Nuclear spectroscopic studies on electric conductivity and dilute magnetism in zinc oxide doped with impurity ions

• Project/Area Number: 26286075
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Quantum beam science
• Research Institution: Kanazawa University
• Principal Investigator: Sato Wataru 金沢大学, 物質化学系, 教授 (90333319)
• Co-Investigator(Kenkyū-buntansha): 大久保 嘉高 京都大学, 複合原子力科学研究所, 教授 (70201374) ; 上野 秀樹 国立研究開発法人理化学研究所, 開拓研究本部, 主任研究員 (50281118)
• Project Period (FY): 2014-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥16,380,000 (Direct Cost: ¥12,600,000、Indirect Cost: ¥3,780,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2015: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000); Fiscal Year 2014: ¥10,140,000 (Direct Cost: ¥7,800,000、Indirect Cost: ¥2,340,000)
• Keywords: 酸化亜鉛 / 摂動角相関 / メスバウアー分光 / ナノ構造体 / 希薄磁性 / 不純物 / インジウム / 局所構造

Outline of Final Research Achievements

Local structures and their thermal behaviors of indium impurities in zinc oxide (ZnO) were investigated on an atomic scale by means of time-differential perturbed angular correlation spectroscopy with the radioactive 111In(→111Cd) probe. We found that In impurities associate in the process of thermal diffusion to form nanoscale clusters in the ZnO matrix under heat treatment in air. Heat treatment under vacuum, however, causes dissociation of the clusters, suggesting that In ions leave the clusters and migrate into the ZnO matrix.
The magnetic properties of ZnO co-doped with several at.% of Co and Mn synthesized by a solid-state reaction were investigated by means of 57Co emission Mossbauer spectroscopy. We found that majority of the probe ions residing in defect-free substitutional Zn sites take 57Fe2+ state. Ferromagnetism was absent at room temperature, but, spectral broadening was observed at 10 K, implying a possible presence of a weak magnetic component.

Academic Significance and Societal Importance of the Research Achievements

安価で資源も比較的豊富な酸化亜鉛は、その透明性や伝導性を利用した機能性材料として、多岐にわたる応用が期待されている。本研究では、希薄不純物イオンを導入することにより、酸化亜鉛の機能性（伝導性、希薄磁性）を高めることを目指している。その基礎研究として、不純物として導入された放射性核種から放出される放射線の角度分布やエネルギー変化を観測することによって、酸化亜鉛中での不純物の存在状態や、不純物によって影響を受けるバルクの物性変化を観測した。その結果、不純物の離合集散過程の制御法を確立することに成功し、また、希薄磁性不純物元素の導入によって、低温における局所磁性を観測することに成功した。

Research Products

• [Journal Article] Investigation of the effects of sintering and indium-doping of zinc oxide using 67Zn magic angle spinning NMR analysis (2018)
  • Author(s): Ohashi Ryutaro、Sato Wataru、Mizuno Motohiro、Ohki Shinobu、Deguchi Kenzo、Tansho Masataka、Shimizu Tadashi
  • Journal Title: Solid State Nuclear Magnetic Resonance Volume: 95 Pages: 12-16
  • DOI: 10.1016/j.ssnmr.2018.09.001
  • Peer Reviewed
• [Journal Article] Thermal behavior of In impurities in ZnO (2018)
  • Author(s): Sato W.、Shimizu H.、Komatsuda S.、Ohkubo Y.
  • Journal Title: Journal of Applied Physics Volume: 124 Issue: 10
  • DOI: 10.1063/1.5046970
  • Peer Reviewed
• [Journal Article] Temperature-dependent thermal behavior of impurity hydrogen trapped in vacancy-type defects in single crystal ZnO (2018)
  • Author(s): Shimizu H.、Sato W.、Mihara M.、Fujisawa T.、Fukuda M.、Matsuta K.
