Contents 42 4. Materials Processing Methodologies 44 4.1. Electric Field Poling 44 4.1.1. Conductivity Issues; Buffer Layers 45 4.1.2. Laser-Assisted Electric Field Poling 45 4.2. Lattice Hardening and Thermal Stability 46 5. Characterization Methods 46 5.1. Methods for Characterizing Molecular First Hyperpolarizability 46 5.2. Methods for Characterizing Electro-optic Activity 48 5.3. Characterization of Poling-Induced Order: VAPRAS 49 5.4. Characterization of Photochemical Stability 49 6. Devices and Applications 50 7. Conclusions and Future Prospects 50 8. Acknowledgments 51 9. References 51
Abstract:We demonstrate a novel mechanism for low power optical detection and modulation in a slotted waveguide geometry filled with nonlinear electro-optic polymers. The nanoscale confinement of the optical mode, combined with its close proximity to electrical contacts, enables the direct conversion of optical energy to electrical energy, without external bias, via optical rectification, and also enhances electro-optic modulation. We demonstrate this process for power levels in the sub-milliwatt regime, as compared to the kilowatt regime in which optical nonlinear effects are typically observed at short length scales. Our results suggest that a new class of detectors based on nonlinear optics may be practical.
Extensive experimental and theoretical study suggests that interchromophore electrostatic interactions are among the most severe impediments to the induction and stability of large electro-optic coefficients in electric-field-poled organic materials. In this report, multichromophore-containing dendritic materials have been investigated as a means to minimize unwanted attenuation of nonlinear optical (electro-optic) activity at high chromophore loading. The dendritic molecular architectures employed were designed to provide optimized molecular scaffolding for electric-field-induced molecular reorientation. Design parameters were based upon past experimental results in conjunction with statistical and quantum mechanical modeling. The electro-optic behavior of these materials was evaluated through experimental and theoretical analysis. Experimental data collected from the dendrimer structures depict a reasonably linear relationship between chromophore number density (N) and electro-optic activity (r(33)) demonstrating a deviation from the dipolar frustration that typically limits r(33) in conventional chromophore/polymer composite materials. The observed linear dependence holds at higher chromophore densities than those that have been found to be practical in systems of organic NLO chromophores dispersed in polymer hosts. Theoretical analysis of these results using Monte Carlo modeling reproduces the experimentally observed trends confirming linear dependence of electro-optic activity on N in the dendrimer materials. These results provide new insight into the ordering behavior of EO dendrimers and demonstrate that the frequently observed asymptotic dependence of electro-optic activity on chromophore number density may be overcome through rational design.
Correlated time-dependent density functional theory (TDDFT) quantum mechanical and pseudo-atomistic Monte Carlo (PAMC) statistical mechanical methods have been used to assist in the understanding of and to guide the improvement of organic electro-optic (OEO) materials, prepared by electric field poling of pi-electron chromophore-containing materials near their glass transition temperature. Theoretical treatment of the effects of dielectric permittivity and optical frequency on molecular (chromophore) first hyperpolarizabilities has been carried out as well as the analysis of the influence of spatially anisotropic intermolecular electrostatic interactions on the poling-induced noncentrosymmetric order of chromophores. Three classes of OEO materials have been considered in correlated theoretical and experimental investigations: (1) traditional chromophore/polymer composite materials, (2) chromophores covalently incorporated into polymers, dendrimers, and dendronized polymers, and (3) recently discovered materials consisting of chromophores incorporated into chromophore-containing host materials. This latter class of materials is referred to as binary chromophore organic glasses (BCOGs). These BCOGs exhibit exceptional electro-optic activity because of a combination of high chromophore number density, the effect of high dielectric permittivity on molecular first hyperpolarizability, and improved acentric order arising from the intermolecular electrostatic interactions among the two types of chromophores. The electrical conductivity of materials can also influence achievable electro-optic activity, and thin metal oxide buffer layers, introduced to limit charge injection, can significantly improve poling efficiency. Chromophore order can also be influenced, in some cases, by novel processing techniques, such as laser-assisted electric field poling. Thermal and photostability are important parameters for practical application of materials and have been improved dramatically in recent times. Diels-Alder and fluorovinyl ether cycloaddition reactions have been used to elevate final material glass transition temperatures to above 200 degrees C. Photostability is dominated by the photoactivation of singlet oxygen and subsequent attack on electro-optic chromophores. Photostability can be improved by more than 4 orders of magnitude by chromophore modification and material packaging.
Two new highly hyperpolarizable chromophores, based on N,N- bis-(4-methoxyphenyl) aryl-amino donors and phenyl-trifluoromethyl-tricyanofuran (CF3-Ph-TCF) acceptor linked together via pi-conjugation through 2,5-divinylenethienyl moieties as the bridge, have been designed and synthesized successfully for the first time. The aryl moieties on the donor side of the chromophore molecules were varied as to be thiophene and 1-n-hexylpyrrole. The linear and nonlinear optical (NLO) properties of all compounds were evaluated in addition to recording relevant thermal and electrochemical data. The properties of the two new molecules were comparatively studied. These results are critically analyzed along with two other compounds, reported earlier from our laboratories and our collaborator's, that contain (i) aliphatic chain-bearing aniline and (ii) dianisylaniline as donors, keeping the bridge (2,5-divinylenethienyl-), and the acceptor (CF3-Ph-TCF), constant. Trends in theoretically (density functional theory, DFT) predicted, zero-frequency gas-phase hyperpolarizability [beta(0;0,0)] values are shown to be consistent with the trends in beta HRS(-2omega;omega,omega), as measured by Hyper-Rayleigh Scattering (HRS), when corrected to zero-frequency using the two-level model (TLM) approximation. Similarly, trends in poling efficiency data (r33/E(p)) and wavelength dispersion measured by reflection ellipsometry (using a Teng-Man apparatus) and attenuated total reflection (ATR) are found to fit the TLM and DFT predictions. A 3-fold enhancement in bulk nonlinearity (r33) is realized as the donor subunits are changed from alkylaniline to dianisylaminopyrrole donors. The results of these studies provide insight into the complicated effects on molecular hyperpolarizability of substituting heteroaromatic subunits into the donor group structures. These studies also demonstrate that, when frequency dependence and electric-field-induced ordering behavior are correctly accounted for, ab initio DFT generated beta(0;0,0) is effective as a predictor of changes in r33 behavior based on chromophore structure modification. Thus DFT can provide valuable insight into the electronic structure origin of complex optical phenomena in organic media.
This definitive guide to modern organic electro-optic and photonic technologies provides critical insight into recent advances in organic electro-optic materials, from the underlying quantum and statistical concepts through to the practical application of materials in modern devices and systems. • Introduces theoretical and experimental methods for improving organic electro-optic and photonic technologies • Reviews the central concepts of nonlinear optics, focusing on multi-scale theoretical methods • Provides clear insight into the structure and function relationships critical to optimizing the performance of devices based on organic electro-optic materials. Serving as a primer for the systematic nano-engineering of soft matter materials, this is an invaluable resource for those involved in the development of modern telecommunication, computing, and sensing technologies depending on electro-optic technology. It is also an indispensable work of reference for academic researchers and graduate students in the fields of chemistry, physics, electrical engineering, materials science and engineering, and chemical engineering.
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