Electro-optic Materials Research Articles

Optimization across-the-Board: Centro-Arylated Push-Pull Tetraene Chromophores and Guest-Host Polymers for Electro-Optics.

The research and development of push-pull tetraene chromophores (PPT-phores) have contributed greatly to the field of organic electro-optic (EO) materials and devices since the inauguration of CLD-1 in 2001. This study is thus a systematic contribution to synthesize and characterize a series of centro-arylated PPT-phores based on strong electron-donating tetrahydroquinolinyl groups and variable strong electron-accepting tricyanofuran derivatives. In particular, we report the crystallographic data to show various packing modes of these PPT-phores with detailed information about bond length alternation and intermolecular interactions, the optical absorption edges of guest-host polymers by the Tauc model, and the anisotropy and dispersion of Pockels tensors for the poled polymers by attenuated total reflection spectroscopy. Such analyses have not been addressed to any significant extent previously and are fundamentally important to the future development of PPT-phore-based EO materials and devices. The poled films of several centro-arylated PPT-phores in polycarbonates exhibited large EO activities, excellent thermal stability, and tunable optical transparency at the telecom O- and C-band. The study demonstrates the effectiveness of π-bridge centro-arylation enabled by molecular shape modification and rigidity enhancement, over the relatively flexible and labile thioether or alkoxy groups, in rational design of hyperpolarizable PPT-phores for high-performance EO polymers.

Synthesis and optical properties of fluorinated polyurethaneimide electro-optic waveguide polymer

Fluorinated polyurethaneimide (PUI) electro-optic waveguide polymer with polyurethane and polyimide chain segment structures was synthesized by stepwise polymerization using the synthesized amino ester oligomer pu and imide oligomer pi as monomers. Since the main chain structure of the synthesized PUI had the functionality of both polyurethane and polyimide chain segment structures, it combines the excellent thermal and film-forming properties of polyurethanes and polyimides, as well as lower optical transmission loss in the near-infrared wavelength band. The glass transition temperature (Tg) of PUI was 182 °C, and the 5% heat loss decomposition temperature was 325 °C. The PUI had good optical properties with an optical propagation loss of 1.10 dB/cm and an electro-optic (EO) coefficient (γ33) of 86 pm/V at a wavelength of 1550 nm. A Mach-Zehnder interferometric polymer waveguide EO modulator had been designed and fabricated by using the PUI as a waveguide electro-optic core layer. The prepared polymer waveguide EO modulator showed a good electro-optic modulation response at a wavelength of 1550 nm under an applied 1 kHz sinusoidal modulation signal. The results showed that the synthesized PUI met the performance requirements for the preparation of polymer optical waveguide devices and was a polymer electro-optic waveguide material with good overall performance.

What can be integrated on the silicon photonics platform and how?

We review the integration techniques for incorporating various materials into silicon-based devices. We discuss on-chip light sources with gain materials, linear electro-optic modulators using electro-optic materials, low-power piezoelectric tuning devices with piezoelectric materials, highly absorbing materials for on-chip photodetectors, and ultra-low-loss optical waveguides. Methodologies for integrating these materials with silicon are reviewed, alongside the technical challenges and evolving trends in silicon hybrid and heterogeneously integrated devices. In addition, potential research directions are proposed. With the advancement of integration processes for thin-film materials, significant breakthroughs are anticipated, leading to the realization of optoelectronic monolithic integration featuring on-chip lasers.

Unveiling High Electro‐Optic Performance in a Proton–π‐Electron‐Coupled Ferroelectric Crystal

AbstractThe convergence of electronics and photonics is attracting attention for its potential to surpass performance limitations of existing information‐processing devices. In particular, the electro‐optic (EO) effect plays a critical role in high‐speed and low‐power conversion between electrical and optical signals, which is demanded for future communication networks. Here, a novel class of EO material is demonstrated, the organic ferroelectric crystal of croconic acid (CRCA). The recently developed birefringence field‐modulation imaging technique enables high‐throughput evaluation of the EO coefficient for as‐grown bulk crystals, unveiling a figure of merit of >400 for CRCA, which exceeds that of 320 in the conventional EO material LiNbO3 in the visible‐light range. Analyses in conjunction with theoretical calculations clarify that its remarkable EO performance is attributable to deformation of the π‐orbital coupled with the proton displacement. This finding provides a new route for the molecular design of high‐performance EO materials: proton–π‐electron‐coupled ferroelectrics.

