光による半導体粒子の形状異方性制御とエネルギー変換材料への応用

• Project/Area Number: 20245031
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Nagoya University
• Principal Investigator: 鳥本 司 Nagoya University, 工学(系)研究科(研究院), 教授 (60271029)
• Co-Investigator(Kenkyū-buntansha): 岡崎 健一 名古屋大学, 大学院・工学研究科, 助教 (70402485)
• Project Period (FY): 2008 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥49,270,000 (Direct Cost: ¥37,900,000、Indirect Cost: ¥11,370,000); Fiscal Year 2011: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2010: ¥7,930,000 (Direct Cost: ¥6,100,000、Indirect Cost: ¥1,830,000); Fiscal Year 2009: ¥14,950,000 (Direct Cost: ¥11,500,000、Indirect Cost: ¥3,450,000); Fiscal Year 2008: ¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
• Keywords: ナノ材料 / 量子ドット / 触媒・化学プロセス / 電子・電気材料 / ZnOナノロッド / 異方性形状 / 自己組織化 / 太陽電池

Research Abstract

シリコン太陽電池に変わる次世代太陽電池の材料として、Cdなどの毒性の高い元素やInなどの希少元素を含まず、かつ高い光活性を示す環境調和型の半導体材料であるCu_2ZnSnS_4(CZTS)が注目され、薄膜太陽電池が試作されている。しかしながら、これまでにCZTSナノ粒子の化学合成はほとんど報告されていなかった。そこで本研究では、高温有機溶媒中における化学反応を利用してCZTSナノ粒子の液相合成を行い、得られた粒子についてその光電気化学特性を調べ、太陽電池の光吸収層としての可能性を検討した。対応する金属イオンの酢酸塩と硫黄粉末を、化学量論比で混合しオレイルアミンに分散させた後、240℃で加熱することにより、5-7nm程度の粒径をもつCZTSナノ粒子を合成した。粒子は、その表面がオレイルアミンで修飾されており、溶液中に安定に分散した状態として得られる。光吸収スペクトルから、粒子のバンドギャップエネルギーは約1.5eVと見積もられる。つぎに、エタンジチオールを架橋剤とする交互吸着法によって、粒子サイズを保ったまま、CZTSナノ粒子を透明電極基板上に積層した。得られたナノ粒子薄膜電極に可視光を照射すると、カソード光電流が得られ、CZTSナノ粒子はp型半導体特性を示した。また、900nm以下の波長の光照射に対して応答した。光電流の立ち上がり電位が、CZTSナノ粒子の価電子帯上端の電位であると見なすと、得られた粒子の伝導帯下端および価電子帯上端の電位は、各々、-1.2Vおよび0.3V vs.Ag/AgClであると見積もることができる。同様の手法を用いることによって、様々な化合物半導体のナノ粒子化が可能となり、本研究成果は、将来の半導体ナノ粒子を用いる太陽電池開発に大いに役立つ。

Research Products

• [Journal Article] Fabrication of Nanoframe Structures by Site-selective Assembly of Gold Nanoparticles on Silver Cubes in an Ionic Liquid (2011)
  • Author(s): K.Okazaki, et al.
  • Journal Title: Chem.Lett. Volume: 40 Pages: 84-86
  • NAID: 10027655381
  • Peer Reviewed
• [Journal Article] Surface-plasmon-enhanced photocurrent generation of CdTe nanoparticle/titania nanosheet composite layers on Au particulate films (2011)
  • Author(s): T.Kameyama, et al.
  • Journal Title: J.Photochem.Photobiol.A Chem. Volume: (In press)
  • Peer Reviewed
• [Journal Article] Immobilization of ZnS-AgInS_2 Solid Solution Nanoparticles on ZnO Rod Array Electrodes and Their Photoresponse with Visible Light Irradiation (2010)
  • Author(s): T.Sasamura, et al.
  • Journal Title: Chem.Lett. Volume: 39 Pages: 619-621
  • Peer Reviewed
• [Journal Article] Preparation and Photoelectrochemical Properties of Densely Immobilized Cu_2ZnSnS_4 Nanoparticle Films (2010)
  • Author(s): T.Kameyama, et al.
