近接場増強型光化学反応の空間・時間集積化

• Project Area: Organic Synthesis based on Integration of Chemical Reactions. New Methodologies and New Materials
• Project/Area Number: 24106746
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: National Institute for Materials Science
• Principal Investigator: 三木 一司 独立行政法人物質・材料研究機構, その他部局等, その他 (30354335)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2013: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2012: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 近接場 / 光化学 / 流体デバイス

Research Abstract

本年度は近接場光反応を起こすために必要な光反応場について研究成果を挙げた。今回、本研究では、直径36 nmの金ナノ粒子をアルカンチオール分子で表面修飾した構造を用いることで導電性基板上に近接場光を用いたモデル光触媒構造を作製した。金ナノ粒子を透明電極材料であるITO基板上に配列化させ、可視光照射で金ナノ粒子近傍に強い光（近接場光）を発生させる。金ナノ粒子間の間隙には、光輝度が強いホットスポットと呼ばれる部分があり、集光したレーザー光と同様な非線型現象が生じるため、可視光の光子二個から紫外光に相当する光励起を起こすことが可能となる。この光励起は、二酸化チタンを光触媒として活性化させることが可能であり、ホットスポットと二酸化チタン光触媒を如何に近づけて固定するかが性能向上のポイントとなる。本研究では、疎水性と親水性の性質の異なる結合部位を有する界面活性剤分子、具体的にはTMOS (C8H17Si(OCH3)3)分子を用いることで、触媒の固定化を実現できた。TMOS分子は1 nm程度の分子層を形成し、疎水性部位が金ナノ粒子表面に固定化され、親水性部位が二酸化チタンを結合する足場となる。本研究では、直径3.5 nmの大きさの二酸化チタン微粒子を結合することで、二酸化チタン薄膜層を形成させた。
今回実証した光触媒は、溶液中にコロイド状に分散して用いる均一触媒ではなく、取扱いが容易な基板上に固定して用いる不均一触媒8)であるため、貴金属を浪費しない。一平方センチメートルの試料の光触媒能を染色色素（メチレンブルー）の分解反応を用いて調べた。その結果、新型光触媒では、太陽光に近い広帯域可視光照射時の反応速度が二酸化チタン単独の場合の6.5倍であることが分かり、可視光応答型光触媒として優れた特性を持っていることが分かった。

