2010B1850                           BL19B2

␗ᖖศᩓຠᯝࢆ฼⏝ࡋࡓ X ⥺ᅇᢡ࡟ࡼࡿࣉࣟࢺࣥఏᑟᛶࣂ࣒ࣜ࢘ࢪࣝࢥࢿ࣮ࢺ᱁Ꮚ୰࡟࠾ࡅࡿࢻ࣮ࣃࣥࢺࡢࢧ࢖ࢺศᕸỴᐃDetermination of Cation Site Occupancy of Dopantin Proton Conducting Barium Zirconate by Powder X-ray Diffraction
Utilizing Anomalous Dispersion Effect⠛⏣ ᘯ㐀 a, Ᏹ⏣ ဴஓ b, 㡑 ᮾ㯌 b
Kozo Shinoda a, Tetsuya Uda b, Donglin Han aaᮾ໭኱Ꮫከඖ≀㉁⛉Ꮫ◊✲ᡤ, b ி㒔኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉ᮦᩱᕤᏛᑓᨷ
 Institute of Multidisciplinary Research for Advanced Materials, Tohoku University,bDepartment of Materials Science and Engineering, Kyoto Universitya Y K ྾཰➃㏆ഐࡢ࢚ࢿࣝࢠ࣮㡿ᇦ࡟࠾ࡅࡿ Y ཎᏊᩓ஘ᅉᏊࡢ␗ᖖศᩓຠᯝࢆ฼⏝ࡋࠊࣉࣟࢺࣥ
ఏᑟయ࡛࠶ࡿ Y ࢻ࣮ࣉ BaZrO3 ⣔」ྜ㓟໬≀ࡢ⤖ᬗ᱁Ꮚ୰࡟࠾ࡅࡿࢻ࣮ࣃࣥࢺࡢࢧ࢖ࢺศᕸホ౯ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊBa0.9Zr0.8Y0.2O3-į ࡟ 2 ✀㢮ࡢ࣌ࣟࣈࢫ࢝࢖ࢺ┦ࡀඹᏑࡋ࡚࠸ࡿࡇ࡜ࡀศ࠿ࡗ
ࡓࠋࡑࡢ࠺ࡕࠊࡦ࡜ࡘࡣ Y-poor ⤌ᡂ࡛࠶ࡗ࡚඲࡚ࡢ Y ࡀ Ba ࢧ࢖ࢺ࡟ධࡾࠊࡶ࠺ࡦ࡜ࡘࡣ Y-rich⤌ᡂ࠿ࡘ Y ࡀ Ba ࡜ Zr ୧ࢧ࢖ࢺ࡟ศ㓄ࡉࢀࡿ࡜࠸࠺ࡇ࡜ࡀゎ᫂ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 ࣉࣟࢺࣥఏᑟయࠊࣂ࣒ࣜ࢘ࢪࣝࢥࢿ࣮ࢺࠊ࢖ࢵࢺ࣒ࣜ࢘ࠊࢧ࢖ࢺศ㓄ᛶࠊ␗ᖖศᩓຠᯝ⫼ᬒ࡜◊✲┠ⓗ㸸 ࣌ࣟࣈࢫ࢝࢖ࢺᵓ㐀㻔ABO3㻕ࢆ᭷ࡍࣂ࣒ࣜ࢘ࢪࣝࢥࢿ࣮ࢺ㻔BaZrO3㻕࡟ᕼᅵ㢮ඖ⣲ࢆࢻ࣮ࣉࡍࢀࡤࠊຍ‵㞺ᅖẼୗ࡛ࡣࣉࣟࢺࣥఏᑟᛶࡀⓎ⌧ࡍࡿࠋ≉࡟ࠊ࢖ࢵࢺ࣒ࣜ࢘㻔Y㻕ࢆࢻ࣮ࣉࡍࡿࡇ࡜࡟ࡼࡾࠊ
