Optical deformations of azobenzene polymers: orientation approach vs. other concepts

It has been 30 years since the discovery of surface restructuring in thin azopolymer films by two independent research groups. A wide variety of topographical structures have been created by the application of two-/four-beam interference patterns, space light modulators and even helical beams. There are a number of comprehensive reviews which describe in detail the advances in superficial photopatterning of azopolymer films and macroscopic deformations of azonetworks. The theoretical approaches are only briefly touched on in these reviews and often are accompanied by the remark that the phenomenon is far from being understood. In this review, we would like to present the polymer theoretist's point of view on this intriguing problem. We begin by describing a multitude of theoretical approaches and commenting on the pluses and drawbacks of each. Importantly, we show that in most cases the presence of an azopolymer matrix is either ignored or limited to a specific class of azopolymers (liquid-crystalline or elastomeric). We then move to early orientation approaches based on the hypothesis that reorientation of azo-chromophores by modulated polarized light is the sole cause of superficial patterning. At the end of the review a modern orientation approach, as proposed by our own group, is presented. This approach has high predictive power because it can explain a large pool of experimental data for different classes of azopolymers including glassy and liquid-crystalline materials. This is made possible by taking into account both the light-induced orientation process and the change of anisotropic interactions between the chromophores upon their isomerization. Last but not least, this is the only approach that provides an estimate of the light-induced stress large enough to cause plastic deformations of glassy azopolymers. Recent finite element modeling results show remarkable similarity to real patterns and even time-dependent data are well explained. With this, we claim that the puzzle is finally understood and the orientation approach is ready for its implementation for major azopolymer classes.