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Electro-optic modulators are essential for sensing, metrology and telecommunications. Most target fiber applications. Instead, metasurface-based architectures that modulate free-space light at gigahertz (GHz) speeds can boost flat optics technology by microwave electronics for active optics, diffractive computing or optoelectronic control. Current realizations are bulky or have low modulation efficiencies. Here, we demonstrate a hybrid silicon-organic metasurface platform that leverages Mie resonances for efficient electro-optic modulation at GHz speeds. We exploit quasi bound states in the continuum (BIC) that provide narrow linewidth (Q = 550 at [Formula: see text] nm), light confinement to the non-linear material, tunability by design and voltage and GHz-speed electrodes. Key to the achieved modulation of [Formula: see text] are molecules with r 33  = 100 pm/V and optical field optimization for low-loss. We demonstrate DC tuning of the resonant frequency of quasi-BIC by [Formula: see text] 11 nm, surpassing its linewidth, and modulation up to 5 GHz (f EO,-3dB  = 3 GHz). Guided mode resonances tune by [Formula: see text] 20 nm. Our hybrid platform may incorporate free-space nanostructures of any geometry or material, by application of the active layer post-fabrication., (© 2022. The Author(s).)

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 β 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 ( r 33 ) and poling efficiencies ( r 33 / E p ) 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 nm 2 V -2 and maximum r 33 value of 1100 ± 100 pm V -1 at 1310 nm on hafnium dioxide (HfO 2 ). 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 nm 2 V -2 and an even greater reduction in k . 1 : 1 BAH-BB : BAH13 showed a higher poling efficiency of 8.4 ± 0.3 nm 2 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 r 33 of 208 pm V -1 at 1550 nm, which is ∼1.7 times higher than JRD1 under equivalent conditions.

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 (r 33 ) 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 r 33 and poling efficiency (r 33 /E p , E p is poling field) with increasing chromophore concentration. 25 wt% BAY1/polymer composite shows a higher poling efficiency (3.9 ± 0.1 nm 2 V -2 ) than state-of-the-art neat chromophores. Using a high-ε charge blocking layer with BAY1, a record-high r 33 (1100 ± 100 pm V -1 ) and poling efficiency (17.8 ± 0.8 nm 2 V -2 ) at 1310 nm are achieved. This is the first reported OEO material with electro-optic response larger than thin-film barium titanate., (© 2021 Wiley-VCH GmbH.)

Tailored nanostructures provide at-will control over the properties of light, with applications in imaging and spectroscopy. Active photonics can further open new avenues in remote monitoring, virtual or augmented reality and time-resolved sensing. Nanomaterials with χ (2) nonlinearities achieve highest switching speeds. Current demonstrations typically require a trade-off: they either rely on traditional χ (2) materials, which have low non-linearities, or on application-specific quantum well heterostructures that exhibit a high χ (2) in a narrow band. Here, we show that a thin film of organic electro-optic molecules JRD1 in polymethylmethacrylate combines desired merits for active free-space optics: broadband record-high nonlinearity (10-100 times higher than traditional materials at wavelengths 1100-1600 nm), a custom-tailored nonlinear tensor at the nanoscale, and engineered optical and electronic responses. We demonstrate a tuning of optical resonances by Δλ = 11 nm at DC voltages and a modulation of the transmitted intensity up to 40%, at speeds up to 50 MHz. We realize 2 × 2 single- and 1 × 5 multi-color spatial light modulators. We demonstrate their potential for imaging and remote sensing. The compatibility with compact laser diodes, the achieved millimeter size and the low power consumption are further key features for laser ranging or reconfigurable optics., (© 2021. The Author(s).)

We present a plasmonic platform featuring efficient, broadband metallic fiber-to-chip couplers that directly interface plasmonic slot waveguides, such as compact and high-speed electro-optic modulators. The metallic gratings exhibit an experimental fiber-to-slot coupling efficiency of -2.7 dB with -1.4 dB in simulations with the same coupling principle. Further, they offer a huge spectral window with a 3 dB passband of 350 nm. The technology relies on a vertically arranged layer stack, metal-insulator-metal waveguides, and fiber-to-slot couplers and is formed in only one lithography step with a minimum feature size of 250 nm. As an application example, we fabricate new modulator devices with an electro-optic organic material in the slot waveguide and reach 50 and 100 Gbit/s data modulation in the O- and C-bands within the same device. The devices' broad spectral bandwidth and their relaxed fabrication may render them suitable for experiments and applications in the scope of sensing, nonlinear optics, or telecommunications.

