The surface stress induced during the formation of alkanethiol [HS(CH 2)nCH3] self-assembled monolayers (SAMs) on gold from the vapor phase was measured using a differential cantilever-based sensor. This custom-built system is capable of surface stress measurements with a sensitivity of 5 x 10-5 N/m using commercially-available atomic force microscopy cantilevers. A second system combining cantilever-based sensing and ellipsometry was also designed and built, capable of yielding simultaneous in situ surface stress and film thickness measurements. Scanning tunneling microscopy (STM) with molecular resolution was also performed ex situ in order to characterize the structure of the resulting SAMs. The complementary use of these tools has provided an all-around view of the self-assembly process. / These measurements were performed in order to gain insight into the mechanisms involved in the self-assembly process and into the origins of the associated surface stress. Moreover, these studies were used to characterize and optimize the response of cantilever-based sensors based on functionalized SAM technology in terms of reliability, sensitivity, and reproducibility. / The evolution of the surface stress induced during alkanethiol SAM formation reveals features associated with coverage-dependent structural phase transitions. These results show that both the kinetics of SAM formation and the resulting SAM structure are strongly influenced by the surface structure of the underlying gold substrate, by the impingement rate of the alkanethiol molecules onto the gold surface, and by the cleanliness of the gold surface. In particular, it was found that a minimum gold grain size is necessary in order for the SAM to achieve the standing-up phase, for which large compressive surface stresses (~10 N/m) are measured. In addition, these results show that alkanethiol SAMs can become kinetically trapped in metastable intermediate states (lying-down phase) for formation on small-grained gold surfaces and/or at low alkanethiol vapor concentrations. Theoretical modeling of the origins of the induced surface stress reveals that inter-molecular Lennard-Jones interactions and electrostatic repulsion between adsorbed species play minimal roles in the development of the surface stress. Changes in the electronic structure of the underlying gold substrate are more likely to account for the large compressive surface stresses observed during alkanethiol SAM formation.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.85551 |
| Date | January 2004 |
| Creators | Godin, Michel |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Physics.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 002238810, proquestno: AAINR12848, Theses scanned by UMI/ProQuest. |
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