Probing the high performance of photoinduced birefringence in V-shaped azo/PMMA guest–host films

Optical birefringence in polymeric films containing azo-chromophores is an important feature related to the development of several technologies such as electro-optic modulators, optical switching, and optical gates, to cite a few. Therefore, it is essential to understand the main underlying mechanisms describing dynamic switching. In this context, we have investigated the optical birefringence performance of a guest–host film produced from a poly(methyl methacrylate) (PMMA) matrix containing a V-shaped azo-chromophore, which exhibited a larger optical response in comparison to the linear chromophores. The optical birefringence was induced by a linearly polarized diode laser (532 nm, writing laser), while a low-intensity HeNe (632.8 nm) laser and a tungsten-halogen lamp are employed, respectively, to monitor the optical storage and the absorption change during the photoinduced birefringence. Our results pointed out that the guest–host film presents maximum residual optical memory at around 50% and local optical birefringence at around 3.3 × 10(−4) in the low concentration and intensity regimes. The high optical birefringence obtained in guest–host films was attributed to the considerable photoisomerization quantum yield in the solid-state (0.15 ± 0.02 for 532 nm). Besides, we have shown that the switching mechanism is driven by angular hole-burning during the first seconds after excitation, and, subsequently, molecular reorientation quickly rises, dominating the photochemical process. The latter mechanism is highly efficient in converting cis to trans molecules (100%), which is responsible for the high residual optical memory obtained. In order to better understand the isomerization mechanism of the azo-chromophore/PMMA film, we performed quantum chemical calculations within the DFT framework. The electronic transitions of the azo-chromophore isomers were determined using the TD-DFT method and potential energy curves (PECs) were constructed to investigate the possibility of the thermal-isomerization process of the V-shaped azo-chromophore through both rotation and inversion mechanisms. For both mechanisms, the amplitude of the energy barrier and activation energy for thermal isomerization are determined and the results are discussed.