Updated on 2025/04/10

Information

 

写真a

 
SPRING MARK ANDREW
 
Organization
Faculty of Engineering Sciences Department of Internationalization and Future Conception Associate Professor
Interdisciplinary Graduate School of Engineering Sciences Department of Interdisciplinary Engineering Sciences(Concurrent)
Title
Associate Professor
Contact information
メールアドレス
Tel
0925838901
Profile
Electro-optic Polymers: Electro-optic (EO) modulators are essential for electrical to optical transitions and high-speed optical interconnects. EO polymers have been used to fabricate modulators on silicon-on-insulator substrates. Optimization of the EO polymer structure is necessary to further reduce the driving voltage, power consumption and optic loss. ROMP has successfully been used to prepare well-controlled EO polymers. The ROMP monomers must exhibit high ring strain and ease of functionalization to include active substituents, while polymers must display excellent solubility allowing them to be spin coated giving films which are flat and homogeneous. Conjugated Polymers: Conjugated Polymers can be deposited from solution on a range of substrates at low temperatures such as paper or plastic to suit the desired application via well established methods such as spin coating, dip coating, ink jet printing, micro stamping and low resolution patterning. The initial research into conjugated electroluminescent materials was one of the major scientific discoveries of the last four decades and since then scientists have been able to optimise important physical properties such as the colour and efficiency of emission, charge mobility and light harvesting by chemically altering the structures. This advancement has led to the fabrication of a wide variety of organic based electronic devices such as OLEDs, OPVs, OFETs and flexible circuits. Carbon Nanotube Inks: The high electrical conductivity, wide spectral range of transparency, nano-porosity, and flexibility render carbon nanotube (CNT) thin films (10−100 nm) attractive as surrogates of semiconducting oxides for electrode fabrication. For practical use in applications, solution processability is desirable as this is amenable to the plastic substrates required for roll-to-roll printing. The avoidance of high vacuum systems furthermore reduces costs significantly. Key requirements for the preparation of high quality CNT films is that stable inks must be formulated with a high degree of nanotube dispersion, the CNTs themselves must be of high quality, and the dispersion aids should be easily removed after coating.
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Degree

  • Doctor of Philosophy (Ph.D.) in Materials Chemistry

  • Master of Chemistry (MChem)

Research History

  • 2002-2005: Master of Chemistry with Honours 1st Class (MChem) - University of Hull, UK. 2006-2010: Doctor of Philosophy in Materials Chemistry (Ph.D.) - University of Manchester, UK. 2010-2011: Postdoctoral Research Fellow - The University of Florida, USA. 2011-2013: Postdoctoral Research Fellow - Kyushu University, Japan. 2013-2018: Assistant Professor, Green Asia Education Center - Kyushu University, Japan. 2018-Present: Associate Professor, Department of Internationalization and Future Conception (IFC) - Kyushu University, Japan.   

Research Interests・Research Keywords

  • Research theme: EO polymeric materials synthesis and applications

    Keyword: EO Polymers

    Research period: 2011.6 - 2018.6

  • Research theme: Macromolecular Materials and Applications.

    Keyword: Polymer Chemistry

    Research period: 2011.6 - 2014.12

Papers

  • Ring-opening metathesis polymerization of homo- and copolymers Based on p-phenylenevinylene and norbornene-dicarboximide: Enhanced thermal stability for optoelectronic applications Reviewed International coauthorship

    Basyouni, Mohamed E. Abdu, Mohammed F. Radwan, Andrew M. Spring

    Journal of Molecular Structure   1338 ( 142296 )   2025.4

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    Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1016/j.molstruc.2025.142296

    DOI: https://doi.org/10.1016/j.molstruc.2025.142296

  • Living ROMP of N-phenothiazinyl norbornene-dicarboximide homopolymer: Synthesis, characterization, and physical behaviour insights Reviewed

    Mohammed F. Radwan*, Mohamed E. Abdu, Mostafa M. Elkady, Mahmoud Z. Basyouni, Andrew M. Spring*

    Polymer   321 ( 128115 )   2025.3   ISSN:00323861

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    Authorship:Last author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.polymer.2025.128115

    DOI: 10.1016/j.polymer.2025.128115

  • Enhancing Optical and Electrical Properties of Acetophenone Azo Anthrone Dye Thin Films Through Cyclodextrin Inclusion Complex” Reviewed International coauthorship

    Mohammed F. Radwan, Moustafa F. Aly, Andrew M. Spring, Amr Attia Abuelwafa

    Journal of Inorganic and Organometallic Polymers and Materials   2024.12

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1007/s10904-024-03515-4

    DOI: https://doi.org/10.1007/s10904-024-03515-4

  • Zeolite Synthesis from Natural and Waste Materials and the Double Environmental Benefits Reviewed International coauthorship

    Denis Mutebi, Frantisek Miksik, Andrew M. Spring, Indri Yaningsih, Takahiko Miyazaki, Kyaw Thu

    Evergreen   11 ( 4 )   3025 - 3058   2024.12   ISSN:21890420

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  • Bio-computational modeling, POM analysis and molecular dynamic simulation for novel synthetic quinolone and benzo[d][1,3] oxazine candidates as antimicrobial inhibitors Reviewed International coauthorship

    Doaa A. Elsayed, Mohamed E. Abdu, Mohammed A. Marzouk, Elsayed M. Mahmoud, Walaa H. El-Shwiniy, Andrew M. Spring, Wesam S. Shehab

    Scientific Reports   14 ( 28709 )   2024.11

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1038/s41598-024-73972-x

    DOI: https://doi.org/10.1038/s41598-024-73972-x

  • Optimization of conventional-zeolite-synthesis from waste pumice for water adsorption Reviewed International coauthorship

    Denis Mutebi, Frantisek Miksik, Andrew M. Spring, Indri Yaningsih, Takahiko Miyazaki, Kyaw Thu

    Advanced Powder Technology   35 ( 104713 )   2024.10

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1016/j.apt.2024.104713

  • Influence of aging on textural properties and symmetry of K-zeolites synthesized via a green route from waste pumice Reviewed

    Denis Mutebi, Frantisek Miksik, Andrew M. Spring, Indri Yaningsih, Takahiko Miyazaki, Kyaw Thu

    Journal of Porous Materials   2024.7

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1007/s10934-024-01663-z

    DOI: https://doi.org/10.1007/s10934-024-01663-z

  • From monomer to polymer: Controlled synthesis and comprehensive analysis of poly(p-phenylene vinylene) via ROMP Reviewed International coauthorship

    Mahmoud Z. Basyouni, Mohamed E. Abdu, Mohammed F. Radwan, Andrew M. Spring

    Journal of Molecular Structure   1310 ( 138001 )   2024.4

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    Authorship:Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1016/j.molstruc.2024.138001

    DOI: https://doi.org/10.1016/j.molstruc.2024.138001

  • Synthesis, Characterization, and Optical Properties of Carbazole-Functionalized Poly(norbornene-dicarboximide) by ROMP Reviewed

    #Mahmoud Z. Basyouni, #Mohammed F. Radwan, #Mohamed E. Abdu, Andrew M. Spring

    EVERGREEN   2024.4

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    Language:English   Publishing type:Research paper (scientific journal)  

    Repository Public URL: https://hdl.handle.net/2324/7172257

  • Conjugated Polymers and ROMP: Synthesis, Applications, and Prospects for Technological Innovations International journal

    #Basyouni, Mahmoud Z, #Ye, Jianhao, Spring, Andrew M.

    International Exchange and Innovation Conference on Engineering and Sciences   2023.10

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    Language:English   Publishing type:Research paper (international conference proceedings)  

  • Synthesis and Ring-Opening Metathesis Polymerization of o‑Dialkoxy Paracyclophanedienes Reviewed International journal

    Yurachat Janpatompong, Andrew M. Spring, Venukrishnan Komanduri, Raja U. Khan, and Michael L. Turner

    Macromolecules   2022.5

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    Repository Public URL: https://hdl.handle.net/2324/7318877

  • High-temperature-resistant silicon-polymer hybrid modulator operating at up to 200 Gbit s-1 for energy-efficient data centres and harsh-environment applications Reviewed International journal

    Lu, Guo-Wei; Hong, Jianxun; Qiu, Feng; Spring, Andrew M.; Kashino, Tsubasa; Oshima, Juro; Ozawa, Masa-aki; Nawata, Hideyuki; Yokoyama, Shiyoshi

    Nature Communications   2020.10

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    To reduce the ever-increasing energy consumption in datacenters, one of the effective approaches is to increase the ambient temperature, thus lowering the energy consumed in the cooling systems. However, this entails more stringent requirements for the reliability and durability of the optoelectronic components. Herein, we fabricate and demonstrate silicon-polymer hybrid modulators which support ultra-fast single-lane data rates up to 200 gigabits per second, and meanwhile feature excellent reliability with an exceptional signal fidelity retained at extremely-high ambient temperatures up to 110 °C and even after long-term exposure to high temperatures. This is achieved by taking advantage of the high electro-optic (EO) activities (in-device n3r33 = 1021 pm V−1), low dielectric constant, low propagation loss (α, 0.22 dB mm−1), and ultra-high glass transition temperature (Tg, 172 °C) of the developed side-chain EO polymers. The presented modulator simultaneously fulfils the requirements of bandwidth, EO efficiency, and thermal stability for EO modulators. It could provide ultra-fast and reliable interconnects for energy-hungry and harsh-environment applications such as datacentres, 5G/B5G, autonomous driving, and aviation systems, effectively addressing the energy consumption issue for the next-generation optical communication.

