Kimberly A. Firestone

Molecular engineering of nanoscale order in organic electro-optic glasses

The rational design of bulk nanoscale order in organic electro-optic materials, where the strong dipole–dipole interactions tend to dominate over the weaker forces exploited for self-assembly processes, remains an attractive yet elusive goal. Towards this end, a series of pseudo-discotic dipolar nonlinear optical chromophores have been synthesized and fully characterized. Theoretical guidance and an iterative molecular design process have succeeded in engineering long-range nanoscale order in organic electro-optic glasses. Small-angle thin-film X-ray diffraction experiments demonstrate a self-assembled lamellar morphology in a majority of these materials. Cryogenic crystallography, using a synchrotron X-ray source, afforded the structure of a representative system. This structure, in concert with thin-film X-ray diffraction, atomic force microscopy, UV-vis-NIR absorption spectroscopy, and refractive index experiments elucidated the nanoscale order in the films. Application of these materials in electro-optics is discussed.

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.

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.

Frequency-agile hyper-Rayleigh scattering studies of electro-optic chromophores

Hyper-Rayleigh scattering (HRS) is used to measure the first-hyperpolarizability (β) of electro-optic (EO) chromophores. One of the inherent concerns in any HRS measurement is the extent to which resonant enhancement contributes to the observed intensity thereby leading to inaccuracies when evaluating chromophore potential for application in electro-optical devices. One way to address this concern is to employ increasingly longer excitation wavelengths far from resonance. However, in charge-transfer-based non-linear optical chromophores, enhanced β generally correlates with a red-shift of the charge transfer absorption band so that even at the longest excitation wavelengths generally employed in HRS studies, resonant enhancement remains an issue. We have adopted an alternative approach in which the wavelength dispersion of the HRS intensity is determined by performing measurements at a variety of excitation wavelengths. This approach allows one to ascertain the role of resonance enhancement thereby allowing for more accurate correlation of improved β with molecular architecture. We report the results of our HRS studies for nine chromophores employing excitation wavelengths ranging from 780 to 1907 nm. Our HRS results demonstrate good agreement with the predictions of density functional theory. This synthesis of experimental and theoretical techniques has resulted in more effective designs for the next generations of electro-optical chromophores.

Optimizing electro-optic activity in chromophore/polymer composites and in organic chromophore glasses

The motivation for use of organic electro-optic materials derives from (1) the inherently fast (sub-picosecond) response of π-electron systems in these materials to electrical perturbation making possible device applications with gigahertz and terahertz bandwidths, (2) the potential for exceptionally large (e.g., 1000 pm/V) electro-optic coefficients that would make possible devices operating with millivolt drive voltages, (3) light weight, which is a concern for satellite applications, and (4) versatile processability that permits rapid fabrication of a wide variety of devices including conformal and flexible devices, three dimensional active optical circuitry, hybrid organic/silicon photonic circuitry, and optical circuitry directly integrated with semiconductor VLSI electronics. The most significant concerns associated with the use of organic electro-optic materials relate to thermal and photochemical stability, although materials with glass transition temperatures on the order of 200°C have been demonstrated and photostability necessary for long term operation at telecommunication power levels has been realized. This communication focuses on explaining the theoretical paradigms that have permitted electro-optic coefficients greater than 300 pm/V (at telecommunication wavelengths) to be achieved and on explaining likely improvements in electro-optic activity that will be realized in the next 1-2 years. Systematic modifications of materials to improve thermal and photochemical stability are also discussed.

New paradigm in NLO chromophore design through a gradient bridge concept

In pursuit of greater understanding of structure property relationships in NLO chromophores, a series of molecules consisting of three aromatic rings was synthesized. The relative positions of benzene and thiophene rings in these molecules were varied. Theoretical calculations also suggest that the use of a slightly electron deficient heteroaromatic, such as thiazole, can increase β through the concept of an electronic gradient. The use of this heteroaromatic in the correct orientation can compensate for the energetic barrier that benzene presents during charge-transfer. Hyper-Raleigh Scattering (HRS) measurements on three of these “gradient bridge” type chromophores show that benzene located at the donor end provided the highest hyperpolarizability. The poor solubility of these three-ring systems severely limited their processability and gave considerable synthetic challenges. The difference in theoretical and experimental trends of β are discussed.

Exploration of a Series Type Multifunctionalized Nonlinear Optical Chromophore Concept

Density functional theory calculations were used to develop understanding of the effects of differing substitution patterns in multiply donor and acceptor substituted nonlinear optical chromophores. A novel series type substitution design was presented and evaluated. Calculations were performed for a number of structures and hyperpolarizability values were compared. The data obtained showed an increase in molecular first hyperpoloarizability in multifunctional chromophores based on this series type design as compared with linear molecules constructed from the same donor-bridge-acceptor components. This data was then used to direct the synthesis of novel nonlinear optical chromophores.

Organic electro-optic glasses for WDM applications

This communication primarily deals with utilizing organic electro-optic (OEO) materials for the fabrication of active wavelength division multiplexing (WDM) transmitter/receiver systems and reconfigurable optical add/drop multiplexers (ROADMs), including the fabrication of hybrid OEO/silicon photonic devices. Fabrication is carried out by a variety of techniques including soft and nanoimprint lithography. The production of conformal and flexible ring microresonator devices is also discussed. The fabrication of passive devices is also briefly reviewed. Critical to the realization of improved performance for devices fabricated from OEO materials has been the improvement of electro-optic activity to values of 300 pm/V (or greater) at telecommunication wavelengths. This improvement in materials has been realized exploiting a theoretically-inspired (quantum and statistical mechanics) paradigm for the design of chromophores with dramatically improved molecular first hyperpolarizability and that exhibit intermolecular electrostatic interactions that promote self-assembly, under the influence of an electric poling field, into noncentrosymmetric macroscopic lattices. New design paradigms have also been developed for improving the glass transition of these materials, which is critical for thermal and photochemical stability and for optimizing processing protocols such as nanoimprint lithography. Ring microresonator devices discussed in this communication were initially fabricated using chromophore guest/polymer host materials characterized by electro-optic coefficients on the order of 50 pm/V (at telecommunication wavelengths). Voltage-controlled optical tuning of the pass band of these ring microresonators was experimental determined to lie in the range 1-10 GHz/V or all-organic and for OEO/silicon photonic devices. With new materials, values approaching 50 GHz/V should be possible. Values as high as 300 GHz/V may ultimately be achievable.

Functionalized guanidines for electro-optic materials

A family of nonlinear optical chromophores has been synthesized containing novel donor systems based on functionalized guanidines. Chromophores utilizing these donor systems display superior transparency and stability properties. The unusual and highly desirable characteristics of these chromophores make them very promising candidates for electro-optic applications. Systematic study of the molecular hyperpolarizabilities and bulk electro-optic properties of polymers containing these chromophores is being used to guide optimization of these systems.