Organic Electro-optic Materials Research Articles

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

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

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.

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.

Silicon-Organic Hybrid Electro-Optic Modulator and Microwave Photonics Signal Processing Applications.

Electro-optic modulator (EOM) is one of the key devices of high-speed optical fiber communication systems and ultra-wideband microwave photonic systems. Silicon-organic hybrid (SOH) integration platform combines the advantages of silicon photonics and organic materials, providing a high electro-optic effect and compact structure for photonic integrated devices. In this paper, we present an SOH-integrated EOM with comprehensive investigation of EOM structure design, silicon waveguide fabrication with Slot structure, on-chip poling of organic electro-optic material, and characterization of EO modulation response. The SOH-integrated EOM is measured with 3 dB bandwidth of over 50 GHz and half-wave voltage length product of 0.26 V·cm. Furthermore, we demonstrate a microwave photonics phase shifter by using the fabricated SOH-integrated dual parallel Mach-Zehnder modulator. The phase shift range of 410° is completed from 8 GHz to 26 GHz with a power consumption of less than 38 mW.

Highly Efficient and Stable Binary Cross-Linkable/ Self-Assembled Organic Nonlinear Optical Molecular Glasses.

The development of electro-optical materials with high chromophore loading levels that possess ultrahigh electro-optic coefficients and high long term alignment stability is a challenging topic. Anthracene-maleimide Diels-Alder (DA) reaction and π-π interaction of Anthracene-pentafluorobenzene and benzene-pentafluorobenzene are developed for making highly efficient binary cross-linkable/self-assembled dendritic chromophores FZL1-FZL4. A covalently or non-covalently cross-linked network is formed by DA reaction or π-π interaction after electric field poling orientation, which greatly improves the long-term alignment stability of the materials. An electro-optic coefficient up to 266pmV-1 and glass transition temperature as high as 178°C are achieved in cross-linked film FZL1/FZL2, and 272-308pmV-1 is achieved for self-assembled films FZL1/FZL4 and FZL3/FZL4 due to high chromophore density (3.09-4.02×1020 moleculescm-3 ). Long-term alignment stability tests show that after heating at 85°C for over 500h, 99.73% of the initial r33 value is maintained for poled crosslinked electro-optic films 1:1 FZL1/FZL2. The poled self-assembled electro-optic films 1:1 FZL1/FZL4 and 1:1 FZL3/FZL4 can still maintain more than 97.11% and 98.23%, respectively, of the original electro-optic coefficient after being placed at room temperature for 500h. The excellent electro-optic coefficient and stability of the material indicate the practical application prospects of organic electro-optic materials.

Low half-wave voltage polymeric electro-optic modulator using CLD-1/PMMA for electrocardiogram (ECG) signal acquisition.

Electro-optic (EO) modulators are typically made of inorganic materials such as lithium niobate; the replacement of these modulators with organic EO materials is a promising alternative due to their lower half-wave voltage (Vπ), ease of handling, and relatively low cost. We propose the design and fabrication of a push-pull polymer electro-optic modulator with voltage-length parameters (VπL) of 1.28 V·cm. The device uses a Mach-Zehnder structure and is made of a second-order nonlinear optical host-guest polymer composed of a CLD-1 chromophore and PMMA polymer. The experimental results show that the loss is 1.7 dB, Vπ drops to 1.6 V, and the modulation depth is 0.637 dB at 1550 nm. The results of a preliminary study show that the device is capable of efficiently detecting electrocardiogram (ECG) signals with performance on par with that of commercial ECG devices.

Resonant plasmonic micro-racetrack modulators with high bandwidth and high temperature tolerance

Resonant modulators encode electrical data onto wavelength-multiplexed optical carriers. Today, silicon microring modulators are perceived as promising to implement such links; however, they provide limited bandwidth and need thermal stabilization systems. Here we present plasmonic micro-racetrack modulators as a potential successor of silicon microrings: they are equally compact and compatible with complementary-metal–oxide–semiconductor-level driving voltages, but offer electro-optical bandwidths of 176 GHz, a 28 times improved stability against operating temperature changes and no self-heating effects. The temperature-resistant organic electro-optic material enables operation at 85 °C device temperature. We show intensity-modulated transmission of up to 408 Gbps at 12.3 femtojoules per bit with a single resonant modulator. Plasmonic micro-racetrack modulators offer a solution to encode high data rates (for example, the 1.6 Tbps envisioned by next-generation communications links) at a small footprint, with low power consumption and marginal, if no, temperature control.

