ㄽᩥᑂᰝࡢせ᪨༤ኈࡢᑓᨷศ㔝ࡢྡ⛠༤ ኈ㸦 ⌮Ꮫ 㸧Ꮫ఩ᤵ୚ࡢせ௳Ꮫ఩つ๎➨ 4 ᮲➨ 1࣭2 㡯ヱᙜẶྡZhao Qingㄽᩥ㢟┠
Nature of chemical bonds in double perovskite-type oxide BaBiO΄ and related oxides
visualized by synchrotron-radiation X-ray diffraction㸦 ᨺᑕග X ⥺ᅇᢡ࡟ࡼࡾྍど໬ࡉࢀࡓ஧㔜࣌ࣟࣈࢫ࢝࢖ࢺᆺ㓟໬≀ BaBiO΄࠾ࡼࡧ㛵㐃㓟໬≀ࡢ໬Ꮫ⤖ྜࡢᛶ㉁ 㸧ㄽᩥᑂᰝᢸᙜ⪅୺  ᰝ   ᩍ ᤵ  㯮ᒾ ⰾᘯᑂᰝጤဨ   ᩍ ᤵ  ᮌᮧ ᫛ኵ                 ᑂᰝጤဨ   ᩍ ᤵ  ⏕ኳ┠ ༤ᩥ㸦ᨺᑕග⛉Ꮫ◊✲ࢭࣥࢱ࣮㸧   ࠝㄽᩥᑂᰝࡢせ᪨ࠞ BaBiO3ࡣࡼࡃ▱ࡽࢀࡓ࣌ࣟࣈࢫ࢝࢖ࢺᆺ㓟໬≀࡛࠶ࡿࡀ㸪㏆ᖺ㸪(Ba, K)(Bi, Pb)O3࡛ࡢ㉸ఏᑟࡢⓎぢࢆዎᶵ࡟㸪BaBiO3ࡣ㉸ఏᑟᮦᩱ➼ࡢẕᮦᩱ࡜ࡋ࡚㸪ࡲࡓ㸪ග࣑ࣝࢿࢵࢭࣥࢫᮦᩱ࡜ࡋ࡚෌ࡧὀ┠ࡉࢀࡿࡼ࠺࡟࡞ࡗ࡚ࡁࡓࠋBaBiO3ෆ࡛ࡢ㟁Ⲵࣂࣛࣥࢫࢆ⪃࠼ࡿ࡜㸪Bi࢖
࢜ࣥࡣ4౯࡛࠶ࡿ࡭ࡁࡔࡀ㸪Bi࢖࢜ࣥࡀ࠸ࢃࡺࡿࣂࣞࣥࢫࢫ࢟ࢵࣃ࣮࡛࠶ࡿࡇ࡜ࢆ⪃៖ࡍࡿ࡜㸪3౯࡜5౯ࡢ≧ែࢆ➼☜⋡࡛ࡶࡘ࡜⪃࠼ࡿࡢࡀ⮬↛࡛࠶ࡿࠋࡇࡢࡇ࡜࡟㛵ࡋ࡚㸪୰ᛶᏊᅇᢡᐇ㦂࡟ࡼࡿඛ⾜◊✲ࡀ࠶ࡾ㸪Bi-O㛫ࡢཎᏊ㛫㊥㞳ࡢ㐪࠸࠿ࡽ⤖ᬗᏛⓗ࡟␗࡞ࡿ2ࡘࡢ
Bi࢖࢜ࣥࢧ࢖ࢺࡀᏑᅾࡋ㸪BaBiO3ࡣBࢧ࢖ࢺ⛛ᗎᆺࡢ஧㔜࣌ࣟࣈࢫ࢝࢖ࢺᆺᵓ㐀ࢆࡶࡘࡇ࡜ࡀᥦ᱌ࡉࢀ࡚࠸ࡓࠋᚑ᮶㸪Biࡢࡼ࠺࡞㹖⥺྾཰ࡢ኱ࡁ࡞㔜ඖ⣲࡜Oࡢࡼ࠺࡞㹖⥺ᩓ஘⬟ࡢప࠸㍍ඖ⣲ࢆྠ᫬࡟ྵࡴ≀㉁ࡢᵓ㐀ゎᯒࡣ୺࡟୰ᛶᏊᅇᢡᐇ㦂࡟ࡼࡾ⾜ࢃࢀ࡚ࡁࡓࠋ୍᪉㸪᭱