Journal of Chemical Physics, Vol.112, No.18, 7839-7847, 2000
Nanometer-scale resolution and depth discrimination in near-field optical microscopy studies of electric-field-induced molecular reorientation dynamics
Electric-field-induced molecular reorientation dynamics in polymer-dispersed liquid crystal (PDLC) films are characterized in detail using near-field scanning optical microscopy (NSOM) methods developed previously [Mei and Higgins, J. Phys. Chem. A 102, 7558 (1998)]. In these experiments, a modulated electric field is applied between the aluminum-coated NSOM probe and an indium-tin-oxide (ITO) substrate. The field causes reorientation of the liquid crystal within the ITO-supported PDLC film. The reorientation process is observed by near-field optical means. In this paper, it is conclusively shown that under appropriate conditions the dynamics observed occur in extremely small volumes, and are substantially confined within the near-field optical regime. The volume in which the dynamics are probed may be controlled by varying the experimental parameters (i.e., field strength and modulation frequency) employed. Conclusive evidence for confinement is obtained from both theoretical arguments and experimental results. Calculations of the electric fields in a model dielectric medium show that the largest fields occur very near the NSOM probe. Experimental observation of spatial variations in the threshold (i.e., the "Frederiks transition") for liquid crystal reorientation provide further evidence. The most direct evidence is provided by the observation of sub-diffraction-limited resolution in dynamics images of approximate to 1 mu m thick samples. Spatial variations in the observed dynamics are interpreted to reflect the energetics of local liquid crystal organization, the details of the reorientation process, and also polymer/liquid-crystal interfacial interactions. Finally, important information on the local rotational viscosity and elastic force constants within individual liquid-crystal droplets is obtained.