Research at the University of Washington regarding organic semiconductors is reviewed, covering four major topics: electro-optics, organic light emitting diodes, organic field-effect transistors, and organic solar cells. Underlying principles of materials design are demonstrated along with efforts toward unlocking the full potential of organic semiconductors. Finally, opinions on future research directions are presented, with a focus on commercial competency, environmental sustainability, and scalability of organic-semiconductor-based devices., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on compact and efficient silicon-organic hybrid (SOH) Mach-Zehnder modulators (MZM) with low phase-shifter insertion loss of 0.7 dB. The 280 µm-long phase shifters feature a π -voltage-length product of 0.41 Vmm and a loss-efficiency product as small as aU π L = 1.0 VdB. The device performance is demonstrated in a data transmission experiment, where we generate on-off-keying (OOK) and four-level pulse-amplitude modulation (PAM4) signals at symbol rates of 100 GBd, resulting in line rates of up to 200 Gbit/s. Bit error ratios are below the threshold for hard-decision forward error correction (HD-FEC) with 7% coding overhead, leading to net data rates of 187 Gbit/s. This is the highest PAM4 data rate ever achieved for a sub-1 mm silicon photonic MZM.

100 Gb/s NRZ-OOK transmission over 14 km standard single mode fiber in the C-band is demonstrated with a simple intensity modulation and direct detection scheme. The transmission concept utilizes single sideband modulation and comprises a single differential digital-to-analog converter with adjustable phase offset, a new dual electrode plasmonic Mach-Zehnder modulator, a laser at 1537.5 nm, standard single mode fibers, a photodiode, an analog-to-digital converter, and linear offline digital signal processing. The presented SSB concept requires no DSP and complex signaling at the transmitter. The demonstrated SSB transmitter increased the possible transmission distance by a factor of 4.6 compared to a DSB transmitter. We also investigated the equalization requirements. A T/2-spaced feedforward equalizer requires 27 taps to achieve transmission over 10 km with a BER below the HD-FEC limit. In comparison to a DSB transmitter, the SSB transmitter reduced the receiver DSP complexity by a factor of 13.7.

Terahertz sources and detectors have enabled numerous new applications from medical to communications. Yet, most efficient terahertz detection schemes rely on complex free-space optics and typically require high-power lasers as local oscillators. Here, we demonstrate a fiber-coupled, monolithic plasmonic terahertz field detector on a silicon-photonics platform featuring a detection bandwidth of 2.5 THz with a 65 dB dynamical range. The terahertz wave is measured through its nonlinear mixing with an optical probe pulse with an average power of only 63 nW. The high efficiency of the scheme relies on the extreme confinement of the terahertz field to a small volume of 10 -8 (λ THz /2) 3 . Additionally, on-chip guided plasmonic probe beams sample the terahertz signal efficiently in this volume. The approach results in an extremely short interaction length of only 5 μm, which eliminates the need for phase matching and shows the highest conversion efficiency per unit length up to date.

To boost electro-optic (EO) performance, a series of multichromophore dendrimers have been developed based on higher hyperpolarizability (CLD-type) chromophore cores that have been used previously (FTC-type dendrimers). The multichromophore dendrimers were molecularly engineered to have either three arms, two arms, or one arm; long or short linkers; and a fluorinated dendron (FD) or tert-butyldiphenylsilyl (TBDPS) shell. The EO performance obtained by FDSD (poling efficiency = 1.60 nm 2 V -2 ), based on succinic diester linkers, was higher than the analogue with longer adipic diester linkers and higher than the analogs with fewer chromophore moieties. Due to the shorter succinic diester linker and improved site isolation, the dendrimer chromophore with TBDPS groups exhibited enhanced glass-transition temperature ( T g = 108 °C) and comparable poling efficiency (1.62 nm 2 V -2 ) to the FD-containing version. These neat EO dendrimers have a higher index of refraction ( n = 1.75-1.84 at 1310 nm) than guest-host polymeric EO materials ( n ≈ 1.6, 1310 nm) and FTC-type EO dendrimers ( n = 1.73, 1310 nm), which is important, because a key metric for Mach-Zehnder modulators is proportional to n 3 . In addition, binary chromophore organic glasses (BCOGs) were prepared by doping a secondary EO chromophore at 25 wt % into neat dendrimers. Enhancements of EO performance were found in all BCOG materials compared with neat dendrimers due to the effect of blending. As a result of increased chromophore density, the n values of the BCOGs improved to 1.81-1.92. One BOCG, in particular, displayed the highest poling efficiency (2.35 nm 2 V -2 ) and largest EO coefficient ( r 33 ) value of 275 pm V -1 at 1310 nm, which represents a high n 3 r 33 figure-of-merit of 1946 pm V -1 . The high poling efficiencies and n 3 r 33 figure-of-merit combined with excellent film forming confirm these neat dendrimers and BCOGs based on them as promising candidates for incorporation into photonic devices.