The change of hydrogen position on π-conjugated bridge to affect NLO property of D(–NH2)-π(DHTPs)-A(–NO2) system

The donor-π-conjugated bridge-acceptor (D-π-A) is a classical framework to design high-performance organic electro-optical materials. In this work, based on the π-conjugated dihydrotetraazapentacenes (DHTPs), four isomers (1–4) with D(–NH2)-π(DHTPs)-A(–NO2) framework are designed and characterized. The 2 and 3 originate from single-hydrogen migration of 1, and 4 derives from double-hydrogen migration of 1. Significantly, the change of hydrogen position on DHTPs bridge can affect their nonlinear optics (NLO) property. Compared with the first hyperpolarizability (βtot) (4.08 × 103a.u.) of 1, the 6.90 × 103-2.56 × 104 a.u. of 2–4 are enhanced. More interestingly, the 4 has largest βtot value of 2.56 × 104, which is approximately equal to the sum of 6.90 × 103 a.u. of 2 and 1.82 × 104 a.u. of 3. Furthermore, the change of hydrogen position on DHTPs brings some distinctive changes in their geometric structure, nucleus-independent chemical shifts (NICS) value, natural population analysis (NPA) charge, UV–vis absorption spectrum along with its other electronic property that might be beneficial to explore their structure–property relationships.

Recent Progress in Design of Organic Electro‐optic Materials with Ultrahigh Electro‐optic Activities†

Comprehensive SummaryRationally designed organic electro‐optic (OEO) materials demonstrate ultra‐large electro‐optic (EO) activities, affording inorganic‐organic hybrid photonic devices with low drive voltage, large bandwidth, low energy consumption, and small footprint. OEO materials hold the potential to achieve EO coefficients (r33) over 1000 pm/V. Over the past decade, however, the best performance of OEO materials is limited to 300—600 pm·V−1. This is partly because of the concern of increasing dipole moment and optical loss due to the redshifted absorbance of high hyperpolarizability chromophores. Recent advance of theory‐guided design enables the OEO materials to achieve greatly enhanced hyperpolarizability and EO activity with dipole moment and propagation loss within acceptable constraints. Simultaneously, progress in hybrid device designs has greatly shortened the length of modulating waveguide, which resulted in significantly reduced sensitivity to propagation loss from redshifted absorption of OEO materials. Driven by theory‐guided design method, several high‐performance OEO materials have been presented with greatly enhanced EO coefficients beyond 1000 pm·V−1. This brief review summarizes the strategies to improve the EO activity including molecular engineering and hyperpolarizability, highlights the recent great progress in design of high‐performance OEO materials, and discusses the problems needed to be solved in application for current OEO materials.

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± 0.8nm2 V-2 ) at 1310nm are achieved. This is the first reported OEO material with electro-optic response larger than thin-film barium titanate.

Self‐Aligned Non‐Centrosymmetric Conjugated Molecules Enable Electro‐Optic Perovskites

AbstractSolution‐processed organic electro‐optic (EO) chromophores are well suited for integration in optical modulators on silicon photonics chips. They contain highly conjugated molecules with polar functional groups offering large dipoles and a large nonlinear optical response. However, these molecules form centrosymmetric aggregates that hinder poling efficiency and the resultant macroscopic EO response. Furthermore, at elevated temperatures, the alignment of poled molecules can be lost, leading to a reduction in the EO response. Inorganic EO materials exhibit excellent thermal stability but lower performance. Here 2D metal halide perovskite scaffolds that align EO molecules are reported. The approach heralds a material design strategy that combines the features of organic and inorganic EO materials. The EO material exhibits promising thermal stability with a performance approaching that of organic EO materials. Anchor diammonium non‐centrosymmetric molecules are anchored inside a 2D metal halide perovskite scaffold, thereby avoiding aggregation. The authors lever the thermal stability of this compound and pole the organic molecules under an electric field at 533 K. The 2D perovskites exhibit a macroscopic EO coefficient of 68 pm V−1—a twofold increase over LiNbO3. Density functional theory calculations show that the in‐plane alignment of the molecular dipole moments can account for the EO response.

Electro-Optic Modulation Using Metal-Free Perovskites.

Electro-optic (EO) modulation is of interest to impart information onto an optical carrier. Inorganic crystals-most notably LiNbO3 and BaTiO3-exhibit EO modulation and good stability, but are difficult to integrate with silicon photonic technology. Solution-processed organic EO materials are readily integrated but suffer from thermal degradation at the temperatures required in operating conditions for accelerated reliability studies. Hybrid organic-inorganic metal halide perovskites have the potential to overcome these limitations; however, these have so far relied on heavy metals such as lead and cadmium. Here, we report linear EO modulation using metal-free perovskites, which maintain the crystalline features of the inorganic EO materials and incorporate the flexible functionality of organic EO chromophores. We find that, by introducing a deficiency of cations, we reduce the symmetry in the perovskite crystal and produce thereby an increased EO response. The best-engineered perovskites reported herein showcase an EO coefficient of 14 pm V-1 at a modulation frequency of 80 kHz, an order of magnitude higher than in the nondefective materials. We observe split peaks in the X-ray diffraction and neutron diffraction patterns of the defective sample, indicating that the crystalline structure has been distorted and the symmetry reduced. Density functional theory (DFT) studies link this decreased symmetry to NH4+ deficiencies. This demonstration of EO from metal-free perovskites highlights their potential in next-generation optical information transmission.

The important role of tetraphenylethene on designing bichromophores for organic nonlinear optical materials

Organic electro-optical (OEO) materials still exist huge challenges to achieve these materials for practical use. In this work, a novel bichromophores Y was synthesized via esterification reaction with julolidine donor chromophores and systematically studied. Chromophore Y presented good solubility, excellent thermal stability, and also with great transparency. Besides, the hyperpolarizability (β) of this new chromophore was computed by density functional theory. To our suprise, in electro-optic activities, the doped film containing chromophore Y performed an extremely small electro-optic coefficient (r33) with 13 pm/V. This outcome indicated that the nonplanar molecular structures of the TPE1 moieties can weaken the electrostatic interactions between molecules, but the size of this chromophore is too big to be polarized, thus leading the macroscopic EO activity decreased sharply.

Bis(4-dialkylaminophenyl)heteroarylamino donor chromophores exhibiting exceptional hyperpolarizabilities

Theory-guided design enables new organic electro-optic (OEO) materials with record hyperpolarizability and high electro-optic activity.

Systematic study of the structure-property relationship of a series of near-infrared absorbing push-pull heptamethine chromophores for electro-optics

This study reports the facile synthesis, characterization and quantitative structure-property relationship analysis of molecular and material properties of tricyanofuran-based (TCF) dipolar heptamethines with different electron donors of indoline ( F1 ), benzo[ e ]- indoline ( F2 ), benz[ cd ]indoline ( F3 ), and Michler’s base derivatives ( M1 and M2 ). The linear and nonlinear optical (NLO) properties of these chromophores have been thoroughly investigated, and the relationship between molecular and bulk response has been analyzed and compared with dipolar tetraene AJLZ53 as one of the best chromophores for electro-optic (EO) devices. In particular, we provide responsible data collection and analysis of optical and EO properties for poled thin films using a widely-recognized and accredited methodology of prism coupling system with the help of rigid oriented gas model. We found that these push-pull heptamethines with synthetic efficacy exhibit high near-infrared absorption, excellent chemical stability and large hyperpolarizabilities ( β ) varied from 1,023×10−30 esu for F1 , 3,047×10−30 esu for M1 , and 3,547×10−30 esu for F3 at 1,304 nm in poled films, respectively. The β values of these molecules are among the highest ones for TCF-based dipolar chromophores, and also agree well with reported analytical results in the solutions. In poled polymers with a modest chromophoric loading density of 1.3× 1020 cm−3, M1 and M2 give a high poled-induced noncentrosymmetric order and relatively large r 33 values around 40 pm V−1 at 1,304 nm, indicative of large μβ values and suitable structural modification for high poling efficiency. Furthermore, a binary EO polymer based on the co-loading of M1 and AJLZ53 achieve a large r 33 value of 143.3 pm V−1 at 1,304 nm. Our studies suggest that concise synthesis and molecular design of push-pull polymethines can be well guided by the tabulation of their linear and NLO properties in bulk materials, and streamline future development of high performance organic EO materials for photonic applications.

A monolithic bipolar CMOS electronic–plasmonic high-speed transmitter

To address the challenge of increasing data rates, next-generation optical communication networks will require the co-integration of electronics and photonics. Heterogeneous integration of these technologies has shown promise, but will eventually become bandwidth-limited. Faster monolithic approaches will therefore be needed, but monolithic approaches using complementary metal–oxide–semiconductor (CMOS) electronics and silicon photonics are typically limited by their underlying electronic or photonic technologies. Here, we report a monolithically integrated electro-optical transmitter that can achieve symbol rates beyond 100 GBd. Our approach combines advanced bipolar CMOS with silicon plasmonics, and addresses key challenges in monolithic integration through co-design of the electronic and plasmonic layers, including thermal design, packaging and a nonlinear organic electro-optic material. To illustrate the potential of our technology, we develop two modulator concepts—an ultra-compact plasmonic modulator and a silicon-plasmonic modulator with photonic routing—both directly processed onto the bipolar CMOS electronics. The monolithic integration of electronic and plasmonic technologies can be used to create electro-optic transmitters capable of symbol rates beyond 100 GBd.

