バルク物性の精密制御による高活性p型化合物半導体光電極の開発

• Project Area: Creation of novel light energy conversion system through elucidation of the molecular mechanism of photosynthesis and its artificial design in terms of time and space
• Project/Area Number: 18H05183
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Research Institution: Konan University
• Principal Investigator: 池田 茂 甲南大学, 理工学部, 教授 (40312417)
• Project Period (FY): 2018-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥6,760,000 (Direct Cost: ¥5,200,000、Indirect Cost: ¥1,560,000); Fiscal Year 2019: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000); Fiscal Year 2018: ¥3,380,000 (Direct Cost: ¥2,600,000、Indirect Cost: ¥780,000)
• Keywords: 化合物半導体 / バルク結晶 / 単結晶 / 光電極 / 人工光合成 / 欠陥制御 / 結晶性 / 太陽光水分解 / 光触媒および光電極 / バルク物性の制御 / 表面の高機能化

Outline of Annual Research Achievements

半導体材料におけるバルク物性は半導体内に生成したキャリアの拡散長を決定する因子である。そのような半導体をベースとする光電極の高機能化では、表面での触媒プロセスの制御に加えて、キャリア拡散長が十分に大きい半導体材料を得ることがきわめて重要である。光電極として有望な多元素化合物からなる半導体では、構成元素の不定比性が欠陥準位の種類や量を決定し、キャリア拡散長はそれらの物性に強く依存する。そのため、光カソードとして高機能化するには、これらの欠陥を定量的に制御することが必要となる。このような観点から、本研究では、計算科学や熱力学理論から予測される欠陥構造とその制御方法に基づいて、バルク結晶をベースとする化合物粉末および薄膜を作製することで、光物性を決定する重要な因子であると考えられる結晶内のバルク物性が精密に制御された、高機能な光触媒および光電極を得ることを目的としている。令和元年度および令和２年度（繰越分、６月まで）では、Cu2ZnSnS4薄膜光電極の元素置換によるCO2光還元反応に対する機能発現の実証、酵素-光触媒ハイブッド電極によるCO2還元反応の実証、酸素発生光触媒であるBiVO4粉末へのキャリアダイナミクス解析、および、CuGaSe2バルクおよび単結晶をベースとしたp型光電極の作成手法の開発を主要な成果として得た。その他関連する研究結果を含むこれらの成果については、国際誌への論文投稿（4件）、関連研究に関する国内および海外での学会（5件）にて対外発表を行った。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Tailored Photoluminescence Properties of Ag(In,Ga)Se2 Quantum Dots for Near-Infrared In Vivo Imaging (2020)
  • Author(s): Tatsuya Kameyama, Hiroki Yamauchi, Takahisa Yamamoto, Toshiki Mizumaki, Hiroshi Yukawa, Masahiro Yamamoto, Shigeru Ikeda, Taro Uematsu, Yoshinobu Baba, Susumu Kuwabata, Tsukasa Torimoto
  • Journal Title: ACS Applied Nano Materials Volume: 3 Issue: 4 Pages: 3275-3287
  • DOI: 10.1021/acsanm.9b02608
  • Peer Reviewed / Open Access
• [Journal Article] Photocarrier Recombination Dynamics in BiVO4 for Visible-Light Driven Water Oxidation (2020)
  • Author(s): I. Abdellaoui, M.M. Islam, M. Remeika, Y. Higuchi, T. Kawaguchi, T. Harada, C. Budich, T. Maeda, T. Wada, S. Ikeda, and T. Sakurai
  • Journal Title: J. Phys. Chem. C Volume: 124 Issue: 7 Pages: 3962-3972
  • DOI: 10.1021/acs.jpcc.9b10621
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Photocathode Characteristics of a Spray-Deposited Cu2ZnGeS4 Thin Film for CO2 Reduction in a CO2-Saturated Aqueous Solution (2019)
  • Author(s): Ikeda Shigeru、Fujikawa Shotaro、Harada Takashi、Nguyen Thi Hiep、Nakanishi Shuji、Takayama Tomoaki、Iwase Akihide、Kudo Akihiko
  • Journal Title: ACS Applied Energy Materials Volume: 2 Issue: 9 Pages: 6911-6918
  • DOI: 10.1021/acsaem.9b01418
  • Peer Reviewed
• [Journal Article] Photoelectrochemical CO2 Reduction to Formate with the Sacrificial Reagent Free System of Semiconductor Photocatalysts and Formate Dehydrogenase (2019)
  • Author(s): Tomoya Ishibashi, Masanobu Higashi, Shigeru Ikeda, Yutaka Amao
  • Journal Title: ChemCatChem Volume: 11 Issue: 24 Pages: 6227-6235
  • DOI: 10.1002/cctc.201901563
  • Peer Reviewed
• [Journal Article] Growth of CuSbS2 Single Crystal as an Environmentally Friendly Thermoelectric Material (2019)
  • Author(s): Nagaoka Akira、Takeuchi Manato、Yoshino Kenji、Ikeda Shigeru、Yasui Shintaro、Taniyama Tomoyasu、Nishioka Kensuke
  • Journal Title: physica status solidi (a) Volume: 216 Issue: 15 Pages: 1800861-1800861
  • DOI: 10.1002/pssa.201800861
  • Peer Reviewed
• [Journal Article] Environmentally friendly Cu2ZnSnS4-based photocathode modified with a ZnS protection layer for efficient solar water splitting (2019)
  • Author(s): Wang Kang、Huang Dingwang、Yu Le、Gu Huaimin、Ikeda Shigeru、Jiang Feng
  • Journal Title: Journal of Colloid and Interface Science Volume: 536 Pages: 9-16
  • DOI: 10.1016/j.jcis.2018.10.032
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Light-driven CO2 Reduction to Formic Acid with a Hybrid System of Biocatalyst and Semiconductor Based Photocatalyst (2018)
  • Author(s): Ishibashi T.、Ikeyama S.、Ito M.、Ikeda S.、Amao Y.
