Gigahertz free-space electro-optic modulators based on Mie resonances.

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 r33 = 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 (fEO,-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.

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 spatial light modulator from an engineered organic layer.

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.

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.

Broadband Metallic Fiber-to-Chip Couplers and a Low-Complexity Integrated Plasmonic Platform.

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.

Organic Semiconductors at the University of Washington: Advancements in Materials Design and Synthesis and toward Industrial Scale Production.

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.

Silicon-organic hybrid (SOH) Mach-Zehnder modulators for 100 GBd PAM4 signaling with sub-1†dB phase-shifter loss.

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 aUπL = 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 GBd IM/DD transmission over 14†km SMF in the C-band enabled by a plasmonic SSB 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.

Compact and ultra-efficient broadband plasmonic terahertz field detector.

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(λTHz/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.

120 GBd plasmonic Mach-Zehnder modulator with a novel differential electrode design operated at a peak-to-peak drive voltage of 178 mV.

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 mVpp 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 (Vπ/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.

Molecular Engineering of Structurally Diverse Dendrimers with Large Electro-Optic Activities.

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 nm2 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 ( Tg = 108 °C) and comparable poling efficiency (1.62 nm2 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 n3. 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 nm2 V-2) and largest EO coefficient ( r33) value of 275 pm V-1 at 1310 nm, which represents a high n3 r33 figure-of-merit of 1946 pm V-1. The high poling efficiencies and n3 r33 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.

Plasmonic IQ modulators with attojoule per bit electrical energy consumption.

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.

Low-loss plasmon-assisted electro-optic modulator.

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 technology3-6, sensing7,8, nonlinear optics9,10, 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.

High-speed plasmonic modulator in a single metal layer.

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.

Nonlinearities of organic electro-optic materials in nanoscale slots and implications for the optimum modulator design.

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 UπL 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.

Direct Conversion of Free Space Millimeter Waves to Optical Domain by Plasmonic Modulator Antenna.

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.

Optimizing calculations of electronic excitations and relative hyperpolarizabilities of electrooptic chromophores.

CONSPECTUS: Organic glasses containing chromophores with large first hyperpolarizabilities (ß) 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 ß 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 ßHRS 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 ßHRS 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 ßHRS. Frequency dependence for ßHRS 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 ß and λmax.

Nanoscale phase analysis of molecular cooperativity and thermal transitions in dendritic nonlinear optical glasses.

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.

Nano-engineering lattice dimensionality for a soft matter organic functional material.

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.

Solvents level dipole moments.

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.