Free-standing smectic films : diffusion

Collaboration with Patrick Oswald, John Bechhoefer and Lydéric Bocquet.

 

Introduction

    Stable, free-standing smectic-liquid-crystal films can be made from two to hundreds of molecular layers thick and uniform over cm2. They are model systems for studying the crossover between two- and three-dimensional phenomena. We performed the first direct study of the diffusion of a tracer molecule in free-standing films of various thicknesses. We measured how the value of the vertically averaged, in-plane diffusion constant evolves in very thin films.

 

Experimental method

    Our measurement method for the diffusion constant is an adaptation of the technique known as fluorescence after photobleaching (FRAP). The general principle is that an intense laser beam is used to photobleach (destroy) the fluorescence of tracer molecules in a small region. A much weaker beam then monitors the recovery of the signal as unbleached molecules diffuse into the bleached area, leading to recovery of the fluorescence signal (Fig.1).

Fig.1: Image of the film after bleaching and concentration profile of the bleached molecules.
A fluorescent dye is introduced in the liquid crystal. An intense laser beam makes possible to bleach a small region of the sample. The diffusion coefficient is deduced from the evolution of the concentration profile after bleaching (The black dots correspond to the experimental concentration profile along the dashed line, the black line to the Gaussian interpolation).

 

Results

    Our measurements show that the diffusion coefficient significantly increases when the film thickness is decreased (Fig.2). The results can be accounted by a model which brings into play the hydrodynamical interactions between the diffusing molecules and the free surfaces of the films. Amazingly, the hydrodynamics seems to provide reliable results even when the film thickness is reduced to a few molecular layers.

Fig.2: Diffusion coefficient vs. film thickness (molecular layers).

Related publications

Experiments on tracer diffusion in thin free-standing liquid-crystal films,
Bechhoefer J., Geminard J.-C., Bocquet L. and Oswald P., Phys. Rev. Lett. 79 (1997) 4922.