Fine-tuning of organic optical double-donor NLO chromophores with DA-supported functional groups.

New strategic chromophores with updated fine-tuning of previously reported BLD1 and BLD3 chromophores were designed. BLD1 and BLD3 have silicon functional groups on the donor unit, and the bridge has a good chance of self-assembling, so in the present study we fine-tuned the isolating groups to the bulky cyclic alkene to improve their dipole moment and organic electro-optic (OEO) properties as well. To demonstrate the impact of cyclic alkenes on the electron-donating groups in sensible NLO chromophore designs, a thorough analysis and comparison of the chromophore synthesis, UV-Vis calculations, solvatochromic behavior of the chromophore, DFT quantum mechanical calculations, thermal stabilities, and much lower dipole moments was conducted.

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.

Systematic Study on Nonlinear Optical Chromophores with Improved Electro-Optic Activity by Introducing 3,5-Bis(trifluoromethyl)benzene Derivative Isolation Groups into the Bridge.

A series of novel chromophores A, B, C, and D, based on the julolidinyl donor and the tricyanofuran (TCF) and CF3-tricyanofuran (CF3-Ph-TCF) acceptors, have been synthesized and systematically investigated. The 3,5-bis(trifluoromethyl)benzene derivative isolation group was introduced into the bridge in the chromophores C and D. These nonlinear optical chromophores showed good thermal stability, and their decomposition temperatures were all above 220 °C. Density functional theory (DFT) was used to calculate the energy gaps and first-order hyperpolarizability (ß). The macroscopic electro-optic (EO) activity was measured using a simple reflection method. The highest EO coefficient of poled films containing 35 wt% of chromophore D doped in amorphous polycarbonate afforded values of 54 pm/V at 1310 nm. The results indicate that the 3,5-bis(trifluoromethyl)benzene isolation group can suppress the dipole-dipole interaction of chromophores. The moderate r33 value, good thermal stability, and good yield of chromophores suggest their potential use in the nonlinear optical area.

Low-voltage and fast-response polymer-stabilized blue-phase liquid crystals achieved using a new organosilicone monomer.

In this paper, two types of polymer-stabilized blue-phase liquid crystals (PS-BPLCs) with different monomers were designed and prepared. The morphology, temperature range and electro-optical properties of the blue phases were studied and discussed. The temperature range of both types of PS-BPLC is greater than 110 °C, and both samples can be stabilized well at room temperature. The organosilicone monomer 3-methacryloxypropyltrimethoxysilane (KH570), which contains double bonds, was introduced to a blue-phase system for the first time. Regarding the electro-optical performance, the on-state voltage of the PS-BPLCs with the KH570 monomer is reduced to 30 V compared with traditional C12A monomer systems in which the on-state voltage is 75 V at 458 nm. Meanwhile, a fast response and suppressed hysteresis are obtained. These results are helpful to the application of displays and photonic devices.

Organic Dye Nanoparticles with a Special D-π-A Structure for Photoacoustic Imaging and Photothermal Therapy.

FTC dye with a D-π-A structure showed outstanding stability, high extinction coefficient, and good photothermal performance. Thus, nanoparticles based on FTC dye were first fabricated by a nanoprecipitation method for photothermal therapy (PTT) which was guided by photoacoustic imaging (PAI). The prepared FTC NPs showed a photothermal conversion efficiency of ∼52.71%, good photoacoustic performance, and excellent stability in in vitro experiments. Moreover, FTC NPs showed good performance in tumor ablation under a 635 nm laser irradiation and low cytotoxicity to the mice model without laser treatment. Histopathological analysis further confirmed that FTC NPs did not harm the major organs of mice. Given the abovementioned features, FTC NPs have great potential to be effective phototheranostic materials for PAI and PTT.

Recent Progress of Imprinted Polymer Photonic Waveguide Devices and Applications.

Polymers are promising materials for fabricating photonic integrated waveguide devices. Versatile functional devices can be manufactured using a simple process, with low cost and potential mass-manufacturing. This paper reviews the recent progress of polymer photonic integrated devices fabricated using the UV imprinting technique. The passive polymer waveguide devices for wavelength filtering, power splitting, and light collecting, and the active polymer waveguide devices based on the thermal-optic tuning effect, are introduced. Then, the electro-optic (EO) modulators, by virtue of the high EO coefficient of polymers, are described. Finally, the photonic biosensors, which are based on low-cost and biocompatible polymer platforms, are presented.

