Study of Metal Growth Mechanism into Nano-space on Supercritical Nano-Plating

2021 Fiscal Year Annual Research Report

• Project/Area Number: 21H01668
• Allocation Type: Single-year Grants
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: 曽根 正人 東京工業大学, 科学技術創成研究院, 教授 (30323752)
• Co-Investigator(Kenkyū-buntansha): 細田 秀樹 東京工業大学, 科学技術創成研究院, 教授 (10251620) ; チャン ツォーフーマーク 東京工業大学, 科学技術創成研究院, 准教授 (10647069) ; 黒子 弘道 奈良女子大学, 工学系, 教授 (20221228)
• Project Period (FY): 2021-04-01 – 2025-03-31
• Keywords: 電気化学反応 / 電気めっき / 超臨界二酸化炭素 / 回転電極 / 貴金属 / 高分子繊維 / 電析 / 電気化学的特性

Outline of Annual Research Achievements

研究代表者らは、超臨界二酸化炭素（Sc-CO2）と電解質溶液を混合して乳濁状態としてめっきを行う方法である超臨界ナノプレーティング（SNP）法を開発した。２０２１年度において、この超臨界ナノプレーティング（SNP）法による電気化学反応を解析するため、新規高圧回転電極セルを設計・製造に成功した。
この高圧回転電極セルを用いて、Sc-CO2を混合した硫酸銅電解めっき液における銅電析の電気化学的特性を、硫酸銅電解めっき液にSc-CO2を混合した場合と混合しない場合の分極特性から調べた。限界電流密度と回転電極の回転速度との関係、いわゆるLevichプロットから、Sc-CO2を混合することで限界電流が大幅に増加すること、およびSc-CO2を混合する前と比較して、拡散係数は2倍以上増加し、動粘性係数は1/2以下に減少することを明らかにした。このことから、Sc-CO2混合めっき液を用いることで、対流による銅イオンの移動が大きく促進され、従来のめっき法では困難であった対流の小さい狭小空間の電析に対しても、Sc-CO2を用いた銅電着では銅イオンの供給が改善されるため、高アスペクト比のTSVのビア・フィリングに有効であることを見出した。
同時に高分子繊維表面においてナノ領域に触媒を輸送して、貴金属を被覆する技術の開発に成功した。特に重要な知見は、金属被覆が難しいとしられているポリエチレンテレフタレート繊維への貴金属被覆であり、新しい触媒反応系を見出し、密着性の高い金属被覆に成功した。

Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

第一に、計画通りにこの超臨界ナノプレーティング（SNP）法による電気化学反応を解析するため、新規高圧回転電極セルを設計・製造に成功している。さらにこの高圧回転電極セルを用いて、Sc-CO2を混合した硫酸銅電解めっき液における銅電析の電気化学的特性を、硫酸銅電解めっき液にSc-CO2を混合した場合と混合しない場合の分極特性から調べ、限界電流密度と回転電極の回転速度との関係から、Sc-CO2を混合することで限界電流が大幅に増加すること、およびSc-CO2を混合する前と比較して、拡散係数は2倍以上増加し、動粘性係数は1/2以下に減少することを明らかにした。この知見は世界的にも独自かつ新しい研究成果であり、２報の学術論文にも報告している。

Strategy for Future Research Activity

上記の２０２１年度の研究実績をもとに、ナノ領域での金属被覆の実現を達成する。具体的には、セラミックスのナノパターンへの金属析出、高分子ナノ領域への金属析出を実現する予定である。

