ワイドギャップ化したカルコパイライト半導体光カソードによる高効率水分解反応

• Project Area: Chemical conversion of solar energy by artificial photosynthesis: a breakthrough by fusion of related fields toward realization of practical processes
• Project/Area Number: 15H00875
• 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: Konan University (2016); Osaka University (2015)
• Principal Investigator: 池田 茂 甲南大学, 理工学部, 教授 (40312417)
• Project Period (FY): 2015-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2016: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 水分解水素発生 / 太陽光利用 / 人工光合成 / 化合物半導体薄膜 / 光電極 / 元素置換 / 太陽エネルギー変換 / 水分解水素製造 / 表面修飾

Outline of Annual Research Achievements

研究代表者等はこれまでに、ナロウギャップ半導体であるCuInS2、Cu2ZnSnS4などのp型化合物半導体薄膜を光吸収層とする水分解水素発生に取り組んできた。この系では、p型薄膜表面に薄いn型半導体層を積層させてp-nヘテロ接合を形成させ、さらにその表面にPt触媒粒子を添加することで外部バイアス電圧印可条件での水分解水素発生が効率よく進行する。太陽光変換効率の向上には、（a）必要な外部バイアス電圧を低下させるためのバンド構造（電子エネルギー構造）の制御と、（b）光生成したキャリアの再結合によるロスを抑制しつつ効率的にとり出すためのp-n界面積の増大が重要である。本研究では、これらに基づいた光電極の設計を実践し、太陽電池に匹敵する超高効率な水分解水素発生光電極を開発することを目的とする。
平成28年度は、前年度までに得られたCuInS2薄膜へのGaおよびAgの部分置換を、Ga全置換とCu2ZnSnS4へのAgの部分置換に応用した。前者のGa全置換で得られたられたCuGaS2薄膜はCuInS2薄膜に比較してポーラスな構造を形成することがわかり、p-n界面積の増大が可能であることがわかった。実際の水の還元電極特性はCuInS2薄膜に比べて低下したが、CuInS2薄膜ではほとんど進行しないCO2の還元反応が進行することを見出した。また、Cu2ZnSnS4へのAg置換では、微少量のAg置換によって、キャリア濃度やキャリ寿命などの薄膜特性が向上することを見出した。

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] Photoelectrochemical Water Reduction over Ag-Alloyed Wide Gap Cu(In,Ga)S2 Thin Film Photocathodes (2017)
  • Author(s): W. Septina, M. Sugimoto, D. Chao, Q. Shen, S. Nakatsuka, Y. Nose, T. Harada, *S. Ikeda
  • Journal Title: Physical Chemistry Chemical Physics Volume: 19 Issue: 19 Pages: 12502-12508
  • DOI: 10.1039/c7cp01348e
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Effect of Indium Doping on Surface Optoelectrical Properties of Cu2ZnSnS4 Photoabsorber and Interfacial/photovoltaic Performance of Cadmium Free In2S3/Cu2ZnSnS4 Heterojunction Thin Film Solar Cell (2016)
  • Author(s): F. Jiang, C. Ozaki, Gunawan, T. Harada, Z. Tang, T. Minemoto, Y. Nose, S. Ikeda
  • Journal Title: Chemistry of Materials Volume: 28 Issue: 10 Pages: 3283-3291
  • DOI: 10.1021/acs.chemmater.5b04984
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Impact of Precursor Compositions on Structural and Photovoltaic Properties of Spray-deposited Cu2ZnSnS4 Thin Films (2016)
  • Author(s): T. H. Nguyen, T. Harada, J. Chantana, T. Minemoto, S. Nakanishia, S. Ikeda
  • Journal Title: ChemSusChem Volume: 9 Issue: 17 Pages: 2414-2420
  • DOI: 10.1002/cssc.201600641
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Cu(In,Ga)(S,Se)2 Thin Film Solar Cell with 10.7 % Conversion Efficiency Obtained by Selenization of the Na-doped Spray-Pyrolyzed Sulfide Precursor Film (2015)
  • Author(s): Wilman Septina, Masaaki Kurihara, Shigeru Ikeda, Yasuhiro Nakajima, Toshiyuki Hirano, Yoshihito Kawasaki, Takashi Harada, Michio Matsumura
  • Journal Title: ACS Applied Materials & Interfaces Volume: 7 Issue: 12 Pages: 6472-6479
  • DOI: 10.1021/am507684x
