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Thermochemical dry etching of noble and near-noble metals using supercritical carbon dioxide fluids

Research Project

Project/Area Number 19K04466
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Review Section Basic Section 21050:Electric and electronic materials-related
Research InstitutionUniversity of Yamanashi

Principal Investigator

Kondoh Eiichi  山梨大学, 大学院総合研究部, 教授 (70304871)

Project Period (FY) 2019-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000)
Fiscal Year 2021: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000)
Fiscal Year 2020: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords貴金属エッチング / 超臨界流体 / 貴金属 / エッチング
Outline of Research at the Start

本研究は、超臨界CO2流体を用いて貴金属・準貴金属(Pt, Cu, Coなど)などの難プラズマエッチング材料を「ドライ」エッチング除去する新規薄膜プロセスに関するものであり、プラズマプロセスや湿式プロセスの欠点を克服した先端デバイス向け新規微細加工技術を提供する。本研究では以下のことを達成する。
・超臨界CO2流体を用いた、反応メカニズムに立脚した難プラズマエッチング金属の
ドライエッチング法開発
・酸化ケミストリ支援による超臨界CO2流体中貴金属エッチングの提案と実証
・超臨界CO2流体中薄膜堆積法と組み合わせた超臨界一貫ドライプロセスの実証

Outline of Final Research Achievements

Removal of noble and near-noble metals using supercritical carbon dioxide fluids using supercritical carbon dioxide fluids was studied in terms of advanced processing of integrated circuits. The removal amount of Pt, Ru, Co, Ni, Cu of those thin films was studied under different process conditions, where a chelating reagent was supplied together with gaseous oxygen at 200-300 degC. Either of the elements was etched when layered on glass or a refractory metal (TiN); in the case of Pt, the addition of oxygen was found necessary. Etch reaction kinetics were studied on Cu and Ni under different temperature and etchant conditions. For this purpose, a novel sudden-shrink reactor was developed and employed.

Academic Significance and Societal Importance of the Research Achievements

先端半導体では貴金属・準貴金属の使用が多くなっている。それらは難ドライエッチング性であり、加工や洗浄が困難である。また従来法ではプラズマダメージや電気化学的腐食の懸念もある。本研究では金属を酸化・錯化させ超臨界二酸化炭素流体に溶解・除去するエッチング方法を検討した。
Pt, Cu, Ni, Coでもエッチング反応が生ずることが確認できた。反応効果を検証するため粉体も用いて実験を行った。温度依存性や濃度依存性のデータから、表面での金属酸化と溶解は同時に起こり両者のバランスがエッチング反応を適切に進めることが重要であることがわかった。
本研究の成果は新たな先端半導体プロセスに投入可能な技術である。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (24 results)

All 2022 2021 2020 2019

All Journal Article (7 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 6 results,  Open Access: 5 results) Presentation (17 results) (of which Int'l Joint Research: 7 results,  Invited: 5 results)

  • [Journal Article] Influence of Plasma Surface Treatment of Polyimide on the Microstructure of Aluminum Thin Films2022

    • Author(s)
      Kondoh Eiichi
    • Journal Title

      Coatings

      Volume: 12 Issue: 3 Pages: 334-334

    • DOI

      10.3390/coatings12030334

    • Related Report
      2021 Annual Research Report
  • [Journal Article] Synthesis and Characterization of Ni-Pt Alloy Thin Films Prepared by Supercritical Fluid Chemical Deposition Technique2021

    • Author(s)
      Sudiyarmanto Sudiyarmanto、Kondoh Eiichi
    • Journal Title

      Nanomaterials

      Volume: 11 Issue: 1 Pages: 151-151

    • DOI

      10.3390/nano11010151

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Supercritical Fluid Processing for Microfabrication2020

    • Author(s)
      KONDOH Eiichi
    • Journal Title

      Journal of the Japan Society for Precision Engineering

      Volume: 86 Issue: 9 Pages: 671-674

    • DOI

      10.2493/jjspe.86.671

    • NAID

      130007897029

    • ISSN
      0912-0289, 1882-675X
    • Year and Date
      2020-09-05
    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Enhancing resistant starch content in brown rice using supercritical carbon dioxide processing2020

    • Author(s)
      Matsubara Masahiro、Nakato Yasuhisa、Kondo Eiichi
    • Journal Title

      Journal of Food Process Engineering

      Volume: 44 Issue: 2

    • DOI

      10.1111/jfpe.13617

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Hydrosilylation of High Porosity Porous Silicon with 1-Hexene in Supercritical CO2 Fluid2020

    • Author(s)
      Naoto Takura、Jin Lianhua、Kondoh Eiichi、Gelloz Bernard
    • Journal Title

      ECS Transactions

      Volume: 98 Issue: 2 Pages: 131-137

    • DOI

      10.1149/09802.0131ecst

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] 超臨界二酸化炭素流体中における薄膜堆積2020

    • Author(s)
      近藤英一
    • Journal Title

      Journal of the Society of Inorganic Materials, Japan

      Volume: 406 Pages: 91-93

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Facile and Efficient Gas-Phase Pressure-Controlled Thermal Functionalization of Nanocrystalline Porous Silicon with 1-Hexene2019