㏆ࡢ㹖⥺ᵓ㐀ゎᯒᢏ⾡ࡢ㐍ᒎࡣ┠ぬࡲࡋࡃ㸪㏱㐣⬟ࡢ㧗࠸㧗࢚ࢿࣝࢠ࣮ᨺᑕග㹖⥺ࢆ⏝࠸ࡓᅇᢡᐇ㦂ࢆ⾜࠼ࡤ㸪ࢃࡎ࠿࡞ᵓ㐀ᅉᏊࡢ㐪࠸ࡲ࡛㆑ู࡛ࡁࡿࡼ࠺࡞⤫ィ⢭ᗘࡢ㧗࠸ᅇᢡࢹ࣮ࢱࡀィ࡛ࡁࡿࡇ࡜ࡀࢃ࠿ࡗ࡚ࡁࡓࠋ୰ᛶᏊࢆ౑ࢃ࡞ࡅࢀࡤᵓ㐀ゎᯒ࡛ࡁ࡞࠸࡜࠸࠺ᖖ㆑ࡀኚ໬ࡋࡘࡘ࠶ࡿࠋᏛ఩⏦ㄳㄽᩥ࡛ࡣ㸪㧗࢚ࢿࣝࢠ࣮ᨺᑕග㹖⥺ᅇᢡᐇ㦂࡟ࡼࡿBaBiO3ࡢ㟁Ꮚᐦᗘ࡛ࣞ࣋ࣝࡢᵓ㐀ゎᯒࡢᡂᯝࡀグࡉࢀ࡚࠸ࡿࠋ㹖⥺ᅇᢡᐇ㦂ࡢ࢔ࢻࣂࣥࢸ࣮ࢪࢆ᭱኱㝈࡟⏕࠿ࡋ㸪ᴟࡵ࡚⢭ᐦ࡞㟁Ꮚᐦᗘศᕸࡢྍど໬࡟ᡂຌࡋ࡚࠸ࡿࠋBi-O㛫ࡢཎᏊ㛫㊥㞳ࡢ㐪࠸࠿ࡽBi࢖࢜ࣥࡢ౯ᩘࢆ᥎ᐃࡋࡓ୰ᛶᏊᅇᢡᐇ㦂࡜ࡣ␗࡞ࡾ㸪ᐇ✵㛫࡛ྍど໬ࡉࢀࡓBi࢖࢜ࣥࡢ኱ࡁࡉࡸ㟁Ꮚᩘ࠿ࡽ୍ぢࡋ࡚Bi࢖࢜ࣥࡢ౯ᩘࡀ㆑ู࡛ࡁ㸪㟁Ⲵ⛛ᗎࡢ┤᥋ドᣐࡀどぬⓗ࡟♧ࡉࢀࡓࡇ࡜ࡣ㧗ࡃホ౯࡛ࡁࡿࠋࡍ࡭࡚ࡢᗘ⠊ᅖ࡛㸪Bi5+-O㛫ࡢ໬Ꮫ⤖ྜ࡟ಀࡿ㌶㐨ΰᡂࡀBi3+-O㛫ࡢࡑࢀࡼࡾࡶ኱ࡁ࠸ࡇ࡜ࡀᐇ㦂ⓗ࡟♧ࡉࢀ࡚࠾ࡾ㸪኱ኚ⯆࿡῝࠸ࠋBaBiO3ࡣ㸪㧗 ࠿ࡽ ᗘࢆୗࡆ࡚࠸ࡃ࡜᭱㧗 ┦ࡢࣉࣟࢺࢱ࢖ࣉᵓ㐀࡜ࡋ࡚ࡢ❧᪉ᬗ┦࠿ࡽ⳻㠃యᬗ┦࡬㸪ࡑࡋ࡚༢ᩳᬗ┦㸯ࢆ⤒ู࡚ࡢ༢ᩳᬗ┦㸰࡬㏲ḟ┦㌿⛣ࡍࡿࠋ㟁Ꮚᐦᗘゎᯒࡢ⤖ᯝ࠿ࡽࢃ࠿ࡿ໬Ꮫ⤖ྜࡢ≉ᚩ࠿ࡽ㸪❧᪉ᬗ┦࡛ࡣ࢖࢜ࣥ⤖ᬗࡢᵝ┦ࢆ࿊ࡋ࡚࠾ࡾ㸪⳻㠃యᬗ┦࡜༢ᩳᬗ┦㸯࡛ࡣ3ḟඖⓗ࡞Bi-O㛫ࡢඹ᭷⤖ྜࡢࢿࢵࢺ࣮࣡ࢡࡀᙧᡂࡉࢀࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋ᭱ࡶ⯆࿡῝࠸ࡇ࡜ࡣ㸪᭱ప ┦ࡢ༢ᩳᬗ┦㸰࡛ࡣ㸪୍ࡘࡢBi3+-O㛫ࡢ⤖ྜࡢ㛗ࡉࡀఙࡧࡿࡇ࡜࡛༢ᩳᬗ┦㸯࡛ࡣほ ࡉࢀࡓBi3+-O㛫ࡢ⤖ྜ㟁Ꮚࡀほࡉࢀ࡞ࡃ࡞ࡿࡇ࡜࡛࠶ࡿࠋࡇࡢࡇ࡜࠿ࡽᵓ㐀ࡢ2ḟඖᛶࡀࡼࡾ࠸ࡗࡑ࠺㧗ࡃ࡞ࡾ㸪BaBiO3ࡣప࡛ᒙ≧≀㉁࡜࡞ࡿࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋࡇࡢᵓ㐀ࡢపḟඖ໬࡜BaBiO3ࡀ㉸ఏᑟ≀㉁ࡢẕᮦᩱ࡜࡞ࡿࡇ࡜࡜ࡢ㛵㐃ࡣ᫂ࡽ࠿࡛ࡣ࡞࠸ࡀ㸪ᵓ㐀≀ᛶࢆ㆟ㄽࡍࡿ࠺࠼࡛㔜せ࡞⤖ᬗᵓ㐀ࡢ≉ᚩࡀ♧ࡉࢀࡓ࡜⪃࠼ࡿࠋࡇࢀࡽࡢ໬Ꮫ⤖ྜࡢ≉ᚩ࡜ᵓ㐀ࡢᏳᐃᛶ࡟ࡘ࠸࡚ࡣ㸪Ꮫ఩⏦ㄳㄽᩥࡢ୰࡛➨୍ཎ⌮㟁Ꮚᵓ㐀ィ⟬࡛ࡶ᳨ウࡉࢀ࡚࠾ࡾ㸪ᐇ㦂࡜⌮ㄽ࡟࠾࠸࡚┦⿵ⓗ࡟ඃࢀࡓ◊✲ᡂᯝࡀ♧ࡉࢀ࡚࠸ࡿࠋ୍᪉㸪BaBiO3࡟㛵㐃ࡍࡿ㓟໬≀࡜ࡋ࡚㓟⣲Ḟᦆ࡟ࡼࡿ୙ᐃẚࡢBaBiO2.5࡟ࡘ࠸࡚㸪㟁Ꮚᐦᗘ࡛ࣞ࣋ࣝࡢ⤖ᬗᵓ㐀࡜ග࣑ࣝࢿࢵࢭࣥࢫ≉ᛶ࡜ࡢ㛵㐃ࡀ㆟ㄽࡉࢀ࡚࠸ࡿࠋBaBiO2.5ࡣᵓ㐀┦㌿⛣ࡏࡎ≉␗࡞Bi-O㛫⤖ྜ࡟ࡼࡿᒙ≧ᵓ㐀ࢆࡶࡘࡇ࡜㸪ࡲࡓ㸪ࡑࡢᒙ≧ᵓ㐀࡟ࡼࡾ㏻
ᖖࡢBi໬ྜ≀࡜ࡣ␗࡞ࡿ㏆㉥እࡢග࣑ࣝࢿࢵࢭࣥࢫ≉ᛶࢆࡶࡘࡇ࡜ࡀ♧ࡉࢀ࡚࠸ࡿࠋᮏᏛ఩⏦ㄳㄽᩥ࡛ࡣ㸪᭱᪂ࡢᨺᑕග㹖⥺ᅇᢡᐇ㦂ᢏ⾡ࢆ⏝࠸࡚㸪Bi ࡢࡼ࠺࡞㔜ඖ⣲ࡢ㟁Ⲵ⛛ᗎᵓ㐀ࢆ㟁Ꮚᐦᗘศᕸࡢ୰࡟ᐇ㦂ⓗ࡟᫂ᛌ࡟♧ࡋ࡚࠸ࡿࡇ࡜ࡀ㧗ࡃホ౯ࡉࢀࡿࠋ⤂௓ࡉࢀࡓ◊✲ᡭἲࡣ㸪ࡇࡢ≀㉁⣔࡟㝈ࡽࡎ㸪௚ࡢ≀㉁⣔࡛ࡢᵓ㐀≀ᛶࢆ㹖⥺ᅇᢡᐇ㦂࡛㆟ㄽࡍࡿ㝿ࡢᣦᶆ࡜࡞ࡿ࡭ࡁࡶࡢ࡛㸪ᩍ⫱ⓗ࡛ࡶ࠶ࡾ኱ࡁ࡞࢖ࣥࣃࢡࢺࢆ୚࠼ࡿ࡜⪃࠼ࡽࢀࡿࠋ௨ୖ㸪ᑂᰝࡢ⤖ᯝ㸪ᮏㄽᩥࡢⴭ⪅ࡣ༤ኈ㸦⌮Ꮫ㸧ࡢᏛ఩ࢆᤵ୚ࡉࢀࡿ༑ศ࡞㈨᱁ࡀ࠶ࡿࡶࡢ࡜ㄆࡵࡿࠋබ ⾲ ㄽ ᩥ(1) Charge Order of Bismuth Ions and Nature of Chemical Bonds in Double Perovskite-typeOxide BaBiO3 Visualized by Synchrotron Radiation X-ray Diffraction.