  • Journal Title: Applied Radiation and Isotopes Volume: 140 Pages: 224-227
  • DOI: 10.1016/j.apradiso.2018.07.025
  • Peer Reviewed
• [Journal Article] In-Beam Mossbauer Spectra of 57Mn Implanted into Ice (2018)
  • Author(s): Y. Yamada, Y. Sato, Y. Kobayashi, M. Mihara, M. K. Kubo, W. Sato, J. Miyazaki, T. Nagatomo, S. Tanigawa, D. Natori, J. Kobayashi, S. Sato, A. Kitagawa
  • Journal Title: Hyperfine Interact. Volume: 238 Issue: 1 Pages: 1-10
  • DOI: 10.1007/s10751-018-1500-8
  • Peer Reviewed / Open Access
• [Journal Article] Nuclear spin relaxation of 111Cd at the A site in spinel oxides, CdFe2O4 and CdIn2O4 (2018)
  • Author(s): Sato W.、Komatsuda S.、Ohkubo Y.
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 316 Issue: 3 Pages: 1289-1293
  • DOI: 10.1007/s10967-018-5855-8
  • Peer Reviewed
• [Journal Article] Chemical reactions of localized Fe atoms in ethylene and acetylene matrices at low temperatures using in-beam Mossbauer spectroscopy (2018)
  • Author(s): Y. Kobayashi, Y. Yamada, M. K. Kubo, M. Mihara, W. Sato, J. Miyazaki, T. Nagatomo, K. Takahashi, S. Tanigawa, Y. Sato, D. Natori, M. Suzuki, J. Kobayashi, S. Sato, A. Kitagawa
  • Journal Title: Hyperfine Interact. Volume: 238 Issue: 1 Pages: 1-9
  • DOI: 10.1007/s10751-018-1494-2
  • Peer Reviewed / Open Access
• [Journal Article] μSR study on hydrogen behavior in palladium (2018)
  • Author(s): Mototsugu Mihara, Hideki Araki, Masataka Mizuno, Koichiro Shimomura, Wataru Higemoto, Kazuki Sugita , Kobayashi Atsushi, Masashi Kondo, Yuki Tanaka, Teiichiro Matsuzaki, Ryosuke Kadono, Wataru Sato, Takehito Nakano and Takashi Fukuda
  • Journal Title: JPS Conference Proceedings Volume: 21
  • DOI: 10.7566/jpscp.21.011031
  • Peer Reviewed / Open Access
• [Journal Article] Mossbauer spectroscopic study on the composition of Fe-containing minerals in ordinary chondrites, Miller Range 07710 and Yamato 790272 (2018)
  • Author(s): Sato W.、Nakagawa M.、Shirai N.、Ebihara M.
  • Journal Title: Hyperfine Interactions Volume: 239 Issue: 1
  • DOI: 10.1007/s10751-018-1489-z
  • Peer Reviewed
• [Journal Article] Chemical states of localized Fe atoms in ethylene matrices using in-beam Mossbauer spectroscopy (2016)
  • Author(s): Y. Kobayashi, Y. Yamada, S. Tanigawa, M. Mihara, M. K. Kubo, W. Sato, J. Miyazaki, T. Nagatomo, Y. Sato, D. Natori, M. Suzuki, J. Kobayashi, S. Sato, and A. Kitagawa
  • Journal Title: Hyperfine Interactions Volume: 237 Issue: 1 Pages: 1511-1516
  • DOI: 10.1007/s10751-016-1353-y
  • Peer Reviewed / Open Access
• [Journal Article] Thermal stability of nonmagntetic Cd and In impurities in Fe3O4 (2016)
  • Author(s): W. Sato, T. Ida, S. Komatsuda, T. Fujisawa, S. Takenaka, and Y. Ohkubo
  • Journal Title: Journal of Applied Physics Volume: 120 Issue: 14
  • DOI: 10.1063/1.4964694
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 銅基析出強化型合金の強ひずみ加工後の析出挙動に及ぼす自然時効の影響 (2016)
  • Author(s): 日比野将和, 渡邊千尋, 門前亮一, 戸高義一, 佐藤 渉
