Chem. Mater., 18 (9), 2357 -2363, 2006. 10.1021/cm052537n S0897-4756(05)02537-8
Web Release Date: March 30, 2006

Copyright © 2006 American Chemical Society

Orientations of Liquid Crystals in Contact with Surfaces that Present Continuous Gradients of Chemical Functionality

Brian H. Clare, Kirill Efimenko, Daniel A. Fischer, Jan Genzer, and Nicholas L. Abbott*

Department of Chemical & Biological Engineering, University of Wisconsin-Madison, Madison, Wisconsin 53706, Department of Chemical & Biomolecular Engineering, North Carolina State University, Raleigh, North Carolina 27695, and Materials Science & Engineering Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899

Received November 17, 2005

Revised Manuscript Received February 15, 2006

Abstract:

We report the formation of continuous spatial gradients in the density of grafted semifluorinated chains on silicon oxide surfaces by vapor-phase diffusion of semifluorinated silanes. We quantify the orientations of the nematic liquid crystal (LC) 4-cyano-4'-pentylbiphenyl on these surfaces as a function of local surface composition obtained by using NEXAFS. These measurements demonstrate that it is possible to obtain the full range of tilt angles of a LC on these surfaces. We also use the data provided by these gradient surfaces to test hypotheses regarding the nature of the interaction between the LC and surfaces that give rise to the range of tilted orientations of the LC. We conclude that the orientations of the LC are not determined solely by the density of grafted semifluorinated chains or by the density of residual hydroxyl groups presented at these surfaces following reactions with the silanes. Instead, our results raise the possibility that the tilt angles of the semifluorinated chains on these surfaces (which are a function of the density of the grafted chains) may influence the orientation of the LC. These results, when combined, demonstrate the potential utility of gradient surfaces for screening surface chemistries that achieve desired orientations of LCs as well as for rapidly assembling experimental data sets that can be used to test propositions regarding mechanisms of anchoring LCs at surfaces.


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