Layered perovskite engineering: design of ferroelectrics through control of oxygen octahedral rotations

• Project/Area Number: 16H04496
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic materials/Physical properties
• Research Institution: Kyoto University
• Principal Investigator: Fujita Koji 京都大学, 工学研究科, 教授 (50314240)
• Co-Investigator(Kenkyū-buntansha): 村井 俊介 京都大学, 工学研究科, 助教 (20378805)
• Research Collaborator: Hojo Hajime
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000); Fiscal Year 2018: ¥2,340,000 (Direct Cost: ¥1,800,000、Indirect Cost: ¥540,000); Fiscal Year 2017: ¥11,440,000 (Direct Cost: ¥8,800,000、Indirect Cost: ¥2,640,000); Fiscal Year 2016: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: 強誘電体 / 誘電体物性 / 誘電体

Outline of Final Research Achievements

Hybrid improper ferroelectricity in layered perovskites, which utilizes nonpolar but ubiquitous rotational/tilting distortions to create polarization, offers an attractive route to the discovery of new ferroelectric and multiferroic materials because its activity derives from geometric rather than electronic origins. In this study, we discover new hybrid improper ferroelectric, Sr3Zr2O7 and (Sr,Ca)3Sn2O7. We also find that the Curie temperature increases linearly up to 800 K with increasing the Ca2+ content in (Sr,Ca)3Sn2O7, i.e., with decreasing the value of tolerance factor. Remarkably, this linear relationship is applicable to the suite of all known A3B2O7 ferroelectrics, indicating that the Curie temperature correlates with the simple crystal-chemistry descriptor based on the ionic-size mismatch.

Academic Significance and Societal Importance of the Research Achievements

膨大なペロブスカイト化合物の中で強誘電体は5%に満たず、応用分野も限定的であった。ハイブリッド間接型強誘電体の物質設計では、元素選択の自由度が直接型の場合と比べて遥かに大きいため、物質探索により高機能な新規強誘電体が登場する可能性は大いにある。また、現在は鉛を含むペロブスカイト強誘電体Pb(Zr,Ti)O3が圧電素子として広範に利用されているが、環境保全の観点からこれを代替する無鉛圧電材料の開発が強く求められている。ハイブリッド間接型強誘電体の開発はそのような産業界の要望にも応えることができる。