A new plasmonic Mach-Zehnder modulator is demonstrated at a bit rate of 120 Gb/s NRZ-OOK with low peak-to-peak driving voltages of 178 mV pp below the HD-FEC limit. Such record low driving voltage requirements potentially translate into an electrical drive power consumption of 862 aJ/bit. The low drive voltages have been made possible by a new differential Mach-Zehnder modulator electrode design. The differential electrode design is optimized for the balanced driving circuitry and reduces the effectively required driving voltage by a factor of four (V π /4). The potential of the transmitter scheme is further demonstrated by a transmission experiment over 500 m of single mode fiber at the C-band with a BER performance below the KP4 FEC limit.

Coherent optical communications provides the largest data transmission capacity with the highest spectral efficiency and therefore has a remarkable potential to satisfy today's ever-growing bandwidth demands. It relies on so-called in-phase/quadrature (IQ) electro-optic modulators that encode information on both the amplitude and the phase of light. Ideally, such IQ modulators should offer energy-efficient operation and a most compact footprint, which would allow high-density integration and high spatial parallelism. Here, we present compact IQ modulators with an active section occupying a footprint of 4 × 25 µm × 3 µm, fabricated on the silicon platform and operated with sub-1-V driving electronics. The devices exhibit low electrical energy consumptions of only 0.07 fJ bit -1 at 50 Gbit s -1 , 0.3 fJ bit -1 at 200 Gbit s -1 , and 2 fJ bit -1 at 400 Gbit s -1 . Such IQ modulators may pave the way for application of IQ modulators in long-haul and short-haul communications alike.

To cope with the high bandwidth requirements of wireless applications1, carrier frequencies are shifting towards the millimetre-wave and terahertz bands2-5. Conversely, data is normally transported to remote wireless antennas by optical fibres. Therefore, full transparency and flexibility to switch between optical and wireless domains would be desirable6,7. Here, we demonstrate for the first time a direct wireless-to-optical receiver in a transparent optical link. We successfully transmit 20 and 10 Gbit/s over wireless distances of 1 and 5 m at a carrier frequency of 60 GHz, respectively. Key to the breakthrough was a plasmonic mixer directly mapping the wireless information onto optical signals. The plasmonic scheme with its subwavelength feature and pronounced field confinement provides a built-in field enhancement of up to 90'000 over the incident field in an ultra-compact and CMOS compatible structure. The plasmonic mixer is not limited by electronic speed and thus compatible with future terahertz technologies., Competing Interests: Competing interests The authors declare no competing interest.

For nearly two decades, researchers in the field of plasmonics 1 -which studies the coupling of electromagnetic waves to the motion of free electrons near the surface of a metal 2 -have sought to realize subwavelength optical devices for information technology 3-6 , sensing 7,8 , nonlinear optics 9,10 , optical nanotweezers 11 and biomedical applications 12 . However, the electron motion generates heat through ohmic losses. Although this heat is desirable for some applications such as photo-thermal therapy, it is a disadvantage in plasmonic devices for sensing and information technology 13 and has led to a widespread view that plasmonics is too lossy to be practical. Here we demonstrate that the ohmic losses can be bypassed by using 'resonant switching'. In the proposed approach, light is coupled to the lossy surface plasmon polaritons only in the device's off state (in resonance) in which attenuation is desired, to ensure large extinction ratios between the on and off states and allow subpicosecond switching. In the on state (out of resonance), destructive interference prevents the light from coupling to the lossy plasmonic section of a device. To validate the approach, we fabricated a plasmonic electro-optic ring modulator. The experiments confirm that low on-chip optical losses, operation at over 100 gigahertz, good energy efficiency, low thermal drift and a compact footprint can be combined in a single device. Our result illustrates that plasmonics has the potential to enable fast, compact on-chip sensing and communications technologies.

