Structural study of pressure-induced phase of hydrogen-bonded supramolecular ferroelectrics

• Project/Area Number: 19K03728
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Review Section: Basic Section 13030:Magnetism, superconductivity and strongly correlated systems-related
• Research Institution: 一般財団法人総合科学研究機構(総合科学研究センター(総合科学研究室)及び中性子科学センター(研究開発
• Principal Investigator: Nakao Akiko 一般財団法人総合科学研究機構(総合科学研究センター(総合科学研究室)及び中性子科学センター(研究開発, 中性子科学センター, 副主任研究員 (90392050)
• Co-Investigator(Kenkyū-buntansha): 宗像 孝司 一般財団法人総合科学研究機構(総合科学研究センター(総合科学研究室)及び中性子科学センター(研究開発, 中性子科学センター, 副主任技師 (00363408)
• Project Period (FY): 2019-04-01 – 2023-03-31
• Project Status: Completed (Fiscal Year 2022)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2021: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2020: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 中性子回折 / 単結晶構造解析 / 有機強誘電体 / プロトン移動 / 圧力誘起 / 水素結合型有機強誘電体 / 結晶構造解析 / 圧力誘起強誘電体 / X線回折 / 水素結合型有機誘電物質

Outline of Research at the Start

柔らかい格子を持つ有機分子性結晶は，外部環境の変化に敏感で多彩な物性を示すが，中でも圧力は直接的に格子変化させることで新規物性を誘起させることが可能となる。
本研究では， 水素結合中のプロトンダイナミクスが誘電応答に重要な役割を果たす有機水素結合系圧力誘起強誘電体において，圧力下における中性子およびX線構造解析によって分子構造と水素位置を決定し，分子の自由度（配列・軌道・構造）と絡み合った相互作用を明らかにする。分子の自由度を物理的に制御し電子相を理解することは，近年急速に発展している有機エレクトロニクス研究において，物質・物性開拓のための設計指針に繋がる。

Outline of Final Research Achievements

Structural studies were performed using neutron diffraction and synchrotron radiation X-ray diffraction to clarify the origin of the dielectric response of hydrogen-bonded ferroelectrics. A single-crystal neutron diffraction method under low temperature and high pressure was established, and hydrogen atom parameters were determined by structural analysis. Structural changes within the hydrogen-bonded chain in the pressure-induced ferroelectric phase suggested polarization due to proton transfer.

Academic Significance and Societal Importance of the Research Achievements

本研究により，高圧下の有機分子性結晶の構造解析を実現し，酸と塩基から成る水素結合型強誘電体の分極起源の理解を深めた。これまで困難であった有機分子性物質の低温・高圧下での回折実験手法の確立は，外部環境の変化に敏感で多彩な物性を示す有機分子性結晶の構造研究への発展に繋がった。また，電子デバイス素子などの有機エレクトロニクスにおける重要な学術要素のひとつとして貢献した。

Research Products

• [Journal Article] Cycloidal Magnetic Ordering in Noncentrosymmetric EuIrGe₃ (2022)
  • Author(s): Matsumura Takeshi、Tsukagoshi Mitsuru、Ueda Yoshihisa、Higa Nonoka、Nakao Akiko、Kaneko Koji、Kakihana Masashi、Hedo Masato、Nakama Takao、Onuki Yoshichika
  • Journal Title: Journal of the Physical Society of Japan Volume: 91 Issue: 7 Pages: 073703-073703
  • DOI: 10.7566/jpsj.91.073703
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Relief of spin frustration through magnetic anisotropy in the quasi-one-dimensional S=1/2 antiferromagnet Na2CuSO4Cl2 (2022)
  • Author(s): M. Fujihala, Y. Sakuma, S. Mitsuda, A. Nakao, K. Munakata, R. A. Mole, S. Yano, D. H. Yu, K. Takehana, Y. Imanaka, M. Akaki, S. Okubo, H. Ohta
