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The dynamics of 4-n-pentyl-4'-cyanobiphenyl (5CB) nematic liquid crystalline thin films have been studied in real time using step-scan Fourier transform infrared spectroscopy (FTIR). In these studies, the liquid crystal was confined in a nanocavity defined and bounded by an interdigitated gold electrode array. The gold microstructures were microfabricated on a zinc selenide (IR-transparent) window. The 5CB interactions with the ZnSe substrate result in surface-induced ordering of the ultrathin layers (on the order of 40 nm). As the films increase in thickness, the nanoscale organization induced by the surface layer becomes a less significant contributor to the overall bulk structure of the sample. Time-resolved FTIR studies have enabled the measurement of rate constants for the orientation and relaxation of the thin films under an applied electric field as a direct function of confinement dimensions. Cell thicknesses ranging from 40 to 300 nm were studied. The measured rate behaviors demonstrate the strong effects of the interactions occurring between the surfaces of the ZnSe crystals and the 5CB on the dynamics of the liquid crystalline assembly. Time-resolved studies reveal kinetically inhomogeneous line shapes for thicker films while ultrathin films maintain kinetically homogeneous peaks, suggesting the development of liquid crystalline domains or other inhomogeneities over this length scale in the transition from the surface layer to bulk.


Originally published as:

Noble-Luginbuhl, A. R., Blanchard, R. M., & Nuzzo, R. G. (2000). Surface effects on the dynamics of liquid crystalline thin films confined in nanoscale cavities. Journal of the American Chemical Society, 122(16), 3917-3926.

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