Ultrahigh Electro-Optic Coefficients, High Index of Refraction, and Long-Term Stability from Diels–Alder Cross-Linkable Binary Molecular Glasses

The development of organic electro-optic (EO) materials that concurrently possess a high electro-optic coefficient (r33), high index of refraction, and long-term or high-temperature stability of ch...

Construction of a simple crosslinking system and its influence on the poling efficiency and oriental stability of organic electro-optic materials.

A new fluorinated polycarbonate was synthesized by solution polymerization of bisphenol AF, anthracen-9-ylmethyl-4,4-bis(4-hydroxyphenyl)pentanoate with triphosgene. This new polycarbonate was used as a host polymer. A traditional chromophore with a D–π–A structure was modified by bisphenol A acrylate affording chromophore A. The large modified group can not only effectively avoid the dipole interaction between chromophores, but also endow the chromophores with the properties of attaching and crosslinking with a host polymer through in situ Diels–Alder “click chemistry” reactions. Such properties can improve both the poling efficiency and the thermal stability of organic electro-optic (EO) polymers. The thermodynamic properties of the crosslinking system showed that the glass transition temperature rose with the increase of the chromophore content. The EO polymer showed a large EO coefficient of about 78.9 pm V−1 at a wavelength of 1310 nm and an excellent long-term stability of about 89% with respect to its initial value and it can be kept after 300 h of heating at 80 °C.

(Keynote) Silicon-Organic Hybrid Photonics: Integration of Electro-Optical Polymers in a Photonic Integrated Circuit Technology

Photonic integrated circuits (PIC) based on silicon-on-insulator technologies play a crucial role for the development of large-scale on-chip optical devices [1]. They address a variety of applications in optical sensing [2] and signal processing [3]. Many research efforts have been undertaken to develop a wafer-scale PIC platform by making use of well-established semiconductor fabrication processes. Active photonic devices based on standard silicon-on-insulator based PICs rely typically on the plasma dispersion effect in silicon to induce a refractive index change as function of an applied voltage. In this case, the silicon waveguide is doped in such a way that it forms a pn-junction. This is, however, accompanied by optical losses due to absorption and fundamental speed restrictions are related to carrier injection and removal. To overcome these limitations, it is desirable to integrate materials with large off-resonant electro-optical (EO) effect, which allows a change of refractive index by applying a dc or modulated electric field. In this way, no carrier transport is necessary giving rise to ultra-high speed data communication. Here, the silicon waveguide is structured like a capacitor. It consists of two silicon rails in which the active EO material is located in between. Functionalized organic materials are from great interest since they exhibit extraordinary high EO effects. In particular, they can exhibit both, a linear and quadratic EO effect [4]. The advantage of organic EO materials is twofold. First, they exhibit strong EO effects and are highly transparent in the telecommunication wavelength range. Second, they exhibit off-resonant EO effects avoiding unwanted non-parametric processes like two photon absorption and free carrier absorption. The combination of organic materials with silicon-on-insulator based waveguides is known as silicon-organic hybrid (SOH) technology. Recent research has demonstrated a high-speed SOH phase shifter having bandwidths above 100 GHz [5]. Besides that, EO modulators with energy consumption in the atto-Joule per-bit regime have been realized, and also higher modulation formats have been demonstrated [6]. These results show clearly the potential of SOH devices for a next generation of signal processing. However, the integration of organic materials into a well-established silicon-on-insulator technology is still challenging because typical semiconductor fabrication processes are used with relatively high process-temperatures destroying the organic materials. To tackle this issue, an integration approach was proposed in which the organic material is deposited in a post-process. In this work, we review recent results on the hybrid integration of organic EO materials in a silicon-on-insulator technology. We outline some of the identified challenges regarding process compatibility and present preliminary results on the integration of organic materials in a photonic integrated circuit (PIC) technology. Here, we are focusing on EO applications for high speed data transfer employing the linear and quadratic EO effect. As an example, we demonstrate an intensity modulator fabricated in a 0.25 µm SiGe BiCMOS pilot line using 200 mm silicon-on-insulator wafers. This approach gives perspective for monolithically hybrid-integrated photonic devices in an electronic PIC (EPIC)-technology.