Marnie Haller

Highly Efficient and Thermally Stable Electro-Optical Dendrimers for Photonics

After a brief review on electro-optical (EO) polymers, the recent development of EO dendrimers is summarized. Both single- and multiple-dendron-modified nonlinear optical (NLO) chromophores in the guest–host polymer systems showed a very significant enhancement of poling efficiency (up to a three-fold increase) due to the minimization of intermolecular electrostatic interactions among large dipole moment chromophores through the dendritic effect. Moreover, multiple NLO chromophore building blocks can also be placed into a dendrimer to construct a precise molecular architecture with a predetermined chemical composition. The site-isolation effect, through the encapsulation of NLO moieties with dendrons, can greatly enhance the performance of EO materials. A very large EO coefficient (r33 = 60 pm/V at 1.55 μm) and high temporal stability (85 °C for more than 1000 h) were achieved in a NLO dendrimer (see Figure) through the double-end functionalization of a three-dimensional phenyl-tetracyanobutadienyl (Ph-TCBD)-containing NLO chromophore with thermally crosslinkable trifluorovinylether-containing dendrons.

Resonance enhanced THz generation in electro-optic polymers near the absorption maximum

The electro-optic (EO) coefficient of an organic nonlinear material exhibits a sharp resonance near the absorption maximum of the material. Due to this resonance, we experimentally observe the amplitude of the THz field generated from a 3.1-μm-thick EO polymer composite to be larger than that emitted from a 1000-μm-thick crystal of ZnTe. This comparison allows us to estimate the resonance enhanced EO coefficient of the polymer composite to be over 1250pm∕V at 800nm.

Recent progress in developing highly efficient and thermally stable nonlinear optical polymers for electro-optics

Recent development of high-performance nonlinear optical polymers for electro-optics (E-O) is reviewed in this paper. A highly efficient and thermally stable nonlinear optical (NLO) chromophore, namely 2-[4-(2-{5-[2-(4-{Bis-(tert-butyl-dimethyl-silanyloxy)-ethyl]-amino}-phenyl)-vinyl]-thiophen-2-yl}-vinyl)-3-cyano-5-trifluoromethyl-5H-furan-2-ylidene]-malononitrile, has been prepared and incorporated in amorphous polycarbonate (APC) composites. The result from high electric field poling shows a very large E-O coefficient (r33 = 94 pm/V at 1.3 μm), ~80% of which can be maintained at 85 °C for more than 500 hours. In addition to this guest/host sysytem, a high Tg side-chain polymer, derived from a 3-D cardo-type polimide with dendron-encapsulated chromophores as pendent groups has also been synthesized and characterized. A high degree of chromophore dipole orientation and a large r33 of 71 pm/V at 1.3 μm can be achieved in this poled polyimide. More than 90% of its E-O activity can be maintained at 85 °C for more than 600 hours. To access the full potential of poled polymers for device applications, we have developed a new lattice-hardening approach to overcome the “nonlinearity-stability-tradeoff” of conventional thermoset methods. By using the Diels-Alder lattice-hardening process, we can achieve the same high poling efficiency and large r33value as in a guest-host system while maintaining good thermal stability seen in densely-crosslinked polymers. By modifying the electronic properties of the crosslinking reagents, we can fine-tune the processing temperature window of the Diels-Alder reactions to achieve hardened materials with optimal properties.

Electro-optic coefficients of 500 pm/V and beyond for organic materials

Theoretical guidance, provided by quantum and statistical mechanical calculations, has aided the recent realization of electro-optic coefficients of greater than 300 pm/V (at 1.3 microns wavelength). This articles attempts to provide physical insight into those recent results and to explore avenues for the further improvement of electro-optic activity by structural modification, including to values of 500 pm/V and beyond. While large electro-optic coefficients are a necessary condition for extensive practical application of organic electro-optic materials, they are not a sufficient condition. Adequate thermal and photochemical stability, modest to low optical loss, and processability are important additional requirements. This article also examines such properties and suggests routes to achieving improved auxiliary properties.

Very large electro-optic coefficients from in situ generated side-chain nonlinear optical polymers

A synthetic/processing method has been developed for achieving highly efficient nonlinear optical polymers. A maleimide-containing chromophore with large molecular nonlinearity was covalently attached onto a anthrathene-containing polymer to generate in situ a side-chain polymer via the Diels-Alder reaction. The poling and covalent side-chain attachment processes can be performed simultaneously in a solid state, resulting in high electro-optic (E-O) coefficients (r33 values up to 50pm∕V at 1310nm) and temporal stability (85% retention of the original dipole alignment after isothermal heating at 85°C for more than 500h). A very high chromophore loading level (39wt%) can be achieved by adding more chromophore into this side-chain polymer without causing any obvious phase separation. Poling of this chromophore-doped side-chain polymer (total dye content: 34wt%) showed a significantly increased E-O coefficient, from 50to110pm∕V.

Low temperature relaxations and effects on poling efficiencies of dendronized nonlinear optical side-chain polymers

Low temperature relaxations in a dendronized nonlinear optical (NLO) side-chain polymer were found to take place at more than 20 °C below the glass transition temperature. Relaxations of localized mobilities, removed from long range relaxations responsible for chromophore aggregation, are shown to offer new gateways for optimized acentric ordering of the chromophores. Supreme electro-optical (EO) activity was achieved by electrical poling close to the critical temperatures of localized mobilities identified as dendronized NLO side-chain relaxations. This study features, in particular, one new instrumental approach to relaxation studies of thin spin coated NLO polymer films; the shear-modulation force microscopy (SM-FM) method. Originating from scanning force microscopy (SFM), the SM-FM method grants access to the detection of low temperature relaxations in constrained thin NLO films not obtainable by conventional means.