    Repository Public URL: https://hdl.handle.net/2324/7318872

  • A high efficiency silicon nitride waveguide grating coupler with a multilayer bottom reflector Reviewed International journal

    Hong, Jianxun; Spring, Andrew M.; Qiu, Feng; Yokoyama, Shiyoshi

    Scientific Reports - Nature Research   2019.9

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    We propose a high efficiency apodized grating coupler with a bottom reflector for silicon nitride photonic integrated circuits. The reflector consists of a stack of alternate silicon nitride and silicon dioxide quarter-wave films. The design, fabrication and optical characterization of the couplers has been presented. The measured fiber to detector insertion loss was −3.5 dB which corresponds to a peak coupling efficiency of −1.75 dB. A 3 dB wavelength bandwidth of 76.34 nm was demonstrated for the grating coupler with a 20-layer reflector. The fabrication process is CMOS-compatible and requires only a single etching step.

    Repository Public URL: https://hdl.handle.net/2324/7318868

  • Adamantyl and carbazole containing trans-poly(norbornene-dicarboximide)s as electro-optic chromophore hosts Reviewed International journal

    Andrew M. Spring Feng Qiu Jianxun Hong #Alisa Bannaron #Xiaoyang Cheng Shiyoshi Yokoyama

    Polymer - Elsevier   172   382 - 390   2019.4

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    A selection of trans-poly(norbornene-dicarboximide) random copolymers incorporating adamantyl and carbazole
    groups have been prepared using the Grubbs 1st generation catalyst. The copolymer with the greatest
    carbazole content was employed as a host for a high activity chromophore guest. The adamantyl groups were
    able to elevate the glass transition and thermal decomposition temperatures of the host copolymers, while the
    carbazole groups were included to facilitate the dispersion of the added chromophores and enhance the poling
    process. The mass of the adamantyl pendant monomer was kept constant as the mass of the carbazole pendant
    monomer was increased gradually. The successful incorporation of the carbazole moiety into the copolymers was
    confirmed by 1H NMR integration. The polymers had a predominantly trans microstructure and the cis/trans
    ratio did not change significantly. The polymer molecular weights increased linearly from 25,758 g/mol to
    56,827 g/mol as more carbazole-pendant monomer was incorporated. Polydispersities ranged from 1.29 to 1.70
    and elemental analysis confirmed an ascending carbon% in the polymers from 72.29% to 76.26%. The glass
    transition temperatures decreased from 240 °C to 126 °C, with the thermal decomposition temperatures (10%
    loss) remaining relatively constant at between 423 °C to 394 °C, indicating the polymers had a good thermal
    stability. The chromophore guest concentration was increased gradually into the copolymer host from 15 wt% to
    65 wt%. When poled at a field of 50 V/μm in thin film it was found that the optimum poling temperature
    decreased linearly from 150 °C to 90 °C as the chromophore concentration was increased, a maximum poling
    efficiency of 1.02 was achieved at a chromophore concentration of 55 wt%.

    DOI: 10.1016/j.polymer.2019.04.015

    Repository Public URL: https://hdl.handle.net/2324/7318867

  • Camera sensor platform for high speed video data transmission using a wideband electro-optic polymer modulator Reviewed International journal

    (#) Xiaoyang Cheng, Feng Qiu, Andrew M. Spring, Masaru Sasaki, Tsubasa Kashino, Masaaki Ozawa, Hideyuki Nawata, Tomohiro Kita, Okihiro Sugihara, and Shiyoshi Yokoyama

    Optics Express   2019.1

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    In this work, 1 GHz video data was collected by a CMOS camera and successfully transmitted by the electro-optic (EO) modulator driven by an external modulation module integrated onto the same chip. For this application, the EO modulator component included a polymer waveguide modulator, which performed a 20 GHz bandwidth, clear eye diagram opening with a Q factor of 10.3 at 32 Gbit/s and a drive voltage of 1.5 V pp . By utilizing a thermally stable EO polymer, the wide-band polymer modular can yield a photonic integrated camera sensor system which is a reliable processing platform for real-time data processing.

    DOI: https://doi.org/10.1364/OE.27.001877

    Repository Public URL: https://hdl.handle.net/2324/7318869

  • Plate-slot polymer waveguide modulator on silicon-on-insulator Reviewed International journal

    Feng Qiu, Andrew. M. Spring, Jianxun Hong, and Shiyoshi Yokoyama

    Optical Society of America (OSA) - Optics Express   26 ( 9 )   11213 - 11221   2018.4

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    Electro-optic (EO) modulators are vital for efficient “electrical to optical” transitions and high-speed optical interconnects. In this work, we applied an EO polymer to demonstrate modulators on silicon-on-insulator substrates. The fabricated Mach-Zehnder interferometer (MZI) and ring resonator consist of a Si and TiO2 slot, in which the EO polymer was embedded to realize a low-driving and large bandwidth modulation. The designed optical and electrical constructions are able to provide a highly concentrated TM mode with low propagation loss and effective EO properties. The fabricated MZI modulator shows a π-voltage-length product of 0.66 V·cm and a 3-dB bandwidth of 31 GHz. The measured EO activity is advantageous to exploit the ring modulator with a resonant tunability of 0.065 nm/V and a 3-dB modulation bandwidth up to 13 GHz.

    DOI: https://doi.org/10.1364/OE.26.011213

    Repository Public URL: https://hdl.handle.net/2324/7318863

  • Silicon waveguide grating coupler based on a segmented grating structure Reviewed International journal

    Jianxun Hong, Feng Qiu, Andrew M. Spring, and Shiyoshi Yokoyama

    Optical Society of America (OSA) - Applied Optics   57 ( 12 )   3301 - 3305   2018.4

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    We present the simulation, fabrication, and experimental results of a high-efficiency and wide-bandwidth segmented waveguide grating coupler on a silicon-on-insulator platform for near vertical optical coupling between the waveguide and optical fiber. The coupler comprises segmented gratings, which can increase vertical coupling to the optical fiber and reduce backward reflection. The proposed grating coupler has a 3 dB bandwidth of 71.4 nm and a coupling efficiency of 51.7% at a wavelength of 1550 nm. Compared with the standard uniform waveguide grating coupler, the coupling efficiency was improved by 25.64%.

    DOI: https://doi.org/10.1364/AO.57.003301

    Repository Public URL: https://hdl.handle.net/2324/7318861

  • Crosslinked poly(norbornene-dicarboximide)s as electro-optic chromophore hosts Reviewed International journal

    Spring Andrew M, Qiu Feng, Hong Jianxun, #Bannaron Alisa, Kashino Tsubasa, Kikuchi Takamasa, Ozawa Masaaki, Nawata Hideyuki, Odoi Keisuke, Yokoyama Shiyoshi

    Elsevier - European Polymer Journal   97   263 - 271   2017.12

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    A series of crosslinked poly(norbornene-dicarboximide)s have been prepared by ring opening metathesis polymerization. Increasing quantities of a bifunctional norbornene-dicarboximide crosslinker was doped into a high Tg cyclohexyl-substituted norbornene-dicarboximide monomer before polymerization. The wt% of the crosslinker was increased from 0.00 to 4.40 wt%, after which the polymers became gelated. Polymer molecular weights increased drastically from 23,500 to 2,135,000 g/mol, the polydispersities increased from 1.18 to 73.47 and the viscosities increased from 5.27 to 538.7 mPa·s as the wt% of the crosslinker was increased. The trans:cis vinylene ratio remained constant at 1:0.18 as well as the Tg and Td with average values of 210 °C and 392 °C being measured. Five of the crosslinked polymers and the reference homopolymer were utilized as hosts for the high activity tert-butyldiphenylsilyl substituted FTC chromophore guest. The polymer host containing 1.96 wt% crosslinker was foundto have amaximum r33 of 78 pm/V whenpolled at 150 °C withan electric fieldstrength of 100 V/μm. The r33 increased linearly from 63 to 78 pm/V as the wt% of the crosslinker was increased from 0.00 to 1.96wt%. The thermal and temporal stability was found to increase slightly with the 0.00 wt% polymer exhibiting a stability of 77%, while the 1.96 wt%polymer exhibited a stability of79% when both were heated to 85 °C and aged for 500 h in air.

