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2007 Fiscal Year Final Research Report Summary

Low Temperature Oxidation of Ultra-High Purity Metals and Stoichiometry Control of Oxide Films

Research Project

Project/Area Number 17360366
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Metal making engineering
Research InstitutionTohoku University

Principal Investigator

ISSHIKI Minoru  Tohoku University, Tohoku University, Institute of Multidisciplinary Research for Advanced Materials, Professor (20111247)

Co-Investigator(Kenkyū-buntansha) MIMURA Kouji  Institute of Multidisciplinary Research for Advanced Materials, 多元物質科学研究所, Associate Professor (00091752)
WANG Jifeng  Institute of Multidisciplinary Research for Advanced Materials, 多元物質科学研究所, Associate Professor (30271977)
Project Period (FY) 2005 – 2007
KeywordsZirconium / Hafnium / Copper / Thin Film / Oxidation
Research Abstract

To clarify the mechanism of surface oxidation of metals is very important to stabilize the metal surface. However, especially, at low temperatures, experimental result is few because of the difficulty of experiments to follow the nano-scale oxidation. Furthermore, nano-scale metal oxide films have been used widely in many electronic devises. Although their electrical properties should be dependent on the quality of the oxide film, such as point defects caused by the deviation from the stoichiometric composition, impurities, structural defects, and so on, there has been no systematic study. In this research project, the effects of impurities, structural defects and native defects on the electrical properties of nano-scale Zr oxide films in addition to clarifying the low temperature oxidation of Cu to establish the guideline to control the quality of nano-scale oxide films.
Single-crystal-copper ((100), (110), (111)) with the purity of 5N and poly-crystal copper specimens with different p … More urities of 2 N, 4 N and 6 N were oxidized at 315 ~ 378 K under 0.1 MPa of oxygen partial pressure. The oxide thickness was measured by in-situ spectroscopic ellipsometry. It was confirmed that oxidation rate of (100) was the highest, and those of (110) and (111) were similar. In the case of poly-crystal, the oxidation of 6 N-copper was the fastest. It is found that the low temperature oxidation kinetics were the inverse-logarithmic law below 5 nm, the cubic law from 5 nm to 25 nm and the parabolic law over 25 nm. In addition the activation energy was estimated and the similar value to that in Cabrera-Mott theory was obtained.
ZrO_2 layers were prepared using a two-step method, i.e., fabrication of pure Zr films by negatively biased ion beam deposition system (IBD), and oxidation of pure Zr films at 473 K for 60 min under 0.1 Mpa O_2 atmosphere, and the effect of Zr film quality on the electrical properties of ZrO_2 layer was investigated. In order to to clarify the influence of purity and structural defects, the purified Zr target was used and Zr films were deposited on the Pt/Si or Si substrate by means of ion beam deposition with applying the negative substrate bias voltage of - 50V. To control the native oxide concentration, Zr films were oxidized with/without UV light irradiation (λ=193 nm, Deep UV lamp). Characterization of Zr and ZrO_2 films were carried out using XRD, FE-SEM, HRTEM and XPS. Capacitance-voltage (C-V) and current-voltage (I-V) measurements were carried out using MIM structure or MOS structure. It was found that the decrease of impurity, the structural defects and the native defects remarkably increase the dielectric constant and decrease the leakage current. Less

  • Research Products

    (63 results)

All 2008 2007 2006 2005 Other

All Journal Article (9 results) (of which Peer Reviewed: 5 results) Presentation (54 results)

  • [Journal Article] Nanoscale investigation of long-term native oxidation of Cu films2008

    • Author(s)
      Jae-Won Lim
    • Journal Title

      Thin Solid Films 516

      Pages: 4040-4046

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Thermodynamic estimation of hydride formation during hydrogen plasma arc melting2007

    • Author(s)
      D. Elanski
    • Journal Title

      Journal of Alloys and Compounds 439

      Pages: 210-214

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Thermodynamic estimastion of hydride formation during plasma arc melting2007

    • Author(s)
      D. Elanski
    • Journal Title

      Journal of Alloys and Compounds 439

      Pages: 210-214

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Influence of negative substrate bias voltage on the impurity concentrations in Zr films2006

    • Author(s)
      J.W. Lim
    • Journal Title

      Materials Chemistry and Physics 96

      Pages: 301-306

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Improvement of Zr purity by using a purified sputtering target and negative substrate bias voltage2006

    • Author(s)
      J.W. Lim
    • Journal Title

      Surface Coating Technology 201

      Pages: 1899-1901

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Influence of negative substrate bias voltage on the impurity concentrations in Zr films2006

