Molecular orientation of a model liquid crystal alignment layer.

An analytical methodology, involving the use of a combination of second harmonic generation (SHG) and linear dichroism, was utilized to probe the molecular orientation and angular distribution of a model liquid crystal (LC) alignment layer. In order to determine which film structure would be best suited for use as an alignment layer, the azo dye o-methyl red (MR) was covalently bound to a glass substrate using both monofunctional and trifunctional silane chemistry. The influence of solvent on the orientation and angular distribution of both thin films was also investigated. For the monofunctional silane film under water, the mean orientation angle of the MR molecular long axis was 67+/-4 degrees and the width of an assumed Gaussian distribution was 32+/-2 degrees . Under hexanes, the mean orientation angle was the same within error (63+/-1 degrees ) but the distribution width narrowed considerably to 22+/-1 degrees . Molecular orientation within the trifunctional silane film exhibited little dependence on solvent. Under water, the mean orientation angle and angular distribution width were 76+/-3 degrees and 30+/-1 degrees , respectively. With hexanes as the solvent, the mean orientation angle and angular distribution width were 79+/-1 degrees and 30+/-1 degrees , respectively. Orientation insensitive SHG measurements indicated that surface coverage in the tri-functional silane film was twice that in the mono-functional silane film. The observed orientational differences were attributed to differences in the forces that dictate molecular orientation for the two systems. Based on the higher orientation angle, higher surface coverage and the lack of solvent dependence, MR-tri exhibits more desirable characteristics for use as an LC alignment layer.