    DOI: https://doi.org/10.1016/j.eurpolymj.2017.10.022

    Repository Public URL: https://hdl.handle.net/2324/7239430

  • High thermal stability 40 GHz electro-optic polymer modulators Reviewed International journal

    #Hiroki Miura, Feng Qiu, Andrew M. Spring, Tsubasa Kashino, Takamasa Kikuchi, Masaaki Ozawa, Hideyuki Nawata, Keisuke Odoi, and Shiyoshi Yokoyama

    Optical Society of America - Optics Express   25 ( 23 )   28643 - 28649   2017.11

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    As a consequence of the urgent demand for an electro-optic (EO) polymer modulator with an elevated temperature stability, we have prepared a selection of EO polymers having glass transition temperatures of up to 194°C. The measured half-wave voltage characteristics of the fabricated Mach-Zehnder interference modulators revealed an excellent thermal resistance at 105°C for approximately 2,000 hours. By utilizing traveling-wave electrodes on the modulator, the high-frequency response at 10-40 GHz was evaluated under ascending temperatures. The advantage of such high-temperature stability EO polymer modulators was clearly demonstrated by the continuous frequency response up to 130°C.

    DOI: https://doi.org/10.1364/OE.25.028643

    Repository Public URL: https://hdl.handle.net/2324/7318857

  • Electro-optic Polymer Ring Resonator Modulator on a Flat Silicon-on-Insulator Reviewed International journal

    Qiu Feng, Spring Andrew M, Hong Jianxun, #Miura Hiroki, Kashino Tsubasa, Kikuchi Takamasa, Ozawa Masaaki, Nawata, Hideyuki, Odoi Keisuke, Yokoyama, Shiyoshi

    Wiley - Laser and Photonics Reviews   11 ( 6 )   1700061   2017.11

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    Optical polymers are a promising material of choice in the development of
    hybrid silicon photonics devices. Particularly, recent progress in electro-optic
    (EO) active polymers has shown a strong Pockels effect. A ring resonator
    modulator is a vital building block for practical applications, such as signal
    processing, routing, and monitoring. However, the properties of the hybrid
    silicon and EO polymer ring modulators are still far from their theoretical
    limits. Here, we demonstrate a unique design of a hybrid ring resonator
    modulator simply located onto a silicon-on-insulator (SOI) substrate. Extra
    doping and etching of the SOI wafer is not required, even so we measured an
    in-device electro-optic coefficient r33 = 129 pm/V. The ring modulator
    exhibited a high sensitivity of the electrically tunable resonance, which
    enabled a 3 dB bandwidth of up to 18 GHz. The proposed technique will
    enable efficient mass-production of the micro-footprint modulators and
    promote the development of integrated silicon photonics.

    DOI: https://doi.org/10.1002/lpor.201700061

    Repository Public URL: https://hdl.handle.net/2324/7318855

  • Fabrication of a high-Q factor ring resonator using LSCVD deposited Si3N4 film Reviewed International journal

    #Xiaoyang Cheng, Jianxun Hong, Andrew M. Spring, and Shiyoshi Yokoyama

    Optical Society of America - Optical Materials Express   7 ( 7 )   2182 - 2187   2017.7

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    High-quality silicon nitride (Si3N4) films with a low stress and optical loss were deposited at low temperature (150°C) using liquid source chemical vapor deposition (LSCVD). The refractive index of the Si3N4 film was optimized by changing the composition ratio and deposition temperature. An integrated photonic structure of micro-ring resonator based on the as-deposited Si3N4 layer has been demonstrated to exemplify its viability as a photonic integration platform. Bragg gratings are fabricated at both ends of the bus waveguide to improve coupling efficiency and testing flexibility. A measured waveguide loss of 2.9 dB/cm and a high Q-factor of 5.2 × 104 are achieved. The LSCVD deposited Si3N4 is therefore a highly promising photonic integration platform for various integrated photonic applications.

    DOI: https://doi.org/10.1364/OME.7.002182

    Repository Public URL: https://hdl.handle.net/2324/7318852

  • A high-speed electro-optic triple-microring resonator modulator Reviewed International journal

    Hong Jianxun, Qiu Feng, #Cheng Xiaoyang, Spring Andrew M, Yokoyama Shiyoshi

    Nature Research - Scientific Reports   7 ( 4682 )   2017.7

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    The coupling intensity modulator based on a triple-microring structure was proposed and numerically investigated for a high speed and a low bit error ratio (BER) operation. The modulator consists of a dual-microring optical cavity and a gate-microring energy feedback path. The optical cavity ensures a high energy storing efficiency, and the feedback path enables modulation with little intracavity energy decay. The bandwidth of 103 GHz and modulation depth of 6.2 dB at 2.0 Vpp were theoretically verified by the analysis of the sinusoidal modulation performance. Pulse modulation resulted in a data rate of 160 Gbps, an extinction ratio of 16.84 dB, and a BER of 1 × 10−8. The proposed modulator is applicable for compact, high-speed, and low-energy photonic integration.

    DOI: doi:10.1038/s41598-017-04851-x

    Repository Public URL: https://hdl.handle.net/2324/7239718

  • Electro-optic properties of a side chain poly(norbornene-dicarboximide) system with an appended phenyl vinylene thiophene chromophore Reviewed International journal

    Spring Andrew M, Qiu Feng, Hong Jianxun, #Bannaron Alisa, Yokoyama Shiyoshi

    Elsevier - Polymer   119   13 - 27   2017.6

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    A side chain EO copolymer series has been synthesized by ROMP using the Grubbs 3rd generation initiator and quenched with ethyl vinyl ether. The copolymers were prepared by combining two norbornene-dicarboximide monomers, one with a cyclohexyl substituent and another substituted with an FTC chromophore. The mol% of the chromophore-substituted monomer was varied from 0.00 mol% to 22.92 mol%, all polymers were obtained in a yield of between 83 and 92% and a purity of between 97 and 98%. The cis:trans vinylene ratio remained constant at 1:1, confirming the polymers were amorphous. Peak molecular weights increased from 29,541 g/mol to 142,113 g/mol and the PDI increased from 1.36 to 4.01 respectively. Glass transition and thermal decomposition temperatures decreased from 206 C to 168 C and 433 C to 382 C as the mol% of the chromophore-substituted monomer was increased. UV evis absorbance spectroscopy was used to quantify the chromophore content. A close correlation (68 e95%) between the measured and calculated absorbance was found. The polymer containing 22.92 mol% of the chromophore-substituted monomer had a maximum r33 of 70 pm/V when polled at an optimum field of 60 V/mm at a polling temperature of 200 C. This equates to a high polling efficiency of 1.16. High current flow in this polymer film at elevated field strength caused a breakdown of the electrode, preventing access to an elevated electro-optic coefficient. This polymer was found to have an excellent stability of 76% when aged at 85 C for 1000 h in air.

    DOI: http://dx.doi.org/10.1016/j.polymer.2017.05.005

    Repository Public URL: https://hdl.handle.net/2324/7239429

  • Low driving voltage Mach-Zehnder interference modulator constructed from an electro-optic polymer on ultra-thin silicon with a broadband operation Reviewed International journal

    #Sato Hiromu, #Miura Hiroki, Qiu Feng, Spring Andrew M, Kashino Tsubasa, Kikuchi Takamasa, Ozawa Masaaki, Nawata Hideyuki, Odoi Keisuke, Yokoyama Shiyoshi

    Optical Society of America (OSA) - Optics Express   25 ( 2 )   768 - 775   2017.1

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    An electro-optic (EO) polymer waveguide using an ultra-thin silicon hybrid has been designed and fabricated. The silicon core has the thickness of 50 nm and a width of 5 μm. The waveguide was completed after covering the cladding with the high temperature stable EO polymer. We have demonstrated a low half-wavelength voltage of 0.9 V at the wavelength of 1.55 μm by using a Mach-Zehnder interference modulator with TM mode operation. The measured modulation corresponded to an effective in-device EO coefficient of 165 pm/V. By utilizing the traveling-wave electrode on the modulator the high-frequency response was tested up to 40 GHz. The 3 dB modulation bandwidth was measured to be 23 GHz. In addition, the high frequency sideband spectral measurement revealed that a linear response of the modulation index against the RF power was confirmed up to 40 GHz signal.