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Photosplitting of Water from Wide-Gap Cu(In,Ga)S2 Thin Films Modified with a CdS Layer and Pt Nanoparticles for a High-Onset Potential Photocathode (2015)
  • Author(s): Wilman Septina, Gunawan, Shigeru Ikeda, Takashi Harada, Masanobu Higashi, Ryu Abe, Michio Matsumura
  • Journal Title: The Journal of Physical Chemistry C Volume: - Issue: 16 Pages: 8576-8583
  • DOI: 10.1021/acs.jpcc.5b02068
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Investigation of the Electric Structures of Heterointerfaces in Pt- and In2S3-Modified CuInS2 Photocathodes Used for Sunlight-Induced Hydrogen Evolution (2015)
  • Author(s): Gunawan, Wilman Septina, Takashi Harada, Yoshitaro Nose, Shigeru Ikeda
  • Journal Title: ACS Appl. Mater. Interfaces Volume: 7 Issue: 29 Pages: 16086-16092
  • DOI: 10.1021/acsami.5b04634
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fabrication of Cu(In,Ga)(S,Se)2 Thin Film Solar Cells via Spray Pyrolysis of Thiourea and N-Methylthiourea-based Aqueous Precursor Solution (2015)
  • Author(s): Masaaki Kurihara, Wilman Septina, Toshiyuki Hirano, Yasuhiro Nakajima, Takashi Harada, Shigeru Ikeda
  • Journal Title: Jpn. J. Appl. Phys. Volume: 54 Issue: 9 Pages: 091203-091203
  • DOI: 10.7567/jjap.54.091203
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Cu2ZnSnS4 Thin Film Solar Cells with 5.8 % of Conversion Efficiency Obtained by a Facile Spray Pyrolysis Technique (2015)
  • Author(s): Thi Hiep Nguyen, Wilman Septina, Shotaro Fujikawa, Feng Jiang, Takashi Harada, Shigeru Ikeda
  • Journal Title: RSC Adv. Volume: 5 Issue: 95 Pages: 77565-77571
  • DOI: 10.1039/c5ra13000j
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Effects of Porosity and Amounts of Surface Hydroxyl Groups of a Porous TiO2 Layer on the Performance of a CH3NH3PbI3 Perovskite Photovoltaic Cell (2015)
  • Author(s): Hasyiya Karimah Adli, Takashi Harada, Wilman Septina, Shuji Hozan, Seigo Ito, Shigeru Ikeda
  • Journal Title: J. Phys. Chem. C Volume: 119 Issue: 39 Pages: 22304-22309
  • DOI: 10.1021/acs.jpcc.5b05986
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Pt/In2S3/CdS/Cu2ZnSnS4 Thin Film as an Efficient and Stable Photocathode for Water Reduction under Sunlight Radiation (2015)
  • Author(s): Feng Jiang, Gunawan, Takashi Harada, Yongbo Kuang, Tsutomu Minegishi, Kazunari Domen, Shigeru Ikeda
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 42 Pages: 13691-13697
  • DOI: 10.1021/jacs.5b09015
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Solar Cell Properties of Cu2ZnSnS4 Thin Film Fabricated by A spray Pyrolysis Technique (2017)
  • Author(s): S. Ikeda, T. H. Nguyen, T. Harada
  • Organizer: Global Photovoltaic Conference (GPVC) 2017
  • Place of Presentation: 光州
  • Year and Date: 2017-03-14
  • Int'l Joint Research / Invited
• [Presentation] Photoelectrochemical Hydrogen Evolution from Water Using Modified Chalcopyryte Thin Films (2017)
  • Author(s): S. Ikeda, T. Kawaguchi, S. Fujikawa, T. Harada, S. Nakanishi
  • Organizer: 2017 International Conference on Artificial Photosynthesis (ICARP 2017)
  • Place of Presentation: 京都
  • Year and Date: 2017-03-02
  • Int'l Joint Research