  • Journal Title: Physical Review B Volume: 105 Pages: 144410-144410
  • Peer Reviewed
• [Journal Article] Charge-Density-Wave Order and Multiple Magnetic Transitions in Divalent Europium Compound EuAl4 (2021)
  • Author(s): Kaneko Koji、Kawasaki Takuro、Nakamura Ai、Munakata Koji、Nakao Akiko、Hanashima Takayasu、Kiyanagi Ryoji、Ohhara Takashi、Hedo Masato、Nakama Takao、Onuki Yoshichika
  • Journal Title: Journal of the Physical Society of Japan Volume: 90 Issue: 6 Pages: 064704-064704
  • DOI: 10.7566/jpsj.90.064704
  • NAID: 40022591342
  • Peer Reviewed / Open Access
• [Journal Article] Magnetic phase diagram of helimagnetic Ba(Fe1-xScx)12O19 (0 < x < 0.2) hexagonal ferrite (2021)
  • Author(s): Kenichi Maruyama, Seiya Tanaka, Shun Natori, Ikuya Bizen, Keisuke Amemiya, Ryoji Kiyanagi, Akiko Nakao, Kentaro Moriyama, Yoshihisa Ishikawa, Yasushi Amako, Taku Iiyama, Ryusuke Futamura, Shigenori Utsumi
  • Journal Title: Journal of Alloys and Compounds Volume: 892 Pages: 162125-162125
  • DOI: 10.1016/j.jallcom.2021.162125
  • Peer Reviewed
• [Journal Article] Oval-cycloidal Magnetic Structure with Phase-shift in the Non-centrosymmetric Tetragonal Compound CePdSi3 (2021)
  • Author(s): Ueta Daichi、Yoshida Masahiro、Kobuke Tomohiro、Ikeda Yoichi、Nakao Akiko、Moyoshi Taketo、Munakata Koji、Liu Yaohua、Masuda Takatsugu、Yoshizawa Hideki
  • Journal Title: Journal of the Physical Society of Japan Volume: 90 Issue: 11 Pages: 114702-114702
  • DOI: 10.7566/jpsj.90.114702
  • NAID: 210000159393
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Correlated Li-ion migration in the superionic conductor Li10GeP2S12 (2021)
  • Author(s): Takeshi Yajima, Yoyo Hinuma, Satoshi Hori, Rui Iwasaki, Ryoji Kanno, Takashi Ohhara, Akiko Nakao, Koji Munakata, Zenji Hiroi
  • Journal Title: J. Mater. Chem. Volume: A9 Issue: 18 Pages: 11278-11284
  • DOI: 10.1039/d1ta00552a
  • Peer Reviewed / Open Access
• [Journal Article] Antiferromagnetic-to-ferrimagnetic phase transition with large electric-polarization change in a frustrated polar magnet CaBaCo4O7 (2021)
  • Author(s): T. Omi, Y. Watanabe, N. Abe, H. Sagayama, A. Nakao, K. Munakata, Y. Tokunaga, T. Arima
  • Journal Title: Physical Review B Volume: 103 Issue: 18 Pages: 184412-184412
  • DOI: 10.1103/physrevb.103.184412
  • Peer Reviewed
• [Journal Article] Programmable Synthesis of Silver Wheels (2021)
  • Author(s): Hyunchul Kwon, Ewa Pietrasiak, Takashi Ohhara, Akiko Nakao, Boknam Chae, Chan-Cuk Hwang, Daesung Jung, In-Chul Hwang, Young Ho Ko, Kimoon Kim, Eunsung Lee
  • Journal Title: Inorg. Chem. Volume: 60 Issue: 9 Pages: 6403-6409
  • DOI: 10.1021/acs.inorgchem.1c00106
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Superconductivity-driven ferromagnetism and spin manipulation using vortices in the magnetic superconductor EuRbFe4As4 (2021)