Plasmonics provides a possible route to overcome both the speed limitations of electronics and the critical dimensions of photonics. We present an all-plasmonic 116-gigabits per second electro-optical modulator in which all the elements-the vertical grating couplers, splitters, polarization rotators, and active section with phase shifters-are included in a single metal layer. The device can be realized on any smooth substrate surface and operates with low energy consumption. Our results show that plasmonics is indeed a viable path to an ultracompact, highest-speed, and low-cost technology that might find many applications in a wide range of fields of sensing and communications because it is compatible with and can be placed on a wide variety of materials., (Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

The performance of highly nonlinear organic electro-optic (EO) materials incorporated into nanoscale slots is examined. It is shown that EO coefficients as large as 190 pm/V can be obtained in 150 nm wide plasmonic slot waveguides but that the coefficients decrease for narrower slots. Possible mechanism that lead to such a decrease are discussed. Monte-Carlo computer simulations are performed, confirming that chromophore-surface interactions are one important factor influencing the EO coefficient in narrow plasmonic slots. These highly nonlinear materials are of particular interest for applications in optical modulators. However, in modulators the key parameters are the voltage-length product U π L and the insertion loss rather than the linear EO coefficients. We show record-low voltage-length products of 70 Vµm and 50 Vµm for slot widths in the order of 50 nm for the materials JRD1 and DLD164, respectively. This is because the nonlinear interaction is enhanced in narrow slot and thereby compensates for the reduced EO coefficient. Likewise, it is found that lowest insertion losses are observed for slot widths in the range 60 to 100 nm.

We demonstrate a plasmonic Mach-Zehnder (MZ) modulator with a flat frequency response exceeding 170 GHz. The modulator comprises two phase modulators exploiting the Pockels effect of an organic electro-optic material in plasmonic slot waveguides. We further show modulation at 100 GBd NRZ and 60 GBd PAM-4. The electrical drive signals were generated using a 100 GSa/s digital to analog converter (DAC). The high-speed and small-scale devices are relevant for next-generation optical interconnects.

In this paper, we demonstrate an integrated microwave phoneeded for beamtonics phased array antenna feeder at 60 GHz with a record-low footprint. Our design is based on ultra-compact plasmonic phase modulators (active area <2.5µm 2 ) that not only provide small size but also ultra-fast tuning speed. In our design, the integrated circuit footprint is in fact only limited by the contact pads of the electrodes and by the optical feeding waveguides. Using the high speed of the plasmonic modulators, we demonstrate beam steering with less than 1 ns reconfiguration time, i.e. the beam direction is reconfigured in-between 1 GBd transmitted symbols.

We demonstrate for the first time a waveguide-based frequency shifter on the silicon photonic platform using single-sideband modulation. The device is based on silicon-organic hybrid (SOH) electro-optic modulators, which combine conventional silicon-on-insulator waveguides with highly efficient electro-optic cladding materials. Using small-signal modulation, we demonstrate frequency shifts of up to 10 GHz. We further show large-signal modulation with optimized waveforms, enabling a conversion efficiency of -5.8 dB while suppressing spurious side-modes by more than 23 dB. In contrast to conventional acousto-optic frequency shifters, our devices lend themselves to large-scale integration on silicon substrates, while enabling frequency shifts that are several orders of magnitude larger than those demonstrated with all-silicon serrodyne devices.

A scheme for the direct conversion of millimeter and THz waves to optical signals is introduced. The compact device consists of a plasmonic phase modulator that is seamlessly cointegrated with an antenna. Neither high-speed electronics nor electronic amplification is required to drive the modulator. A built-in enhancement of the electric field by a factor of 35,000 enables the direct conversion of millimeter-wave signals to the optical domain. This high enhancement is obtained via a resonant antenna that is directly coupled to an optical field by means of a plasmonic modulator. The suggested concept provides a simple and cost-efficient alternative solution to conventional schemes where millimeter-wave signals are first converted to the electrical domain before being up-converted to the optical domain.

Plasmonic modulators might pave the way for a new generation of compact low-power high-speed optoelectronic devices. We introduce an extremely compact transmitter based on plasmonic Mach-Zehnder modulators offering a capacity of 4 × 36 Gbit/s on a footprint that is only limited by the size of the high-speed contact pads. The transmitter array is contacted through a multicore fiber with a channel spacing of 50 μm.