  • Journal Title: 銅と銅合金 Volume: 55 Pages: 197-201
  • NAID: 40020925794
  • Peer Reviewed
• [Journal Article] Local fields at nonmagntetic impurity sites in a perovskite La0.7Ca0.3MnO3 (2016)
  • Author(s): W. Sato, S. Komatsuda, A. Osa, T. K. Sato, and Y. Ohkubo
  • Journal Title: Hyperfine Interactions Volume: 237 Issue: 1
  • DOI: 10.1007/s10751-016-1325-2
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Mossbauer spectra obtained using β-γ coincidence method after 57Mn implantation into LiH and LiD (2016)
  • Author(s): Y. Sato, Y. Kobayashi, Y. Yamada, M. K. Kubo, M. Mihara, T. Nagatomo, W. Sato, J. Miyazaki, S. Tanigawa, D. Natori, S. Sato, and A. Kitagawa
  • Journal Title: Hyp. Int. Volume: 237 Issue: 1 Pages: 12990-12997
  • DOI: 10.1007/s10751-016-1299-0
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Study on chemical reactions of isolated Mossbauer probes in solid gas matrices using in-beam Mössbauer spectroscopy (2016)
  • Author(s): S. Tanigawa, Y. Kobayashi, Y. Yamada, M. Mihara, M. K. Kubo, J. Miyazaki, W. Sato, T. Nagatomo, D. Natori, Y. Sato, S. Sato, and A. Kitagawa
  • Journal Title: Hyp. Int. Volume: 237 Issue: 1 Pages: 12611-12618
  • DOI: 10.1007/s10751-016-1261-1
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Local fields in Co and Mn co-doped ZnO (2016)
  • Author(s): W. Sato, Y. Kano, T. Suzuki, M. Nakagawa, and Y. Kobayashi
  • Journal Title: Hyperfine Interactions Volume: 237 Issue: 1
  • DOI: 10.1007/s10751-016-1231-7
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Local structures at In impurity sites in ZnO probed by the TDPAC technique (2015)
  • Author(s): W. Sato, S. Komatsuda, Y. Yamada, and Y. Ohkubo
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 303 Issue: 2 Pages: 1201-1204
  • DOI: 10.1007/s10967-014-3446-x
  • Peer Reviewed / Open Access
• [Journal Article] Evaluation of vacancy-type defects in ZnO by the positron annihilation lifetime spectroscopy (2015)
  • Author(s): R. Ono, T. Togimitsu, and W. Sato
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 303 Issue: 2 Pages: 1223-1226
  • DOI: 10.1007/s10967-014-3452-z
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Thermal stability of locally-associated Al and In impurities in zinc oxide (2015)
  • Author(s): S. Komatsuda, W. Sato, and Y. Ohkubo
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 303 Issue: 2 Pages: 1249-1252
  • DOI: 10.1007/s10967-014-3460-z
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Local structure of 57Mn/57Fe implanted into lithium hydride (2015)
  • Author(s): Jun Miyazaki, Takashi Nagatomo, Yoshio Kobayashi, Michael Kenya Kubo, Yasuhiro Yamada, Mototsugu Mihara, Wataru Sato, Shinji Sato, and Atsushi Kitagawa
  • Journal Title: Journal of Radioanalytical and Nuclear Chemistry Volume: 303 Issue: 2 Pages: 1155-1158
  • DOI: 10.1007/s10967-014-3456-8
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Atomic-level observation of Ag-ion hopping motion in AgI (2015)