Research Products

• [Int'l Joint Research] Universite de Rennes/Institut Laue-Langevin(フランス)
• [Int'l Joint Research] Rutherford Appleton Laboratory(英国)
• [Int'l Joint Research] Pennsylvania State University/Northwestern University(米国)
• [Int'l Joint Research] Universite de Rennes(フランス)
• [Int'l Joint Research] Rutherford Appleton Laboratory(英国)
• [Int'l Joint Research] Pennsylvania State University/Northwestern University(米国)
• [Int'l Joint Research] Universite de Rennes(France)
• [Int'l Joint Research] Pennsylvania State University(米国)
• [Int'l Joint Research] Rutherford Appleton Laboratory(英国)
• [Int'l Joint Research] ANSTO(Australia)
• [Journal Article] Hybrid Improper Ferroelectricity in (Sr,Ca)3Sn2O7 and Beyond: Universal Relationship between Ferroelectric Transition Temperature and Tolerance Factor in n = 2 Ruddlesden?Popper Phases (2018)
  • Author(s): Yoshida Suguru、Akamatsu Hirofumi、Tsuji Ryosuke、Hernandez Olivier、Padmanabhan Haricharan、Sen Gupta Arnab、Gibbs S. Alexandra、Mibu Ko、Murai Shunsuke、Rondinelli M. James、Gopalan Venkatraman、Tanaka Katsuhisa、Fujita Koji
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 46 Pages: 15690-15700
  • DOI: 10.1021/jacs.8b07998
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Enhanced photoluminescence and directional white-light generation by plasmonic array (2018)
  • Author(s): Kamakura Ryosuke、Murai Shunsuke、Yokobayashi Yusuke、Takashima Keijiro、Kuramoto Masaru、Fujita Koji、Tanaka Katsuhisa
  • Journal Title: Journal of Applied Physics Volume: 124 Issue: 21 Pages: 213105-213105
  • DOI: 10.1063/1.5050993
  • NAID: 120006542088
  • Peer Reviewed / Open Access
• [Journal Article] Visible and near-infrared photoluminescence enhanced by Ag nanoparticles in Sm3+-doped aluminoborate glass (2018)
  • Author(s): Gao Yuan、Murai Shunsuke、Fujita Koji、Tanaka Katsuhisa
  • Journal Title: Optical Materials Volume: 86 Pages: 611-616
  • DOI: 10.1016/j.optmat.2018.10.018
  • Peer Reviewed
• [Journal Article] Demonstration of temperature-plateau superheated liquid by photothermal conversion of plasmonic titanium nitride nanostructures (2018)
  • Author(s): Ishii Satoshi、Kamakura Ryosuke、Sakamoto Hiroyuki、Dao Thang D.、Shinde Satish L.、Nagao Tadaaki、Fujita Koji、Namura Kyoko、Suzuki Motofumi、Murai Shunsuke、Tanaka Katsuhisa
  • Journal Title: Nanoscale Volume: 10 Issue: 39 Pages: 18451-18456
  • DOI: 10.1039/c8nr05931d
  • Peer Reviewed / Open Access
• [Journal Article] Enhanced Photoluminescence from Organic Dyes Coupled to Periodic Array of Zirconium Nitride Nanoparticles (2018)
  • Author(s): Kamakura Ryosuke、Murai Shunsuke、Fujita Koji、Tanaka Katsuhisa
  • Journal Title: ACS Photonics Volume: 5 Issue: 8 Pages: 3057-3063
  • DOI: 10.1021/acsphotonics.8b00320
  • Peer Reviewed
• [Journal Article] Ferroelectric Sr3Zr2O7: Competition between Hybrid Improper Ferroelectric and Antiferroelectric Mechanisms (2018)
  • Author(s): Yoshida Suguru、Fujita Koji、Akamatsu Hirofumi、Hernandez Olivier、Sen Gupta Arnab、Brown Forrest G.、Padmanabhan Haricharan、Gibbs Alexandra S.、Kuge Toshihiro、Tsuji Ryosuke、Murai Shunsuke、Rondinelli James M.、Gopalan Venkatraman、Tanaka Katsuhisa
  • Journal Title: Advanced Functional Materials Volume: 28 Issue: 30 Pages: 1801856-1801856
  • DOI: 10.1002/adfm.201801856
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Collective plasmonic modes excited in Al nanocylinder arrays in the UV spectral region (2018)
  • Author(s): Kawachiya Yuki、Murai Shunsuke、Saito Motoharu、Sakamoto Hiroyuki、Fujita Koji、Tanaka Katsuhisa
  • Journal Title: Optics Express Volume: 26 Issue: 5 Pages: 5970-5970
  • DOI: 10.1364/oe.26.005970
  • Peer Reviewed / Open Access