  • Author(s): Shigeyuki Ishida, Daniel Kagerbauer, Sigrid Holleis, Kazuki Iida, Koji Munakata, Akiko Nakao, Akira Iyo, Hiraku Ogino, Kenji Kawashima, Michael Eisterer, and Hiroshi Eisaki
  • Journal Title: Proceedings of the National Academy of Sciences of the United States of America Volume: 118 Issue: 37
  • DOI: 10.1073/pnas.2101101118
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Hybridization-Gap Formation and Superconductivity in the Pressure-Induced Semimetallic Phase of the Excitonic Insulator Ta2NiSe5 (2021)
  • Author(s): Matsubayashi K、Okamura H、Mizokawa T、Katayama N、Nakano A、Sawa H、Kaneko T、Toriyama T、Konishi T、Ohta Y、Arima H、Yamanaka R、Hisada A、Okada T、Ikemoto Y、Moriwaki T、Munakata K、Nakao A、Nohara M、Lu Y、Takagi H、Uwatoko Y
  • Journal Title: Journal of the Physical Society of Japan Volume: 90 Issue: 7 Pages: 074706-074706
  • DOI: 10.7566/jpsj.90.074706
  • NAID: 40022620524
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Helimagnetism of Ba(Fe1－xScx)12O19 Studied by Magnetization Measurement and Neutron Diffraction (2021)
  • Author(s): Kenichi Maruyama, Seiya Tanaka, Ryoji Kiyanagi, Akiko Nakao, Kentaro Moriyama, Yoshihisa Ishikawa, and Shigenori Utsumi
  • Journal Title: JPS Conf. Proc. Volume: 33 Pages: 011061-011061
  • DOI: 10.7566/jpscp.33.011061
  • Peer Reviewed
• [Journal Article] Determination of Crystallographic Planes for a Polyhedral Single Crystal (2021)
  • Author(s): Akiko Nakao, Taketo Moyoshi, Kentaro Moriyama, Takeshi Matsumura, Kenshirou Iba, Shigeo Ohara, Yoshihisa Ishikawa, Koji Munakata, Takashi Ohhara, and Ryoji Kiyanagi
  • Journal Title: JPS Conf. Proc. Volume: 33 Pages: 011067-011067
  • DOI: 10.7566/jpscp.33.011067
  • Peer Reviewed / Open Access
• [Journal Article] q=0 long-range magnetic order in centennialite CaCu3(OD)6Cl2・0.6D2O: A spin-1/2 perfect kagome antiferromagnet with J1-J2-Jd; (2020)
  • Author(s): K. Iida, H. K. Yoshida, A. Nakao, H. O. Jeschke, Y. Iqbal, K. Nakajima, S. Ohira-Kawamura, K. Munakata, Y. Inamura, N. Murai, M. Ishikado, R. Kumai, T. Okada, M. Oda, K. Kakurai, and M. Matsuda
  • Journal Title: Phys. Rev. B Volume: 101 Issue: 22 Pages: 220408-220408
  • DOI: 10.1103/physrevb.101.220408
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Field-induced spin reorientation in the antiferromagnetic Dirac material EuMnBi2 revealed by neutron and resonant x-ray diffraction (2020)
  • Author(s): H. Masuda, H. Sakai, H. Takahashi, Y. Yamasaki, A. Nakao, T. Moyoshi, H. Nakao, Y. Murakami, T. Arima, S. Ishiwata
  • Journal Title: Physical Review B Volume: 101 Issue: 17 Pages: 174411-174411
  • DOI: 10.1103/physrevb.101.174411
  • Peer Reviewed