Exploring Favorable Supramolecular Interactions of Multifluorinated Aromatics in Dendronized Push-Pull Chromophores for Electro-Optics.

Multifluorinated aromatics serve as supramolecular synthons in the research of organic electro-optic (EO) materials by exploiting π-π stacking interaction between the aromatic hydrocarbon and multifluorinated aromatic groups for performance improvement. However, non-classical hydrogen bonding remains largely unexplored in fluorinated EO dendrimers. In this study, three Fréchet-type generation 1 benzyl ether co-dendrons were synthesized by replacing one benzyl group with 2,3,5,6-tetrafluorobenzyl (p-HF4Bz), pentafluorobenzyl (C6F5Bz), and 2,3,4,5-tetrafluorobenzyl (o-HF4Bz) groups, to afford the benzoic acid derivatives D1, D2, and D3, which were further bonded to the donor and π-bridge moieties to afford three co-dendronized push-pull phenyltetraene chromophores EOD1, EOD2, and EOD3, respectively. The weak C-H⋅⋅⋅X (X=O, F) interactions in the crystal structure of D1 cumulatively add to the benzoic acid dimers to form an extended hydrogen-bonded network, while D2 is crystallized into a centric one-dimensional chain with strong intermolecular interactions. The poled films of EOD1 with PMMA exhibited the largest and most stable EO activity with optical homogeneity among the series. The results identify the effectiveness of weak but favorable hydrogen bonds enabled by the enhanced carbon acidity of p-HF4Bz synthon in D1, over the interactions in D2 and D3, for the rational design of supramolecular EO dendrimers.

Enhancement of terahertz fields in LiTaO3 waveguides using a conical pulse front.

The development of methods for the generation of strong ultrafast electromagnetic pulses in the terahertz (THz) spectral range has led to a surge of progress in nonlinear THz spectroscopy and THz control of molecular and collective responses. For spectroscopy in the 1-THz range, the submillimeter wavelengths and associated large spot sizes, large optical elements, and short distances between final focusing elements and samples can lead to cumbersome experimental setups that are incompatible with some sample environments. Here, we introduce a novel terahertz ring excitation (TREx) optical pumping geometry to generate superposing, focusing fields in planar THz waveguides made out of the electro-optic material lithium tantalate. High THz fields, >175 kV/cm, are generated and measured optically with no free-space THz propagation. The field level achieved by pumping with a sequence of concentric rings of excitation light exceeds by about 20× the result of a single cylindrically focused line of pump light that has been used routinely in previous work. The technique opens new prospects for compact waveguide-based linear and nonlinear THz spectroscopy and signal processing.

Organic Electro-Optic Materials with High Electro-Optic Coefficients and Strong Stability.

The preparation of high-performance electro-optical materials is one of the key factors determining the application of optoelectronic communication technology such as 5G communication, radar detection, terahertz, and electro-optic modulators. Organic electro-optic materials have the advantage of a high electro-optic coefficient (~1000 pm/V) and could allow the utilization of photonic devices for the chip-scale integration of electronics and photonics, as compared to inorganic electro-optic materials. However, the application of organic nonlinear optical materials to commercial electro-optic modulators and other fields is also facing technical bottlenecks. Obtaining an organic electro-optic chromophore with a large electro-optic coefficient (r33 value), thermal stability, and long-term stability is still a difficulty in the industry. This brief review summarizes recent great progress and the strategies to obtain high-performance OEO materials with a high electro-optic coefficient and/or strong long-term stability. The configuration of D-π-A structure, the types of materials, and the effects of molecular engineering on the electro-optical coefficient and glass transition temperature of chromophores were summarized in detail. The difficulties and future development trends in the practical application of organic electro-optic materials was also discussed.