We report on high-speed plasmonic-organic hybrid Mach-Zehnder modulators comprising ultra-compact phase shifters with lengths as small as 19 µm. Choosing an optimum phase shifter length of 29 µm, we demonstrate 40 Gbit/s on-off keying (OOK) modulation with direct detection and a BER < 6 × 10(-4). Furthermore, we report on a 29 µm long binary-phase shift keying (BPSK) modulator and show that it operates error-free (BER < 1 × 10(-10)) at data rates up to 40 Gbit/s and with an energy consumption of 70 fJ/bit.

We demonstrate silicon-organic hybrid (SOH) electro-optic modulators that enable quadrature phase-shift keying (QPSK) and 16-state quadrature amplitude modulation (16QAM) with high signal quality and record-low energy consumption. SOH integration combines highly efficient electro-optic organic materials with conventional silicon-on-insulator (SOI) slot waveguides, and allows to overcome the intrinsic limitations of silicon as an optical integration platform. We demonstrate QPSK and 16QAM signaling at symbol rates of 28 GBd with peak-to-peak drive voltages of 0.6 V(pp). For the 16QAM experiment at 112 Gbit/s, we measure a bit-error ratio of 5.1 × 10⁻⁵ and a record-low energy consumption of only 19 fJ/bit.

CONSPECTUS: Organic glasses containing chromophores with large first hyperpolarizabilities (β) are promising for compact, high-bandwidth, and energy-efficient electro-optic devices. Systematic optimization of device performance requires development of materials with high acentric order and enhanced hyperpolarizability at operating wavelengths. One essential component of the design process is the accurate calculation of optical transition frequencies and hyperpolarizability. These properties can be computed with a wide range of electronic structure methods implemented within commercial and open-source software packages. A wide variety of methods, especially hybrid density-functional theory (DFT) variants have been used for this purpose. However, in order to provide predictions useful to chromophore designers, a method must be able to consistently predict the relative ordering of standard and novel materials. Moreover, it is important to distinguish between the resonant and nonresonant contribution to the hyperpolarizabiliy and be able to estimate the trade-off between improved β and unwanted absorbance (optical loss) at the target device's operating wavelength. Therefore, we have surveyed a large variety of common methods for computing the properties of modern high-performance chromophores and compared these results with prior experimental hyper-Rayleigh scattering (HRS) and absorbance data. We focused on hybrid DFT methods, supplemented by more computationally intensive Møller-Plesset (MP2) calculations, to determine the relative accuracy of these methods. Our work compares computed hyperpolarizabilities in chloroform relative to standard chromophore EZ-FTC against HRS data versus the same reference. We categorized DFT methods used by the amount of Hartree-Fock (HF) exchange energy incorporated into each functional. Our results suggest that the relationship between percentage of long-range HF exchange and both βHRS and λmax is nearly linear, decreasing as the fraction of long-range HF exchange increases. Mild hybrid DFT methods are satisfactory for prediction of λmax. However, mild hybrid methods provided qualitatively incorrect predictions of the relative hyperpolarizabilities of three high-performance chromophores. DFT methods with approximately 50% HF exchange, and especially the Truhlar M062X functional, provide superior predictions of relative βHRS values but poorer predictions of λmax. The observed trends for these functionals, as well as range-separated hybrids, are similar to MP2, though predicting smaller absolute magnitudes for βHRS. Frequency dependence for βHRS can be calculated using time-dependent DFT and HF methods. However, calculation quality is sensitive not only to a method's ability to predict static hyperpolarizability but also to its prediction of optical resonances. Due to the apparent trade-off in accuracy of prediction of these two properties and the need to use static finite-field methods for MP2 and higher-level hyperpolarizability calculations in most codes, we suggest that composite methods could greatly improve the accuracy of calculations of β and λmax.

We demonstrate frequency comb sources based on silicon-organic hybrid (SOH) electro-optic modulators. Frequency combs with line spacings of 25 GHz and 40 GHz are generated, featuring flat-top spectra with less than 2 dB power variations over up to 7 lines. The combs are used for WDM data transmission at terabit/s data rates and distances of up to 300 km.