450oC ࡛ 10-2 Scm-1 ࡢ㧗࠸ࣉࣟࢺࣥఏᑟ⋡ࡀ⏕ࡌࡿ[1]ࡓࡵࠊࣉࣟࢺࣥఏᑟᆺ⇞ᩱ㟁ụࡢ㟁ゎ㉁࡜ࡋ
࡚ᮇᚅࡉࢀ࡚࠸ࡿࠋ୍᪉ࠊ⦓ᐦ࡞ BaZrO3 㟁ゎ㉁ࡢస〇࡟ࡣࠊ1600oC ࡢ㧗 ↝⤖ࡀᚲせ࡛࠶ࡿࠋࡇࡢ㧗 ୗ࡛ࡣࠊ୍㒊ࡢ BaO ࡀ⵨Ⓨࡋ࡚⏕ࡌࡿ Ba Ḟᦆࡀࠊఏᑟ⋡ࡢ㞀ᐖ࡜࡞ࡿᜍࢀࡀ࠶ࡿࠋ
Yamazaki ࡽࡢ◊✲[2]࡟ࡼࡾࠊBa Ḟᦆࡢ⏕ᡂ࡟క࠸ Y ࡢ୍㒊ࡀ Ba ࢧ࢖ࢺ࡟ධࡿࡇ࡜࡛ࠊࣉࣟࢺࣥࡢᑟධ࡟ᚲせ࡞㓟⣲✵Ꮝࡀᾘ㈝ࡉࢀࡿࡇ࡜ࡀఏᑟ⋡పୗࡢཎᅉ࡜⪃࠼ࡓࠋ୍᪉ࠊAzad ࡽ[3]ࡣఏᑟ⋡పୗࡢせᅉ࡜ࡋ࡚ࠊ2 ࡘࡢ࣌ࣟࣈࢫ࢝࢖ࢺ┦࡬ࡢศ㞳࡛࠶ࡿ࡜ᥦၐࡋࡓࠋࡑࡇ࡛ࠊᮏ◊✲࡛ࡣࠊBa Ḟᦆࢆ᭷ࡍヨᩱ㻔Ba0.9Zr0.8Y0.2O3-į㻕ࢆ㧗࢚ࢿࣝࢠ࣮ᨺᑕග࡛ ᐃࡋࠊᅇᢡࣃࢱ࣮ࣥࡢゎᯒ
ࢆ㏻ࡌ࡚ࠊヱᙜヨᩱࡢ⤌⧊ཬࡧࢻ࣮ࣃࣥࢺ࢖࢜ࣥࡢࢧ࢖ࢺศ㓄ᛶࢆ⪃ᐹࡋࡓࠋᐇ㦂㸸 ヨᩱࡣᅛ┦཯ᛂἲ࡟ࡼࡾస〇ࡋࡓࠋBaCO3, ZrO2 ࡜ Y2O3 ࢆฟⓎཎᩱ࡜ࡋ࡚ΰྜࡋࠊ24 ᫬㛫ࡢ࣮࣑࣎ࣝࣜࣥࢢࢆ⾜ࡗࡓᚋࠊ1000oC ࡛ 10 ᫬㛫ࡢ⇕ฎ⌮ࢆ⾜ࡗࡓࠋࡑࡢᚋࠊࡉࡽ࡟ 10 ᫬㛫ࡢ࣮࣑࣎ࣝࣜࣥࢢ࡜ 1300 oC ࡛ 10 ᫬㛫ࡢ⇕ฎ⌮ࢆ⾜ࡗࡓୖ࡛ヨᩱࢆ࣌ࣞࢵࢺ≧࡟ᡂᙧࡋࠊ4 oC/min ࡢ᪼㏿ᗘ࡛↝⤖ ᗘࡢ 1600 oC ࡲ࡛᪼ ࡋࠊ24 ᫬㛫ಖᣢࡋࡓᚋࠊᐊ ࡲ࡛⅔෭ࡋࡓࠋ᭱ᚋ࡟ࠊࡶ࠺୍
ᗘ 1600 oC ࡲ࡛᪼ ࡋࠊ24 ᫬㛫ಖᣢࡋࡓᚋࠊᐊ ࡟ࢡ࢚ࣥࢳࡋࡓࠋࡇࡢヨᩱࢆෆᚄ 0.3mm ࡢࣜࣥࢹ࣐ࣥ࢞ࣛࢫ〇࢟ࣕࣆ࣮ࣛࣜ࡟඘ሸࡋࠊBL19B2 ࡢࣅ࣮࣒ࣛ࢖ࣥ࡟タ⨨ࡉࢀࡓࢹࣂ࢖-ࢩ࢙࣮࣓ࣛ࢝ࣛࢆ฼⏝ࡋࠊ⢊ᮎ X ⥺ᅇᢡࢆ⾜ࡗࡓࠋ ᅗ 1 ࡟♧ࡍࡼ࠺࡟ࠊ␗ᖖศᩓ㡯ࢆ⪃៖ࡋ࡞࠸ሙྜࠊZr㻔IV㻕࡜ Y㻔III㻕㝧࢖࢜ࣥࡢᩓ஘ᅉᏊࡢᕪࡀᑠࡉࡃࠊCuKĮ ➼ࡢ≉ᛶ X ⥺ࢆ⏝࠸ࡓ㏻ᖖࡢ⢊ᮎ X ⥺ᅇᢡ࡛ࡣࠊࡇࢀࡽ㝧࢖࢜ࣥࡢࢧ࢖ࢺศᕸᐃ㔞ࡣᅔ㞴࡛࠶ࡗࡓࠋ୍᪉ࠊᅗ 2 ࠿ࡽศ࠿ࡿࡼ࠺࡟ࠊධᑕ X ⥺࢚ࢿࣝࢠ࣮ࡀ Y K ྾཰➃㏆ഐࡢ㡿ᇦࠊ≉࡟྾཰➃ࡢప࢚ࢿࣝࢠ࣮ഃ࡛ࡣࠊཎᏊᩓ஘ᅉᏊࡢ␗ᖖศᩓ㡯ᐇ㒊 f '㻔E㻕ࡢᕪࡀ኱ࡁࡃ࡞ࡾࠊZr㻔IV㻕࡜ Y㻔III㻕㝧࢖࢜ࣥࢆࡼࡾ᫂☜࡟㆑ู࡛ࡁࡿୖ࡟ࠊZr ࡜ẚ㍑ࡋ࡚ Y ࡢ f '㻔E㻕್ࡢ࢚ࢿࣝࢠ࣮౫