    • Author(s)
      J. W. Lim
    • Journal Title

      Materials Chemistry and Physics 96

      Pages: 301-306

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Improvement of Zr purity by using a purified sputtering target and negative substrate bias voltage2006

    • Author(s)
      J. W. Lim
    • Journal Title

      Surface Coating Technology 201

      Pages: 1899-1901

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Effect of negative substrate bias voltage on the nucleation and growth of Cu films during the initial stage of ion beam deposition

    • Author(s)
      Jae-Won Lim
    • Journal Title

      Metals and Materials International (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Effect of negative substrate bias voltage on the nucleation and Growth of Cu films during the initial stage of ion beam deposition

    • Author(s)
      Jae-Won Lim
    • Journal Title

      Metals and Materials International (In press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] 高純度Cuの低温酸化挙動2008

    • Author(s)
      藤田健資
    • Organizer
      日本金属学会春期大会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Low Temperature Oxidation of High Purity Cu2008

    • Author(s)
      K.Fujita
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-27
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] HC1水溶液中における陰イオン交換樹脂へのHf及びZrの分配係数,東京2008

    • Author(s)
      打越雅仁
    • Organizer
      日本金属学会春期大会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-26
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Distribution Coefficient of Hf and Zr to Anion Exchange Resin in HCl Aqueous Solution2008

    • Author(s)
      M.Uchikoshi
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Tokyo
    • Year and Date
      2008-03-26
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Plasma arc melting and refining of titanium and hafnium2007

    • Author(s)
      Kouji Mimura
    • Organizer
      International Symposium of Resource Recycling 2007
    • Place of Presentation
      Jeju (Korea)
    • Year and Date
      2007-11-27
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Plasma arc melting and refining of titanium and hafnium2007

    • Author(s)
      Kouji Mimura J.-W. Lim, G.-S. Choi, Minoru Isshiki
    • Organizer
      International Symposium of Resource Recycling 2007
    • Place of Presentation
      Korea, Jeju
    • Year and Date
      2007-11-27
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] 酸素雰囲気中における単結晶Cuの低温酸化挙動2007

    • Author(s)
      藤田健資
    • Organizer
      日本金属学会秋期大会
    • Place of Presentation
      岐阜市
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] 低温酸化により作製したZrO2/Pt/Si構造の電気特性に対するUV照射の影響2007

    • Author(s)
      斐俊佑
    • Organizer
      日本金属学会秋期大会
    • Place of Presentation
      岐阜市
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Zrを低温酸化させたZrO2薄膜の電気特性に対するZr純度と組織の影響2007

    • Author(s)
      斐俊佑
    • Organizer
      日本金属学会秋期大会
    • Place of Presentation
      岐阜市
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Low Temperature Oxidation of Cu Single Crystals in Oxygen Atmosphere2007

    • Author(s)
      K.Fujita
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Gifu
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of UV irradiation on the Electrical Properties of ZrO2/Pt/Si Structure Fabricated by Low Temperature Oxidation2007

    • Author(s)
      J.W.Bae
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Gifu
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of Purity and Texture of Zr on the Electrical Properties of ZrO2 Thin Films Prepared by Oxidizing Zr Films at Low Temperature2007

    • Author(s)
      J.W.Bae
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Gifu
    • Year and Date
      2007-09-19
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Purification of Rare Metals by Special Melting Method2007

    • Author(s)
      Kouji Mimura
    • Organizer
      The International Symposium on Metals Root Technology, 2007 Spring Conference of the Korea Institute of Metals and Materials
    • Place of Presentation
      ChangWon (Korea)
    • Year and Date
      2007-04-26
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Purification of Rare Metals by Special Melting Method2007

    • Author(s)
      Kouji Mimura
    • Organizer
      The International Symposium on Metals Root Technology, 2007 Spring Conference of the Korea Institute of Metals and Materials
    • Place of Presentation
      Korea, ChangWon
    • Year and Date
      2007-04-26
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Preparation and Characterization of High Purity Metals2007

    • Author(s)
      M. Isshiki
    • Organizer
      2007 International Symposium on Minerals and Materials Processing
    • Place of Presentation
      Daejeon (Korea)
    • Year and Date
      2007-04-20
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Refining Effect of Hydrogen Plasma Arc Melting and Trace Impurity Analysis by Glow Discharge Mass Spectrometry2007

    • Author(s)
      Jae-Won Lim
    • Organizer
      2007 International Symposium on Minerals and Materials Processing
    • Place of Presentation
      Daejeon (Korea)
    • Year and Date
      2007-04-20
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Preparation and Characterization of High Purity Metals2007