Recent progress in developing highly efficient nonlinear optical chromophores and side-chain dendronized polymers for electro-optics

Recent progress in developing high-performance nonlinear optical chromophores and polymers for electro-optics is reviewed. Using the single-mode focused microwave irradiation, a diversified family of 2,5-dihydrofuran derivatives has been synthesized as a new class of tunable electron acceptors. Very large r33 values (128 and 116 pm/V at 1.3 μm) have been demonstrated by doping one of the 2-dicyanomethylen-3-cyano-4,5,-dimethyl-5-trifluoromethyl-2,5-dihydrofuran (CF3-TCF)-based chromophores in poly(methyl methacrylate) (PMMA) and a high Tg polyquinoline (PQ-100), respectively. An excellent long-term temporal stability at 85°C has also been maintained in the PQ system. Two side-chain dendronized NLO polymers have been synthesized. Using a mild, simple, and generally applicable post-functionalization method, highly polarizable chromophores with dendritic modification has been covalently attached to side chains of poly(4-hydroxystryene). This approach provides the combined advantages of achieving better poling efficiency through the dendritic effect and shortening the development time required for E-O dendrimer synthesis. Systematic property comparison between these polymers and other conventional NLO polymers, such as guest-host and simple side-chain polymers, has been performed. Exceptionally high poling efficiency (a very large E-O coefficient of 97 pm/V at 1.3 μm) and good temporal stability at room temperature were dmeonstrated in this dendronized side-chain polymer system.

Highly efficient and thermally stable organic/polymeric electro-optic materials by dendritic approach

A series of dendron-modified nonlinear optical (NLO) chromophores and multiple chromophore-containing crosslinkable NLO dendrimers have been developed. The enhancement of poling efficiency (40%) in the dendritic NLO chromophore/polymer guest/host system was obtained due to the significant minimization of intermolecular electrostatic interactions among chromophores by the dendritic effect. Multiple NLO chromophore building blocks can be further placed into a dendrimer to construct precise molecular architecture with predetermined chemical composition. The site-isolation effect, through the encapsulation of NLO moieties by dendrons, can greatly enhance the performance of electro-optic (E-O) materials. A very large E-O coefficient (r33=60 pm/V at 1.55 micrometers ) and high temporal stability (85 degree(s)C for more than 1000 h) were achieved in a NLO dendrimer developed through the double-end functionalization of a 3D shape phenyl-tetracyanobutadienyl (Ph-TCBD)- containing NLO chromophore with thermally crosslinkable trifluorovinylether-containing dendrons.

Acentric lattice electro-optic materials by rational design

Quantum and statistical mechanical calculations have been used to guide the improvement of the macroscopic electro-optic activity of organic thin film materials to values greater than 300 pm/V at telecommunication wavelengths. Various quantum mechanical methods (Hartree-Fock, INDO, and density functional theory) have been benchmarked and shown to be reliable for estimating trends in molecular first hyperpolarizability, β, for simple variation of donor, bridge, and acceptor structures of charge-transfer (dipolar) chromophores. β values have been increased significantly over the past five years and quantum mechanical calculations suggest that they can be further significantly improved. Statistical mechanical calculations, including pseudo-atomistic Monte Carlo calculations, have guided the design of the super/supramolecular structures of chromophores so that they assemble, under the influence of electric field poling, into macroscopic lattices with high degrees of acentric order. Indeed, during the past year, chromophores doped into single- and multi-chromophore-containing dendrimer materials to form binary glasses have yielded thin films that exhibit electro-optic activities at telecommunication wavelengths of greater than 300 pm/V. Such materials may be viewed as intermediate between chromophore/polymer composites and crystalline organic chromophore materials. Theory suggests that further improvements of electro-optic activity are possible. Auxiliary properties of these materials, including optical loss, thermal and photochemical stability, and processability are discussed. Such organic electro-optic materials have been incorporated into silicon photonic circuitry for active wavelength division multiplexing, reconfigurable optical add/drop multiplexing, and high bandwidth optical rectification. A variety of all-organic devices, including stripline, cascaded prism, Fabry-Perot etalon, and ring microresonator devices, have been fabricated and evaluated.

Nanoscale architectural control of organic functional materials for photonics

Recent progress in developing high-performance organic polymers for electro-optics and photonics is reviewed. A highly fluorinated hyperbranched aromatic polymer with the degree of branching around 0.51 was prepared by a mild one-step polyesterification of an AB2 type monomer. Further post-functionalization with and thermally cross-linking by aromatic trifluorovinyl ethers (TFVE) afforded thermally stable, low loss optical polymer with improved solvent resistance. By more precisely controlling the molecular nano-architecture, we have developed a series of highly fluorinated crosslinkable dendrimers. These materials possess most of the desirable properties needed for the fabrication of optical waveguides, such as high solubility in common organic solvents (up to 50 wt%), very low optical loss, and excellent thermal stability. To overcome the “nonlinearity-stability tradeoff,” a facile and reversibly crosslinkable NLO polymer system is developed that combines both advantages of high poling efficiency and good alignment thermal stability. By smartly controlling the poling and crosslinking processes through the reversible Diels-Alder (DA) reactions, it allows highly polarizable chromophores to be efficiently poled at the stage of low viscosity linear thermoplastic polymer. The resulting nonlinear optical polymer exhibits a combination of a very large r33 value (76 pm/V at 1.3 μm) and good temporal stability at 70°C.