  • Author(s): W. Sato, S. Komatsuda, R. Mizuuci, N. Irioka, S. Kawata, and Y. Ohkubo
  • Journal Title: Hyperfine Interactions Volume: 231 Issue: 1-3 Pages: 107-113
  • DOI: 10.1007/s10751-014-1091-y
  • Peer Reviewed / Open Access
• [Journal Article] Detection of spinel ZnIn2O4 formed as nanostructures in ZnO (2014)
  • Author(s): W. Sato, S. Komatsuda, Y. Yamada, and Y. Ohkubo
  • Journal Title: Physical Review B Volume: 90 Issue: 23 Pages: 235204-235204
  • DOI: 10.1103/physrevb.90.235204
  • Peer Reviewed / Open Access
• [Journal Article] Formation energy of oxygen vacancies in ZnO determined by investigating thermal behavior of Al and In impurities (2014)
  • Author(s): S. Komatsuda, W. Sato, and Y. Ohkubo
  • Journal Title: Journal of Applied Physics Volume: 116 Issue: 18 Pages: 183502-183502
  • DOI: 10.1063/1.4901211
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Extranuclear dynamics of 111Ag(→111Cd) doped in AgI nanoparticles (2014)
  • Author(s): W. Sato, R. Mizuuci, N. Irioka, S. Komatsuda, S. Kawata, T. Azuma, and Y. Ohkubo
  • Journal Title: Chemical Physics Letters Volume: 609 Pages: 104-107
  • DOI: 10.1016/j.cplett.2014.06.044
  • Peer Reviewed / Open Access
• [Journal Article] Time-resolved Mossbauer spectra obtained after 57Mn implantation in Si (2014)
  • Author(s): Y. Kobayashi, M. Mihara, T. Nagatomo, Y. Yamada, M. K. Kubo, J. Miyazaki, W. Sato, S. Sato, and A. Kitagawa
  • Journal Title: Hyperfine Interactions Volume: 226 Issue: 1-3 Pages: 679-685
  • DOI: 10.1007/s10751-013-0949-8
  • Peer Reviewed
• [Journal Article] In-beam Mossbauer study of 57Mn implanted into a low-temperature Xe (2014)
  • Author(s): Y. Yamada, Y. Kobayashi, M. K. Kubo, M. Mihara, T. Nagatomo, W. Sato, J. Miyazaki, S. Sato, and A. Kitagawa
  • Journal Title: Hyperfine Interactions Volume: 226 Issue: 1-3 Pages: 35-40
  • DOI: 10.1007/s10751-013-0913-7
  • Peer Reviewed
• [Presentation] 南極隕石MIL07710およびY-790272の鉱物組成 (2018)
  • Author(s): 佐藤 渉、中川 真結、白井 直樹、海老原 充
  • Organizer: 2018日本放射化学会年会・第62回放射化学討論会
• [Presentation] 四酸化三鉄中に導入された 不純物インジウムの原子ジャンプ (2018)
  • Author(s): 佐藤 渉、小松田沙也加、藤沢照功、竹中聡汰、杉本友亮、大久保嘉高
  • Organizer: 平成30年度「短寿命RIを用いた核分光と核物性研究Ⅴ」専門研究会
• [Presentation] オンラインガンマ線摂動角相関法によるコンドライト隕石の鉱物組成分析 (2018)
  • Author(s): 佐藤 渉
  • Organizer: 新学術領域研究「宇宙観測検出器と量子ビームの出会い。新たな応用への架け橋。」 キックオフシンポジウム
• [Presentation] Contrastive environments of impurity sites in spinel oxides (2017)
  • Author(s): W. Sato, S. Komatsuda, and Y. Ohkubo
  • Organizer: 6th Asia-Pacific Symposium on Radiochemistry (APSORC 2017)
  • Int'l Joint Research
• [Presentation] Mossbauer spectroscopic study on the composition of Fe-containing minerals in chondrites (2017)
  • Author(s): W. Sato, M. Nakagawa, N. Shirai, and M. Ebihara
  • Organizer: The International Conference on the Applications of the Mossbauer Effect (ICAME 2017)
  • Int'l Joint Research
