界面制御による貴金属フリー強誘電体キャパシタの高品質化と高集積化プロセス開発

• Project/Area Number: 14J12298
• Research Category: Grant-in-Aid for JSPS Fellows
• Allocation Type: Single-year Grants
• Section: 国内
• Research Field: Reaction engineering/Process system
• Research Institution: Osaka Prefecture University
• Principal Investigator: 髙田 瑶子 大阪府立大学, 工学研究科, 特別研究員(DC1)
• Project Period (FY): 2014-04-25 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥2,800,000 (Direct Cost: ¥2,800,000); Fiscal Year 2016: ¥900,000 (Direct Cost: ¥900,000); Fiscal Year 2015: ¥900,000 (Direct Cost: ¥900,000); Fiscal Year 2014: ¥1,000,000 (Direct Cost: ¥1,000,000)
• Keywords: 強誘電体キャパシタ / 導電性酸化物電極 / 白金フリー / 水素劣化 / 疲労劣化 / 信頼性改善 / 非貴金属酸化物電極 / 飛行時間型二次イオン質量分析法 / 中間層 / 水素劣化耐性 / 疲労特性 / TOF-SIMS

Outline of Annual Research Achievements

強誘電体キャパシタ用電極材料の多くは、難加工性かつ高価な貴金属類であり、また、水素に対して触媒活性を示すため、半導体製造工程中での還元性雰囲気による強誘電性劣化（水素劣化）の原因となる。本研究では、貴金属に代わる電極材料として、非貴金属酸化物導電体であるSnドープIn2O3（ITO）を電極に用いた強誘電体(Pb,La)(Zr,Ti)O3（PLZT）キャパシタの水素劣化耐性を調査し、Pt電極に対する有効性を評価してきた。昨年度までは、上部電極のみITOを適用した強誘電体キャパシタ（ITO/PLZT/Pt）を重水素雰囲気下でアニールして強制劣化を行い、水素劣化に伴う強誘電体キャパシタ中の水素分布を飛行時間型二次イオン質量分析法を用いて評価していた。本年度は、ITOを下部および上部電極に用いた強誘電体キャパシタを試み、Ptフリー強誘電体キャパシタの作製を目指し、強誘電体キャパシタの信頼性改善を試みた。
ITO下部および上部電極を有する強誘電体ITO/PLZT/ITOキャパシタにおいてヒステリシス曲線が得られ、Pt電極を全く用いないPtフリー強誘電体キャパシタでも良好な強誘電性が得られた。また、ITO下部および上部電極を有する強誘電体キャパシタに対して、3%重水素雰囲気下、200℃、1 Torrで45分間アニールし、強制劣化に伴う強誘電性評価を行った結果、Pt/PLZT/Ptキャパシタでは、アニール直後から2Prが著しく減少し、45分後まで2Prは減少し続けたが、ITO/PLZT/ITOキャパシタでは、重水素雰囲気下で強制劣化させても2Prはほぼ変化しなかった。
本研究では、ITO電極のみを用い、Ptを全く使用しない強誘電体キャパシタの作製および良好な強誘電性を得ることに成功した。また、ITO電極の適用により、キャパシタの低コスト化および信頼性改善に成功した。

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] Evaluatioion of deuterium ion profile in (Pb,La)(Zr,Ti)O3 capacitors structures with conductive oxide top electrode by time of flight secondary ion mass spectrometry (2017)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Rie Shishido
  • Journal Title: Proc. 2016 IEEE ISAF/ECAPD/PFM Volume: - Pages: 1-4
  • DOI: 10.1109/isaf.2016.7819734
  • Acknowledgement Compliant
• [Journal Article] Fabrication and electrical properties of a (Pb,La)(Zr,Ti)O3 capacitor with pulsed laser deposited Sn-doped In2O3 bottom electrode on Al2O3(0001) (2017)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: Japanese Journal of Applied Physics Volume: -
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Fabrication of doped Pb(Zr,Ti)O3 capacitors on Pt substrates with different orientations (2016)
  • Author(s): Rika Tamano, Taiga Amano, Yoko Takada, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: Electronics Letters Volume: 52 Issue: 16 Pages: 1399-1401
  • DOI: 10.1049/el.2016.1949
  • Peer Reviewed
• [Journal Article] Comparative study of ferroelectric (K,Na)NbO3 thin films pulsed laser deposition on platinum substrates with different orientation (2016)
  • Author(s): Rika Tamano, Yoko Takada, Naoki Okamoto, Takeyasu Saito, Koji Higuchi, Akira Kitajima, Takeshi Yoshimura, and Norifumi Fujimura,
  • Journal Title: Proc. 2016 IEEE ISAF/ECAPD/PFM Volume: - Pages: 1-4
  • DOI: 10.1109/isaf.2016.7578063
• [Journal Article] Comparative study of hydrogen- and deuterium- induced degradation of ferroelectric (Pb,La)(Zr,Ti)O3 capacitors using time of flight secondary ion measurement (2016)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Rie Shishido
  • Journal Title: IEEE Trans. Ultrason. Ferroelectr. Freq. Control Volume: 63 Issue: 10 Pages: 1668-1673
  • DOI: 10.1109/tuffc.2016.2593585
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Reliability of the properties of (Pb,La)(Zr,Ti)O3 capacitors with non-noble metal oxide electrodes stored in an H2 atmosphere (2016)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Rie Shishido
  • Journal Title: MRS Advances Volume: 1 Issue: 5 Pages: 369-374
  • DOI: 10.1557/adv.2016.139
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Al:ZnO top electrodes deposited with various oxygen pressures for ferroelectric (Pb,La)(Zr,Ti)O3 capacitors (2016)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: Electronics Letters Volume: 52 Issue: 3 Pages: 230-232