Cu-doped KTN crystal with controllable, reversible, and fast photochromic properties: A superior electro-optical material for improving beam deflection performance

Improving the deflection performance of a beam deflector is urgently required to acquire optical signals for space laser communication and change the attitude and position of space targets and spacecraft. In this work, a Cu-doped potassium tantalate niobate (Cu-KTN) single crystal with fast photochromic and increased beam deflection properties is synthesized using the top-seeded solution growth method. When a Cu-KTN single crystal is irradiated with 405 nm light or ultraviolet (UV) light, the color changes from pale green to reddish brown. After light irradiation, the color gradually returns to yellowish green. Decolorization is accelerated under irradiation with green light or long-wavelength light, and the color changes to pale green. The origin of reversible photochromism reveals the fast valence change of Cu ions. In addition, ion doping improves the beam deflection angle of the secondary electro-optical effect of Cu-KTN (4.3 mrad, 1000 V) crystal compared with pure KTN (3.2 mrad, 1000 V). This study successfully synthesizes Cu-KTN single crystals with photochromic uses and establishes a new route for beam deflectors with significant deflection angles.

Reconfigurable quantum photonic circuits based on quantum dots.

Quantum photonic integrated circuits, composed of linear-optical elements, offer an efficient way for encoding and processing quantum information on-chip. At their core, these circuits rely on reconfigurable phase shifters, typically constructed from classical components such as thermo- or electro-optical materials, while quantum solid-state emitters such as quantum dots are limited to acting as single-photon sources. Here, we demonstrate the potential of quantum dots as reconfigurable phase shifters. We use numerical models based on established literature parameters to show that circuits utilizing these emitters enable high-fidelity operation and are scalable. Despite the inherent imperfections associated with quantum dots, such as imperfect coupling, dephasing, or spectral diffusion, we show that circuits based on these emitters may be optimized such that these do not significantly impact the unitary infidelity. Specifically, they do not increase the infidelity by more than 0.001 in circuits with up to 10 modes, compared to those affected only by standard nanophotonic losses and routing errors. For example, we achieve fidelities of 0.9998 in quantum-dot-based circuits enacting controlled-phase and - not gates without any redundancies. These findings demonstrate the feasibility of quantum emitter-driven quantum information processing and pave the way for cryogenically-compatible, fast, and low-loss reconfigurable quantum photonic circuits.

High performance electrically-derived single-pixel magnetophotonic spatial light modulator

Spatial light modulators (SLMs) utilize components such as magnetophotonic crystals (MPCs) to alter specific characteristics of a light beam in space. In magneto-optical (MO) spatial light modulators, MPCs play a crucial role in spatially modulating light by manipulating local light intensity and polarization rotation. This study explores how the refractive indices of birefringent electro-optical materials within MPCs influence MO rotation and reflection. In this order, using a transfer matrix method, we designed thin MPCs with a MO rotation around 90° and almost full reflection, for having SLMs with high contrast. The direction of applied voltage to the structure was found to be a critical factor, leading to significant reduction in power consumption for SLMs incorporating the MPCs. These characteristics render the designed MO spatial light modulator well-suited for applications in projectors and displays.

Significantly enhanced transmittance and EO property in PMN-PT via optimized two-step pressure-free sintering

It is a great challenge to prepare Pb(Mg1/3Nb2/3)O3–PbTiO3 (PMN-PT) ceramics of very high transparency with only oxygen atmosphere pressureless sintering process. To address this issue, this work proposed an optimal low-cost two-step oxygen atmosphere sintering process with a first step at high temperature (T1) for minutes, followed by a second step at lower temperature (T2) for hours without applied pressure. High transmittance of 70 % in the near-infrared wavelength was achieved by our novel two-step process, which far exceeds the performance of PMN–PT ceramics prepared by only oxygen atmosphere sintering process reported in the past and demonstrates comparable performance compared to the costly hot-pressing sintering process. Meanwhile, it shows a high quadratic electro-optic (EO) coefficient of 42.1 × 10−16 m2 V−2, which is meaningful for applications in EO devices. Furthermore, the effect of the temperature difference between the first and second sintering step on the microstructure, transmittance, domain structure, ferroelectric and dielectric property, and polarization switching were discussed. The enhanced transparency is mainly attributed to the higher relative density, and weaker photoluminescence effect with lesser light absorption loss at optimal T1-T2. The improved EO property is due to greater polarization response originating from the interaction of defect dipoles and nanodomains. Such a process should facilitate the cost-effective preparation of other transparent electro-optic materials for practical applications.

GALILEO: Galactic Axion Laser Interferometer Leveraging Electro-Optics.

We propose a novel experimental method for probing light dark matter candidates. We show that an electro-optical material's refractive index is modified in the presence of a coherently oscillating dark matter background. A high-precision resonant Michelson interferometer can be used to read out this signal. The proposed detection scheme allows for the exploration of an uncharted parameter space of dark matter candidates over a wide range of masses-including masses exceeding a few tens of microelectronvolts, which is a challenging parameter space for microwave cavity haloscopes.