Research Products

• [Journal Article] Effect of current density on micro-mechanical property of electrodeposited gold film evaluated by micro-compression (2022)
  • Author(s): Omura Taro、Chen Chun-Yi、Chang Tso-Fu Mark、Yamane Daisuke、Ito Hiroyuki、Machida Katsuyuki、Masu Kazuya、Sone Masato
  • Journal Title: Surface and Coatings Technology Volume: 436 Pages: 128315～128315
  • DOI: 10.1016/j.surfcoat.2022.128315
  • Peer Reviewed
• [Journal Article] Supercritical carbon dioxide-assisted functionalization of polyethylene terephthalate (PET) toward flexible catalytic electrodes (2022)
  • Author(s): Cheng Po-Wei、Chen Chun-Yi、Ichibayashi Taku、Chang Tso-Fu Mark、Sone Masato、Nishimura Suzushi
  • Journal Title: The Journal of Supercritical Fluids Volume: 180 Pages: 105455～105455
  • DOI: 10.1016/j.supflu.2021.105455
  • Peer Reviewed
• [Journal Article] Sample size effect in Ni-TiO2 composites fabricated by supercritical CO2 emulsified CO-electroplating for miniaturized device (2022)
  • Author(s): Chien Yu-An、Chen Chun-Yi、Sone Masato、Chang Tso-Fu Mark
  • Journal Title: Micro and Nano Engineering Volume: 15 Pages: 100135～100135
  • DOI: 10.1016/j.mne.2022.100135
  • Peer Reviewed / Open Access
• [Journal Article] Supercritical carbon dioxide-assisted platinum metallization of polyethylene terephthalate textile toward wearable device (2022)
  • Author(s): Mitsumoto Masaki、Chen Chun-Yi、Chiu Wan-Ting、Chang Tso-Fu Mark、Watanabe Yasushi、Jinno Arisa、Kurosu Hiromichi、Sone Masato
  • Journal Title: Micro and Nano Engineering Volume: 15 Pages: 100132～100132
  • DOI: 10.1016/j.mne.2022.100132
  • Peer Reviewed / Open Access
• [Journal Article] Electrode Kinetic Study of Cu Electrodeposition with Supercritical CO₂ by High Pressure Rotating Disk Electrode Method (2022)
  • Author(s): Higuchi Kazuhito、Chang Tso-Fu Mark、Sone Masato
  • Journal Title: Journal of The Electrochemical Society Volume: 169 Pages: 020558～020558
  • DOI: 10.1149/1945-7111/ac534a
  • Peer Reviewed / Open Access
• [Journal Article] Supercritical carbon dioxide assisted co-electrodeposition of nickel-titanium dioxide composite film and the dispersity (2022)
  • Author(s): Chien Yu-An、Chen Chun-Yi、Sone Masato、Chang Tso-Fu Mark
  • Journal Title: The Journal of Supercritical Fluids Volume: 181 Pages: 105495～105495
  • DOI: 10.1016/j.supflu.2021.105495
  • Peer Reviewed
• [Journal Article] Development of polypyrrole/nano-gold composite for non-enzymatic glucose sensors (2022)
  • Author(s): Kawakami Hiroki、Ito Yuki、Chien Yu-An、Chen Chun-Yi、Chiu Wan-Ting、Chakraborty Parthojit、Nakamoto Takamichi、Sone Masato、Chang Tso-Fu Mark
  • Journal Title: Micro and Nano Engineering Volume: 14 Pages: 100109～100109
  • DOI: 10.1016/j.mne.2022.100109
  • Peer Reviewed / Open Access
• [Journal Article] The Structure and Micro-Mechanical Properties of Electrodeposited Cobalt Films by Micro-Compression Test (2021)
  • Author(s): Luo Xun、Chen Chun-Yi、Chang Tso-Fu Mark、Sone Masato、Zhang Qiong、Zhang Jinzhu
  • Journal Title: Journal of The Electrochemical Society Volume: 168 Pages: 102502～102502
  • DOI: 10.1149/1945-7111/ac2be9
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Presentation] Co-Electrodeposition of TiO2 Nanoparticle Reinforced High Strength Ni Film Assisted by Supercritical Carbon Dioxide for Miniaturized Electronics (2021)
  • Author(s): Yu-An Chien , Chun-Yi Chen , Tso-Fu Mark Chang , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Micro-Mechanical Characterization of Electrodeposited Ni-Co Alloys toward Design of MEMS Components (2021)
  • Author(s): Yiming Jiang , Chun-Yi Chen , Tso-Fu Mark Chang , Xun Luo , Daisuke Yamane , Masanori Mizoguchi , Osamu Kudo , Ryu Maeda , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Mechanical Property of Gold Micro-Cantilevers for Application in Microelectronics and the Sample Geometry Effect (2021)