Current Status of Research Progress

Reason

25年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

25年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Visible light-driven plasmonic photocatalyst. (2014)
  • Author(s): Francesca Pincella, Katsuhiro Isozaki, and Kazushi Miki
  • Journal Title: Light: Science & Applications Volume: 3 Issue: 1 Pages: e133-e133
  • DOI: 10.1038/lsa.2014.14
  • NAID: 120005367809
  • Peer Reviewed / Open Access
• [Journal Article] 金ナノ粒子二次元配列を利用した可視光駆動型光触 (2014)
  • Author(s): 磯崎勝弘，三木一司
  • Journal Title: コロイド界面部会ニュースレター(C&I Commun.) Volume: 39 Pages: 36-38
• [Journal Article] Plasmon-resonant optics on an indium-tin-oxide film exciting a two-photon photochromic reaction (2013)
  • Author(s): Takao Ochiai, Katsuhiro Isozaki, Francesca Pincella, Tomoya Taguchi, Koh-ichi Nittoh, and Kazushi Miki
  • Journal Title: Appl. Phys. Express Volume: 6 Issue: 10 Pages: 102001-102001
  • DOI: 10.7567/apex.6.102001
  • Peer Reviewed
• [Journal Article] Gold Nanoparticle 2D-Arrays Chemically Immobilized as Large-Area Near-Field Light Source (2013)
  • Author(s): Kazushi Miki, Katsuhiro Isozaki, Takao Ochiai, Tomoya Taguchi and Koh-ichi Nittoh
  • Journal Title: ECS Trans. Volume: 50(6) Issue: 6 Pages: 205-213
  • DOI: 10.1149/05006.0205ecst
  • Peer Reviewed
• [Journal Article] Anisotropic charge transport and contact resistance of 6,13-bis(triisopropylsilylethynyl) pentacene field-effect transistors fabricated by a modified flow-coating method (2012)
  • Author(s): Kenji Sakamoto, Junichi Ueno, Kirill Bulgarevich, Kazushi Miki
  • Journal Title: Applied Physics Letters Volume: 100 Issue: 12
  • DOI: 10.1063/1.3695169
  • Peer Reviewed
• [Journal Article] 2. Light exposure dependence of field-effect mobility of pentacene thin films deposited on very thin polyimide photo-alignment layers (2012)
  • Author(s): Kenji Sakamoto, Junichi Ueno, Takamitsu Yonezawa, Takeshi Yasuda, and Kazushi Miki
  • Journal Title: Journal of Applied Physics Volume: 111 Issue: 12 Pages: 123702-123702
  • DOI: 10.1063/1.4729046
  • Peer Reviewed
• [Journal Article] Enhanced Catalytic Activity of Self-Assembled-Monolayer-Capped Gold Nanoparticles (2012)
  • Author(s): T. Taguchi, K. Isozaki,* and K. Miki*
  • Journal Title: Adv. Mater Volume: 24 Issue: 48 Pages: 6462-6467
  • DOI: 10.1002/adma.201202979
  • Peer Reviewed
• [Presentation] 金ナノ粒子2次元配列を利用した可視光駆動型光触媒 (2013)
  • Author(s): 磯崎 勝弘，Francesca Pincella，三木 一司
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 京都
  • Year and Date: 2013-03-24
• [Presentation] Self-Assembled Monolayer-Capped Gold Nanoparticle 2D-arrays as Enhanced Catalysis (2013)
  • Author(s): K. Miki , T. Taguchi, and K. Isozaki
  • Organizer: Symposium on Surface and Nano Science 2013 (SSNS’13)
  • Place of Presentation: Zao, Yamagata
  • Year and Date: 2013-01-16
  • Invited
• [Presentation] Gold Nanoparticle 2D-Arrays Chemically Immobilized as Large-Area Near-Field Light Source (2012)
  • Author(s): Kazushi Miki, Katsuhiro Isozaki, Takao Ochiai, Tomoya Taguchi, Koh-ichi Nittoh
  • Organizer: The 222nd ECS Meeting
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2012-10-12
• [Presentation] Near-field multi-photon induced photoluminescence imaging of Au nanoparitcle-array with well-regulated gap (2012)
  • Author(s): akao Ochiai, Tetsuya Narushima, Katsuhiro Isozaki, Hiromi Okamoto, Kazushi Miki
  • Organizer: The IUMRS Int'l Conf. on Electronic Materials (IUMRS-ICEM2012)
  • Place of Presentation: Yokohama, Kanagawa
  • Year and Date: 2012-09-24
• [Presentation] 極薄ポリイミド光配向膜上に形成したペンタセン薄膜の電界効果移動度と表面形状 (2012)
  • Author(s): 坂本 謙二，上野 純一，三木 一司
  • Organizer: 第73回応用物理学会学術講演会
  • Place of Presentation: 松山、愛媛
  • Year and Date: 2012-09-14
• [Presentation] Silica coated gold nanoparticles 2D array for enhanced fluorescence sensing (2012)
  • Author(s): Fancesca Pincella, Katsuhiro Isozaki, Kazushi Miki
  • Organizer: JSAP-OSA Joint Symposia, The 73rd JSAP Autumn Meeting 2012
  • Place of Presentation: Matsuyama, Ehime
  • Year and Date: 2012-09-11
• [Presentation] Enhanced Catalysis of Self-Assembled Monolayer-Capped Gold Nanoparticle 2D-arrays (2012)
  • Author(s): K. Isozaki, T. Taguchi, K. Miki
  • Organizer: The 6th Intern. Conf. on Gold Science Technology and its applications (GOLD2012)
  • Place of Presentation: Tokyo
  • Year and Date: 2012-09-08
• [Presentation] Large-Area Gold Nanoparticle 2D-Arrays for Plasmonic Applications (2012)
  • Author(s): Kazushi Miki, Katsuhiro Isozaki, Takao Ochiai, Tomoya Taguchi, Koh-ichi Nittoh
  • Organizer: The 6th Intern. Conf. on Gold Science Technology and its applications (GOLD2012)
  • Place of Presentation: Tokyo
  • Year and Date: 2012-09-06
• [Presentation] Fabrication of Large-Area Near-Field Lighting Layer of Chemically Immobilized Gold Nanoparticle 2D-Arrays (2012)
  • Author(s): K. Isozaki, T. Ochiai, T. Taguchi, K. Nittoh, and K. Miki
  • Organizer: Interface International Association of Colloid and Interface Scientists (IACIS2012)
  • Place of Presentation: Sendai, Miyagi
  • Year and Date: 2012-05-16
• [Presentation] Molecular Recognition-Enhanced Catalysis of Gold Nanoparticle 2D-Arrays with Hydrophobic (2012)
  • Author(s): K. Isozaki, T. Taguchi, K. Miki
  • Organizer: Interface International Association of Colloid and Interface Scientists (IACIS2012)
  • Place of Presentation: Sendai, Miyagi
  • Year and Date: 2012-05-16
• [Presentation] Catalytic Enhancement Effect of Alkanethiol-Self-Assembled-Monolayer on Gold Nanoparticles
  • Author(s): Katsuhiro Isozaki, Tomoya Taguchi and Kazushi Miki
  • Organizer: The Eighth International Symposium on Integrated Synthesis
  • Place of Presentation: Todaiji Temple Cultural Center, Nara
• [Presentation] Visible light photocatalyst based on plasmon-enhanced two-photon absorption
  • Author(s): Francesca Pincella, Katsuhiro Isozaki, Kazushi Miki
  • Organizer: The 2nd JSAP-OSA Joint Symposia (The 74th JSAP Autumn Meeting 2013)
  • Place of Presentation: Doshisya Univ., Kyoto
• [Presentation] Dense 2D arrays of Au@Ag and Au@Ag@Au as efficient SERS substrates
  • Author(s): Yeji Song, Pincella Francesca, Katsuhiro Isozaki, Kazushi Miki
  • Organizer: The 2nd JSAP-OSA Joint Symposia (The 74th JSAP Autumn Meeting 2013)
  • Place of Presentation: Doshisya Univ., Kyoto
• [Presentation] 204. Enhanced Catalysis of Self-Assembled-Monolayer-Capped Gold Nanoparticles
  • Author(s): Katsuhiro Isozaki, Tomoya Taguchi and Kazushi Miki
  • Organizer: Challenges in Organic Materials & Supramolecular Chemistry (ISACS10)
  • Place of Presentation: Kyoto Univ., Kyoto
• [Presentation] 金ナノ粒子２次元配列を用いる可視光駆動型光触媒
  • Author(s): 磯崎 勝弘，Francesca Pincella，三木 一司
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 琉球大学千原キャンパス、沖縄
• [Remarks] NIMS界面機能グループ
  • URL: http://www.nims.go.jp/nanoarchi_gr/