Ellipsometric study of the poling effect on nonlinear-optical side-chain polymers containing disperse red 1

Abstract

The purpose of this work is to investigate the effect of corona poling on the optical functions of the nonlinear-optical (NLO) polymers. We measured the complex refractive indices of NLO polymers deposited on glasses before and after corona poling using spectroscopic ellipsometry at room temperature at various incidence angles. In addition, we observed the absorption spectral change using ultraviolet-visible spectroscopy after corona poling, which is attributed to the chromophore orientation. In order to make NLO polymers, we attached a NLO active dye and photocrosslinkable moieties as side chains of poly(4-hydroxystyrene), deposited the polymer thin films on glass substrates by spin-coating, and corona-poled it along the surface-normal direction to align the dipoles of the chromophores along the electric field direction. In detail, PSDR1-25 designates a poly(4-hydroxystyrene) where 25% of hydroxyl groups in the side chain are substituted by disperse red 1 (DR1) and PSDR1-50 means the same except for 50% substitution. PSDR1 has the second-order NLO property, which is expected to show an acentric ordering by poling electric field. We used a parametric optical constant model to estimate the complex refractive index of the polymers. We found that the poling induced the uniaxial property of the complex refractive index of the polymers by aligning the chromophores along the poling direction. With increased poling voltage, we found that the oscillator strength of the major peak near the 2.4eV (designated as Ea) peak decreases in the surface-parallel direction (x), whereas that of the surface-normal direction (z) increases. Moreover, a detailed analysis of the dielectric functions using the standard critical point model showed that the poling induced a new peak Ec (∼2.6eV) between dominant Ea (∼2.3eV) and weak Eb (∼2.9eV) peaks for PSDR1-50 polymers. With increased poling voltage, the Ec peak strength increased compared to those of Ea and Eb peaks. We tentatively attribute Ec to lower symmetry, possibly Stark effect, induced in the chromophores by the corona poling.