Nonlinear optical absorption and refraction study of metallophthalocyanine dyes

Metallophthalocyanines and related conjugated ring molecules have attracted recent interest because, as confined, reduced-dimensionality (2D) delocalized electronic systems, large electronic nonlinearities are expected. This has led to interest in: (1) developing a fundamental understanding of the mechanisms which contribute to the nonlinear optical response, (2) obtaining well defined and accurate measurements of the refractive and absorptive contributions to the observed nonlinearities, and (3) identifying means of enhancing and maximizing the nonlinear susceptibilities. This dissertation deals with the characterization of the nonlinear absorption and refraction of two representative metallophthalocyanine dyes: chloro aluminum phthalocyanine dissolved in methanol, referred to as CAP, and a silicon naphthalocyanine derivative dissolved in toluene, referred to as SiNc. Using the Z-scan technique, the experiments are performed on both the picosecond and nanosecond timescales at a wavelength of 0.532 {dollar}mu{dollar}m.; The Z-scan technique separates nonlinear absorption and nonlinear refraction by measuring both the total transmittance and far field axial transmittance of a focused Gaussian beam as a function of the position (z) of the material relative to the beam waist.; In the picosecond regime, Z-scan experiments using pulses of different widths indicate that both nonlinear absorption and refraction are fluence dependent. Therefore, we determine the dominant nonlinearities are excited state absorption (ESA) and excited state refraction (ESR). Through nanosecond Z-scan measurements, we see additional nonlinear absorption and nonlinear refraction. By power limiting measurements using single picosecond pulses and trains of picosecond pulses separated by 7 nanosecond, this additional nonlinear absorption is determined due to intersystem crossing to the triplet state with subsequent triplet state ESA. Therefore, a five state model is used to explain the nonlinear absorption. On the other hand, axial Z-scans with pulse trains show a negative nonlinear refraction which is opposite to that observed with single picosecond pulses. We therefore propose a thermal effect to explain the nonlinear refraction observed with nanosecond pulses.; To improve the limiting capabilities of CAP and SiNc, we hybridize them with ZnSe which is a good picosecond limiter at 0.532 {dollar}mu{dollar}m.