• [Journal Article] Magnetically induced electric polarization in Ba3Fe2O5Cl2 with tunable direction in three dimensions (2020)
  • Author(s): N. Abe, S. Shiozawa, K. Matsuura, H. Sagayama, A. Nakao, T. Ohhara, Y. Tokunaga, T. Arima
  • Journal Title: Physical Review B Volume: 101 Issue: 18 Pages: 180407-180407
  • DOI: 10.1103/physrevb.101.180407
  • Peer Reviewed / Open Access
• [Journal Article] Helical and collinear spin-density-wave orders in S=1/2 one-dimensional frustrated chain compound NaCuMoO4(OH) investigated by neutron scattering (2020)
  • Author(s): S. Asai, T. Oyama, K. Nawa, A. Nakao, K. Munakata, K. Kuwahara, M. Hagihala, S. Itoh, Z. Hiroi, and T. Masuda
  • Journal Title: Phys. Rev. B Volume: 101 Issue: 14 Pages: 144437-144437
  • DOI: 10.1103/physrevb.101.144437
  • Peer Reviewed
• [Journal Article] Flux Growth and Magnetic Properties of Helimagnetic Hexagonal Ferrite Ba(Fe1-xScx)12O19 Single Crystals (2020)
  • Author(s): Shigenori Utsumi, Seiya Tanaka, Kenichi Maruyama, Nao Hatakeyama, Kenichi Itoh, Jun Koike, Akihiro Horikawa, Hiroki Iriyama, Hajime Kanamaru, Yasushi Amako, Taku Iiyama, Ryusuke Futamura, Ryoji Kiyanagi, Akiko Nakao, Kentaro Moriyama, Yoshihisa Ishikawa, and Nobuyuki Momozawa
  • Journal Title: ACS Omega Volume: 5(38) Issue: 38 Pages: 24890-24897
  • DOI: 10.1021/acsomega.0c03671
  • Peer Reviewed
• [Journal Article] muSR and Neutron Scattering Studied on Possible Partially-Disordered Magnetic State Coexisting with Heavy Quasiparticles in SmPt2Si2 (2020)
  • Author(s): Naoki Nakamura, Ryuji Higashinaka, Kengo Fushiya, Ryo Tsubota, Takashi U. Ito, Wataru Higemoto, Akiko Nakao, Ryoji Kiyanagi, Takashi Ohhara, Koji Kaneko, Tatsuma D. Matsuda, and Yuji Aoki
  • Journal Title: J. Phys. Soc. Cof. Volume: 29 Pages: 12009-12009
  • DOI: 10.7566/jpscp.29.012009
  • Peer Reviewed / Open Access
• [Journal Article] Magnetic Structure of a Chiral Magnet DyNi3Al9 (2020)
  • Author(s): Iba Kenshirou、Matsumura Takeshi、Nakao Akiko、Ishikawa Yoshihisa、Ohishi Kazuki、Kiyanagi Ryoji、Kousaka Yusuke、Ohara Shigeo
  • Journal Title: JPS Conf. Proc. Volume: 30 Pages: 011164-6
  • DOI: 10.7566/jpscp.30.011164
  • NAID: 130008152271
  • Peer Reviewed / Open Access
• [Journal Article] Successive Phase Transitions in R3Ir4Sn13 (R: La and Ce) Investigated Using Neutron and X-ray Diffraction (2020)
  • Author(s): Nakazato Seiya、Iwasa Kazuaki、Hashimoto Daisuke、Shiozawa Mami、Kuwahara Keitaro、Nakao Hironori、Sagayama Hajime、Ishikado Motoyuki、Ohhara Takashi、Nakao Akiko、Munakata Koji、Kiyanagi Ryoji
  • Journal Title: JPS Conf. Proc. Volume: 30 Pages: 011128-011128
  • DOI: 10.7566/jpscp.30.011128
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Multi-Step Magnetic Transitions in EuNiIn4 (2020)