A broad nanoscopic study of a wide-range of dendritic organic nonlinear optical (NLO) self-assembly molecular glasses reveals an intermediate thermal phase regime responsible for both enhanced electric field poling properties and strong phase stabilization after poling. In this paper, the focus is on dendritic NLO molecular glasses involving quadrupolar, liquid crystal, and hydrogen bonding self-assembly mechanisms that, along with chromophore dipole-dipole interactions, dictate phase stability. Specifically, dendritic face-to-face interactions involving arene-perfluoroarene are contrasted to coumarin-containing liquid crystal mesogen and cinnamic ester hydrogen interactions. Both the strength of dendritic interactions and the impact of dipole fields on the relaxation behavior have been analyzed by nanoscale energetic probing and local thermal transition analysis. The presence of dendritic groups was found to fundamentally alter transition temperatures and the molecular relaxation behavior. Thermal transition analysis revealed that molecules with dendritic groups possess an incipient transition (T(1)) preceding the glass transition temperature (T(2)) that provides increased stability and a well-defined electric field poling regime (T(1) < T < T(2)), in contrast to molecular groups lacking dendrons that exhibit only single transitions. On the basis of enthalpic and entropic energetic analyses, thermally active modes below T(1) were found to be intimately connected to the dendron structure. Their corresponding activation energies, which are related to thermal stability, increased moving from cinnamic ester groups to coumarin moieties to arene-perfluoroarene interacting groups. While dendritic NLO materials were found to possess only enthalpic stabilization energies at temperatures relevant for device operation (T < T(1)), the apparent molecular binding energies above T(1) contain a substantial amount (up to ~80%) of cooperative entropic energy. The multiple interactions (from dipole-dipole interactions to local noncovalent dendritic interactions) are discussed and summarized in a model that describes the thermal transitions and phases.

A high performing electro-optic (EO) chromophore with covalently attached coumarin-based pendant groups exhibits intermolecular correlation of coumarin units through molecular dynamics (MD) simulations. Unique, orthogonal molecular orientations of the chromophore and coumarin units are also evident when investigated optically. Such molecular orientation translates to reduced lattice dimensionality of the bulk C1 soft matter material system, leading to increased acentric order and EO activity. Results are corroborated by nanorheological experimental methods., (Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The dipole moments of highly polar molecules measured in solution are usually smaller than the molecular dipole moments that are calculated with reaction field methods, whereas vacuum values are routinely calculated in good agreement with available vapor phase data. Whether from Onsager's theory (or variations thereof) or from quantum mechanical methods, the calculated molecular dipoles in solution are found to be larger than those measured. The reason, of course, is that experiments measure the net dipole moment of solute together with the polarized (perturbed) solvent "cloud" surrounding it. Here we show that the reaction field charges that are generated in the quantum mechanical self-consistent reaction field (SCRF) method give a good estimate of the net dipole moment of the solute molecule together with the moment arising from the reaction field charges. This net dipole is a better description of experimental data than the vacuum dipole moment and certainly better than the bare dipole moment of the polarized solute molecule.

Organic materials with a high second-order optical nonlinearity have an important application for the next generation of computing, telecommunications, and other industries. Because of a high electro-optic coefficient and low dielectric constant, N-benzyl-2-methyl-4-nitroaniline (BNA) single crystals have been grown and their optical properties have been extensively studied. In this Letter, a poled BNA thin film material was prepared through simultaneous vacuum evaporation and laser-assisted electrical poling. The linear electro-optic coefficients of BNA were measured by a Young's two-slit interference electro-optic measurement method. The dependence of the resulting electro-optic properties on optical power was explored. Enhancement induced by laser illumination was demonstrated. The BNA thin film can exhibit an r(33) value comparable to that of BNA single crystals., (© 2011 Optical Society of America)

Nonlinear optical molecules can be vacuum deposited into uniform thin films using thermal evaporation. Alignment order can be achieved during thin film deposition by an in-plane electrical field poling using electrodes patterned on the substrate. Electro-optic (EO) coefficients, r33 and r13 are independently measured using Young's interferometry technique. Thin-films of N-benzyl-2-methyl-4-nitroaniline (BNA) can exhibit an EO coefficient, r33, comparable to that of BNA single crystals. EO coefficients of BNA at different poling fields, wavelengths, and frequencies are investigated.