  • Journal Title: J.Mater.Chem. Volume: 20 Pages: 5319-5324
  • Peer Reviewed
• [Journal Article] Fabrication of Transition Metal Oxide Nanoparticles Highly Dispersed in Ionic Liquids by Sputter Deposition (2010)
  • Author(s): T.Suzuki, et al.
  • Journal Title: Chem.Left. Volume: 39 Pages: 1072-1074
  • Peer Reviewed
• [Journal Article] Nanosize-Controlled Syntheses of Indium Metal Particles and Hollow Indium Oxide Particles via the Sputter Deposition Technique in Ionic Liquids (2010)
  • Author(s): T.Suzuki, et al.
  • Journal Title: Chem.Mater. Volume: 22 Pages: 5209-5215
  • Peer Reviewed
• [Journal Article] Preparation of Luminescent AgInS_2-AgGaS_2 Solid Solution Nanoparticles and Their Optical Properties (2010)
  • Author(s): T.Uematsu, et al.
  • Journal Title: J.Phys.Chem.Lett. Volume: 1 Pages: 3283-3287
  • Peer Reviewed
• [Journal Article] Oxygen Reduction Catalytic Ability of Platinum Nanoparticles Prepared by Room-temperature Ionic Liquid-sputtering Method (2010)
  • Author(s): T.Tsuda, et al.
  • Journal Title: J.Power Sources Volume: 195 Pages: 5980-5985
  • Peer Reviewed
• [Journal Article] Catalytic Activity and Regeneration Property of a Pd Nanoparticle Encapsulated in a Hollow Porous Carbon Sphere for Aerobic Alcohol Oxidation (2010)
  • Author(s): T.Harada, et al.
  • Journal Title: Langmuir Volume: 26 Pages: 17720-17725
  • Peer Reviewed
• [Journal Article] New Frontiers in Materials Science Opened by Ionic Liquids (2010)
  • Author(s): T.Torimoto, et al.
  • Journal Title: Adv.Mater. Volume: 22 Pages: 1196-1221
  • Peer Reviewed
• [Journal Article] Room-Temperature Ionic Liquid. A New Medium for Material Production and Analyses under Vacuum Conditions (2010)
  • Author(s): S.Kuwabata, et al.
  • Journal Title: J.Phys.Chem.Lett. Volume: 1 Pages: 3177-3188
  • Peer Reviewed
• [Journal Article] 半導体ナノ粒子の組織化と光機能:量子ドット配列制御による高機能性材料の創製 (2010)
  • Author(s): 亀山達矢, ら
  • Journal Title: 化学と工業 Volume: 63 Pages: 327-329
  • Peer Reviewed
• [Journal Article] 低毒性元素からなる新規半導体ナノ粒子の作製と光機能材料への応用 (2010)
  • Author(s): 笹村哲也, ら
  • Journal Title: 日本写真学会誌 Volume: 73 Pages: 290-296
• [Journal Article] 半導体ナノ粒子の液相合成・固定化と光機能材料への応用 (2010)
  • Author(s): 鳥本司, ら
  • Journal Title: 光技術コンタクト Volume: 49 Pages: 11-17
• [Journal Article] Size Control and Immobilization of Gold Nanoparticles Stabilized in an Ionic Liquid on Glass Substrates for Plasmonic Applications (2010)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Phys.Chem.Chem.Phys 12 Pages: 1804-1811
  • Peer Reviewed
• [Journal Article] Remarkable Photoluminescence Enhancement of ZnS-AgInS2 Solid Solution Nanoparticles by Postsynthesis Treatment (2010)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Chem.Commun. 46 Pages: 2082-2084
  • Peer Reviewed
• [Journal Article] Studies on Reaction Conditions for Size-selective Photoetching of Cadmium Telluride Nanocrystals (2010)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Electrochemistry 78 Pages: 170-174
  • NAID: 130002150584
  • Peer Reviewed
• [Journal Article] New Frontiers in Materials Science Opened by Ionic Liquids (2010)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Adv.Mater 22 Pages: 1196-1221
  • Peer Reviewed
• [Journal Article] Photocatalytic Electron Flow through the Interface of Titania Nanosheets and Mesoporous Silica Hybrid Films (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: J.Photochem.Photobiol.A : Chem 207 Pages: 135-142
  • Peer Reviewed
• [Journal Article] Electrochemical Deposition of Gold Frame Structure on Silver Nanocubes (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Chem.Commun. Pages: 2917-2919