  • Author(s): S. Ikeda, K. kneko, Y. Tanaka, T. Kawasaki, T. Hanashima, K. Munakata, A. Nakao, R. Kiyanagi, T. Ohhara, K. Mochizuki, A. Kondo, K. Kindo, Y. Homma, M. D. Frontzek, H. Kobayashi
  • Journal Title: J. Phys. Soc. Jpn. Volume: 89 Issue: 1 Pages: 014707-014707
  • DOI: 10.7566/jpsj.89.014707
  • NAID: 210000157872
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Magnetic phase diagram enriched by chemical substitution in a noncentrosymmetric helimagnet (2019)
  • Author(s): Tatsuki Sato, Yusuke Araki, Atsushi Miyake, Akiko Nakao, Nobuyuki Abe, Masashi Tokunaga, Shojiro Kimura, Yusuke Tokunaga, Taka-hisa Arima
  • Journal Title: Physical Review B Volume: 101 Issue: 5 Pages: 54414-54414
  • DOI: 10.1103/physrevb.101.054414
  • Peer Reviewed
• [Journal Article] Magnetic, thermal, and neutron diffraction studies of a coordination polymer: bis(glycolato)cobalt(ii) (2019)
  • Author(s): Nakane Tomohiro、Yoneyama Shota、Kodama Takeshi、Kikuchi Koichi、Nakao Akiko、Ohhara Takashi、Higashinaka Ryuji、Matsuda Tatsuma D.、Aoki Yuji、Fujita Wataru
  • Journal Title: Dalton Transactions Volume: 48 Issue: 1 Pages: 333-338
  • DOI: 10.1039/c8dt04358b
  • Peer Reviewed / Open Access
• [Journal Article] Unique Helical Magnetic Order and Field-Induced Phase in Trillium Lattice Antiferromagnet EuPtSi (2019)
  • Author(s): Kaneko Koji、Frontzek Matthias D.、Matsuda Masaaki、Nakao Akiko、Munakata Koji、Ohhara Takashi、Kakihana Masashi、Haga Yoshinori、Hedo Masato、Nakama Takao、Onuki Yoshichika
  • Journal Title: Journal of the Physical Society of Japan Volume: 88 Issue: 1 Pages: 013702-013702
  • DOI: 10.7566/jpsj.88.013702
  • NAID: 40021772136
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Nonlinear piezomagnetoelectric effect in CuFeO2 (2019)
  • Author(s): H. Tamatsukuri, S. Mitsuda, T. Shimizu, M. Fujihala, H. Yokota, K. Takehana, Y. Imanaka, A. Nakao, and K. Munakata
  • Journal Title: Phys. Rev. B Volume: 100 Issue: 20
  • DOI: 10.1103/physrevb.100.201105
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Coexisting spin resonance and long-range magnetic order of Eu in EuRbFe4As4 (2019)
  • Author(s): K. Iida, Y. Nagai, S. Ishida, M. Ishikado, N. Murai, A. D. Christianson, H. Yoshida, Y. Inamura, H. Nakamura, A. Nakao, K. Munakata, D. Kagerbauer, M. Eisterer, K. Kawashima, Y. Yoshida, H. Eisaki, and A. Iyo
  • Journal Title: Physical Review B Volume: 100 Issue: 1 Pages: 014506-014506
  • DOI: 10.1103/physrevb.100.014506
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Molecular diamond lattice antiferromagnet as a Dirac semimetal candidate (2019)
  • Author(s): Y. Shimizu, A. Otsuka, M. Maesato, M. Tsuchiizu, A. Nakao, H. Yamochi, T. Hiramatsu, Y. Yoshida, and G. Saito
  • Journal Title: Phys. Rev. B Volume: 99 Issue: 17 Pages: 174417-174417
  • DOI: 10.1103/physrevb.99.174417
  • Peer Reviewed