    DOI: http://dx.doi.org/10.1364/OE.25.000768

    Repository Public URL: https://hdl.handle.net/2324/7239431

  • High stability poly(N-adamantyl-exo-norbornene-5,6-dicarboximide) and phenyl vinylene thiophene electro-optic host-guest system Reviewed International journal

    Spring, Andrew M, Qiu, Feng, Yokoyama Shiyoshi

    Elsevier - European Polymer Journal   84   89 - 99   2016.11

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    Poly(N-adamantyl-exo-norbornene-5,6-dicarboximide) was prepared by ring opening metathesis polymerization. This was achieved in chloroform using the Grubbs 1st generation initiator and quenched with ethyl vinyl ether. The polymer had a weight average molecular weight of 27,000 g/mol with a polydispersity index of 2.19, a high glass transition temperature of 281 °C and a high thermal decomposition temperature of 385 °C (10% loss). The trans:cis vinylene ratio was 1.00:0.19 making the polymer amorphous. The polymer was used as a host for 5 guest nonlinear optical chromophores. The relationship between the chromophore structure and the electro-optic coefficient was investigated. A range of chromophore concentrations were evaluated and it was found that the ideal chromophore structure included a bulky tert-butyldiphenylsilane side group. A maximum r33 of 80 pm/V was obtained at a chromophore concentration of 45 wt% and a poling temperature of 160 °C. A host-guest system containing 35 wt% of the tert-butyldiphenylsilane substituted chromophore had a stability of 85% at a temperature of 85 °C for 500 h. The stability at 105 °C was 72%. In comparison amorphous polycarbonate under the same conditions achieved a stability of just 58% at 85 °C, while poly(methyl methacrylate) had a stability of 0% at 85 °C.

    DOI: https://doi.org/10.1016/j.eurpolymj.2016.09.012

    Repository Public URL: https://hdl.handle.net/2324/7239418

  • An electro-optic polymer-cladded TiO2 waveguide modulator Reviewed International journal

    Qiu Feng, #Miura Hiroki, Spring Andrew M, Hong Jianxun, Maeda Daisuke, Ozawa Masa-aki, Odoi Keisuke, Yokoyama Shiyoshi

    Applied Physics Letter (APL)   109 ( 17 )   173301-1 - 173301-4   2016.10

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    Organic electro-optic (EO) materials and their hybrid systems have received considerable attention for high-performance modulators. In this work, we demonstrate the design and fabrication of an EO modulator with a low half-wave voltage (Vp) and a RF modulation response up to at least 10GHz. The polymer used in this work has a glass transition temperature of 172C, which makes it stable even under high temperature RF sputtering. As a result, an EO polymer-cladded titanium dioxide (TiO2) waveguide structure can be utilized to enlarge the confinement factor, and thus, enable a low Vp. The response of the modulator from 4 to 10GHz has been measured, which shows a flat frequency response up to 10 GHz and a potential for the application in several tens GHz.

    DOI: http://dx.doi.org/10.1063/1.4966272

    Repository Public URL: https://hdl.handle.net/2324/7239425

  • Alkyl substituted poly(p-phenylene vinylene)s by ring opening metathesis polymerisation Reviewed International journal

    Lidster Benjamin J, Kumar Dharam R, Spring, Andrew M, Yu, Chin-Yang, Turner Michael L

    Royal Society of Chemistry (RSC) - Polymer Chemistry   7 ( 35 )   5544 - 5551   2016.6

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    The ring opening metathesis polymerisation (ROMP) of three n-octyl substituted [2.2]paracyclophane1,9-dienes, initiated by Grubbs ruthenium carbene complexes is reported. The molecular weight of the resulting alkyl-substituted poly(p-phenylene vinylene)s is determined by the monomer to initiator ratio and the polymers are isolated with relatively narrow polydispersities and control of the end groups. Only the pseudo-geminal isomer of the tetra-alkyl substituted [2.2]paracyclophane-1,9-diene was susceptible to ROMP. The optical properties of the two series of polymers was investigated.

    DOI: 10.1039/c6py01186a

    Repository Public URL: https://hdl.handle.net/2324/7239427

  • Alkyl substituted [2.2]paracyclophane-1,9-dienes Reviewed International journal

    Lidster Benjamin J, Kumar Dharam R, Spring Andrew M, Yu Chin-Yang, Helliwell Madeleine, Raftery James, Turner, Michael L

    Royal Society of Chemistry (RSC) - Organic & Biomolecular Chemistry   14 ( 25 )   6079 - 6087   2016.5

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    [2.2]Paracyclophane-1,9-dienes substituted with n-octyl chains have been synthesised from the corresponding dithia[3.3]paracyclophanes using a benzyne induced Stevens rearrangement. The use of 2-(trimethylsilyl)phenyl trifluoromethanesulfonate and tetra-n-butylammonium fluoride as the in situ benzyne source gave significantly improved yields over traditional sources of benzyne and enabled the preparation of n-octyl substituted [2.2]paracyclophane-1,9-dienes on a multi-gram scale.

    DOI: 10.1039/c6ob00885b

    Repository Public URL: https://hdl.handle.net/2324/7239428

  • Athermal Hybrid Silicon/Polymer Ring Resonator Electro-optic Modulator Reviewed International journal

    Qiu Feng Spring Andrew M, #Miura Hiroki, Maeda Daisuke, Ozawa Masa-aki, Odoi, Keisuke, Yokoyama, Shiyoshi

    American Chemical Society (ACS) Photonics   3 ( 5 )   780 - 783   2016.5

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    In this work, we have demonstrated a hybrid silicon/polymer ring resonator electro-optic (EO) modulator with a temperature-independent modulation. The waveguide consisted of an ultrathin silicon core with an EO polymer cladding. Using ultrathin silicon is advantageous, as it allows a reduction in the side-wall scattering loss and also offers excellent light distribution to enable athermal operation. With a radius of 60 μm, the ring exhibited a 9.7 dB extinction depth and a Q value of 1.25 × 104. After poling of the EO polymer, the ring resonator functioned well as an EO modulator and operated in a stable manner between 25 and 55 °C.

    DOI: 10.1021/acsphotonics.5b00695

    Repository Public URL: https://hdl.handle.net/2324/7239422

  • Ultra-thin silicon/electro-optic polymer hybrid waveguide modulators Reviewed International journal

    Qiu Feng, #Sato Hiromu, Spring Andrew M, Maeda Daisuke, Ozawa Masa-aki, Odoi Keisuke, Aoki Isao, Otomo Akira, Yokoyama, Shiyoshi

    Applied Physics Letters (APL)   107 ( 12 )   123302-1 - 123302-5   2015.9

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    Ultra-thin silicon and electro-optic (EO) polymer hybrid waveguide modulators have been designed and fabricated. The waveguide consists of a silicon core with a thickness of 30nm and a width of 2lm. The cladding is an EO polymer. Optical mode calculation reveals that 55% of the optical field around the silicon extends into the EO polymer in the TE mode. A Mach-Zehnder interferometer (MZI) modulator was prepared using common coplanar electrodes. The measured half-wave voltage of the MZI with 7lm spacing and 1.3cm long electrodes is 4.6V at 1550nm. The evaluated EO coefficient is 70pm/V, which is comparable to that of the bulk EO polymer film. Using ultra-thin silicon is beneficial in order to reduce the side-wall scattering loss, yielding a propagation loss of 4.0dB/cm. We also investigated a mode converter which couples light from the hybrid EO waveguide into a strip silicon waveguide. The calculation indicates that the coupling loss between these two devices is small enough to exploit the potential fusion of a hybrid EO polymer modulator together with a silicon micro-photonics device.

