Holographic studies of photoinduced anisotropy in molecular glassy films containing diphenylamine azochromophores

Abstract

Photoinduced anisotropy (PA) is experimentally studied in three molecular glassy films synthesized in our Faculty and containing diphenylamine based azochromophores {4-((4-nitrophenyl)diazenyl)-N-(4-((4-nitrophenyl)diazenyl)phenyl)-N-(2-trityloxy)ethyl) benzeneamine (shortly K-D-24), 4-((2-chloro-4-tritylphenyl)diazenyl)-N-(4-((2-chloro-4-tritylphenyl)diazenyl)phenyl)-N-(2-(trityloxy)ethyl)benzenamine (shortly K-D-25), 4,4'-(2-(trityloxy)ethylazanediyl)bis(4,1-phenylene)bis(diazene-2,1-diyl)dibenzonitrile (shortly K-D-32) } and, for comparison, in an a-As2S3 film. Holographic method enabling simultaneous measurements of s- and p-polarized diffracted light powers was applied in both transmission and reflection modes. Holographic grating recording with the period of 2 μm was made by two equally strong 532 nm p- polarized laser beams with total light intensity of 0.81 W/cm2. The readout was made by 633 nm circularly polarized beam, and the s- and p-polarized components of diffracted light were separated by polarization beam splitter prism. PA was characterized by diffracted power difference (DPD), Ps − Pp, and by anisotropy contrast A = (ns − np)/(ns + np), ns and np being the diffraction efficiencies for s- and p-polarized light. DPD exhibited markedly different kinetic behaviour in transmission and reflection modes. There was a negative minimum in transmission mode in all samples, and a growth with oscillations up to saturation in reflection mode. Small initial DPD maxima were specific to a-As2S3 film. The highest PA was found in K-D-24 film in transmission mode (A=-0.23) and in K-D-25 film in reflection mode (A=0.49). Holographic recording efficiency and PA do not correlate. In our opinion, PA in transmission mode of molecular glasses is due to the photoinduced volume processes including trans-cis photoisomerization, chromophore orientation and mechanical stress modulation. In the case of a-As2S3 film these photoinduced volume processes include photoinduced structural changes, D-centre orientation and, again, mechanical stress modulation. All these processes lead to a photoinduced birefringence. Surface relief grating recording and polarization-dependent reflection are responsible for diffractive anisotropy in reflection mode.