  • DOI: 10.1049/el.2015.3539
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Ferroelectric properties of (Pb,La)(Zr,Ti)O3 capacitors wmploying Al-doped ZnO top electrodes prepared by pulased laser deposition under different oxygen pressures (2016)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: Japanese Journal of Applied Physics Volume: 印刷中
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hydrogen profile measurement of (Pb,La)(Zr,Ti)O3 capacitor with conductive electrode after hydrogen annealing (2015)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, Hideo Iwai, and Rie Shishido
  • Journal Title: Proc. 2015 IEEE ISAF/ISIF/PFM Volume: - Pages: 163-166
  • DOI: 10.1109/isaf.2015.7172695
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Effect of excess Pb on ferroelectric characteristics of conductive Al-doped ZnO and Sn-doped In2O3 top electrodes in PbLaZrTiOx capacitors (2015)
  • Author(s): Yoko Takada, Toru Tsuji, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: International Journal of Materials Research Volume: 106 Issue: 1 Pages: 83-87
  • DOI: 10.3139/146.111154
  • Peer Reviewed
• [Journal Article] Effect of Al-doped ZnO or Sn-doped In2O3 electrode on ferroelectric properties of (Pb,La)(Zr,Ti)O3 capacitors (2015)
  • Author(s): Yoko Takada, Toru Tsuji, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Hideo Iwai
  • Journal Title: Japanese Journal of Applied Physics Volume: 54 Issue: 5S Pages: 05ED03-05ED03
  • DOI: 10.7567/jjap.54.05ed03
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The effect of H2 distribution in (Pb,La)(Zr,Ti)O3 capacitors with conductive oxide electrodes on the degradation of ferroelectric properties (2015)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Hideo Iwai
  • Journal Title: Mater. Res. Soc. Symp. Proc. Volume: 1729 Pages: 93-98
  • DOI: 10.1557/opl.2015.263
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Improved reliability properties of (Pb,La)(Zr,Ti)O3 ferroelectric capacitors by thin aluminium-doped zinc oxide buffer layer (2014)
  • Author(s): Yoko Takada, Toru Tsuji, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Journal Title: Electronics Letters Volume: 50 Issue: 11 Pages: 799-800
  • DOI: 10.1049/el.2014.0187
  • Peer Reviewed
• [Journal Article] Aluminum-doped zinc oxide electrode for robust (Pb,La)(Zr,Ti)O3 capacitors: effect of oxide insulator encapsulation and oxide buffer layer (2014)
  • Author(s): Yoko Takada, Toru Tsuji, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Akihiro Oshima
  • Journal Title: Journal of Materials Science: Materials in Electronics Volume: 25 Issue: 5 Pages: 2155-2161
  • DOI: 10.1007/s10854-014-1853-y
  • Peer Reviewed
• [Presentation] 異なる酸素圧力でPLDにより作製した(K,Na)NbO3キャパシタの評価 (2017)
  • Author(s): 玉野 梨加, 髙田 瑶子, 岡本 尚樹, 齊藤 丈靖, 樋口 宏二, 北島 彰
  • Organizer: 第64回 応用物理学会春季学術講演会
  • Place of Presentation: パシフィコ横浜, 神奈川
• [Presentation] Fabrication and electrical properties for ferroelectric (Pb,La)(Zr,Ti)O3 capacitors with Sn:In2O3 bottom and top electrodes (2017)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: The International Conference on Electroceramics 2017
  • Place of Presentation: Nagoya University, Aichi
  • Int'l Joint Research
• [Presentation] Effect of dopant ions and crystallographic orientation on ferroelectric properties of Pb(Zr,Ti)O3 thin films (2016)
  • Author(s): Yoko Takada, Taiga Amano, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: 2016 Joint IEEE ISAF/ECAPD/PFM
  • Place of Presentation: Technische Universitat Darmstadt, Darmstadt, Germany
  • Int'l Joint Research
• [Presentation] Comparative study of ferroelectric (K,Na)NbO3 thin films pulsed laser deposited on platinum substrates with different orientation (2016)
  • Author(s): Rika Tamano, Taiga Amano, Yoko Takada, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: 2016 Joint IEEE ISAF/ECAPD/PFM