A linearized dual parallel Mach-Zehnder modulator (DPMZM) based on electro-optic (EO) polymer was both fabricated, and experimentally used to suppress the third-order intermodulation distortion (IMD3) in a coherent analog fiber optic link. This optical transmitter design was based on a new EO chromophore called B10, which was synthesized for applications dealing with the fiber-optic communication systems. The chromophore was mixed with amorphous polycarbonate (APC) to form the waveguide's core material. The DPMZM was configured with two MZMs, of different lengths in parallel, with unbalanced input and output couplers and a phase shifter in one arm. In this configuration each of the MZMs carried a different optical power, and imposed a different depth of optical modulation. When the two optical beams from the MZMs were combined to generate the transmitted signal it was possible to set the IMD3 produced by each modulator to be equal in amplitude but 180° out of phase from the other. Therefore, the resulting IMD3 of the DPMZM transmitter was effectively canceled out during two-tone experiments. A reduction of the IMD3 below the noise floor was observed while leaving fifth-order distortion (IMD5) as the dominant IMD product. This configuration has the capability of broadband operation and shot-noise limited operation simultaneously., (© 2011 Optical Society of America)

Experimental and computational studies of the solvent dependence of the first molecular hyperpolarizability (β) for two donor-bridge-acceptor chromophores (CLD-1 and YLD156) are presented. Hyper-Rayleigh scattering (HRS) measurements are performed with 1907 nm excitation in a series of solvents with dielectric constants ranging from ~2 (toluene) to ~36 (acetonitrile). For both chromophores an approximately 2-fold increase in β is observed by HRS over this range of dielectric constants. Computational studies employing a polarized continuum model to represent the solvent are capable of reproducing this experimental result. The experimental and computational results are compared to the predictions of the widely employed two-state model (TSM) for β. Surprisingly, for the chromophores studied here the TSM predicts that β should decrease with increasing dielectric constant over the range investigated. The results presented here demonstrate that the TSM provides neither a quantitative nor qualitative description of the solvent dependence of β for CLD-1 and YLD156. The enhancement of β with increased dielectric constant suggests that modification of the dielectric surrounding the chromophore is one path by which the performance of nonlinear optical devices employing these chromophores may be significantly enhanced.

Organic nonlinear electrooptical (ONLO) chromophores must be acentrically ordered for the ONLO material to have electrooptic (EO) activity. The magnitude of the order is characterized by the acentric order parameter, , where β is the major Euler angle between the main axis of the chromophore and the poling field which imposes the acentric order. The acentric order parameter, which is difficult to measure directly, is related to the centrosymmetric order parameter, defined as = ½(3-1), through the underlying statistical distribution. We have developed a method to determine centrosymmetric order of the ONLO chromophores when the order is low (i.e., < 0.1). We have extended the method (begun by Graf et al. J. Appl. Phys. 1994, 75, 3335.) based on the absorption of light to determine the centrosymmetric order parameter induced by a poling field on a thin film sample of ONLO material. We find that the order parameters, analyzed by two different methods, are similar and also consistent with theoretical estimates from modeling of the system using coarse-grained Monte Carlo statistical mechanical methods.

Identification of electronic intermolecular electrostatic interactions that can significantly enhance poling-induced order is important to the advancement of the field of organic electro-optics. Here, we demonstrate an example of such improvement achieved through exploitation of the interaction of coumarin pendant groups in chromophore-containing macromolecules. Acentric order enhancement is explained in terms of lattice-symmetry effects, where constraint of orientational degrees of freedom alters the relationship between centrosymmetric and acentric order. We demonstrate both experimentally and theoretically that lattice dimensionality can be defined using the relationship between centrosymmetric order and acentric order. Experimentally: Acentric order is determined by attenuated total reflection measurement of electro-optic activity coupled with hyper-Rayleigh scattering measurement of molecular first hyperpolarizability, and centrosymmetric order is determined by the variable angle polarization referenced absorption spectroscopy method. Theoretically: Order is determined from statistical mechanical models that predict the properties of soft condensed matter.

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.

A mode size converter for efficient fiber coupling to silicon slot waveguides was proposed and demonstrated. It consists of two inverted lateral tapers that extend from the two strips of the silicon slot waveguide, and an overlaid low index waveguide with expanded mode size. Parameters including taper length and taper tip width were optimized with computer simulations. Samples were fabricated with a combined electron beam and photolithography process on a silicon-on-insulator wafer. The measured coupling loss to a standard single mode optical fiber was reduced by 8 dB for TE mode and 5.2 dB for TM mode with the converter.

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.