• [Journal Article] 層状ペロブスカイト圧電体NaRTiO4（Rは希土類）－酸素配位八面体回転による結晶構造の反転対称性の破れ－ (2018)
  • Author(s): 藤田晃司
  • Journal Title: 固体物理 Volume: 53 Pages: 41-48
  • Peer Reviewed
• [Journal Article] Plasmonic-Photonic Hybrid Modes Excited on a Titanium Nitride Nanoparticle Array in the Visible Region (2017)
  • Author(s): Kamakura Ryosuke、Murai Shunsuke、Ishii Satoshi、Nagao Tadaaki、Fujita Koji、Tanaka Katsuhisa
  • Journal Title: ACS Photonics Volume: 4 Issue: 4 Pages: 815-822
  • DOI: 10.1021/acsphotonics.6b00763
  • Peer Reviewed
• [Journal Article] Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of InーO Covalency on Structural Stabilization in Comparison with Rare-Earth Series (2017)
  • Author(s): Fujita Koji、Kawamoto Takahiro、Yamada Ikuya、Hernandez Olivier、Akamatsu Hirofumi、Kumagai Yu、Oba Fumiyasu、Manuel Pascal、Fujikawa Ryo、Yoshida Suguru、Fukuda Masayuki、Tanaka Katsuhisa
  • Journal Title: Inorganic Chemistry Volume: 56 Issue: 18 Pages: 11113-11122
  • DOI: 10.1021/acs.inorgchem.7b01426
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Competing Structural Instabilities in the Ruddlesden－Popper Derivatives HRTiO4 (R = Rare Earths): Oxygen Octahedral Rotations Inducing Noncentrosymmetricity and Layer Sliding Retaining Centrosymmetricity (2017)
  • Author(s): A. S. Gupta, H. Akamatsu, F. G. Brown, M. T. Nguyen, M. E. Strayer, S. Lapidus, S. Yoshida, K. Fujita, K. Tanaka, I. Tanaka, T. E. Mallouk, and V. Gopalan
  • Journal Title: Chemistry of Materials Volume: 29 Issue: 2 Pages: 656-665
  • DOI: 10.1021/acs.chemmater.6b04103
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Giant Faraday rotation through Fe0n states in superparamagnetic FeO-SiO2 vitreous films (2017)
  • Author(s): Yuko Nakatsuka, Kilian Pollok, Torsten Wieduwilt, Falko Langenhorst, Markus A. Schmidt, Koji Fujita, Shunsuke Murai, Katsuhisa Tanaka, and Lothar Wondraczek
  • Journal Title: Advanced Science Volume: － Issue: 4
  • DOI: 10.1002/advs.201600299
  • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] LiNbO3-type InFeO3: Room-temperature polar magnet without second-order Jahn Teller active ions (2016)
  • Author(s): Koji Fujita, Takahiro Kawamoto, Ikuya Yamada, Olivier Hernandez, Naoaki Hayashi, Hirofumi Akamatsu, William Lafargue-Dit-Hauret, Xavier Rocquefelte, Masafumi Fukuzumi, Pascal Manuel, Andrew J. Studer, Christopher Knee, and Katsuhisa Tanaka
  • Journal Title: Chemistry of Materials Volume: 28 Issue: 18 Pages: 6644-6655
  • DOI: 10.1021/acs.chemmater.6b02783
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] ZnTaO2N: Stabilized High-Temperature LiNbO3-type Structure (2016)
  • Author(s): Kuno, Y.; Tassel, C.; Fujita, K.; Batuk, D.; Abakumov, A. M.; Shitara, K.; Kuwabara, A.; Moriwake, H.; Watabe, D.; Ritter, C.; Brown, C. M.; Yamamoto, T.; Takeiri, F.; Abe, R.; Kobayashi, Y.; Tanaka, K.; Kageyama, H.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Issue: 49 Pages: 15950-15955
  • DOI: 10.1021/jacs.6b08635
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Structural phase transitions in EuNbO3 perovskite (2016)
  • Author(s): Yoshiro Kususe, Suguru Yoshida, Koji Fujita, Hirofumi Akamatsu, Masafumi Fukuzumi, Shunsuke Murai, and Katsuhisa Tanaka
  • Journal Title: Journal of Solid State Chemistry Volume: 239 Pages: 192-199
  • DOI: 10.1016/j.jssc.2016.04.032
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Presentation] 層状ぺロブスカイト酸化物における酸素八面体回転による反転対称性の破れ (2019)
  • Author(s): 藤田晃司
  • Organizer: 強的秩序とその操作に関わる第8回研究会
• [Presentation] 極性構造を持つカ チオン欠陥ペロブスカイト型酸化物の構造解析 (2019)
  • Author(s): 三宅 仁介、吉田 傑、村井 俊介、Hernandez Olivier、Ritter Clemens、田中 勝久、藤田 晃司
  • Organizer: 第 57 回セラミックス基礎科学討論会
