量子ドットの禁制遷移準位での多数励起子生成による新規光反応の開発

• Project Area: Application of Cooperative-Excitation into Innovative Molecular Systems with High-Order Photo-functions
• Project/Area Number: 15H01082
• 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: Nagoya University
• Principal Investigator: 鳥本 司 名古屋大学, 工学研究科, 教授 (60271029)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥8,450,000 (Direct Cost: ¥6,500,000、Indirect Cost: ¥1,950,000); Fiscal Year 2016: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2015: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
• Keywords: 半導体ナノ粒子 / 量子ドット / 多数励起子生成 / 低毒性ナノ粒子 / 多元半導体 / 光物性 / 光反応 / ナノ材料

Outline of Annual Research Achievements

近赤外域にエネルギーギャップ（Eg）を持つ半導体ナノ粒子は、太陽光を効率よく吸収できるために、新規光エネルギー変換材料として注目されている。昨年度までに、約1.0 eVの狭いEgを有するAgInTe2ナノ粒子にZnTeを固溶化させることで、ZnTe-AgInTe2固溶体（(AgIn)xZn2(1-x)Te2, ZAITe）ナノ粒子を合成し、そのバンドギャップと電子エネルギー構造が粒子組成に依存して連続的に変化することを見出した。そこで、本年度は、合成したZAITeナノ粒子の光電気化学特性に及ぼす粒子組成の影響を調べた。
ZAITeナノ粒子は、対応する金属酢酸塩とトリオクチルホスフィンに溶解させたテルルを1-ドデカンチオールに加えて加熱することで作製した。得られた粒子をITO電極上に高密度で担持して光電極とし、Ptを対極，Ag/AgCl電極を参照極、電解液をEu(NO3)3 水溶液とする三極セルでその光電気化学特性を評価した。
ZAITeナノ粒子担持ITO電極にXeランプ光（λ > 350 nm）を光照射をすると、粒子組成xに関わらず、いずれの組成の粒子においてもカソード光電流を生じ、p型半導体類似の特性を示した。光電流の立ち上がり電位は、光電子収率分光測定により求めた価電子帯上端の電位とよく一致した。光電流の作用スペクトルは、立ち上がり波長付近では粒子の吸収スペクトルと一致したものの、約500 nm以下の短波長側では吸収スペクトルよりも大きく増加した。このことは、ZAITeナノ粒子に短波長の光照射を行うと、非線形な光電流生成メカニズムが生じることを示唆する。