  • Journal Title: Chemistry Letters Volume: 47 Issue: 12 Pages: 1505-1508
  • DOI: 10.1246/cl.180731
  • NAID: 130007534746
  • Peer Reviewed / Open Access
• [Journal Article] Photoelectrochemical Reduction of CO2 to CO Using a CuGaS2 Thin-film Photocathode Prepared by a Spray Pyrolysis Method (2018)
  • Author(s): Ikeda Shigeru、Tanaka Yuta、Kawaguchi Takato、Fujikawa Shotaro、Harada Takashi、Takayama Tomoaki、Iwase Akihide、Kudo Akihiko
  • Journal Title: Chemistry Letters Volume: 47 Issue: 11 Pages: 1424-1427
  • DOI: 10.1246/cl.180720
  • NAID: 130007504931
  • Peer Reviewed / Open Access
• [Journal Article] Over 1% Efficient Unbiased Stable Solar Water Splitting Based on a Sprayed Cu2ZnSnS4 Photocathode Protected by a HfO2 Photocorrosion-Resistant Film (2018)
  • Author(s): Huang Dingwang、Wang Kang、Yu Le、Nguyen Thi Hiep、Ikeda Shigeru、Jiang Feng
  • Journal Title: ACS Energy Letters Volume: 3 Issue: 8 Pages: 1875-1881
  • DOI: 10.1021/acsenergylett.8b01005
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Structural and electric properties of CuSbS2 compound semiconductor bulk crystals (2018)
  • Author(s): Ikeda Shigeru、Kawaguchi Takato、Koda Yuriko、Iiyama Naoki、Harada Takashi、Nakanishi Shuji、Nakatsuka Shigeru、Nose Yoshitaro
  • Journal Title: Japanese Journal of Applied Physics Volume: 57 Issue: 8S3 Pages: 08RC09-08RC09
  • DOI: 10.7567/jjap.57.08rc09
  • NAID: 210000149514
  • Peer Reviewed
• [Journal Article] Effects of Zirconium Doping Into a Monoclinic Scheelite BiVO4 Crystal on Its Structural, Photocatalytic, and Photoelectrochemical Properties (2018)
  • Author(s): Ikeda Shigeru、Kawaguchi Takato、Higuchi Yui、Kawasaki Naoto、Harada Takashi、Remeika Mikas、Islam Muhammad M.、Sakurai Takeaki
  • Journal Title: Frontiers in Chemistry Volume: 6 Pages: 266-266
  • DOI: 10.3389/fchem.2018.00266
  • NAID: 120007133960
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] CuGaSe2単結晶を用いた光電極での水の光電気化学的還元反応 (2020)
  • Author(s): 藤田わかば, 勝部涼司, 野瀬嘉太郎, 吉野賢二, 池田 茂
  • Organizer: 第9回JACI/GSCシンポジウム（オンライン）
• [Presentation] Cu(InGa)Se2バルク結晶のオフストイキオメトリー制御と物性 (2019)
  • Author(s): 藤田わかば, 勝部涼司, 野瀬嘉太郎, 吉野賢二, 池田 茂
  • Organizer: 第80回応用物理学会秋季学術講演会
• [Presentation] Recombination mechanism in BiVO4 photocatalyst studied by photoluminescence (2019)
  • Author(s): I. Abdellaoui, K. Tajima, T. Kawaguchi, S. Ikeda, M. M. Islam, T. Sakurai
  • Organizer: 第80回応用物理学会秋季学術講演会
• [Presentation] Preparation of a CuGaSe2 bulk crystal and its photoelectrochemical properties (2019)
  • Author(s): W. Fujita, T. Wada, K. Yoshino, Y. Nose, T. Harada, S. Ikeda
  • Organizer: International Conference on Artificial Photosynthesis-2019 (ICARP2019)
• [Presentation] Photoelectrochemical CO2 reduction over a spray-deposited Cu2ZnGeS4 thin film photocathode (2019)
  • Author(s): K. Mizutani, S. Fujikawa, T. Harada, S. Nakanishi, T. Takayama, A. Iwase, A. Kudo, S. Ikeda
  • Organizer: International Conference on Artificial Photosynthesis-2019 (ICARP2019)