Nonlinear optical chromophores based on Dewar's rules: enhancement of electro-optic activity by introducing heteroatoms into the donor or bridge.

In this work, we investigated the enhancement of the electro-optic response by introducing electron-rich heteroatoms as additional donors into the donor or bridge of a conventional second-order nonlinear optical chromophore. A series of chromophores C2-C4 based on the same tricyanofuran acceptor (TCF) but with different heteroatoms in the alkylamino phenyl donor (C2 or C3) or thiophene bridge (C4) have been synthesized and systematically investigated. Density functional theory calculations suggested that chromophores C2-C4 had a smaller energy gap and larger first-order hyperpolarizability (ß) than traditional chromophore C1 due to the additional heteroatoms. Single crystal structure analyses and optimized configurations indicate that the rationally introduced heteroatom group would bring larger ß and weaker intermolecular interactions which were beneficial for translating molecular ß into macro-electro-optic activity in electric field poled films. The electro-optic coefficient of poled films containing 25 wt% of these new chromophores doped in amorphous poly-carbonate afforded values of 83 and 91 pm V(-1) at 1310 nm for chromophores C3 and C4, respectively, which are two times higher than that of the traditional chromophore C1 (39 pm V(-1)). High r33 values indicated that introducing heteroatoms to the donor and bridge of a conventional molecular structure can efficiently improve the electron-donating ability, which improves the ß. The long-chain on the donor or bridge part, acting as the isolation group, may reduce inter-molecular electrostatic interactions, thus enhancing the macroscopic EO activity. These results, together with good solubility and compatibility with the polymer, show the new chromophore's potential application in electro-optic devices.

The synthesis of new double-donor chromophores with excellent electro-optic activity by introducing modified bridges.

A series of chromophores y1­y3 based on the same bis(N,N-diethyl)aniline donor and the tricyanofuran acceptor (TCF) linked together via the modified thiophene π-conjugation with different isolated groups have been synthesized and systematically investigated in this paper. Density functional theory (DFT) was used to calculate the HOMO­LUMO energy gaps and first-order hyperpolarizability (ß) of these chromophores. Besides, to determine the redox properties of these chromophores, cyclic voltammetry (CV) experiments were performed. After introducing the isolation group into the thiophene, reduced energy gaps of 1.03 and 1.02 eV were obtained for chromophores y2 and y3, respectively, much lower compared to chromophore y1 (ΔE = 1.13 eV). These chromophores showed better thermal stability with their decomposition temperatures all above 220 °C. Besides, compared with results obtained from the chromophore (y1) without the isolated group, these new chromophores show better intramolecular charge-transfer (ICT) absorption. Most importantly, the high molecular hyperpolarizability (ß) of these chromophores can be effectively translated into large electro-optic (EO) coefficients (r33) in poled polymers. The electro-optic coefficient of poled films containing 25% wt of these new chromophores doped in amorphous polycarbonate (APC) afforded values of 149, 139 and 125 pm V(−1) at 1310 nm for chromophores y1­y3, respectively. Besides, when the concentration was increased, the film containing chromophores y1 and y3 showed obvious phase separation, while the film with chromophore y2 showed the maximum r33 value of 146 pm V(−1). Moreover, the electro-optic film prepared with these new chromophores showed greater stability. High r33 values indicated that the double donors of the bis(N,N-diethyl)aniline unit can efficiently improve the electron-donating ability and the isolated groups on the thiophene bridge can reduce intermolecular electrostatic interactions, thus enhancing the macroscopic EO activity. These properties, together with the good solubility, suggest the potential use of these new chromophores as advanced material devices.

Synthesis and characterization of a novel second-order nonlinear optical chromophore based on a new julolidine donor.