• [Presentation] 新規機能性酸化物の創製と機能発現機構の解明 (2018)
  • Author(s): 藤田晃司
  • Organizer: 日本セラミックス協会関西支部 平成２９年度協会賞受賞記念講演会
  • Invited
• [Presentation] 層状ペロブスカイト強誘電体におけるキュリー温度と許容因子の関係 (2018)
  • Author(s): 吉田 傑、赤松 寛文、辻 涼 介、Hernandez Olivier、Padmanabhan Haricharan、Sen Gupta Arnab、Gibbs S. Alexandra、壬生 功、村井 俊介、Gopalan Venkatraman、田中 勝久、藤田 晃司
  • Organizer: 日本セラミックス協会 第 31 回秋季シンポジウム
• [Presentation] ペロブスカイト型酸化物 CuNbO3の高圧合成とその特異な熱分解挙動 (2018)
  • Author(s): 福田 真幸、山田 幾也、北條 元、田中 勝久、藤田 晃司
  • Organizer: 日本セラミックス協会 第 31 回秋季シンポジウム
• [Presentation] 新規機能性酸化物の創製と機能発現機構の解明 (2018)
  • Author(s): 藤田晃司
  • Organizer: 日本セラミックス協会 2018年年会
  • Invited
• [Presentation] 酸素欠損ペロブスカイト化合物における極性構造と弱強磁性の共存 (2018)
  • Author(s): 辻涼介、藤田晃司、吉田傑、三宅仁介、村井俊介、田中勝久
  • Organizer: 日本セラミックス協会 2018年年会
• [Presentation] 層状ペロブスカイト強誘電体に見られる準安定な反極性構造 (2018)
  • Author(s): 吉田傑、藤田晃司、赤松寛文、Hernandez Olivier、Sen Gupta Arnab、Gibbs S. Alexandra、久家俊洋、辻涼介、村井俊介、Gopalan Venkatraman、田中勝久
  • Organizer: 第65回応用物理学会 春季学術講演会
• [Presentation] 新規ペロブスカイト型ニッケル酸化物の高圧合成、結晶構造および磁気的性質 (2017)
  • Author(s): 菅智樹、藤田晃司、河本崇博、田中勝久、山田幾也
  • Organizer: 日本セラミックス協会 2017年年会
  • Place of Presentation: 日本大学駿河台キャンパス
  • Year and Date: 2017-03-17
• [Presentation] Coexistence of ferroelectricity and weak ferromagnetism in iron-based layered compound (2017)
  • Author(s): Tsuji Ryosuke、Fujita Koji、Yoshida Suguru、Miyake Jinsuke、Murai Shunsuke、Tanaka Katsuhisa
  • Organizer: IUMRS－ICAM2017
  • Int'l Joint Research
• [Presentation] ルドルスデンーポッパー相における強誘電性と構造相転移 (2017)
  • Author(s): 吉田傑、藤田晃司、赤松寛文、Hernandez Olivier、Sen Gupta Arnab、Gibbs S. Alexandra、久家俊洋、辻涼介、村井俊介、Gopalan Venkatraman、田中勝久
  • Organizer: 第78回応用物理学会 秋季学術講演会
• [Presentation] 層状ペロブスカイト型酸化物における間接型強誘電性と構造相転移 (2017)
  • Author(s): 吉田傑、藤田晃司、赤松寛文、Hernandez Olivier、Sen Gupta Arnab、Gibbs S. Alexandra、久家俊洋、辻涼介、村井俊介、Gopalan Venkatraman、田中勝久
  • Organizer: 日本セラミックス協会 第30回秋季シンポジウム
• [Presentation] 層状ペロブスカイトARTiO4 (A=アルカリ、R=希土類) における 酸素配位八面体回転に対す るカチオンサイズ効果 (2016)
  • Author(s): 赤松 寛文、藤田晃司、田中勝久、田中功、Venkatraman Gopalan
  • Organizer: 日本金属学会秋期講演大会
  • Place of Presentation: 大阪大学豊中キャンパス
  • Year and Date: 2016-09-21
• [Presentation] Large Faraday Effect of Amorphous Iron Silicate Thin Films by Metallic Iron (2016)
  • Author(s): Yuko Nakatsuka, Kilian Pollok, Falko Langenhorst, Lothar Wondraczek, Shunsuke Murai, Koji Fujita, and Katsuhisa Tanaka
  • Organizer: JSAP Autumn Meeting
  • Place of Presentation: Toki Messe, Niigata
  • Year and Date: 2016-09-13
  • Int'l Joint Research
• [Presentation] 新規ペロブスカイト型鉄酸フッ化物の合成と物性 (2016)
  • Author(s): 竹入史隆、山本隆文、藤田晃司、細川三郎、小林洋治、陰山洋、林直 顕、池田一貴、本田孝志、大友季哉
  • Organizer: 日本セラミックス協会 第29回秋季シンポジウム
  • Place of Presentation: 広島大学 東広島キャンパス
  • Year and Date: 2016-09-07
• [Presentation] Novel Oxynitride Perovskite with a High-Temperature-type LiNbO3 Structure (2016)
  • Author(s): Cedric Tassel, Yoshinori Kuno, Koji Fujita, Daichi Watabe, Dmitry Batuk, Artem M. Abakumov, Kazuki Shitara, Akihide Kuwabara, Hiroki Moriwake, Clemens Ritter, Craig M. Brown, Takafumi Yamamoto, Ryu Abe, Yoji Kobayashi, Katsuhisa Tanaka, Hiroshi Kageyama
  • Organizer: 日本セラミックス協会 第29回秋季シンポジウム
  • Place of Presentation: 広島大学 東広島キャンパス
  • Year and Date: 2016-09-07
• [Book] How Can We Control the “Element-Blocks” in Transition Metal Oxide Crystals?. In: Chujo Y. (eds) New Polymeric Materials Based on Element-Blocks（分担執筆） (2019)
  • Author(s): Tanaka Katsuhisa、Fujita Koji
  • Total Pages: 444
  • Publisher: Springer、Singapore
  • ISBN: 9789811328886
• [Remarks] 京都大学大学院工学研究科 材料化学専攻 機能材料設計学講座 藤田研究室
  • URL: http://www1.kuic.kyoto-u.ac.jp
• [Remarks] 京都大学 大学院工学研究科 材料化学専攻 無機材料化学講座 応用固体化学分野 田中研究室
  • URL: http://dipole7.kuic.kyoto-u.ac.jp