  • Author(s): Kazuya Fujita , Kosuke Suzuki , Chun-Yi Chen , Tso-Fu Mark Chang , Daisuke Yamane , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Development of Polypyrrole/Gold Nanoparticle Composite Electrode for Electrochemical Sensor (2021)
  • Author(s): Hiroki Kawakami , Yuki Ito , Yu-An Chien , Wan-Ting Chiu , Parthojit Chakraborty , Chun-Yi Chen , Tso-Fu Mark Chang , Takamichi Nakamoto , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Pt/PET Composite Fiber Prepared by Supercritical CO2 Catalyzation for Wearable Device Applications (2021)
  • Author(s): Masaki Mitsumoto , Wan-Ting Chiu , Chun-Yi Chen , Tso-Fu Mark Chang , Arisa Jinno , Hiromichi Kurosu , Yasushi Watanabe , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Effect of Current Density on Mechanical Properties of Electrodeposited Gold Evaluated by Micro-Compression Test (2021)
  • Author(s): Taro Omura , Chun-Yi Chen , Tso-Fu Mark Chang , Daisuke Yamane , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Micro-Mechanical Property Evaluation of Gold-Nickel Alloys toward Design of MEMS Component (2021)
  • Author(s): Takumi Akiyama , Chun-Yi Chen , Tso-Fu Mark Chang , Daisuke Yamane , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: Micro and Nano Engineering Conference 2021 (MNE2021)
  • Int'l Joint Research
• [Presentation] Supercritical Carbon Dioxide Assisted Metallization of 3D-Printed Polymer Structure as Functional Components in Electronic Devices (2021)
  • Author(s): Po-Wei Cheng , Chun-Yi Chen , Taku Ichibayashi , Tso-Fu Mark Chang , Masato Sone , Suzushi Nishimura
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Effect of Current Density on Micro-Mechanical Characteristic of Electrodeposited Gold Evaluated from Cyanide Bath (2021)
  • Author(s): Taro Omura , Chun-Yi Chen , Tso-Fu Mark Chang , Daisuke Yamane , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Non-enzymatic Polypyrrole/Nano-Gold Composite Electrode for Glucose Oxidation (2021)
  • Author(s): Hiroki Kawakami , Yuki Ito , Yu-An Chien , Wan-Ting Chiu , Parthojit Chakraborty , Chun-Yi Chen , Tso-Fu Mark Chang , Takamichi Nakamoto , Masato Sone
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Electrodeposition of Nickel-Cobalt Alloy Films and their Micro-Mechanical Property (2021)
  • Author(s): Yiming Jiang , Chun-Yi Chen , Xun Luo , Daisuke Yamane , Masanori Mizoguchi , Osamu Kudo , Ryu Maeda , Masato Sone , Tso-Fu Mark Chang
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Micro-Mechanical Property of Single Crystal Gold for Applications in Microelectronics (2021)
  • Author(s): Kazuya Fujita , Kosuke Suzuki , Chun-Yi Chen , Tso-Fu Mark Chang , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Nanoparticle Reinforced High Strength Ni-TiO2 Composite Film Electroplated by Supercritical Carbon Dioxide Assisted Method (2021)
  • Author(s): Yu-An Chien , Chun-Yi Chen , Masato Sone , Tso-Fu Mark Chang
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Alloy Electrodeposition of Gold-Nickel Alloys and the Mechanical Property in Micro-Scale (2021)
  • Author(s): Takumi Akiyama , Chun-Yi Chen , Tso-Fu Mark Chang , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Masato Sone
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Presentation] Study of Pt/PET Composite Fiber Prepared by Supercritical CO2 Catalyzation (2021)
  • Author(s): Masaki Mitsumoto , Wan-Ting Chiu , Chun-Yi Chen , Tso-Fu Mark Chang , Arisa Jinno , Hiromichi Kurosu , Yasushi Watanabe , Masato Sone
  • Organizer: TACT2021 International Thin Films Conference
  • Int'l Joint Research
• [Book] めっき技術の最新動向 (2021)
  • Author(s): 曽根正人 , Tso-Fu Mark Chang
  • Total Pages: 282
  • Publisher: シーエムシー出版
  • ISBN: 978-4-7813-1599-7
• [Book] Advances in Microelectronics: Reviews, Vol. 3 (2021)
  • Author(s): Tso-Fu Mark Chang , Hideaki Nakajima , Chun-Yi Chen , Daisuke Yamane , Toshifumi Konishi , Hiroyuki Ito , Katsuyuki Machida , Kazuya Masu , Hiroshi Toshiyoshi , Masato Sone
  • Total Pages: 534
  • Publisher: IFSA PUBLISHING, S.L.