• [Presentation] Fabrication of Copper-based Kesterite Thin Films Using A Facile Spray Deposition Technique (2017)
  • Author(s): T. Kawaguchi, S. Fujikawa, T. H. Nguyen, T. Harada, S. Nakanishi, S. Ikeda
  • Organizer: 2017 International Conference on Artificial Photosynthesis (ICARP 2017)
  • Place of Presentation: 京都
  • Year and Date: 2017-03-02
  • Int'l Joint Research
• [Presentation] Hydrogen Evolution from Water Using Modified Chalcogenide Photocathodes (2016)
  • Author(s): S. Ikeda, F. Jiang, Q. Shen, Y. Nose, T. Harada
  • Organizer: acific Rim Meeting on Electrochemical and Solid-state Science (PRiME) 2016
  • Place of Presentation: ホノルル
  • Year and Date: 2016-10-02
  • Int'l Joint Research / Invited
• [Presentation] Structural and Solar Cell Properties of Cu2ZnSnS4 Thin Film Fabricated by a Facile Spray Pyrolysis Method (2016)
  • Author(s): S. Ikeda, T. H. Nguyen, S. Fujikawa, T. Harada
  • Organizer: 20th International Conference on Ternary and Multinary Compounds
  • Place of Presentation: Halle
  • Year and Date: 2016-09-05
  • Int'l Joint Research
• [Presentation] スプレー熱分解法によるCu2ZnSnS4薄膜太陽電池の作製 (2016)
  • Author(s): 川口誉人、Nguyen Thi Hiep、藤川祥太朗、Jakapan Chantana、原田隆史、中西周次、Chantana Jakapan、峯元高志、池田 茂
  • Organizer: 第77回応用物理学会秋季学術講演会
  • Place of Presentation: 新潟
  • Year and Date: 2016-09-05
• [Presentation] 化合物薄膜太陽電池の研究動向 (2016)
  • Author(s): 池田 茂
  • Organizer: 第９回ワークショップ「固体材料合成および評価技術の新展開」
  • Place of Presentation: 二本松（福島）
  • Year and Date: 2016-09-01
  • Invited
• [Presentation] A Highly Efficient Kesterite Thin Film Solar Cells Obtained by a Facile Spray Pyrolysis Method Electrochemical Technique (2016)
  • Author(s): S. Ikeda
  • Organizer: International Union of Materials Research Societies-International Conference on Electronic Materials (IUMRS-ICEM) 2016
  • Place of Presentation: シンガポール
  • Year and Date: 2016-07-04
  • Int'l Joint Research / Invited
• [Presentation] Efficient Photocathode Material for Water Splitting Based on a Kesterite Thin Film Modified with an Indium Sulfide/Cadmium Sulfide Double Layer and Platinum Deposites (2016)
  • Author(s): S. Ikeda, F. Jiang, T. Harada
  • Organizer: 26th IUPAC International Symposium on Photochemistry
  • Place of Presentation: 大阪
  • Year and Date: 2016-04-03
  • Int'l Joint Research / Invited
• [Presentation] ワイドギャップカルコパイライト光カソード電極による水分解水素発生 (2016)
  • Author(s): 寳山修士, 杉本実里, 池田 茂, 原田隆史, 中西周次
  • Organizer: 日本化学会第96春季年会(2016)
  • Place of Presentation: 同志社大学京田辺キャンパス（京都府京田辺市）
  • Year and Date: 2016-03-24
• [Presentation] 化合物半導体薄膜を用いる太陽光エネルギー変換 (2016)
  • Author(s): 池田 茂
  • Organizer: 名古屋大学グリーン自然科学国際教育研究プログラムIGERシンポジウム「高機能性材料・省エネルギー材料の最前線」
  • Place of Presentation: 名古屋
  • Invited
• [Presentation] 太陽電池および水分解反応に用いる半導体薄膜における光電気化学測定の実際 (2016)
  • Author(s): 池田 茂
  • Organizer: 第26回キャラクタリゼーション講習会「触媒および表面の解析に役立つキャラクタリゼーションの基礎と実際」
  • Place of Presentation: 大阪
  • Invited
• [Presentation] スプレー法で調製したCdS修飾ワイドギャップカルコパイライト光カソードによる水からの水素発生 (2015)
  • Author(s): 池田 茂
  • Organizer: 第25回日本MRS年次大会
  • Place of Presentation: 横浜市開港記念会館（神奈川県横浜市）
  • Year and Date: 2015-12-10
  • Invited