    • Author(s)
      M. Isshiki
    • Organizer
      2007 International Symposium on Minerals and Materials Processing
    • Place of Presentation
      Korea, Daejeon
    • Year and Date
      2007-04-20
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Refining Effect of Hydrogen Plasma Arc Melting and Trace Impurity Analysis by Glow Discharge Mass Spectrometry2007

    • Author(s)
      Jae-Won Lim
    • Organizer
      2007 International Symposium on Minerals and Materials Processing
    • Place of Presentation
      Korea, Daejeon
    • Year and Date
      2007-04-20
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] イオンビームデポジション法の基板バイアスの影響が酸化膜の電気特性に及ぼす影響2007

    • Author(s)
      BAE Joonwoo
    • Organizer
      日本金属学会
    • Place of Presentation
      習志野市
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] 金属ハフニウムの高純度精製2007

    • Author(s)
      松本圭吾
    • Organizer
      日本金属学会
    • Place of Presentation
      習志野市
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Effect of Substrate Bias Voltage during Ion Beam Deposition on Electrical Properties of Oxide Films2007

    • Author(s)
      BAE Joonwoo
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Narasino
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Purification of Hafnium2007

    • Author(s)
      K.Matumoto
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Narasino
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Nanoscale investigation of long-term native oxidation of Cu thin films2006

    • Author(s)
      J.-W. Lim
    • Organizer
      Advanced Metallization Conference 2006 (ADMETA2006)
    • Place of Presentation
      東京
    • Year and Date
      2006-09-26
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Nanoscale Investigation of Long-term Native Oxidation of Cu Thin Films2006

    • Author(s)
      J. -W. Lime
    • Organizer
      Advanced Metallization Conference 2006
    • Place of Presentation
      Tokyo
    • Year and Date
      2006-09-26
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of substrate bias voltage on the microstructure and electrical properties of Pt films deposited by ion beam deposition2006

    • Author(s)
      J.-W. Bae
    • Organizer
      IUVSTA ECM-100 special Symposium & Highlight Seminar
    • Place of Presentation
      Seoul (Korea)
    • Year and Date
      2006-09-18
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Electrical resistivity of Cu films deposited by ion beam deposition: Effects of grain size, impurities, and morphological defect2006

    • Author(s)
      J.-W. Lim, M. Isshiki
    • Organizer
      Global Convention of Ethnic Korean Scientists and Engineers
    • Place of Presentation
      Seoul (Korea)
    • Year and Date
      2006-09-18
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Effect of substrate bias voltage on the microstructure and electrical properties of Pt films deposited by ion beam deposition2006

    • Author(s)
      J. -W. Bae
    • Organizer
      IUVSTA ECM-100 Special Symposium & Highlight Seminar
    • Place of Presentation
      Seoul
    • Year and Date
      2006-09-18
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Electrical resistivity of Cu films deposited by ion beam deposition: Effects of grain size, impurities, and morphological defect2006

    • Author(s)
      J. -W. Lim
    • Organizer
      Global Convention of Ethnic Korean Scientists and Engineers
    • Place of Presentation
      Seoul
    • Year and Date
      2006-09-18
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Long-term Native Oxidation of Cu Thin Films at Room Temperature2006

    • Author(s)
      林載元
    • Organizer
      日本金属学会
    • Place of Presentation
      新潟
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] イオンビームデポジション法で作製されたPt膜の結晶組織に及ぼす基板バイアスの影響2006

    • Author(s)
      裴俊佑
    • Organizer
      日本金属学会
    • Place of Presentation
      新潟
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] 金属Hfの高純度精製2006

    • Author(s)
      松本圭吾
    • Organizer
      日本金属学会
    • Place of Presentation
      新潟
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Long-term Native Oxidation of Cu Thin Films at Room Temperature2006

    • Author(s)
      J. -W. Lim
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Niigata
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of Substrate Bias on the Texture of Pt Films prepared by Ion Beam Deposition2006

    • Author(s)
      J. -W. Bae
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Niigata
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Purification of High Purity Hafunium2006

    • Author(s)
      K.Matumoto
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Niigata
    • Year and Date
      2006-09-16
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] 高純度Zr薄膜の作製:ターゲット純度と基板バイアスの影響2006

    • Author(s)
      裴俊佑
    • Organizer
      日本金属学会
    • Place of Presentation
      東京
    • Year and Date
      2006-03-21
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Protective role of CuO layer regarding impurity effect2006

    • Author(s)
      朱永福
    • Organizer
      日本金属学会
    • Place of Presentation
      東京
    • Year and Date
      2006-03-21
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Preparation of High Purity Zr Thin Film: Effect of Target Purity and Substrate Bias2006

