Design and synthesis of chromophores with enhanced electro-optic activities in both bulk and plasmonic-organic hybrid devices.

This study demonstrates enhancement of in-device electro-optic activity via a series of theory-inspired organic electro-optic (OEO) chromophores based on strong (diarylamino)phenyl electron donating moieties. These chromophores are tuned to minimize trade-offs between molecular hyperpolarizability and optical loss. Hyper-Rayleigh scattering (HRS) measurements demonstrate that these chromophores, herein described as BAH, show >2-fold improvement in ß versus standard chromophores such as JRD1, and approach that of the recent BTP and BAY chromophore families. Electric field poled bulk devices of neat and binary BAH chromophores exhibited significantly enhanced EO coefficients (r33) and poling efficiencies (r33/Ep) compared with state-of-the-art chromophores such as JRD1. The neat BAH13 devices with charge blocking layers produced very large poling efficiencies of 11.6 ± 0.7 nm2 V-2 and maximum r33 value of 1100 ± 100 pm V-1 at 1310 nm on hafnium dioxide (HfO2). These results were comparable to that of our recently reported BAY1 but with much lower loss (extinction coefficient, k), and greatly exceeding that of other previously reported OEO compounds. 3 : 1 BAH-FD : BAH13 blends showed a poling efficiency of 6.7 ± 0.3 nm2 V-2 and an even greater reduction in k. 1 : 1 BAH-BB : BAH13 showed a higher poling efficiency of 8.4 ± 0.3 nm2 V-2, which is approximately a 2.5-fold enhancement in poling efficiency vs. JRD1. Neat BAH13 was evaluated in plasmonic-organic hybrid (POH) Mach-Zehnder modulators with a phase shifter length of 10 µm and slot widths of 80 and 105 nm. In-device BAH13 achieved a maximum r33 of 208 pm V-1 at 1550 nm, which is ∼1.7 times higher than JRD1 under equivalent conditions.

Electro-Optic Activity in Excess of 1000 pm V-1 Achieved via Theory-Guided Organic Chromophore Design.

High performance organic electro-optic (OEO) materials enable ultrahigh bandwidth, small footprint, and extremely low drive voltage in silicon-organic hybrid and plasmonic-organic hybrid photonic devices. However, practical OEO materials under device-relevant conditions are generally limited to performance of ≈300 pm V-1 (10× the EO response of lithium niobate). By means of theory-guided design, a new series of OEO chromophores is demonstrated, based on strong bis(4-dialkylaminophenyl)phenylamino electron donating groups, capable of EO coefficients (r33 ) in excess of 1000 pm V-1 . Density functional theory modeling and hyper-Rayleigh scattering measurements are performed and confirm the large improvement in hyperpolarizability due to the stronger donor. The EO performance of the exemplar chromophore in the series, BAY1, is evaluated neat and at various concentrations in polymer host and shows a nearly linear increase in r33 and poling efficiency (r33 /Ep , Ep is poling field) with increasing chromophore concentration. 25 wt% BAY1/polymer composite shows a higher poling efficiency (3.9 ± 0.1 nm2 V-2 ) than state-of-the-art neat chromophores. Using a high-ε charge blocking layer with BAY1, a record-high r33 (1100 ± 100 pm V-1 ) and poling efficiency (17.8 ± 0.8 nm2 V-2 ) at 1310 nm are achieved. This is the first reported OEO material with electro-optic response larger than thin-film barium titanate.

Modeling the optical behavior of complex organic media: from molecules to materials.

For the past three decades, a full understanding of the electro-optic (EO) effect in amorphous organic media has remained elusive. Calculating a bulk material property from fundamental molecular properties, intermolecular electrostatic forces, and field-induced net acentric dipolar order has proven to be very challenging. Moreover, there has been a gap between ab initio quantum-mechanical (QM) predictions of molecular properties and their experimental verification at the level of bulk materials and devices. This report unifies QM-based estimates of molecular properties with the statistical mechanical interpretation of the order in solid phases of electric-field-poled, amorphous, organic dipolar chromophore-containing materials. By combining interdependent statistical and quantum mechanical methods, bulk material EO properties are predicted. Dipolar order in bulk, amorphous phases of EO materials can be understood in terms of simple coarse-grained force field models when the dielectric properties of the media are taken into account. Parameters used in the statistical mechanical modeling are not adjusted from the QM-based values, yet the agreement with the experimentally determined electro-optic coefficient is excellent.

Self-organization of a wedge-shaped surfactant in monolayers and multilayers.

The self-organization behavior of a wedge-shaped surfactant, disodium-3,4,5-tris(dodecyloxy)phenylmethylphosphonate, was studied in Langmuir monolayers (at the air-water interface), Langmuir-Blodgett (LB) monolayers and multilayers, and films adsorbed spontaneously from isooctane solution onto a mica substrate (self-assembled films). This compound forms an inverted hexagonal lyotropic liquid crystal phase in the bulk and in thick adsorbed films. Surface pressure isotherm and Brewster angle microscope (BAM) studies of Langmuir monolayers revealed three phases: gas (G), liquid expanded (LE), and liquid condensed (LC). The surface pressure-temperature phase diagram was determined in detail; a triple point was found at approximately 10 degrees C. Atomic force microscope (AFM) images of LB monolayers transferred from various regions of the phase diagram were consistent with the BAM images and indicated that the LE regions are approximately 0.5 nm thinner than the LC regions. AFM images were also obtained of self-assembled films after various adsorption times. For short adsorption times, when monolayer self-assembly was incomplete, the film topography indicated the coexistence of two distinct monolayer phases. The height difference between these two phases was again 0.5 nm, suggesting a correspondence with the LE/LC coexistence observed in the Langmuir monolayers. For longer immersion times, adsorbed multilayers assembled into highly organized periodic arrays of inverse cylindrical micelles. Similar periodic structures, with the same repeat distance of 4.5 nm, were also observed in three-layer LB films. However, the regions of organized periodic structure were much smaller and more poorly correlated in the LB multilayers than in the films adsorbed from solution. Collectively, these observations indicate a high degree of similarity between the molecular organization in Langmuir layers/LB films and adsorbed self-assembled films. In both cases, monolayers progress through an LE phase, into LE/LC coexistence, and finally into LC phase as surface density increases. Following the deposition of an additional bilayer, the film reorganizes to form an array of inverted cylindrical micelles.

Periodic arrays of interfacial cylindrical reverse micelles.

We report an approach for the fabrication of periodic molecular nanostructures on surfaces. The approach involves biomimetic self-organization of synthetic wedge-shaped amphiphilic molecules into multilayer arrays of cylindrical reverse micelles. The films were characterized by atomic force microscopy and X-ray reflectivity. These nanostructured films self-assemble in solution but remain stable upon removal and exposure to ambient conditions, making them potentially suitable for a variety of dry pattern transfer methods. We illustrate the generality of this approach by using two distinct molecular systems that vary in size by a factor of 2.