We present a new design of wavelength selective reflector composed of a Y junction and a singly coupled microring resonator, and demonstrate its biochemical sensing applications with a prototype device. In contrast with other reflectors like distributed Bragg reflectors, this device acts as notch filter at its reflection port. One promising application of the device is for remote sensing of harsh or inaccessible site, where only one optical fiber is required to transmit the input and reflected light signal over a long distance. The design can also be used to make microring cavity lasers.

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.

A novel technique for the fabrication of polarization selective electro-optic polymer waveguide devices with direct electron beam writing was described. Birefringence induced by the electric field poling in the electro-optic polymer film was erased in the electron beam exposed regions. The formed waveguides had stronger confinement for the light polarized along the poling direction. High fabrication resolution on the 100 nm scale or smaller could be achieved. Fabrication of polymer polarizer and polarization selective microring resonators with this technique was reported. The highest polarization extinction ratio was measured to be 21.4 dB.

Electro-optic polymer waveguides in electron beam sensitive polymethyl methacrylate (PMMA) polymer matrix doped with organic nonlinear chromophores could be directly patterned by electron beam exposure with high resolution and smoothness. The polymer in the exposed regions was removed with standard electron beam resist developer and without damaging the chromophore containing polymer waveguides. Feature sizes on the order of 100 nm could be clearly resolved. High quality microring resonators made of YL124/PMMA electro-optic polymer were successfully fabricated with this technique. The measured resonance extinction ratios were more than 16 dB and quality factors were in the range of 10(3) approximately 10(4).

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.

The prediction of nonlinear electro-optic (EO) behavior of molecules with quantum methods is the first step in the development of organic-based electro-optic devices. Typical EO molecules may require calculations with several hundred electrons, which prevents all but the fastest methods (semiempirical and density functional theory (DFT)) from being used for EO estimation. To test the reliability of these methods, we compare dipole moments, polarizabilities, and first-order hyperpolarizabilities for a wide range of structures of experimental interest with Hartree-Fock (HF), intermediate neglect of differential overlap (INDO), and DFT methods. The relative merits of molecules are consistently predictable with every method.

Efficient noncentrosymmetric arrangement of nonlinear optical (NLO) chromophores with high first-order hyperpolarizability (beta) for increased electro-optical (EO) efficiency has proven challenging as strong dipolar interactions between the chromophores encourage antiparallel alignment, attenuating the macroscopic EO effect. This work explores a novel approach to simultaneously achieve large beta values while providing an adjustable dipole moment by linking a strong neutral-ground-state (NGS) NLO chromophore with positive beta to a zwitterionic (ZWI) chromophore with negative beta in an antiparallel fashion. It is proposed that the overall beta of such a structure will be the sum of the absolute values of the two types of chromophores while the dipole moment will be the difference. Molecules 1-3 were synthesized to test the feasibility of this approach. Molecular dynamics calculations and NMR data supported that the NGS chromophore component and the ZWI chromophore component self-assemble to an antiparallel conformation in chloroform. Calculations showed that the dipole moment of 1 is close to the difference of the two component chromophores. Hyper-Rayleigh scattering (HRS) studies confirmed that the first hyperpolarizability of 1 is close to the sum of the two component chromophores. These results support the idea that an antiparallel-aligned neutral-ground-state chromophore and a zwitterionic chromophore can simultaneously achieve an increase in beta and a decrease of the dipole moment.

A macrocyclic trichromophore bundle 1 with parallel-aligned dipole moments has been synthesized to study the influence of aggregation and orientation of a nonlinear optical (NLO) chromophore on its optical properties. The linear and nonlinear optical properties of 1 and a single chromophore standard 2 have been studied by UV-vis absorption, fluorescence, solvatochromic spectrometry, and hyper-Rayleigh scattering (HRS). Reduced first-order hyperpolarizability beta, hypsochromic shift, enhanced solvatochromic shifts, and fluorescence quenching for individual chromophores were observed when 1 was compared with 2. Analysis of the data showed that the transition dipole moment changes only slightly when the chromophores are parallel aligned in the bundle architecture. However, the apparent hyperpolarizability of the individual chromophores decreased significantly by about 20%. The reduction in beta for the individual chromophores in 1 is largely due to the hypsochromic shift, i.e., excitation energy increase of the interband (charge-transfer) energy gap and the reduced difference between the ground-state and excited-state dipole moments. The hypsochromic shift and fluorescence quenching are consistent with exciton theory. Possible reasons for the enhanced solvatochromic shift are discussed.