In this study we report investigation of the polymer film morphology modifications during their corona poling for fabrication of nonlinear optically (NLO) active materials. We demonstrate that at certain poling conditions surface and spatial inhomogeneities in the poled area of the sample appear. Densities of the inhomogeinities depend on the strength of the poling field, the sample temperature during the poling, and the prepoling conditions. Optimization of the poling conditions directed toward avoiding surface modifications enables us to increase the overall observable effective nonlinearity of the sample up to 10 times. To investigate, understand, and eventually explain the formation of the spatial and surface structure inhomogeinites in the poled material we have used optical, second harmonic, and scanning electron microscope measurements, as well as the conductivity measurements of the thin films. We present results of poled polymer host-guest films where (dimethylamino)benzylidene-1,3-indandione and low dipole moment 2,2',2″-(4,4',4″-nitrilotribenzylidene)triindan-1,3-dione were used as guests in poly(methyl methacrylate), polystyrol, and polysulfone matrixes doped at 10 wt %.
The corona discharge is described focusing on the advantages of corona triode techniques for the direct current (DC) positive poling of optical polymers. The proposed experimental setup allows the corona poling of nonlinear optical (NLO) polymers in the modes of DC constant current (the lowest 1nA) and of the fixed corona-grid voltage, making it possible to carry out the corona-onset poling at elevated temperature (COPET) up to 200 oC. The setup also provides a wide range of the corona discharge voltage (3 kV - 15 kV), variable reciprocal distance of electrodes as well as the possibility to choose from different types of the corona electrode (needle, multi-needle, wire, etc.). By keeping the corona-to-grid voltage constant, a stable corona discharge at electrode is attained. The grid voltage can be varied in the range from 0 to 3kV. The corona poling area on the sample surface is pre-defined by placing ring spacers above it. The setup is completely computerized, allowing both control and monitoring of the corona discharge, which promotes research into the process of charging NLO polymer samples and selection of the optimal poling mode. Using the voltage-current characteristics and the second-harmonic measurements of a poled polymer we also demonstrate the influence of the setup parameters on the efficiency of poling the thin film NLO polymers.
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