• [Presentation] スピネル型化合物中111Cdの核スピン緩和 (2017)
  • Author(s): 佐藤 渉, 小松田沙也加, 大久保嘉高
  • Organizer: 平成29年度 KUR専門研究会 短寿命RIを用いた核分光と核物性研究IV
• [Presentation] La0.7Ca0.3MnO3中に導入した 不純物位置の超微細場測定 (2016)
  • Author(s): 佐藤 渉, 小松田沙也加, 越智憲崇, 川田 知, 大久保嘉高
  • Organizer: 平成２８年度KUR専門研究会 短寿命RIを用いた核分光と核物性研究III
  • Place of Presentation: 京都大学原子炉実験所（大阪府）
  • Year and Date: 2016-12-20
• [Presentation] ペロブスカイト型酸化物La0.7Ca0.3MnO3中の超微細場測定 (2016)
  • Author(s): 佐藤 渉, 小松田沙也加, 大久保嘉高
  • Organizer: 2016日本放射化学会年会
  • Place of Presentation: 新潟大学五十嵐キャンパス（新潟県）
  • Year and Date: 2016-09-10
• [Presentation] Local fields at nonmagnetic impurity sites in a perovskite La0.7Ca0.3MnO3 (2016)
  • Author(s): W. Sato, S. Komatsuda, A. Osa, T. K. Sato, and Y. Ohkubo
  • Organizer: International Conference on Hyperfine Interactions and Their Applications
  • Place of Presentation: Leuven (Belgium)
  • Year and Date: 2016-07-03
  • Int'l Joint Research
• [Presentation] Supertransferred hyperfine field at a unique residential site of 111Cd in Fe3O4 (2015)
  • Author(s): W. Sato, S. Komatsuda, and Y. Ohkubo
  • Organizer: International Chemical Congress of Pacific Basin Societies 2015
  • Place of Presentation: Honolulu (U.S.A.)
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] マグネタイト中超微細場の摂動角相関測定 (2015)
  • Author(s): 佐藤渉、小松田沙也加、大久保嘉高
  • Organizer: KUR専門研究会 短寿命RIを用いた核分光と核物性研究II
  • Place of Presentation: 京都大学原子炉実験所（大阪府）
  • Year and Date: 2015-11-04
• [Presentation] 酸化亜鉛中にナノ構造体として生成した新規スピネルZnIn2O4 (2015)
  • Author(s): 佐藤渉、小松田沙也加、山田康洋、大久保嘉高
  • Organizer: 2015日本放射化学会年会
  • Place of Presentation: 東北大学川内キャンパス（宮城県）
  • Year and Date: 2015-09-25
• [Presentation] Local fields in Co and Mn co-doped ZnO (2015)
  • Author(s): W. Sato, Y. Kano, T. Suzuki, and M. Nakagawa
  • Organizer: International Conference on the Applications of the Mossbauer Effect
  • Place of Presentation: University of Hamburg (Germany)
  • Year and Date: 2015-09-13
  • Int'l Joint Research
• [Presentation] 酸化亜鉛中に不純物Inが生成した微視的構造 ー ZnIn2O4スピネルの検出 ー (2014)
  • Author(s): 佐藤 渉、小松田沙也加、山田康洋、大久保嘉高
  • Organizer: KUR専門研究会「短寿命RIを用いた核分光と核物性研究」
  • Place of Presentation: 京都大学原子炉実験所（大阪府）
  • Year and Date: 2014-12-17 – 2014-12-18
• [Presentation] Atomic level observation of Ag-ion hopping motion in AgI nanoparticles (2014)
  • Author(s): W. Sato, R. Mizuuchi, N. Irioka, S. Komatsuda, S. Kawata, A. Taoka, Y. Ohkubo
  • Organizer: Joint international conference on hyperfine interactions and symposium on nuclear quadrupole interactions 2014
  • Place of Presentation: The Shine Dome (Australia)
  • Year and Date: 2014-09-21 – 2014-09-26
• [Presentation] 超イオン伝導体ヨウ化銀中の111Agのダイナミクス (2014)
  • Author(s): 佐藤 渉、水内理映子、入岡奈津美、小松田沙也加、川田 知、 田岡 東、大久保嘉高
  • Organizer: 2014日本放射化学会年会
  • Place of Presentation: 名古屋大学（愛知県）
  • Year and Date: 2014-09-11 – 2014-09-13
• [Book] 放射化学の事典 (2015)
  • Author(s): 石岡典子、榎本秀一、海老原充、柿内秀樹、木村貴海、工藤久昭、久保謙也、酒井陽一、佐々木隆之、篠原 厚、田上恵子、永目諭一郎 他
  • Total Pages: 376
  • Publisher: 朝倉書店