A new chromophore HK containing the cis,cis-1,7-diethoxy-3-isopropyljulolidine group as a novel electron-donor, thiophene as a π-conjugated bridge and a tricyanofuran (TCF) acceptor has been synthesized and systematically investigated in this paper. Its corresponding chromophore FTC using 4-(diethyl amino)benzyl as the electron donor group was also prepared for comparison. This is the first time that the cis,cis-1,7-diethoxy-3-isopropyljulolidine group was introduced into NLO materials. Density functional theory (DFT) was used to calculate the HOMO-LUMO energy gap and first-order hyperpolarizability (ß) of the new chromophore. The HOMO-LUMO gap was also investigated by cyclic voltammetry (CV). Upon using the cis,cis-1,7-diethoxy-3-isopropyljulolidine group as the donor, a reduced energy gap of 1.007 eV was obtained compared with chromophore FTC (ΔE = 1.529 eV). The high molecular hyperpolarizability of the new chromophore can be effectively translated into large electro-optic (EO) coefficients (r33) in poled polymers. The doped films containing the new chromophore HK showed a value of 72 pm V(-1) at the concentration of 25 wt% at 1310 nm. This value is almost two times higher than the EO activity of the usually reported traditional (N,N-diethyl) aniline nonlinear optical (NLO) chromophore FTC. High r33 values indicated that the new julolidine donor can efficiently improve the electron-donating ability and reduce intermolecular electrostatic interactions, thus enhancing the macroscopic EO activity. These properties, together with good solubility, suggest the potential use of the new chromophore in advanced materials devices.

Synthesis of novel nonlinear optical chromophore to achieve ultrahigh electro-optic activity.

A new diene-conjugated chromophore WJ1 was synthesized with high yield of 36% through an H-bonding induced Vilsmeier reaction. By simple guest-host doping, a large electro-optic efficiency of 337 pm V(-1) at 1310 nm and excellent temporal stability at 75 °C have been achieved in poled films of WJ1/APC with a high loading density of 40 wt%.

Optical properties of LaF3:Er,Yb nanoparticle-doped organic-inorganic hybrid material.

Oleic acid (OA)-modified LaF3:Er,Yb nanoparticle-doped organic-inorganic hybrid material (OIHM) was prepared. The absorption spectrum and photoluminescence spectrum were analyzed. The full width at half maximum (FWHM) of the photoluminescence spectrum was about 83 nm. The Judd-Ofelt theory was used to analyze the absorption spectrum of Er3+ and obtain the intensity parameters: omega2 = 2.11 x 10(-20) cm2, omega4 = 0.78 x 10(-200 cm2, omega6 = 0.56 x 10(-20)cm2. The line strengths predict spontaneous transition probabilities, and the radiative lifetimes are calculated with the Judd-Ofelt intensity parameters. The calculated radiative lifetime of the excited 4I13/2 state of Er3+ is 13.34 ms. Based on the parameters we calculated, OA-modified LaF3:Er,Yb nanoparticle-doped OIHM is a potential material for polymeric optical waveguide amplifiers.

Near-infrared luminescence properties of erbium complexes with the substituted phthalocyaninato ligands.

Two homoleptic bis(phthalocyaninato) erbium(III) complexes Er[Pc(beta-OR/R)4]2 and two half-sandwich phthalocyaninato erbium(III) complexes (acac)Er[Pc(beta-OR/R)4] (OR = 1-n-pentyloxy and R = tert-butyl) have been investigated. Then we studied the near-infrared luminescence properties of the compounds. When the phthalocyanine ligands were excited, half-sandwich phthalocyaninato erbium(III) complexes showed strong near-infrared luminescence at 1540 nm while homoleptic bis(phthalocyaninato) erbium(III) complexes showed no signals. The full width at half maximum (FWHM) centered at 1540 nm in the emission spectrum of the half-sandwich complexes in solution and in solid state are 67 nm and 78 nm respectively, which shows potential for optical-amplification applications. Erbium-doped standard polymethyl-methacrylate (PMMA) matrix which was synthesized has also displayed NIR emission.

One-step synthesis of highly water-soluble LaF(3):Ln(3+) nanocrystals in methanol without using any ligands.

Water-soluble infrared-to-visible fluorescent LaF(3) nanocrystals doped with different lanthanide ions (Er(3+)/Yb(3+), Eu(3+), Nd(3+), Tb(3+)) have been synthesized in methanol without using any ligands. These nanocrystals are easily dispersed in water, producing a transparent colloidal solution. The colloids of the Er(3+)/Yb(3+), Eu(3+), Nd(3+), Tb(3+) doped nanocrystals exhibit strong luminescence in the visible and near-infrared spectral regions.