We report here a light-induced phenomenon—a self-induced rotation of the azimuth of elliptically polarized light passing through photobirefringent azopolymers. The experiments are carried out with films of amorphous and liquid-crystalline polymers. It has been shown that the induced rotation angle depends on the ellipticity of the input light. A theoretical analysis of the phenomenon has been done and it has been shown that light induces chiral structure in the polymer films.
We investigate parameters associated with optical data storage in a variety of amorphous side-chain azobenzene-containing polyesters denoted as E1aX. The polyesters possess a common cyano-substituted azobenzene chromophore as a side chain, but differ in their main-chain polyester composition. Seventeen different polymers from the E1aX family divided into four classes, depending on the type of the main-chain substituent (one-, two-, and three-ring aromatic or alicyclic) have been thoroughly investigated. Various parameters characterizing the photoinduced birefringence in these materials, such as the response time, thermal and light stability, and long-term stability under ambient light at room temperature have been measured. Each of these parameters is quantitatively represented and therefore it is possible to make a clear comparison between the properties of the polymers. The results indicate that the long-term stability at ambient temperature is closely related to the thermal stability of the photoinduced birefringence. A strong correlation has also been found between the response time and the stability of the induced anisotropy toward illumination with unpolarized white light. One of the classes of E1aX polymers characterized by two-ring aromatic substituent in the main chain is a good candidate for optical data storage media. A recording energy of approximately 2 J/cm2 is sufficient to induce high refractive-index modulations of deltan = 0.13 in these materials, which is retained even at elevated temperatures (>130 degrees C). Long-term stability of greater than one year for the induced anisotropy has also been achieved.
Hybrid materials based on combination of polymers and inorganic nanoparticles (NP) attracted considerable attention in the last decade due to their advantageous electrical, optical, or mechanical properties. Recently, we reported a significant improvement of the photoresponse by doping azopolymers with ZnO NP. To study the influence of the composition of the dopant, in our present work we have synthesized anisotropic organic/inorganic nanocomposite materials by incorporating 5-15 nm sized SiO2 NP in a side-chain azopolymer. As a result we observe an enhancement of the photoinduced birefringence in these composite materials with about 20% compared to the nondoped sample. Additionally, we discuss possible mechanisms leading to this enhancement related with the scattering caused by the NP and the increased mobility of the azochromophores in the vicinity of NP.
We employ two approaches to tune the properties of concurrently inscribed volume polarization and surface relief gratings in nanocomposite thin films containing the azopolymer PAZO (poly[1-4-(3-carboxy-4-hydrophenylazo)benzensulfonamido]-1,2-ethanediyl, sodium salt]) and goethite (α-FeOOH) nanorods. The first one is applied on the stage of sample preparation by varying the concentration of the goethite nanorods from 0% to 15%. Then, different angles between the recording beams are set in the holographic scheme, which allow us to obtain gratings with spatial periods in the range from 0.86 to 2.51 µm. Surface relief modulation close to 300 nm is achieved as well as total diffraction efficiency in the ±1 diffracted orders of more than 50%. The influence of the incorporated goethite nanorods on the properties of both volume birefringence and the surface relief grating are discussed.
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