    DOI: https://doi.org/10.1063/1.4931490

    Repository Public URL: https://hdl.handle.net/2324/7239402

  • Athermal and High-Q Hybrid TiO2–Si3N4 Ring Resonator via an Etching-Free Fabrication Technique Reviewed International journal

    Qiu Feng, Spring Andrew M and Yokoyama, Shiyoshi

    American Chemical Society (ACS) Photonics   2 ( 3 )   405 - 409   2015.3

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    In this work, we have demonstrated a hybrid TiO2−Si3N4 ring resonator with a high-Q and a temperature-insensitive resonance. The waveguide consists of a thermo-optic positive Si3N4 slab and a negative TiO2 overcladding. The TiO2 layer has a shallow ridge structure, which has been designed to realize an athermal operation and maintain a low scattering loss. During the fabrication of this waveguide, there was no need to utilize the dryetching process. The method affords a straightforward fabrication and a precise control over the waveguide dimensions. As a result, the ring resonator exhibits a high Q value of 1.55 × 105,a low propagation loss of 0.4 dB/cm, and a small temperature-dependent wavelength shift of 0.14 pm/°C between 25 and 60 °C.

    DOI: DOI:10.1021/ph500450n

    Repository Public URL: https://hdl.handle.net/2324/7239410

  • A hybrid electro-optic polymer and TiO2 double-slot waveguide modulator Reviewed International journal

    Qiu Feng, Spring Andrew M, Maeda Daisuke, Ozawa Masa-aki, Odoi Keisuke, Otomo Akira, Aoki Isao, Yokoyama, Shiyoshi

    Nature research - Scientific Reports   5 ( 8561 )   1 - 6   2015.2

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    An electro-optic (EO) modulator using a TiO2 slot hybrid waveguide has been designed and fabricated. Optical mode calculations revealed that the mode was primarily confined within the slots when using a double-slot configuration, thus achieving a high EO activity experimentally. The TiO2 slots also acted as an important barrier to induce an enhanced DC field during the poling of the EO polymer and the driving of the EO modulator. The hybrid phase modulator exhibited a driving voltage (Vπ) of 1.6 V at 1550 nm, which can be further reduced to 0.8 V in a 1 cm-long push-pull Mach–Zehnder interferometer (MZI) structure. The modulator demonstrated a low propagation loss of 5 dB/cm and a relatively high end-fire coupling efficiency.

    DOI: doi:10.1038/srep08561

    Repository Public URL: https://hdl.handle.net/2324/7239414

  • An analysis of the structural, thermal and optical characteristics as well as the electrical resistivity of tert-butyldiphenylsilyl substituted poly(norbornene-dicarboximide)s Reviewed International journal

    Andrew M. Spring, Daisuke Maeda, Masaaki Ozawa, Keisuke Odoi, Feng Qiu, Kazuhiro Yamamoto, Shiyoshi Yokoyama

    Elsevier - Polymer   56 ( 15 )   189 - 198   2014.12

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    A sequence of well controlled tert-butyldiphenylsilyl substituted poly(norbornene-dicarboximide)s with ascending mol. wts. have been prepd. using the Grubbs 1st generation catalyst in anhyd. chloroform. The kinetics of the polymn. was examd. using NMR spectroscopy and gel permeation chromatog. By decreasing the Grubbs catalyst concn., the polymer mol. wts. increased linearly. The glass transition temps. and thermal decompn. temps. initially increased with polymer mol. wt., then reached a plateau. Regardless of mol. wt. the polydispersities remained narrow. The polymers exhibited a predominantly trans microstructure and matrix-assisted laser desorption/ionization mass spectrometry was utilized to det. polymer end groups and to calc. the abs. mol. wts. The residual ruthenium content of the polymers was quantified using inductively coupled plasma mass spectrometry and the influence on the resistivity, refractive indexes and thin film optical transmittance was evaluated.

    DOI: http://dx.doi.org/10.1016/j.polymer.2014.11.043

    Repository Public URL: https://hdl.handle.net/2324/7239400

  • Glass transition temperature control by poly(norbornene-dicarboximide) copolymers Reviewed International journal

    Andrew M. Spring, Daisuke Maeda, Masaaki Ozawa, Keisuke Odoi, Feng Qiu, Kazuhiro Yamamoto, Shiyoshi Yokoyama

    Springer - Polymer Bulletin   72 ( 3 )   503 - 521   2014.12

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    By the precise combination of both cyclohexyl- and octyl-substituted norbornene-dicarboximide monomers, a series of copolymers were prepd. by ring-opening metathesis polymn. utilizing the Grubbs first-generation initiator. This allowed an excellent control over the glass transition temp. between 215 and 126 °C depending upon the percentage of the octyl moiety in the copolymer. Initially two homopolymers, poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) and poly(N-octyl-exo-norbornene-5,6-dicarboximide), were prepd. to det. the desirable conditions for copolymer prepn. The kinetics of the two homopolymers were monitored using proton NMR spectroscopy and size-exclusion chromatog., with monomer conversion being achieved after 120 min in both cases.

    DOI: DOI 10.1007/s00289-014-1283-2

    Repository Public URL: https://hdl.handle.net/2324/7239384

  • A straightforward electro-optic polymer covered titanium dioxide strip line modulator with a low driving voltage Reviewed International journal

    Feng Qiu, Andrew M. Spring, Daisuke Maeda, Masa-aki Ozawa, Keisuke Odoi, Isao Aoki, Akira Otomo, and Shiyoshi Yokoyama

    Applied Physics Letters (AIP)   105   073305-1 - 073305-4   2014.8

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    An electrooptic (EO) modulator composed of an EO polymer/TiO2 (TiO2) hybrid waveguide was designed and fabricated. By using a TiO2 strip line (0.3 × 0.3 μm2 cross-section) as the core, the confinement factor in the EO polymer is optimized, thus achieving a high EO activity. The coplanar electrode spacing is tuned to enable an effective poling and a small propagation loss. The measured in-device EO coeff. is 100 pm/V at 1550 nm, with a driving voltage (Vπ) 3.2 V for the 12 mm-electrode length. The results also predict a possible Vπ of ∼1 V in a push-pull MZI structure. The EO activity of the modulator exhibited an excellent temporal stability at 85° for 500 h due to the high glass transition temp. of the EO polymer and the temp.-insensitive TiO2 strip line.

    DOI: http://dx.doi.org/10.1063/1.4893925

    Repository Public URL: https://hdl.handle.net/2324/7239375

  • TiO2 ring-resonator-based EO polymer modulator Reviewed International journal

    Qiu Feng, Spring Andrew M, Maeda Daisuke, Ozawa Masa-Aki, Odoi Keisuke, Aoki Isao, Otomo Akira, Yokoyama Shiyoshi

    The Optical Society of America (OSA) - Optics Express   22   14101 - 14107   2014.6

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    In this work, an electro-optic (EO) ring resonator modulator was designed and fabricated in a waveguide consisting of a titanium dioxide (TiO2) core, silicon dioxide (SiO2) buffer layer, EO polymer claddings, and electrodes. By optimizing the thickness of the TiO2 and SiO2 layers, the modulator could satisfy the single-mode requirement; furthermore 52.5% TM mode was confined in the active EO polymer layers. The designed modulator could also pole the EO polymer effectively regardless of its resistivity. Therefore, the EO modulator was obsd. to show a high resonance wavelength shift of 2.25 × 10-2 nm/V. The intensity modulation at 1550 nm showed a Vp-p = 1.9 V for a 3dB distinction ratio.

    DOI: DOI:10.1364/OE.22.014101

    Repository Public URL: https://hdl.handle.net/2324/7239383

  • Carbon Nanotube Adsorptive Materials Derived from Acid Degradable Poly(acetals) Reviewed International journal

    Andrew M. Spring, Leandro A. Estrada, Svetlana V. Vasilyeva, Andrew G. Rinzler, and John R. Reynolds

    American Chemical Society (ACS) - Macromolecules   47   2556 - 2560   2014.4

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    In this paper, we report the synthesis and characterization of a well-controlled and acid degradable poly(acetal) which can adsorb strongly to the surface of carbon nanotubes (CNTs). These polymers, generated via acyclic diene metathesis (ADMET), incorporate pendant pyrene groups that are well-known to associate strongly to CNTs by noncovalent interactions. Films and solutions of the
    polymer were degraded through the controlled addition of aqueous hydrochloric acid in ethanol. The polymer’s ability to adsorb to and be removed from a CNT film was also evaluated.