Qing Zhao, Tomohiro Abe, Chikako Moriyoshi, Sangwook Kim, Ayako Taguchi, HirokiMoriwake, Hong-Tao Sun, and Yoshihiro Kuroiwa,Japanese Journal of Applied Physics, accepted August 17, 2020.

ཧ ⪃ ㄽ ᩥ(1) Transformation of Perovskite BaBiO3 into Layered BaBiO2.5 Crystals Featuring Unusual
Chemical Bonding and Luminescence.
Hong Li, Qing Zhao, Bo-Mei Liu, Jun-Ying Zhang, Zhi-Yong Li, Shao-Qiang Guo, Ju-Ping
Ma, Yoshihiro Kuroiwa, Chikako Moriyoshi, Li-Rong Zheng, and Hong-Tao Sun,
Chemistry A European Journal 2018, 24, 8875−8882.
(2) Cs4PbBr6/CsPbBr3 Perovskite Composites with Near-Unity Luminescence Quantum Yield:
Large -Scale Synthesis, Luminescence and Formation Mechanism, and White Light-Emitting
Diode Application.
Ya-Meng Chen, Yang Zhou, Qing Zhao, Jun-Ying Zhang, Ju-Ping Ma, Tong-Tong Xuan,
Shao-Qiang Guo, Zi-Jun Yong, Jing Wang, Yoshihiro Kuroiwa, Chikako Moriyoshi, andHong-Tao Sun,ACS Applied Materials & Interfaces, 2018, 10, 15905−15912.
(3) Ion-Exchangeable Microporous Polyoxometalate Compounds with Off-Center Dopants
Exhibiting Unconventional Luminescence.
Dan-Dan Zhou, Qing Zhao, Fu-Ping Zhu, Zhi-Gang Zhang, Yang Zhou, Zi-Jun Yong, Ju-Ping
Ma, Yoshihiro Kuroiwa, Chikako Moriyoshi, Yong-Zheng Fang, Jia-Li Gu, Jie Shu, Zhi-Yong
Li, Jian-Mei Chen, Li-Rong Zheng, and Hong-Tao Sun,
Chemistry A European Journal 2018, 24, 9976−9982.
(4) X-ray-activated long persistent phosphors featuring strong UVC afterglow emissions.
Yan-Min Yang, Zhi-Yong Li, Jun-Ying Zhang, Yue Lu, Shao-Qiang Guo, Qing Zhao, Xin
Wang, Zi-Jun Yong, Hong Li, Ju-Ping Ma, Yoshihiro Kuroiwa, Chikako Moriyoshi, Li -Li Hu,
Li-Yan Zhang, Li-Rong Zheng, and Hong-Tao Sun,
Light: Science & Applications 2018, 7, 88/1-11.
(5) Defective [Bi2O2]2+ Layers Exhibiting Ultrabroad Near-Infrared Luminescence.
Hong Li, Xiao-Fang Jia, Qing Zhao, Ju-Ping Ma, Jian-Dang Liu, Bang-Jiao Ye, Yoshihiro
Kuroiwa, Chikako Moriyoshi, Zhi-Yong Li, Qi Liu, Jun-Ying Zhang, and Hong-Tao Sun,
Chem. Eur. J. 2019, 25, 12842−12848.
(6) Defect-Triggered Phase Transition in Cesium Lead Halide Perovskite Nanocrystals.
Ju-Ping Ma, Jun Yin, Ya-Meng Chen, Qing Zhao, Yang Zhou, Hong Li, Yoshihiro Kuroiwa,Chikako Moriyoshi, Zhi -Yong Li, Osman M. Bakr, Omar F. Mohammed, and Hong-Tao Sun,ACS Materials Letters 2019, 1, 185−191.
(7) Doping Induces Structural Phase Transitions in All-Inorganic Lead Halide Perovskite
Nanocrystals.
Ju-Ping Ma, Jia-Kai Chen, Jun Yin, Bin-Bin Zhang, Qing Zhao, Yoshihiro Kuroiwa, ChikakoMoriyoshi, Lili Hu, Osman M. Bakr, Omar F. Mohammed, and Hong-Tao Sun,ACS Materials Letters 2020, 2, 367−375.