    • Author(s)
      J. -W. Bae
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Tokyo
    • Year and Date
      2006-03-21
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Protective role of CuO layer regarding impurity effect2006

    • Author(s)
      Y. F. Zhu
    • Organizer
      Spring Meeting of JIM
    • Place of Presentation
      Tokyo
    • Year and Date
      2006-03-21
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Thickness dependence of electrical resistivity for Cu films2006

    • Author(s)
      J.-W. Lim
    • Organizer
      The 30th Annual Conference of Korean Vacuum Society
    • Place of Presentation
      Seoul (Korea)
    • Year and Date
      2006-02-16
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Thickness dependence of electrical resistivity for Cu films2006

    • Author(s)
      J. -W. Lim
    • Organizer
      The 30th Annual Conference of Korean Vacuum Society
    • Place of Presentation
      Seoul
    • Year and Date
      2006-02-16
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Measurement and interpretation of impurities in Hf films with/without negative substrate bias voltage2006

    • Author(s)
      J.W. Bae
    • Organizer
      The 6th International Conference on Reactive Plasma and 23rd Symposium on Plasma Processing
    • Place of Presentation
      仙台
    • Year and Date
      2006-01-24
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Measurement and interpretation of impurities in Hf films with/without negative substrate bias voltage2006

    • Author(s)
      J. W. Bae
    • Organizer
      The 6th International Conference on Reactive Plasma and 23rd Symposium on Plasma Processing
    • Place of Presentation
      Sendai
    • Year and Date
      2006-01-24
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of film thickness, grain size, impurities, and morphological defect on the resistivity of Cu films deposited by ion beam deposition2005

    • Author(s)
      J. -W. Lim
    • Organizer
      International Conference on Frontiers of Materials Science
    • Place of Presentation
      仙台
    • Year and Date
      2005-12-07
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Effect of film thickness, grain size, impurities, and morphological defect on the resistivity of Cu films deposited by ion beam deposition2005

    • Author(s)
      J. -W. Lim
    • Organizer
      International Conference on Frontiers of Materials Science
    • Place of Presentation
      Sendai
    • Year and Date
      2005-12-07
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] IBD法で作製したHf薄膜中の不純物に及ぼす基板バイアスの影響2005

    • Author(s)
      裴 俊佑
    • Organizer
      日本金属学会
    • Place of Presentation
      東広島市
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Initial Oxidation of Cu-Mg Dilute Alloy s at 400℃2005

    • Author(s)
      朱永福
    • Organizer
      日本金属学会
    • Place of Presentation
      東広島市
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] 銅薄膜の比抵抗に及ぼす膜厚、結晶粒径、不純物、微細構造の影響2005

    • Author(s)
      林載元
    • Organizer
      日本金属学会
    • Place of Presentation
      東広島市
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Effect of Substrate Bias on Impurity Cioncentration in Hf Thin Films Prepared by IBD Method2005

    • Author(s)
      J. -W. Bae
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Higasihiroshima
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Initial Oxidation of Cu-Mg Dilute Alloys at 400℃2005

    • Author(s)
      Y. F. Zhu
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Higasihiroshima
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Effect of Thickness, Grain Size, Impurity and Microstructure on Electrical Resistivity of Cu Thin Film2005

    • Author(s)
      J. -W. Lim
    • Organizer
      Autumn Meeting of JIM
    • Place of Presentation
      Higasihiroshima
    • Year and Date
      2005-09-28
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Aqueous Purification Processes to Produce Advanced Materials for the Electronic and Semiconductors Industry2005

    • Author(s)
      Minoru Isshiki
    • Organizer
      EUROMAT 2005
    • Place of Presentation
      Prague
    • Year and Date
      2005-09-07
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Aqueous Purification Processes to Produce Advanced Materials for the Electronic and Semiconductors Industry2005

    • Author(s)
      Minoru Isshiki
    • Organizer
      EUROMAT 2005
    • Place of Presentation
      Czech Republic, Prague
    • Year and Date
      2005-09-07
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Concentrations change of impurities in thin films by applying negative substrate bias voltage2005

    • Author(s)
      J. -W. Lim
    • Organizer
      The Eight International Symposium on Sputtering & Plasma Processes
    • Place of Presentation
      金沢
    • Year and Date
      2005-06-08
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Concentrations change of impurities in thin films by applying negative substrate bias voltage2005

    • Author(s)
      J. -W. Lim
    • Organizer
      The Eight International Symposium on Sputtering & Plasma Processes
    • Place of Presentation
      Kanazawa
    • Year and Date
      2005-06-08
    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2010-02-04  

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