    DOI: dx.doi.org/10.1021/ma500009s

    Repository Public URL: https://hdl.handle.net/2324/7238804

  • The preparation of well-controlled poly(N-cyclohexyl-exo-norbornene-5,6-dicarboximide) polymers Reviewed International journal

    Andrew M Spring, #Feng Yu, Feng Qiu, Kazuhiro Yamamoto and Shiyoshi Yokoyama

    Nature Publishing Group - Polymer Journal   46   576 - 583   2014.3

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    We have studied the ring-opening metathesis polymerization of N-cyclohexyl-exo-norbornene-5,6-dicarboximide using the
    following 4 initiators: Grubbs 1, Grubbs 2, Hoveyda–Grubbs 1 (HG1) and Hoveyda–Grubbs 2 (HG2). Only the Grubbs 1 initiator
    was able to precisely control the polymer molecular weight. Polymerizations initiated by the HG1, Grubbs 2 and HG2 initiators
    could not be controlled well. Both the Grubbs 1 and HG1 yielded polymers with a high trans % (85–98%), whereas Grubbs 2
    and HG2 yielded polymers with a lower trans % (50–52%). The level of molecular weight control for the four initiators
    decreased in the order Grubbs 14HG14HG24Grubbs 2. We also demonstrated that, in the case of polymers produced using
    Grubbs 1, the refractive indices (RIs) of the polymers decreased in a linear and controllable fashion from 1.539 to 1.534 at
    633 nm, as the molecular weight was increased from 6700 to 26 400. This change represented a decrease in the RI of 0.005.

    DOI: doi:10.1038/pj.2014.26

    Repository Public URL: https://hdl.handle.net/2324/7238805

  • Electro-optic properties of a bi-chromophore norbornene polymer brush system Reviewed International journal

    #Yue Jia, Andrew M. Spring, Feng Qiu, #Feng Yu, Kazuhiro Yamamoto, Isao Aoki, Akira Otomo, and Shiyoshi Yokoyama*

    IOP Science - Japanese Journal of Applied Physics (JJAP)   53 ( 01AF04 )   01AF041 - 01AF04-5   2013.12

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    A selection of poly(norbornene-exo-dicarboximide) brush-type polymers decorated with a pendent azobenzene dye have been prepared for use as electro-optic (EO) hosts. These polymer brushes were employed as EO polymer hosts for a high molecular hyperpolarizability phenyl vinylene thiophene vinylene (FTC) chromophore guest. These polymer brushes contained methoxy or cyano azobenzene substituents, which were able to manipulate the electronic polarization, refractive index, and EO activity. The concentration of the azobenzene dye was increased from 6 to 38%, in order to find the optimum and to maximise the EO coefficient. The refractive index of the mixtures could also be tuned by changing the azobenzene content. Ultimately an EO coefficient of nearly 95 pm/V could be realized using a methoxy substituted azobenzene brush at a concentration of 25% with an added FTC chromophore.

    DOI: http://dx.doi.org/10.7567/JJAP.53.01AF04

    Repository Public URL: https://hdl.handle.net/2324/7239371

  • A Norbornene Polymer Brush for Electro-optic Applications Reviewed International journal

    #Jia Yue, Spring Andrew M, #Yu Feng, Yamamoto Kazuhiro, Aoki Isao, Otomo Akira, Yokoyama, Shiyoshi

    Elsevier - Thin Solid Films   554   175 - 179   2013.7

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    Norbornenedicarboximide derived polymer brushes containing Disperse Red 1 appended chromophores have been prepared by sequencial ring opening metathesis polymerization and atom transfer radical polymerization. This brush was then employed as an electro-optic polymer host for high molecular hyperpolarizability phenyl vinylene thiophene vinylene (FTC) bridge chromophores in a binary chromophore system. The r33 of the polymer brush/bi-chromophore network was evaluated via in situ poling and was measured as 94 pm/V compared to the benchmark polymethylmethacrylate (PMMA) system of 76 pm/V with an identical chromophore. Furthermore, our polymer brush/bi-chromophore network exhibited an enhanced poling efficiency of 1.37 (nm/V)2 as compared to a simple PMMA - FTC host - guest 0.70 (nm/V)2.

    DOI: https://doi.org/10.1016/j.tsf.2013.06.071

    Repository Public URL: https://hdl.handle.net/2324/7239385

  • Thin TiO2 Core and Electro-optic Polymer Cladding Waveguide Modulators Reviewed International journal

    Qiu Feng, Spring Andrew M, #Yu Feng, Aoki Isao, Otomo Akira, Yokoyama Shiyoshi

    American Institute of Physics (AIP) - Applied Physics Letters (APL)   102   233504-1 - 2335043   2013.6

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    In this letter, we have fabricated a thin TiO2 core and electro-optic (EO) polymer cladding derived rib-waveguide and demonstrated its optical modulation at 1550 nm with a VpL figure of merit of 3.3 V cm. We utilized the high refractive index TiO2 to confine a large fraction of light in the relatively low refractive index EO polymer layer. Furthermore, this TiO2 core enables the modulator to be constituted without a transparent top cladding and also can increase the EO activity to a much higher level. As a result, the waveguide has an enhanced in-device r33, corresponding to a VpiL of 165 V cm in a pushpull MachZehnder interferometer structure.

    DOI: https://doi.org/10.1063/1.4809818

    Repository Public URL: https://hdl.handle.net/2324/7238796

  • Electro-optic Polymer/Titanium Dioxide Hybrid Core Ring Resonator Modulators Reviewed International journal

    Qiu Feng, Spring Andrew M, #Yu Feng, Aoki Isao, Otomo Akira, Yokoyama Shiyoshi

    Laser and Photonics Reviews   7   L84 - L88   2013.4

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    Compact electro-optic (EO) modulators are desirable for a number of applications. In this study, a ring modulator has been fabricated in the titanium dioxide (TiO2) core and EO polymer cladding waveguide structure. A 250-nm thick TiO2 core was utilized to minimize the ring radius down to 100 μm, to avoid using the top cladding between the EO polymer and the electrode, and to improve the poling efficiency. The resonance obtained by the ring modulator was observed to shift by 0.02 nm/V due to the enhanced in-device EO coefficient of 105 pm/V. A modulation depth of 3 dB was observed at the frequency response function at 20 kHz using 2-V Vp–p clock signal.

    DOI: https://doi.org/10.1002/lpor.201300089

    Repository Public URL: https://hdl.handle.net/2324/7238792

  • Complementary Metal-Oxide-Semiconductor compatible athermal Silicon Nitride/Titanium Dioxide Hybrid Micro Ring Resonators Reviewed International journal

    Qiu Feng, Spring Andrew M, #Yu Feng, Yokoyama Shiyoshi

    American Institute of Physics (AIP) - Applied Physics Letters (APL)   102   051106 1 - 051106-3   2013.2

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    Micro-ring resonators have been widely utilized in silicon photonics. However they often exhibit a high sensitivity to ambient temperature fluctuations. In this letter, we have demonstrated a complementary metal–oxide–semiconductor compatible athermal micro-ring resonator made from titanium dioxide (TiO2) and silicon nitride (SiNx). We have exploited the negative thermo–optic
    coefficient of TiO2 to counterbalance the positive coefficient of SiNx. By a precise control over the TiO2 layer thickness, an athermal condition remarkably consistent with the simulation can be achieved. Therefore, a SiNx–TiO2 hybrid micro-ring resonator with a temperature dependent wavelength shift of 0073 pm/C has been realized.

    DOI: https://doi.org/10.1063/1.4790440

    Repository Public URL: https://hdl.handle.net/2324/7238799

  • An Enhanced Host-Guest Electro-Optical Polymer System Using Poly(norbornene-dicarboximides) via ROMP Reviewed International journal

    #Yu Feng, Spring Andrew M, Li Lu, Qiu Feng, Yamamoto Kazuhiro, Maeda Daisuke, Ozawa Masaaki, Odoi Keisuke, Yokoyama Shiyoshi

    About Wiley Online Library - Journal of Polymer Science, Part A: Polymer Chemistry   51   1278 - 1284   2012.11

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    High glass transition temperature poly(N-cyclohexyl-5-norbornene-2,3-dicarboximide)s (NDI)s prepared by ring opening metathesis polymerization yielded polymers with a narrow polydispersity and well-controlled molecular weight materials when using the Grubbs first generation initiator. Polymers produced using the Grubbs second generation initiator could not be controlled easily. By initiator selection it was also possible to synthesize polymers with either 98 or 52% trans microstructures. These materials were employed as electro-optic (EO) polymer hosts for high molecular hyperpolarizability phenyl vinylene thiophene vinylene bridge chromophores. This chromophore was modified by the incorporation of a tert-butyldiphenylsilane group. The addition was able to further increase its EO coefficient (r33) to reach 93 pm/V in a trans rich poly(NDI) produced by the Grubbs first generation initiator, compared to a benchmark chromophore / polymer combination. We investigated in detail the
    relationship between polymer microstructure and their absolute molecular weight on forming the best host–guest with the high polarizability chromophore. Our results indicate that by utilizing a very simple host–guest system a high r33 can be realized.