Synthesis and characterization of fluorinated polyurethaneimide electro-optic waveguide material with novel structure

Abstract Structurally novel fluorinated polyurethaneimide (PUI) electro-optic polymer based on chromophore molecule b, diisocyanate MDI and anhydride BPAFDA was synthesized by stepwise polymerization of oligomer PUI with fluorinated aromatic diamines BATB and BATPP. Electro-optic (EO) PUI chain structure had the structure of polyimide and polyurethane chain segments, integrating the advantages of polyimide and polyurethane. The PUI possessed good film-forming property, a high glass transition temperature (T g = 193 °C) and good thermal stability (5 % weight loss temperature T d up to 320 °C). Y-Structured inverted ridge polymer optical waveguides were designed and fabricated using the PUI as the waveguide core material. The PUI had good optical performance with an EO coefficient (γ33) of 79 pm/V and 1.1 dB/cm optical propagation loss at a wavelength of 1550 nm. The results showed that the synthesized PUI met the performance requirements for the preparation of polymer optical waveguide devices and was suitable as a polymer electro-optic waveguide material.

Dynamic light manipulation via silicon-organic slot metasurfaces

Active metasurfaces provide the opportunity for fast spatio-temporal control of light. Among various tuning methods, organic electro-optic materials provide some unique advantages due to their fast speed and large nonlinearity, along with the possibility of using fabrication techniques based on infiltration. In this letter, we report a silicon-organic platform where organic electro-optic material is infiltrated into the narrow gaps of slot-mode metasurfaces with high quality factors. The mode confinement into the slot enables the placement of metallic electrodes in close proximity, thus enabling tunability at lower voltages. We demonstrate the maximum tuning sensitivity of 0.16nm/V, the maximum extinction ratio of 38% within ± 17V voltage at telecommunication wavelength. The device has 3dB bandwidth of 3MHz. These results provide a path towards tunable silicon-organic hybrid metasurfaces at CMOS-level voltages.

Synthesis and characterization of a julolidine-based electro-optic molecular glass.

Organic electro-optic (EO) materials have recently gained considerable attention owing to their advantages compared to inorganic EO materials. Among different kinds of organic EO materials, organic EO molecular glass exhibits desired prospect because of its high chromophore loading density and large macroscopic EO activity. The objective of this study is to design and synthesize a novel organic EO molecular glass JMG utilizing julolidine moiety as the electron donor, thiophene moiety as the conjugated bridge, trifluoromethyl substituted tricyanofuran derivate (Ph-CF3-TCF) as the electron acceptor. The JMG's structure was characterized through NMR and HRMS. The photophysical property, glass transition temperature, first hyperpolarizability (β) and dipole moment (μ) of JMG were determined through UV-vis spectra, DSC test and DFT calculation. JMG's Tg reached to 79 °C and it can form high-quality optical film. The theoretical calculation shows that the first hyperpolarizability (β) and dipole moment (μ) of JMG were calculated to 730×10-30 esu and 21.898 D. After connecting poling with the poling voltage of 49 V/μm at 90 ℃for 10 min, the highest EO coefficient (r33) of the poled JMG films reached to 147 pm/V. A novel julolidine-based NLO chromophore with two tert-butyldiphenylsilyl (TBDPS) groups was successfully prepared and characterized. TBDPS group is introduced as the film-forming group, and it also plays the role of isolation group, which can suppress the electrostatic interaction between chromophores, improve the poling efficiency and further enhance the EO activity. The excellent performances endow JMG with potential applications in device fabrication.

Measuring dielectric and electro-optic responses of thin films using plasmonic devices.

This paper introduces a simple method for the measurement of the relative permittivity and the Pockels coefficient of electro-optic (EO) materials in a waveguide up to sub-THz frequencies. By miniaturizing the device and making use of plasmonics, the complexities of traditional methods are mitigated. This work elaborates the fabrication tolerance and simplicity of the method, and highlights its applicability to various materials, substrates and configurations. The method is showcased using drop-casted perovskite barium titanate (BaTiO3, BTO) nano-particle thin-films and it has previously been used to measure epitaxial thin film BTO. In this work we show the effective relative permittivity of drop casted BTO to be εeff ∼ 30 at 200 MHz, dropping to ∼ 18 at 67 GHz and similarly, the effective Pockels coefficient was found to be reff ∼ 16 at 350 MHz and ∼ 8 at 70 GHz. These values are a factor > 50 below the values found for thin film BTO. Yet, the fact that the method can be applied to such different samples and Pockels strengths gives testimony to its versatility and sensitivity.

