Photo-induced isomerization of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene ultra-thin solid film prepared by Langmuir–Blodgett technique

The photo-induced response of an ultra thin polymeric film of poly 4′-(6-acryloxy) hexyloxy-4-methoxyazobenzene (P5) is investigated. A monolayer of P5 at a gas–water interface possesses a mean molecular area of 28.0 Å2/monomer-repeat. Multilayer films of P5 were prepared by horizontal deposition at a surface pressure of 25 mN/m2. The uniformity of the transfer process is shown by UV–vis absorption spectra where a linear relationship between the absorption maxima and the number of transferred layer was observed. The average layer thickness of the transferred film determined by XRD measurements is 34.0 Å. This is longer than the length of the azobenzene side group. The transferred film shows a blue shift of the π–π∗ transition from 357 nm for the P5 in solution to 340 nm for the P5 in the film. This suggests the formation of H-aggregate with a head-to-head arrangement of the dipole within the film. The optical property of the transferred film is changed by the irradiation of the film with the UV light at 385 nm. An irreversible change in its molecular packing in the film is seen in the shift of the UV–vis absorption maxima and the change in morphology as observed by AFM. The film morphology changes from being a smooth film into an island-like surface when exposed to the UV irradiation. The layer structure in the film is destroyed. A mass transport is observed during the cis–trans thermal back isomerization process. This suggests that movement of the P5 took place in both the trans–cis isomerization process and the cis–trans back isomerization process. The first movement leads to a molecular expansion while the second, to a molecular contraction.