    DOI: 10.1002/pola.26505

    Repository Public URL: https://hdl.handle.net/2324/7238803

  • Thermal Sensitive Wavelength Filter Based on Polymer Waveguide and Polarization-maintaining Fiber Reviewed International journal

    Feng Qiu #Feng Yu, Andrew M. Spring, and Shiyoshi Yokoyama

    Journal of the Optical Society of America B (OSA) Optical Physics   29   3069 - 3071   2012.10

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    A simple thermal tuning wavelength filter is experimentally demonstrated by using a high polarization extinction ratio polymer waveguide and a polarization-maintaining fiber. This filter can be tuned with its free spectral range, on/off ratio, and filtered wavelength. The large temperature dependence wavelength shift of 0.65 nm=°C also makes it a suitable candidate of thermal sensors.

    DOI: https://doi.org/10.1364/JOSAB.29.003069

    Repository Public URL: https://hdl.handle.net/2324/7238785

  • Athermal Silicon Nitride Ring Resonator by Photobleaching of Disperse Red 1-Doped Poly(methylmethacrylate) Polymer Reviewed International journal

    Qiu Feng, #Yu Feng, Spring Andrew M, Yokoyama Shiyoshi

    Optical Society of America (OSA) - Optics Letters   19   4086 - 4088   2012.7

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    To fabricate athermal silicon nitride waveguides, the dimensions of both the core and cladding, refractive index, and thermo-optic coefficients must be controlled precisely. We present a simple and effective method for the postfabrication trimming of silicon nitride ring resonators that overcomes the highly demanding fabrication. In order to manipulate the polymer’s refractive index and thermo-optic coefficient, we bleached the Disperse Red 1-doped poly(methyl methacrylate) (DR1/PMMA) top cladding using UV irradiation. After a suitable bleaching time, the temperature-dependent wavelength shift of the ring resonator was reduced from −9.8 to −0.018 pm∕°C, which is the lowest shift that we are aware of for an athermal waveguide realized by overlaying a polymer cladding to date.

    DOI: https://doi.org/10.1364/OL.37.004086

    Repository Public URL: https://hdl.handle.net/2324/7238786

  • Homopolymers and Block Copolymers of p-Phenylenevinylene-2,5-diethylhexyloxy-p-phenylenevinylene and m-Phenylenevinylene-2,5-diethylhexyloxy-p-phenylenevinylene by Ring-Opening Metathesis Polymerisation Reviewed International journal

    Chin-Yang Yu, Masaki Horie, Andrew M. Spring, Kim Tremel, and Michael L. Turner*

    American Chemical Society (ACS) - Macromolecules   43   222 - 232   2009.10

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    p-Phenylenevinylene-2,5-diethylhexyloxypphenylenevinylene and m-phenylenevinylene-2,5-diethylhexyloxy-p-phenylenevinylene homopolymers have been prepared by the ring-opening metathesis polymerization (ROMP) of strained cyclophanedienes, initiated by the second generation Grubbs catalyst. The as-formed polymers have a backbone of alternating cis- and trans-vinylene linkages due to the opening of only one vinylene of the cyclophanediene. Irradiation with UV light results in an isomerization to an all-trans-vinylene microstructure for all polymers. The polymer chain ends remain active after complete consumption of the cyclophanediene, and block copolymers can be prepared by addition of further cyclophanediene. The optical and electronic properties of the homopolymers and block copolymers are reported

    DOI: 10.1021/ma901966g

    Repository Public URL: https://hdl.handle.net/2324/7178739

  • MEH-PPV by microwave assisted ring-opening metathesis polymerisation Reviewed International journal

    Andrew M. Spring, Chin-Yang Yu, Masaki Horie and Michael L. Turner*

    Royal Society of Chemistry (RSC) - Chemical Communications   19   2676 - 2678   2009.3

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    Excellent control in the synthesis of MEH-PPV can be achieved by microwave assisted, ring-opening metathesis polymerization
    (ROMP) of [2.2]paracyclophanedienes.

    DOI: 10.1039/b901075k

    Repository Public URL: https://hdl.handle.net/2324/7238775

▼display all

Presentations

  • Living Polymerizations for Engineering Applications Invited International conference

    Andrew M. Spring

    CSS-EEST22  2020.10 

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    Event date: 2020.10

    Language:English   Presentation type:Oral presentation (general)  

    Venue:Online   Country:Japan  

    Well-controlled living polymerization mechanisms allow a fine tuning of bulk polymer properties to suit a range of high-tech engineering applications. Ring Opening Metathesis Polymerization (ROMP) is one of the most versatile and interesting of these techniques. The key requirement is that monomers must be cyclic alkenes which exhibit a large degree of ring strain. Typically, Grubbs catalysts are utilized to afford the narrow dispersity homopolymers, random copolymers, block copolymers and other more complex macromolecules.

  • Poly(Phenylenevinylenes) by Microwave Assisted Ring Opening Metathesis Polymerization. International conference

    Andrew Mark Spring

    IUPAC  2009.6 

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    Event date: 2009.6

    Language:English   Presentation type:Symposium, workshop panel (public)  

    Venue:Montral   Country:Canada  

    Excellent control in the synthesis of MEH-PPV can be achieved
    by microwave assisted, ring-opening metathesis polymerization
    (ROMP) of [2.2]paracyclophanedienes.

  • Novel Optical Polymer Hosts via Ring Opening Metathesis Polymerization (ROMP)

    Andrew Mark Spring

    SPSJ  2012.5 

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    Language:English   Presentation type:Oral presentation (general)  

    Country:Japan  

    In the goal to achieve a high electrooptic coefficient (r33 > 100 pm/V), there are three common strategies. Firstly utilization of a high Tg polymer (typically hyperbranched) as a host for a high hyperpolarizability (β) chromophore (Guest-Host), alternatively appending directly the chromophore via some covalent linking moiety to the polymer (Side-Chain)1 and finally post polymerization crosslinking by addition of a small quantity of crosslinking molecule or spontaneous heat/light induced chemical reaction (Cross-linked). Our research while attempting all three of the previous strategies is primarily focused on the design and synthesis of a small library of strained norbornene derived monomers, with various active substituents, which may be polymerized via ring opening metathesis polymerization (ROMP) using the commercially available Grubbs initiators (Grubbs 1st and 2nd generation). Such polymers have been shown to exhibit a narrow polydispersity, controllable molecular weights, rapid polymerization and allow the preparation of well defined block copolymers. Control over the Tg, refractive index and resistivity is feasible by this method. Generally for any polymer to be a successful candidate for EO host, it must exhibit key physical properties such as a high optical
    transparency, high thermal stability and a high glass transition temperature (Tg). PolyN-norbornene dicarboximide’s as well as similar polynorbornene’s have demonstrated such favorable properties as well as the additional attractive feature of being living polymerizations.

  • An Enhanced Host-Guest Electro-Optical Polymer System using Poly(norbornene-dicarboximides) via ROMP.

    Andrew Mark Spring

    SPSJ  2012.12 

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    Language:English   Presentation type:Oral presentation (general)  

    Venue:9th SPSJ International Polymer Conference (IPC2012), Kobe, Japan.   Country:Japan  

    As our candidate host polymer we selected high Tg poly(NDI)s which were prepared via ROMP. By catalyst selection (G1 or G2), polymers with a 98% or 52% trans microstructure were produced. In this paper we investigated the relationship between polymer microstructure and molecular weight on the r33, in order to identify the optimum host polymer.

    The monomer Cy(NDI) (1) (Scheme 1) was prepared according to the literature. As a consequence of the high ring strain, polymerization was initiated by G1 or G2 and the molecular weight was controlled by manipulating the [monomer] / [initiator] ratio. Two series of poly(NDI)s, as shown in Scheme 1 (2a-f) and (3a-f) were prepared. Polymerization by G1 yielded trans rich polymers (98% trans) whilst G2 gave polymers with a (52% trans) microstructure. The four polymers 2a, 2f, 3a and 3f were selected to investigate the effect of microstructure and polymer molecular weight on the r33. Two chromophores were used to evaluate poly(NDI) as a host, one having a tertbutyldiphenylsilane large electron donating substituent (C1) and one un-substituted (C2), with all results being compared to the control polymer PMMA. By using the high trans content poly(NDI)s as hosts (2a and 2f) and chromophore C1 as a guest, we observed a maximum r33 of 93 pm/V which is a 70% enhancement compared to PMMA. The optimum poling temperature for this system was probed in order to maximize the r33 signal (Figure 1). It was found that the maximum r33 was achieved at a poling temperature of 137°C, this value is 63°C lower than the Tg of the host polymer. The poly(NDI) systems also displayed excellent temporal stability at 85°C after 500 hours, which may be attributed to the high Tg of the poly(NDI) hosts (Figure 2).