  • Peer Reviewed
• [Journal Article] Stacked-Structure-Dependent Photoelectrochemical Properties of CdS Nanoparticle/Layered Double Hydroxide (LDH) Nanosheet Multilayer Films Prepared by Layer-by-layer Accumulation (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Phys.Chem.Chem.Phys 11 Pages: 5369-5376
  • Peer Reviewed
• [Journal Article] A Facile Synthesis of AuAg Alloy Nanoparticles Using a Chemical Reaction Induced by Sputter Deposition of Metal onto Ionic Liquids (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Electrochemistry 77 Pages: 636-638
  • NAID: 130002150619
  • Peer Reviewed
• [Journal Article] Tuning of the Fluorescence Wavelength of CdTe Quantum Dots with 2nm Resolution by Size-selective Photoetching (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Nanotechnology 20 Pages: 215302-215302
  • Peer Reviewed
• [Journal Article] Emission Quench of Water-soluble ZnS-AgInS2 Solid Solution Nanocrystals and Its Application to Chemosensors (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Journal Title: Chem.Commun. Pages: 7485-7487
  • Peer Reviewed
• [Journal Article] イオン液体へのスパッタ蒸着による金属ナノ粒子の合成 (2009)
  • Author(s): 岡崎健一, など
  • Journal Title: PETROTECH 32 Pages: 328-333
  • NAID: 10025531265
• [Journal Article] Photochemical Shape Control of Cadmium Sulfide Nanorods Coated with an Amorphous Silica Thin Layer (2009)
  • Author(s): T. Torimoto, et al.
  • Journal Title: J. Nanosci. Nanotechnol. 9 Pages: 506-513
  • Peer Reviewed
• [Journal Article] Photo-Induced Electron Migrations in the Nano-Cavities of Mesoporous Silica Sensitized by a Cationic Porphyrin Dye (2009)
  • Author(s): T. Torimoto, K. Takagi, et al.
  • Journal Title: J. Nanosci. Nanotechnol. 9 Pages: 495-500
  • Peer Reviewed
• [Journal Article] Thermally Induced Self-assembly of Gold Nanoparticles Sputter-deposited in Ionic Liquids on Highly Ordered Pyrolytic Graphite Surfaces (2009)
  • Author(s): T. Torimoto, et al.
  • Journal Title: Chem. Lett. 38 Pages: 330-331
  • NAID: 10025120762
  • Peer Reviewed
• [Journal Article] Photoluminescence Enhancement of ZnS-AgInS_2 Solid Solution Nanoparticles Layer-by-layer-assembled in Inorganic Multilayer Thin Films (2008)
  • Author(s): T. Kameyama, T. Torimoto, et al.
  • Journal Title: Chem. Lett. 37 Pages: 700-701
  • NAID: 10021081945
  • Peer Reviewed
• [Presentation] Photocatalytic activity of core-shell-structured Au-SiO_2-CdS nanocomposite particles (2010)
  • Author(s): T.Torimoto, et al.
  • Organizer: International Chemical Congress of Pacific Basin Societies (PACIFICHEM 2010)
  • Place of Presentation: Honolulu, USA
• [Presentation] Stacked-structure-dependent Photoluminescence Properties of CdTe-Au Multilayer films (2010)
  • Author(s): T.Torimoto, et al.
  • Organizer: 217th Electrochemical Society Meeting
  • Place of Presentation: Vancouver, Canada
• [Presentation] Photocatalytic Activity of CdS Nanoparticles Immobilized on Au-core/SiO_2-shell Particles (2010)
  • Author(s): T.Torimoto
  • Organizer: 18th International Conference on Photochemical Conversion and Storage of Solar Energy (IPS-18)
  • Place of Presentation: Seoul, Korea
• [Presentation] Changes in the Photocatalytic Activity of CdS Nanoparticles with the Immobilization on Au Particles (2010)
  • Author(s): T.Torimoto
  • Organizer: International Conference on Nanoscopic Colloid and Surface Science (NCSS2010)
  • Place of Presentation: Chiba, Japan
• [Presentation] Size control of gold nanoparticles sputter-deposited in ionic liquids by heat treatment (2009)
  • Author(s): Takashi Kurimoto, et al.