Research Progress Status

28年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

28年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Shushi Suzuki, Yuuki Hattori, Susumu Kuwabata, and Tsukasa Torimoto (2017)
  • Author(s): Improvement of Photoluminescence Stability of ZnS-AgInS2 Nanoparticles through Interactions with Ionic Liquids
  • Journal Title: J. Photochem. Photobiol. A Chem. Volume: 332 Pages: 371-375
  • DOI: 10.1016/j.jphotochem.2016.08.034
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Influence of Zn on the Photoluminescence of Colloidal (AgIn)xZn2(1-x)S2 Nanocrystals (2017)
  • Author(s): Dharmendar Kumar Sharma, Shuzo Hirata, Lukasz Bujak, Vasudevanpillai Biju, Tatsuya Kameyama, Marino Kishi, Tsukasa Torimoto and Martin Vacha
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 19 Issue: 5 Pages: 3963-3969
  • DOI: 10.1039/c6cp07550a
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Formation of a Pt-decorated Au Nanoparticle Monolayer Floating on Ionic Liquid by the Ionic Liquid/Metal Sputtering Method and Tunable Electrocatalytic Activities of the Resulting Monolayer (2016)
  • Author(s): Daisuke Sugioka, Tatsuya Kameyama, Susumu Kuwabata, Takahisa Yamamoto, and Tsukasa Torimoto
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 8 Issue: 17 Pages: 10874-10883
  • DOI: 10.1021/acsami.6b01978
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Single-particle Spectroscopy of I-III-VI Semiconductor Nanocrystals: Spectral Diffusion and Suppression of Blinking by Two-color Excitation (2016)
  • Author(s): Dharmendar Kumar Sharma, Shuzo Hirata, Lukasz Bujak, Vasudevanpillai Biju, Tatsuya Kameyama, Marino Kishi, Tsukasa Torimoto, and Martin Vacha
  • Journal Title: Nanoscale Volume: 8 Issue: 28 Pages: 13687-13694
  • DOI: 10.1039/c6nr03950b
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Single-step Preparation of Indium Tin Oxide Nanocrystals Dispersed in Ionic Liquids via Oxidation of Molten In-Sn Alloys (2016)
  • Author(s): Daisuke Sugioka, Tatsuya Kameyama, Takahisa Yamamoto, Susumu Kuwabata, and Tsukasa Torimoto
  • Journal Title: Chem. Commun. Volume: 52 Issue: 82 Pages: 12241-12244
  • DOI: 10.1039/c6cc06517a
  • NAID: 120006220237
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 多元系半導体量子ドットの液相合成と光化学特性制御 (2016)
  • Author(s): 鳥本 司, 亀山 達矢, 桑畑 進
  • Journal Title: 光化学 Volume: 47 Pages: 9-18
  • NAID: 40020839219
  • Peer Reviewed
• [Journal Article] Crystal Phase-controlled Synthesis of Rod-shaped AgInTe2 Nanocrystals for in vivo Imaging in the Near-infrared Wavelength Region (2016)
  • Author(s): T. Kameyama, Y. Ishigami, H. Yukawa, T. Shimada, Y. Baba, T. Ishikawa, S. Kuwabata, T. Torimoto
  • Journal Title: Nanoscale Volume: 8 Issue: 10 Pages: 5435-5440
  • DOI: 10.1039/c5nr07532g
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Single-step Preparation of Two-dimensionally Organized Gold Particles via Ionic Liquid/Metal Sputter Deposition (2015)
  • Author(s): D. Sugioka, T. Kameyama, S. Kuwabata, T. Torimoto
  • Journal Title: Phys. Chem. Chem. Phys. Volume: 17 Issue: 19 Pages: 13150-13159
  • DOI: 10.1039/c5cp01602a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Controlling the Electronic Energy Structure of ZnS-AgInS2 Solid Solution Nanocrystals for Photoluminescence and Photocatalytic Hydrogen Evolution (2015)
  • Author(s): T. Kameyama, T. Takahashi, T. Machida, Y. Kamiya, T. Yamamoto, S. Kuwabata, T. Torimoto
  • Journal Title: J. Phys. Chem. C Volume: 119 Issue: 44 Pages: 24740-24749
  • DOI: 10.1021/acs.jpcc.5b07994
  • Peer Reviewed
• [Journal Article] イオン液体/金属スパッタリングによる金属ナノ粒子複合体の合成とサイズ・組成の精密制御 (2015)
  • Author(s): 鳥本 司, 亀山 達矢, 桑畑 進
  • Journal Title: 溶融塩および高温化学 Volume: 58 Pages: 111-118
  • NAID: 40020696558
• [Presentation] Photocatalytic Activity of Anisotropic-shaped ZnS-AgInS2 Solid Solution Nanoparticles (2017)
  • Author(s): Tsukasa Torimoto, Yutaro Kamiya, Susumu Kuwabata, and Tatsuya Kameyama
  • Organizer: Materials Challenges in Alternative and Renewable Energy 2017(MCARE 2017)
  • Place of Presentation: Jeju, Korea
  • Year and Date: 2017-02-20
  • Int'l Joint Research / Invited
• [Presentation] Preparation and Photochemical Properties of ZnS-AgInS2 Solid Solution Nanoparticles (2016)
  • Author(s): Tsukasa Torimoto, Takahiro Machida, Yutaro Kamiya, Susumu Kuwabata. and Tatsuya Kameyama
  • Organizer: 9th Asian Photochemistry Conference Singapore (APC2016)
  • Place of Presentation: Singapore
  • Year and Date: 2016-12-04
  • Int'l Joint Research / Invited
• [Presentation] Shape-Dependent Photocatalytic H2 Evolution Activity of ZnS-AgInS2 Solid Solution Nanoparticles (2016)
  • Author(s): T. Torimoto, Y. Kamiya, S. Kuwabata, and T. Kameyama
  • Organizer: PRiMe 2016
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2016-10-02
  • Int'l Joint Research / Invited
• [Presentation] Preparation of multinary metal chalcogenide semiconductor nanocrystals and their size-and composition-dependent photochemical properties (2016)
  • Author(s): 鳥本 司
  • Organizer: 2016年光化学討論会
  • Place of Presentation: 東京
  • Year and Date: 2016-09-06
  • Invited
• [Presentation] Size- and Composition-Dependent Photocatalytic Activity of ZnS-AgInS2 Solid Solution Nanoparticles (2016)
  • Author(s): T. Torimoto, Y. Kamiya, T. Kameyama, and S. Kuwabata
  • Organizer: 229tn ECS Meeting
  • Place of Presentation: San Diego, USA
  • Year and Date: 2016-05-29
  • Int'l Joint Research / Invited
• [Presentation] カルコパイライト型量子ドットの組成・形状の精密制御とその光化学特性 (2016)
  • Author(s): 鳥本 司
  • Organizer: 日本化学会 第96春季年会
  • Place of Presentation: 京田辺
  • Year and Date: 2016-03-24
  • Invited
• [Presentation] Size-controlled synthesis of ZnS-AgInS2 solid solution nanoparticles and their visible-light-driven photocatalytic activity (2015)
  • Author(s): Tsukasa Torimoto, Yutaro Kamiya, Tatsuya Kameyama, Susumu Kuwabata
  • Organizer: PACIFICHEM2015
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2015-12-15
  • Int'l Joint Research / Invited
• [Presentation] サイズと組成に依存したZnS-AgInS2固溶体ナノ結晶の光触媒活性 (2015)
  • Author(s): 鳥本 司
  • Organizer: 第25回日本MRS年次大会
  • Place of Presentation: 横浜
  • Year and Date: 2015-12-08
  • Invited
• [Presentation] Tunable Electronic Energy Structure of Znse-AgInSe2 Solid Solution Nanoparticles for Solar Energy Conversion (2015)
  • Author(s): Tsukasa Torimoto, Yusuke Douke, Hiroko Shibakawa, Susumu Kuwabata, Tatsuya Kameyama
  • Organizer: 227th ECS Meeting
  • Place of Presentation: Chicago, USA
  • Year and Date: 2015-05-24
  • Int'l Joint Research / Invited
• [Presentation] イオン液体への金属スパッタリングによる金属ナノ構造体の創製と機能材料への応用 (2015)
  • Author(s): 鳥本 司
  • Organizer: グリーンケミストリー研究会
  • Place of Presentation: 大阪
  • Year and Date: 2015-05-08
  • Invited
• [Book] "Nanocatalysis in Ionic Liquids", Ch. 9 (Top-Down Synthesis Methods for Nanoscale Catalysts) (2016)
  • Author(s): Tsukasa Torimoto, Tatsuya Kameyama and Susumu Kuwabata
  • Total Pages: 300
  • Publisher: Wiley