  • Recent Innovations in Electro-optic Polymeric Materials and Chromophore Design.

    Andrew Mark Spring

    SPSJ  2014.5 

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    Language:English   Presentation type:Oral presentation (general)  

    Venue:63rd SPSJ Annual Meeting, Nagoya, Japan.   Country:Japan  

    Abstract: Organic electro-optic (NLO) materials have undergone significant developments in both the range of polymer architectures available and the selection of photonic devices which they can be utilized in. Polymers were initially utilized in simple host-guest dispersions, with the next logical step being the side chain system. The practical limitations of these two architectures were later addressed by the cross-linked, dendritic, brush, hyper branched and self-assembled EO-polymers. Whichever specific means of immobilization is utilized, the common requirements are that the EO material must exhibit a large EO coefficient, be optically transparent as not to impede device utilization, be thermally stable to survive the harsh poling conditions and lastly but not least important, they should be highly soluble in a range of common organic solvents to facilitate their solution casting onto a range of conductive substrates.

  • Electro-optic Polymeric Materials derived from High Tg Norbornene-Dicarboximide (NDI) Homopolymers and NDI / MMA Polymer Brushes.

    Andrew Mark Spring

    SPSJ  2014.9 

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    Language:English   Presentation type:Oral presentation (general)  

    Venue:63rd SPSJ Symposium on Macromolecules, Nagasaki, Japan.   Country:Japan  

    Over the last decade, organic electro-optic (NLO) materials have undergone significant developments in both the range of polymer architectures available and the selection of photonic devices which they can be utilized in. Key material properties include the ability to exhibit a large EO coefficient, optical transparency as not to impede device utilization, thermal stability to survive the harsh poling conditions and lastly but not least important, they should be highly soluble in a range of common organic solvents to facilitate their solution casting onto a range of conductive substrates. Poly(norbornene-dicarboximide) (NDI) homopolymers as well as polymer brushes derived from an NDI backbone, with methyl methacrylate (MMA) side arms display many of these important features.

  • Synthesis and Characterization of Poly(norbornene-dicarboximides) and their Application as Electro-optic Polymeric Materials International conference

    Andrew Mark Spring

    SPSJ  2014.12 

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    Language:English   Presentation type:Oral presentation (general)  

    Venue:The 10th SPSJ International Polymer Conference (IPC2014)   Country:Japan  

    The academic interest in poly(norbornene-dicarboximides) (poly(NDI)s) has increased substantially as a consequence of their favorable thermal, mechanical and optical properties, giving them a range of practical uses in optics. Provided that the cyclic monomers exhibit a high ring strain and low steric hindrance ROMP allows the preparation of well-defined homopolymers, random copolymers, block copolymers and polymer brushes.

    An optimal organic electro-optic (EO) material must exhibit a large EO coefficient, optical transparency, thermal stability, temporal stability and a good solubility. These key requirements can be met by the use of poly(norbornene-dicarboximide) (NDI) homopolymers and polymer brushes with an NDI backbone and methyl methacrylate (MMA) side arms. The EO affect quantifies the relationship between the refractive index change (Δn) of a material upon application of an electric field (E). The magnitude of this change is related to the materials EO coefficient (r33) as described by the equation: Δn=-1/2n3r33E. Typical FTC chromophores encompass a strongly donating aromatic amine, an extended thiophene bridge and a strong tricyano containing heterocyclic electron accepting moiety. We have manipulated the structures of FTC chromophores in order to tune the properties, enhancing the hyperpolarizability and steric interactions and investigated the feasibility of using various Poly(norbornene)dicarboximide homopolymers, copolymers and polymer brushes as hosts for such chromophores.

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Industrial property rights

Patent   Number of applications: 2   Number of registrations: 0
Utility model   Number of applications: 0   Number of registrations: 0
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Professional Memberships

  • Royal Society of Chemistry (UK)

  • The Society of Polymer Science, Japan. (SPSJ)

Educational Activities

  • Physical Property of Polymer Materials II course (15 classes)
    Fundamental's of Green Engineering (1 class)

Class subject

  • 高分子材料物性学Ⅱ

    2023.10 - 2024.3   Second semester

  • 高分子材料物性学Ⅱ

    2023.10 - 2024.3   Second semester

  • 高分子材料物性学Ⅱ

    2023.10 - 2024.3   Second semester

  • 総合理工学修士実験

    2023.4 - 2024.3   Full year

  • 総合理工学修士演習

    2023.4 - 2024.3   Full year

  • 総合理工学修士実験

    2023.4 - 2024.3   Full year

  • 総合理工学修士演習

    2023.4 - 2024.3   Full year

  • 高分子材料物性学Ⅱ

    2022.10 - 2023.3   Second semester

  • 高分子材料物性学Ⅱ

    2022.10 - 2023.3   Second semester

  • 高分子材料物性学Ⅱ

    2022.10 - 2023.3   Second semester

  • 総合理工学修士実験

    2022.4 - 2023.3   Full year

  • 総合理工学修士演習

    2022.4 - 2023.3   Full year

  • 総合理工学修士実験

    2022.4 - 2023.3   Full year

  • 総合理工学修士演習

    2022.4 - 2023.3   Full year

  • 総合理工学修士実験

    2022.4 - 2023.3   Full year

  • 総合理工学修士演習

    2022.4 - 2023.3   Full year

  • 国内インターンシップ

    2022.4 - 2022.9   First semester

  • 国内インターンシップ

    2022.4 - 2022.9   First semester

  • 国内インターンシップ

    2022.4 - 2022.9   First semester

  • 高分子材料物性学Ⅱ

    2021.10 - 2022.3   Second semester

  • 高分子材料物性学Ⅱ

    2021.10 - 2022.3   Second semester

  • 高分子材料物性学Ⅱ

    2021.10 - 2022.3   Second semester

  • 物質理工学修士演習第二

    2021.4 - 2022.3   Full year

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    2021.4 - 2022.3   Full year

  • International Internship

    2021.4 - 2021.9   First semester

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    2021.4 - 2021.9   First semester

  • International Internship

    2021.4 - 2021.9   First semester

  • Domestic Internship

    2021.4 - 2021.9   First semester

  • International Internship

    2021.4 - 2021.9   First semester

  • Domestic Internship

    2021.4 - 2021.9   First semester

  • International Internship

    2021.4 - 2021.9   First semester

  • Domestic Internship

    2021.4 - 2021.9   First semester

  • International Internship

    2021.4 - 2021.9   First semester

  • Domestic Internship

    2021.4 - 2021.9   First semester

  • International Internship

    2021.4 - 2021.9   First semester

  • Domestic Internship

    2021.4 - 2021.9   First semester

  • 高分子材料物性学

    2020.10 - 2021.3   Second semester

  • Discussion Leading & Organizing

    2020.10 - 2021.3   Second semester

  • 物質理工学修士演習第二

    2020.4 - 2021.3   Full year

  • 物質理工学修士実験第二

    2020.4 - 2021.3   Full year

  • Domestic Internship

    2020.4 - 2020.9   First semester

  • International Internship

    2020.4 - 2020.9   First semester

  • 高分子材料物性学

    2019.10 - 2020.3   Second semester

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    2019.4 - 2020.3   Full year

  • Domestic Internship

    2019.4 - 2020.3   Full year

  • Practice School

    2019.4 - 2020.3   Full year

  • Domestic Internship

    2019.4 - 2019.9   First semester

  • International Internship

    2019.4 - 2019.9   First semester

  • International Internship

    2018.4 - 2018.9   First semester

  • Practice School

    2018.4 - 2018.9   First semester

  • Domestic Internship

    2018.4 - 2018.9   First semester

  • Domestic Internship

    2017.10 - 2018.3   Second semester

  • International Internship

    2017.10 - 2018.3   Second semester

  • Practice School

    2017.10 - 2018.3   Second semester

  • Practice School

    2017.10 - 2018.3   Second semester

  • Practice School

    2017.10 - 2018.3   Second semester

  • Domestic Internship

    2017.10 - 2018.3   Second semester

  • International Internship

    2017.10 - 2018.3   Second semester

  • Practice School

    2017.4 - 2017.9   First semester

  • Fundamentals of Polymer Chemistry (makeup class for Environmental Systems)

    2017.4 - 2017.9   First semester

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FD Participation

  • 2021.10   Role:Participation   Title:Share Q and SIAG Activity

    Organizer:University-wide