Formation of surface relief grating in polymers with pendant azobenzene chromophores as studied by AFM/UFM

We studied peculiarities of the structural reconstruction within holographically recorded gratings on the surface of several different amorphous azobenzene-containing polymers. Under illumination with a light interference pattern, two processes take place in this type of polymer. The first process is the light-induced orientation of azobenzene units perpendicular to the polarization plane of the incident light. The second one is a transfer of macromolecules along the grating vector (i.e. perpendicular to the grating lines). These two processes result in the creation of a volume orientation grating (alternating regions of different direction or degree of molecular orientation) and a surface relief grating (SRG)-i.e. modulation of film thickness. One can assume that both orientation of molecules and their movement might change the local mechanical properties of the material. Therefore, formation of the SRG is expected to result also in modulation of the local stiffness of the polymer film. To reveal and investigate these stiffness changes within the grating, spin-coated polymer films were prepared and the gratings were recorded on them in two different ways: with an orthogonal circular or orthogonal linear polarization of two recording light beams. A combination of atomic force microscopy (AFM) and ultrasonic force microscopy (UFM) techniques was applied for SRG development monitoring. We demonstrate that formation of the phase gratings depends on the chemical structure of polymers being used, polymer film thickness, and recording parameters, with the height of grating structures (depth of modulation) increasing with both the exposure time and the film thickness. UFM images suggest that the slopes of the topographic peaks in the phase gratings exhibit an increased stiffness with respect to the grating depressions.