• [Journal Article] Lattice Dynamics Coupled to Charge and Spin Degrees of Freedom in the Molecular Dimer-Mott Insulator κ-(BEDT-TTF)2;Cu[(N(CN2)]Cl (2019)
  • Author(s): Masato Matsuura, Takahiko Sasaki, Satoshi Iguchi, Elena Gati, Jens Muller, Oliver Stockert, Andrea Piovano, Martin Bohm, Jitae T. Park, Sananda Biswas, Stephen M. Winter, Roser Valenti, Akiko Nakao, and Michael Lang
  • Journal Title: Phys Rev Lett. Volume: 123 Issue: 2 Pages: 027601-027601
  • DOI: 10.1103/physrevlett.123.027601
  • Peer Reviewed / Int'l Joint Research
• [Presentation] Ishigaki, Magnetic ordering and chiral structure phase transitions of Nd3T4Sn13 (T = Rh and Ir) (2022)
  • Author(s): Ami Shimoda, Kazuaki Iwasa, Keitaro Kuwahara, Hajime Sagayama, Hironori Nakao, Motoyuki Ishikado, Takashi Ohhara, Akiko Nakao, Akinori Hoshikawa, and Toru Ishigaki
  • Organizer: 29th International Conference on Low Temperature Physics (LT29)
  • Int'l Joint Research
• [Presentation] Nd3T4Sn13(T=Rh, Ir)におけるカイラル対称結晶構造相転移と反強磁気秩序 (2022)
  • Author(s): 下田愛海, 岩佐和晃, 桑原慶太郎, 星川晃範, 石垣徹, 中尾裕則, 佐賀山基, 大原高志, 中尾朗子, 石角元志
  • Organizer: 日本物理学会2022年秋季大会
• [Presentation] La5Mo4O16における長時間磁気緩和と超格子反射 (2022)
  • Author(s): 飯田一樹, 梶本亮一, 中尾朗子, 大原高志, 石川喜久, 熊井玲児, 水野雄介, 勝藤拓郎
  • Organizer: 日本物理学会2022年秋季大会
• [Presentation] 反転心を持たない磁性体EuIrGe3におけるサイクロイド型磁気構造 (2022)
  • Author(s): 松村武, 上田祥央, 塚越舜, 比嘉野々花, 中尾朗子, 金子耕士, 垣花将司, 辺土正人, 仲間隆男, 大貫惇睦
  • Organizer: 日本物理学会2022年秋季大会
• [Presentation] 立方晶Nd3Rh4Sn13の磁気励起に見られる擬1次元量子スピン反強磁性 (2022)
  • Author(s): 下田愛海, 岩佐和晃, 桑原慶太郎, 石角元志, 河村聖子, 村井直樹, 星川晃範, 石垣徹, 中尾朗子, 大原高志, 佐賀山基, 中尾裕則
  • Organizer: 日本物理学会2023年春季大会
• [Presentation] SmAu3Al7が示す重い電子状態と共存した部分無秩序相における磁気構造 (2022)
  • Author(s): 東中隆二, 北川紘章, 金子耕士, 伊藤孝, 大原高志, 田端千紘, 鬼柳亮嗣, 萩原雅人, 中尾朗子, 神戸振作, 松田達磨, 青木勇二
  • Organizer: 日本物理学会2023年春季大会
• [Presentation] 単結晶中性子回折によるSmAu3Al7が示す部分無秩序相の研究 (2022)
  • Author(s): 北川紘章, 東中隆二, 金子耕士, 伊藤孝, 大原高志, 田端千紘, 鬼柳亮嗣, 萩原雅人, 中尾朗子, 神戸振作, 松田達磨, 青木勇二
  • Organizer: 日本物理学会2023年春季大会
• [Presentation] 1144型鉄系超伝導体Ca1-xLaxKFe4As4における超伝導と競合秩序相 (2022)
  • Author(s): 石田茂之, 飯田一樹, 宗像孝司, 中尾朗子, 土屋佳則, 藤久裕司, 後藤義人, 中川駿吾, 柏木隆成, 中尾裕則, 伊豫彰, 荻野拓, 川島健司, 永崎洋
  • Organizer: 日本物理学会2023年春季大会
• [Presentation] Identification of crystallographic planes of a polyhedral crystal at SENJU (2021)
  • Author(s): A. Nakao, T. Moyoshi, K. Moriyama, T. Matsumura, K. Iba, S. Ohara, Y. Ishikawa, K. Munakata, T. Ohhara, R. Kiyanag
  • Organizer: 25th Congress of the International Union of Crystallography
  • Int'l Joint Research
• [Presentation] Development of absorption correction based on measured crystal faces at SENJU (2019)
  • Author(s): A. Nakao, T. Moyoshi, K. Moriyama, T. Matsumura, K. Iba, S. Ohara, Y. Ishikawa, K. Munakata, T. Ohhara and R. Kiyanagi
  • Organizer: The 3rd J-PARC symposium
  • Int'l Joint Research