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Polymer composition with phenanthrenequinone for recording relief holographic gratings

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The formation of periodic reliefs of the thickness of photosensitive polymer layers after recording holographic gratings in them and stimulating material deformations by reversible plasticization in a non-solvent liquid is considered. The phenomenon was studied for the composition of a copolymer with side anthracene groups — phenanthrenquinone. Phenantrenquinone transfers the energy of electronic excitation to oxygen molecules entering through the open surface of the polymer layer which then cause the oxidation of anthracene fragments. Holographic gratings with a period of 2–5 μm were recorded by laser radiation at a wavelength of 532 nm in layers about 1 μm thick. The photoreliefs were formed during the subsequent swelling of the layer in the medium of a hydrocarbon developer. The photosensitized oxidation of the anthracene groups of the new polymer under the action of optical radiation in the spectral range 408–532 nm was studied using the electron absorption spectra. It is shown that approaching the excitation wavelength to the long-wavelength absorption maximum of phenanthrenquinone (410 nm) makes it possible to increase the sensitivity of the material layer by a factor of 15 compared to layers with methylene blue as a photosensitizer. It has been experimentally established that the amplitude of weak periodic reliefs of a deformation nature (height less than 0.01 μm), which appear immediately after the recording of holographic gratings, increases many times during the treatment of the layer with liquid hydrocarbon. Their maximum value reaches 25 % of the thickness of the recording layer. Presumably, the deformation of the inhomogeneously irradiated layer is stimulated by the transfer of the polymer material into a highly elastic state during its swelling. Photoreliefs are stable after drying. Their strength can be increased by photocrosslinking the material as a result of photodimerization of residual anthracene groups under uniform irradiation with light at a wavelength of 365 nm. The non-sinusoidality of the photorelief reduces the diffraction efficiency achievable with total reflection to values less than 0.20. The studied polymer composition can be used to form relief-phase diffractive optical elements by radiation in the blue-green region of the spectrum, provided by a number of high-power laser sources.

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