  • Organizer: International Symposium on Integrated Molecular/Materials Engineering (ISIME2009)
  • Place of Presentation: Chengdu, China
  • Year and Date: 2009-10-26
• [Presentation] Preparation and photoelectrochemical properties of Cu2ZnSnS4 nanoparticles (2009)
  • Author(s): Takaaki Osaki, et al.
  • Organizer: International Symposium on Integrated Molecular/Materials Engineering (ISIME2009)
  • Place of Presentation: Chengdu, China
  • Year and Date: 2009-10-26
• [Presentation] Photoelectrochemical properties of ZnO nanorod thin films loaded with ZnS-AgInS2 solid solution nanoparticle (2009)
  • Author(s): Tetsuya Sasamura, et al.
  • Organizer: International Symposium on Integrated Molecular/Materials Engineering (ISIME2009)
  • Place of Presentation: Chengdu, China
  • Year and Date: 2009-10-26
• [Presentation] Layer-by-layer immobilization and photochemical properties of ZnS-AgInS2 solid solution nanoparticle thin films (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Organizer: International Symposium on Integrated Molecular/Materials Engineering (ISIME2009)
  • Place of Presentation: Chengdu, China
  • Year and Date: 2009-10-26
• [Presentation] Photochemical properties of highly luminescent ZnS-AgInS2 solid solution nanoparticles (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Organizer: XXIV International Conference on Photochemistry
  • Place of Presentation: Toledo, Spain
  • Year and Date: 2009-07-24
• [Presentation] Staked-structure-dependent photocurrent generation in LDH/CdS multilayer thin films (2009)
  • Author(s): Tatsuya Kameyama, et al.
  • Organizer: XXIV International Conference on Photochemistry
  • Place of Presentation: Toledo, Spain
  • Year and Date: 2009-07-24
• [Presentation] Preparation of AuAg alloy nanoparticles using a chemical reaction induced by sputter deposition of metal onto ionic liquids (2009)
  • Author(s): Toshimasa Suzuki, et al.
  • Organizer: 3rd Congress on Ionic Liquids (COIL-3)
  • Place of Presentation: Cairns, Australia
  • Year and Date: 2009-06-02
• [Presentation] Immobilization of gold nanoparticles sputter-deposited in ionic liquids on highly-ordered pyrolytic graphite via a thermal treatment (2009)
  • Author(s): Ken-chi.Okazaki, et al.
  • Organizer: 3rd Congress on Ionic Liquids (COIL-3)
  • Place of Presentation: Cairns, Australia
  • Year and Date: 2009-06-01
• [Presentation] Layer-by-layer accumulation of ZnS-AgInS2 solid solution nanoparticles and their photoluminescence properties (2009)
  • Author(s): Tsukasa Torimoto, et al.
  • Organizer: 215th ECS Meeting
  • Place of Presentation: San Francisco, USA
  • Year and Date: 2009-05-25
• [Presentation] Color-Tunable Photoluminescence of ZnS-AgInS_2 Solid Solution Nanoparticles (2008)
  • Author(s): T. Torimoto, et al.
  • Organizer: PRiME 2008 (Joint International Meeting)
  • Place of Presentation: Honolulu, U.S.A.
• [Presentation] Preparation of Alloy Nanoparticles by a Simultaneous Sputter Deposition of Au and Ag onto Ionic Liquids (2008)
  • Author(s): K. Okazaki, T. Torimoto, et al.
  • Organizer: PRiME 2008 (Joint International Meeting)
  • Place of Presentation: Honolulu, U.S.A.
• [Presentation] Preparation and Photochemical Properties of Highly Luminescent ZnS-AgInS_2 Solid Solution Nanoparticles (2008)
  • Author(s): T. Torimoto, et al.
  • Organizer: 17th International Conference on Photochemical Conversion and Storage of Solar Energy
  • Place of Presentation: Sydney, Australia.
• [Patent(Industrial Property Rights)] 半導体ナノ粒子及びその製法 (2009)
  • Inventor(s): 鳥本司, ほか
  • Industrial Property Rights Holder: 名古屋大学ほか
  • Industrial Property Number: 2009-046785
  • Filing Date: 2009-02-27