6295. doi: 10.1039/c7nr02420g.

Nanocylindrical confinement imparts highest structural order in molecular self-assembly of organophosphonates on aluminum oxide.

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Institut für Halbleitertechnik, TU Braunschweig, Germany.


We report the impact of geometrical constraint on intramolecular interactions in self-assembled monolayers (SAMs) of alkylphosphonates grown on anodically oxidized aluminum (AAO). Molecular order in these films was determined by sum frequency generation (SFG) spectroscopy, a more sensitive measure of order than infrared absorption spectroscopy. Using SFG we show that films grown on AAO are, within detection limits, nearly perfectly ordered in an all-trans alkyl chain configuration. In marked contrast, films formed on planar, plasma-oxidized aluminum oxide or α-Al2O3 (0001) are replete with gauche defects. We attribute these differences to the nanocylindrical structure of AAO, which enforces molecular confinement.


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