    • Author(s)
      Gelloz Bernard、Iriyama Takuma、Takura Naoto、Kondoh Eiichi、Jin Lianhua
    • Journal Title

      ECS Journal of Solid State Science and Technology

      Volume: 8 Issue: 9 Pages: R109-R113

    • DOI

      10.1149/2.0051909jss

    • Related Report
      2019 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] 超臨界CO2金属エッチングの温度・エッチャント濃度依存性2022

    • Author(s)
      竹内創太,近藤英一
    • Organizer
      2022電気化学春季大会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 集積回路配線金属薄膜表面の防食層のエリプソメトリその場解析2021

    • Author(s)
      近藤英一
    • Organizer
      2021電気化学春季大会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] Copper oxide as Cu/glass adhesion layer and its stability under reduction chemistry2021

    • Author(s)
      Eiichi Kondoh, Takeshi Ito
    • Organizer
      Interfinish 2020
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Application of Supercritical Carbon Dioxide Fluids to Advanced Metallization2020

    • Author(s)
      Eiichi Kondoh
    • Organizer
      IEEE International Interconnect Technology Conference
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Deposition of Ni-Based Thin Films in Supercritical Carbon Dioxide Solution Via Flow-Type Reaction System2020

    • Author(s)
      Sudiyarmanto, Eiichi Kondoh
    • Organizer
      Pacific rim meeting on electrochemical and solid state science (PRiME)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] Hydrosilylation of High Porosity Porous Silicon with 1-Hexene in Supercritical CO2 Fluid2020

    • Author(s)
      Takura Naoto, Lianhua Jin, Eiichi Kondoh and Bernard Gelloz
    • Organizer
      Pacific Rim Meeting on Electrochemical and Solid State Science 2020 (PRiME 2020)
    • Related Report
      2020 Research-status Report
    • Int'l Joint Research
  • [Presentation] BTA-H2O2混合溶液中におけるCo表面その場分光エリプソメトリ測定2020

    • Author(s)
      竹内翔太,金 蓮花,近藤英一,濵田聡美,小篠諒太,嶋 昇平,檜山浩國
    • Organizer
      表面技術協会第141回講演大会
    • Related Report
      2019 Research-status Report
  • [Presentation] 1-ヘキセンを用いた多孔率ポーラスシリコンの超臨界CO2流体中のヒドロシリル化2020

    • Author(s)
      田倉 直人,金 蓮花,近藤 英一,ジェローズ ベルナール
    • Organizer
      第67回応用物理学会春季学術講演会
    • Related Report
      2019 Research-status Report
  • [Presentation] Oxygen-assisted etching/removal of Pt in supercritical CO2 solutions2019

    • Author(s)
      Eiichi Kondoh
    • Organizer
      Materials Research Society Spring Meetings
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Etching, photoetching of porous silicon in hydrofluoric acid studied by photoconduction and monochromatic light2019

    • Author(s)
      Gelloz, H. Fuwa, E. Kondoh, and L. Jin
    • Organizer
      3rd International Symposium on Anodizing Science and Technology (AST2019)
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 超臨界流体半導体プロセス応用2019

    • Author(s)
      近藤英一
    • Organizer
      NEDIA材料部品部会 第二十三回勉強会
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 超臨界流体半導体プロセス応用~薄膜形成・エッチングを中心として~2019

    • Author(s)
      近藤英一
    • Organizer
      超臨界流体部会第18回サマースクール
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] 超臨界流 CO2流体を用いた金属ドライエッチング2019

    • Author(s)
      近藤英一
    • Organizer
      半導体集積回路シンポジウム
    • Related Report
      2019 Research-status Report
    • Invited
  • [Presentation] マイクロ流通セルを用いたBTA-H2O2混合溶液中におけるCu表面のその場分光エリプソメトリ解析2019

    • Author(s)
      近藤英一,遠山真央,濵田聡美,嶋 昇平,檜山浩國
    • Organizer
      表面技術協会第140回講演大会
    • Related Report
      2019 Research-status Report
  • [Presentation] Initial changes of Cu surfaces in H2O2-BTA aqueous solutions studied by using microfluidic reactor2019

    • Author(s)
      Eiichi Kondoh, Mao Toyama, Lianhua Jin, Satomi Hamada, Shohei Shima, Hirokuni Hiyama
    • Organizer
      Advanced Metallzation Conference Asian Session
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 超臨界二酸化炭素流体中における薄膜堆積・表面反応プロセス~半導体製造応用を視野に~2019

    • Author(s)
      近藤英一
    • Organizer
      INCHEM2019
    • Related Report
      2019 Research-status Report
  • [Presentation] 田倉 直人,金 蓮花,近藤 英一,ジェローズ ベルナール2019

    • Author(s)
      超臨界CO2流体中の1-ヘキセンを用いたナノクリスタルシリコンのヒドロシリル化
    • Organizer
      第四回フォトニクス研究会
    • Related Report
      2019 Research-status Report

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Published: 2019-04-18   Modified: 2023-01-30  

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