Silicon nitride electric-field poled microresonator modulator

Stoichiometric silicon nitride is a highly regarded platform for its favorable attributes, such as low propagation loss and compatibility with complementary metal-oxide-semiconductor technology, making it a prominent choice for various linear and nonlinear applications on a chip. However, due to its amorphous structure, silicon nitride lacks second-order nonlinearity; hence, the platform misses the key functionality of linear electro-optical modulation for photonic integrated circuits. Several approaches have been explored to address this problem, including integration with electro-optic active materials, piezoelectric tuning, and utilization of the thermo-optic effect. In this work, we demonstrate electro-optical modulation in a silicon nitride microring resonator enabled by electric-field poling, eliminating the complexities associated with material integration and providing data modulation speeds up to 75 Mb/s, currently only limited by the electrode design. With an estimated inscribed electric field of 100 V/μm, we achieve an effective second-order susceptibility of 0.45 pm/V. In addition, we derive and confirm the value of the material’s third-order susceptibility, which is responsible for the emergence of second-order nonlinearity. These findings broaden the functionality of silicon nitride as a platform for electro-optic modulation.

Optimization of donors, acceptors and bridges for novel organic electro-optic materials

The effects of different donors, acceptors and electron bridges on various properties of novel organic electro-optic materials were investigated.

Hybrid multi-channel electrically tunable bandstop filter based on DAST electro-optical material

A voltage tunable hybrid multi-channel bandstop filter based on a metal–insulator–metal (MIM) waveguide is presented in this work, which can realize three narrowband and one broadband filtering functions simultaneously. The filter comprises two asymmetric composite cavities, which are filled with organic electro-optical material of 4-dimethylamino-N-methyl-4-toluenesulfonate (DAST). The composite cavity is composed of a rectangular cavity and an annular cavity, and the annular cavity is formed by two rectangular cavities connected with two semi-elliptical annular cavities. The transmission spectrum and magnetic field distribution of the filter are studied and analyzed by the finite element method (FEM), and the effects of the structure parameters on the transmission spectrum are discussed. Our analysis indicates that the bandstop filter has minimum transmittances of 0.02%, 0.29%, and 0.1%, minimum bandwidths of 5 nm, 9 nm, and 25 nm, and maximum quality factors (Q) of 123.7, 87.1, and 44.2, respectively, in three narrowband modes. The stopband bandwidth at the broadband mode is 70 nm, and the adjustable range is 1695–2065 nm. Additionally, the filter characteristics can be adjusted by imposing a control voltage, providing a high degree of tunability and maintaining stable filter performance. Finally, the basic structure is optimized yielding an increased bandwidth of 238 nm for the broadband mode, which does retain great electrical tuning characteristics. Consequently, the proposed structure can be applied with huge potential in high-density integrated circuits and nano-optics.

Non-linear optical scattering PUF: enhancing security against modeling attacks for authentication systems.

With the rapid expansion of the Internet of Things (IoT), ensuring the security of personal and group information has become increasingly crucial. However, conventional optical scattering physical unclonable function (OS-PUF) faces challenges due to its linear scattering behavior. In this article, we propose a non-linear OS-PUF (NOS-PUF) that integrates electro-optic materials. By leveraging random refractive index fluctuations generated by the NOS-PUF, we mitigate modeling attacks based on the OS-PUF and bolster the overall security of the authentication process. Moreover, we introduce a novel modeling attack methodology based on scattering invariant modes (SIMs) that poses a significant threat to conventional OS-PUF and NOS-PUF authentication systems. Through extensive simulations, we demonstrate that our NOS-PUF achieves a remarkably lower false accept rate for modeling attacks utilizing SIMs, surpassing the entropy limit imposed by the Gabor filtering algorithm by more than five orders of magnitude. These results highlight the heightened security and increased information entropy offered by the proposed NOS-PUF, making it particularly suitable for applications demanding robust and high-security authentication measures.