• [Presentation] Highly active Zr-doped BiVO4 photocatalyst for O2 evolution obtained by a solution route (2019)
  • Author(s): H. Yui, I. Abdellaoui, M. M. Islam, T. Sakurai, S. Ikeda
  • Organizer: International Conference on Artificial Photosynthesis-2019 (ICARP2019)
• [Presentation] 化合物半導体を用いた太陽光－水素エネルギー変換 (2019)
  • Author(s): 池田 茂
  • Organizer: 「元素の起源に関する探求プロジェクト」特別公開講演会
  • Invited
• [Presentation] Cu(InGa)Se2バルク結晶を利用した光電極の作製 (2019)
  • Author(s): 池田 茂, 藤田わかば, 川口誉人, 原田隆史, 永岡 章, 吉野賢二
  • Organizer: 第123回触媒討論会
• [Presentation] 光電気化学エネルギー変換への応用を目的とするCuGaSe2バルク結晶の合成 (2019)
  • Author(s): 藤田わかば, 川口誉人, 竹内麻奈人, 吉野賢二, 野瀬嘉太郎, 原田隆史, 池田 茂
  • Organizer: 第66回応用物理学会春季学術講演会
• [Presentation] Impacts of Zr-doping into Crystalline Lattices of BiVO4 Powder and Thin Film on Their Photocatalytic and Photoelectrochemical Activities (2019)
  • Author(s): T. Kawaguchi, Takashi Harada, Y. Higuchi, N. Kawasaki, T. Harada, M. Remeika, M. M. Islam, T. Sakurai, S. Ikeda
  • Organizer: International Symposium on Solar Energy Materials
  • Int'l Joint Research
• [Presentation] Silver-incorporated Cu2ZnSnS4 Thin film Utilized for Solar Cells and Photoelectrochemical Water Splitting (2019)
  • Author(s): T. Kawaguchi, T. H. Nguyen, T. Harada, S. Nakanishi, M. Higashi, R. Abe, and S. Ikeda
  • Organizer: International Symposium on Solar Energy Materials
  • Int'l Joint Research
• [Presentation] Silver-incorporated Cu2ZnSnS4 Thin film as An Absorber for Solar Cells and A Cathode for Photoelectrochemical Water Splitting (2018)
  • Author(s): T. Kawaguchi, T. H. Nguyen, T. Harada, S. Nakanishi, M. Higashi, R. Abe, and S. Ikeda
  • Organizer: NMC2018
  • Int'l Joint Research
• [Presentation] Impacts of Zr-doping into Crystalline Lattices of Bismuth Vanadate Powder and Thin Film on Their Photocatalytic and Photoelectrochemical Properties (2018)
  • Author(s): T. Kawaguchi, Y. Higuchi, N. Kawasaki, T. Harada, M. Remeika, M. M. Islam, T. Sakurai, S. Ikeda
  • Organizer: NMC2018
  • Int'l Joint Research
• [Presentation] Solar Cell and Photoelectrochemical Properties of Cu2ZnSnS4 Thin Films Fabricated by Wet Chemical Techniques (2018)
  • Author(s): S. Ikeda, F. Jiang, T. H. Nguyen, T. Harada
  • Organizer: NMC2018
  • Int'l Joint Research / Invited
• [Presentation] Characterization of Ag-incorporated Cu2ZnSnS4 Thin Films as Phoabsrobers for Photovoltaic and Photoelectrochemical Water Reduction (2018)
  • Author(s): S. Ikeda, T. H. Nguyen, T. Kawaguchi, T. Harada, S. Nakanishi, M. Higashi, R. Abe
  • Organizer: TOCAT8
  • Int'l Joint Research
• [Presentation] Photocatalytic and Photoelectrochemical Properties of Zirconium-doped Bismuth Vanadate (2018)
  • Author(s): T. Kawaguchi, Y. Higuchi, N. Kawasaki, T. Harada, M. Remeika, M. M. Islam, T. Sakurai, S. Ikeda
  • Organizer: TOCAT8
  • Int'l Joint Research
• [Presentation] Thin Tilm Solar Cells Prepared by Chemical Routes (2018)
  • Author(s): S. Ikeda, T. H. Nguyen, and T. Harada
  • Organizer: CIMTEC 2018
  • Int'l Joint Research / Invited