  • Place of Presentation: Technische Universitat Darmstadt, Darmstadt, Germany
  • Int'l Joint Research
• [Presentation] Evaluation of deuterium ion profile in (Pb,La)(Zr,Ti)O3 capacitors structures with conductive oxide top electrode by time of flight secondary ion mass spectrometry (2016)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, and Rie Shishido
  • Organizer: 2016 Joint IEEE ISAF/ECAPD/PFM
  • Place of Presentation: Technische Universitat Darmstadt, Darmstadt, Germany
  • Int'l Joint Research
• [Presentation] スパッタによるAlドープZnO電極を有する強誘電体キャパシタの作製と評価 (2016)
  • Author(s): 髙田 瑶子, 玉野 梨加, 岡本 尚樹, 齊藤 丈靖, 吉村 武, 藤村 紀文, 樋口 宏二, 北島 彰
  • Organizer: 化学工学会 第48回秋季大会
  • Place of Presentation: 徳島大学(常三島キャンパス), 徳島
• [Presentation] Pulsed laser deposited conductive oxide electrode on Al2O3 (0001) for (Pb,La)(Zr,Ti)O3 capacitor (2016)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: ADMETA Plus2016
  • Place of Presentation: 東京大学(本郷キャンパス), 東京
  • Int'l Joint Research
• [Presentation] Fabrication and electrical properties for ferroelectric capacitors with Al-doped ZnO films on sapphire substrate structure (2016)
  • Author(s): Yoko Takada, Rika Tamano, Naoki Okamoto, Takeyasu Saito, Takeshi Yoshimura, Norifumi Fujimura, Akira Kitajima, and Koji Higuchi
  • Organizer: 2016 MRS Fall Meeting
  • Place of Presentation: Hynes Convention Center, Boston, Massachusetts, USA
  • Int'l Joint Research
• [Presentation] Reliability properties studies of (Pb,La)(Zr,Ti)O3 capacitor with non-noble metal oxide electrode by storing H2 atmosphere (2015)
  • Author(s): Yoko Takada, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, Rie Shishido
  • Organizer: 2015 MRS Fall Meeting
  • Place of Presentation: Hynes Convention Center, Boston, Massachusetts, USA
  • Year and Date: 2015-11-29
  • Int'l Joint Research
• [Presentation] Ferroelectric properties of (Pb,La)(Zr,Ti)O3 capacitors using Al:ZnO top electrodes pulsed laser deposited with different oxygen pressure (2015)
  • Author(s): Yoko Takada, Takeyasu Saito, Naoki Okamoto, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: ADMETA Plus 2015
  • Place of Presentation: Seoul National University, Seoul, Korea
  • Year and Date: 2015-09-16
  • Int'l Joint Research
• [Presentation] 異なる酸素圧力で作製した導電性酸化物電極を有する強誘電体キャパシタの電気特性 (2015)
  • Author(s): 髙田瑶子,天野泰河, 岡本尚樹, 齊藤丈靖, 近藤和夫, 吉村 武, 藤村紀文, 樋口宏二, 北島 彰
  • Organizer: 化学工学会 第47回秋季大会
  • Place of Presentation: 北海道大学(札幌キャンパス), 北海道
  • Year and Date: 2015-09-09
• [Presentation] Hydrogen profile measurement of PbLaZrTiOx capacitor with conductive electrode after hydrogen annealing (2015)
  • Author(s): Yoko Takada, Taiga Amano, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, Akira Kitajima, abd Hideo Iwai
  • Organizer: 2015 Joint IEEE ISAF-ISIF-PFM
  • Place of Presentation: Biopolis, Ｓｉｎｇａｐｏｒe, Republic of Singapore
  • Year and Date: 2015-05-24
  • Int'l Joint Research
• [Presentation] The effect of H2 distribution in the PLZT capacitors with conductive oxide electrodes on the degradation of ferroelectric properties (2014)
  • Author(s): Yoko Takada, Taiga Amano, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: 2014 MRS Fall Meeting
  • Place of Presentation: Hynes Convention Center, Boston, Massachusetts, USA
  • Year and Date: 2014-11-30 – 2014-12-05
• [Presentation] Comparative study of the ferroelectric properties employed with Al:ZnO and Sn:In2O3 electrode PbLaZrTiOx capacitors (2014)
  • Author(s): Yoko Takada, Taiga Amano, Naoki Okamoto, Takeyasu Saito, Kazuo Kondo, Takeshi Yoshimura, Norifumi Fujimura, Koji Higuchi, and Akira Kitajima
  • Organizer: ADMETA Plus 2014
  • Place of Presentation: Yayoi Auditorium Ichijo Hall, The University of Tokyo, Tokyo, Japan
  • Year and Date: 2014-10-22 – 2014-10-24
• [Presentation] 導電性酸化物電極を用いた強誘電体キャパシタの作製と劣化機構 (2014)
  • Author(s): 髙田瑶子, 天野泰河, 岡本尚樹, 齊藤丈靖, 近藤和夫, 吉村 武, 藤村紀文, 樋口宏二, 北島 彰
  • Organizer: 化学工学会 第46回秋季大会
  • Place of Presentation: 九州大学 (伊都キャンパス), 福岡市
  • Year and Date: 2014-09-17 – 2014-09-19