Ꮡኚ໬ࡀ኱ࡁࡃ࡞ࡿࡇ࡜ࢆ฼⏝ࡋ࡚ࠊࡑࢀࡽࡢࢧ࢖ࢺศᕸࢆṇ☜࡟ホ౯࡛ࡁࡿࠋᮏᐇ㦂࡛ࡣࠊヨᩱ࡟ධᑕࡍࡿ X ⥺ࡢ࢚ࢿࣝࢠ࣮ࢆ Y K ྾཰➃ࡼࡾ 25 eV, 139 eV ప࠸ 17.023 keV, 16.898 keV ࡜タᐃࡋࠊ⢊ᮎ X ⥺ᅇᢡࢆ⾜ࡗࡓࠋࡇࢀࡽࡢ X ⥺࢚ࢿࣝࢠ࣮ࡣ NIST ᶆ‽ CeO2 ࢆ⏝࠸࡚ࡑࢀࡒࢀ 17.026keV ࡜ 16.908 keV ࡜ᰯṇࡉࢀࡓࠋᅗ 1㸬Y ࢻ࣮ࣉ BaZrO3 ࡟࠾ࡅࡿྛ
࢖࢜ࣥࡢᩓ஘ᅉᏊ㸦f0㻔sinș/Ȝ㻕㸧ᅗ 2㸬Zr ࡜ Y ࡢཎᏊᩓ஘ᅉᏊࡢ␗ᖖศᩓ㡯ࡢᐇᩘ㒊㸦f’㻔E㻕㸧ཬࡧ⹫ᩘ㒊㸦f’’㻔E㻕㸧⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
ᅗ 3 ࡟♧ࡍࡼ࠺࡟ࠊᅇᢡࣃࢱ࣮ࣥ࡟⌧ࢀࡿྛᅇᢡ⥺ࡢ㧗ゅᗘഃ࡟ࡣࠊᚲࡎࢩࣙࣝࢲ࣮ࡀほ ࡉࢀࡓࠋࡲࡓࠊྠࡌヨᩱ࡟ᑐࡋ࡚ TEM-EDX ᐃࢆ⾜ࡗࡓ⤖ᯝࠊࡇࡢ⢊ᮎヨᩱࡀ Ba0.74Zr0.55Y0.45O3-į࠾ ࡼ ࡧ Ba0.87Zr0.96Y0.04O3-į ࡜ ⤌ ᡂ ࡢ ␗ ࡞ ࡿ ⢏ Ꮚ ࢆ ྵ ࡴ ࡇ ࡜ ࢆ ☜ ㄆ ࡋ ࡓ ࠋ ௨ ୖ ࡢ ⤖ ᯝ ࡼ ࡾ ࠊBa0.9Zr0.8Y0.2O3-į ࡟࠾࠸࡚ࡣ 2 ✀ࡢ␗࡞ࡿ࣌ࣟࣈࢫ࢝࢖ࢺ┦ࡢඹᏑࡀ♧ࡉࢀࡓࠋᅗ 3㸬17.026 keV ࡢධᑕ X ⥺࢚ࢿࣝࢠ࣮࡛ ᐃࡋࡓ Ba0.9Zr0.8Y0.2O3-į ࡢᅇᢡࣃࢱ࣮ࣥ ḟ࡟ࠊBruker AXS 〇ゎᯒࢯࣇࢺ TOPAS ࢆ⏝࠸࡚࣮ࣜࢺ࣋ࣝࢺゎᯒࢆ⾜࠸ࠊ⤌ᡂࡀ␗࡞ࡿࡇࢀ
ࡽ஧✀㢮ࡢ⤖ᬗ┦࡟࠾ࡅࡿ㝧࢖࢜ࣥࡢࢧ࢖ࢺศᕸホ౯ࢆ⾜ࡗࡓࠋධᑕ X ⥺࢚ࢿࣝࢠ࣮17.026 keV࡛ ᐃࡋࡓᅇᢡࣃࢱ࣮ࣥࡢࣇ࢕ࢵࢸ࢕ࣥࢢࣉࣟࣇ࢓࢖ࣝࢆᅗ 4 ࡟♧ࡍࠋࡇࡢሙྜ࡛ࡣࠊRwp ࡀ 7.45%
࡛࠶ࡗࡓࠋࡲࡓࠊ17.026 ࠾ࡼࡧ 16.898 keV ࡟࠾࠸࡚ᚓࡽࢀࡓᅇᢡࣃࢱ࣮ࣥࡢ࣮ࣜࢺ࣋ࣝࢺゎᯒ⤖ᯝࢆ⾲ 1 ࡟ࡲ࡜ࡵࡓࠋᖹᆒ⤌ᡂ Ba0.87Zr0.96Y0.04O3-į ࡢ࣌ࣟࣈࢫ࢝࢖ࢺ┦࡛ࡣࠊY ⤌ᡂࡣᑡ࡞࠸࡞ࡀ
ࡽࠊ඲࡚ࡢ Y ࡀ Ba ࢧ࢖ࢺ࡟ධࡿࡇ࡜ࡀศ࠿ࡗࡓࠋ୍᪉ࠊᖹᆒ⤌ᡂ Ba0.74Zr0.55Y0.45O3-į ࡢ࣌ࣟࣈࢫ࢝࢖ࢺ┦࡛ࡣࠊY ࡣ Ba ࡜ Zr ୧ࢧ࢖ࢺ࡟ศ㓄ࡍࡿࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋ

ᅗ 4㸬௙㎸⤌ᡂ Ba0.9Zr0.8Y0.2O3-į ヨᩱࡢ࣮ࣜࢺ࣋ࣝࢺゎᯒࣉࣟࣇ࢓࢖ࣝ
⾲ 1㸬Y ࡢ K ྾཰➃㏆ഐࡢ࢚ࢿࣝࢠ࣮ࢆ᭷ࡍ X ⥺࡛ ᐃࡋࡓ Ba0.9Zr0.8Y0.2O3-į ᅇᢡࣃࢱ࣮ࣥࡢ࣮ࣜࢺ࣋ࣝࢺゎᯒ⤖ᯝEnergy /keV

Site Occupancy
Rwp

17.026

7.45

16.908

6.98

Phase Composition

A-siteB-siteBaY

Zr

Y

Ba0.87Zr0.96Y0.04O3-į

0.91

0.04

1.00

0.00

Ba0.74Zr0.55Y0.45O3-į

0.80

0.08

0.59

0.41

Ba0.87Zr0.96Y0.04O3-į

0.91

0.04

1.00

0.00

Ba0.74Zr0.55Y0.45O3-į

0.82

0.10

0.61

0.39

௒ᚋࡢㄢ㢟㸸㐣ཤࡢᩥ⊩[4]࡜ࡢᩚྜᛶࢆ⪃࠼ࡿ࡜ࠊBa0.9Zr0.8Y0.2O3-į ࡟࠾࠸࡚஧ࡘࡢ࣌ࣟࣈࢫ࢝࢖ࢺ┦ࡀඹᏑࡋ࡚࠸ࡓࡢࡣࠊ1600oC ࡛ࡢ↝⤖ฎ⌮᫬࡟ࡑࡢ ᗘ࡟࠾ࡅࡿᖹ⾮≧ែ࡜࡞ࡗ࡚࠸࡞࠿ࡗࡓࡇ࡜ࡀཎᅉ࡛࠶ࡿྍ⬟ᛶࡀ࠶ࡿࠋࡇࡢྍ⬟ᛶࢆ⪃ᐹࡍࡿࡓࡵ࡟ࠊ௒ᅇヨᩱࡢ↝⤖ࣉࣟࢭࢫ᮲௳ࢆኚ᭦ࡋࠊணࡵฎ⌮ ᗘ࡛࠶ࡿ 1600oC ࡟ಖᣢࡋ࡚࠾࠸ࡓ㟁Ẽ⅔ෆ࡟ヨᩱࢆᢞධࡋ࡚ 24 ᫬㛫⇕ฎ⌮ࡋࡓᚋࠊᐊ ࡲ࡛ࢡ࢚ࣥࢳࡍࡿࠋࡑ࠺ࡋ࡚ᚓࡽࢀࡓヨᩱ࡟ᑐࡋࠊࡶ࠺୍ᗘᮏᐇ㦂࡜ྠ᮲௳ࡢᨺᑕග฼⏝ X⥺ᅇᢡᐇ㦂ࢆᐇ᪋ࡋࡓ࠸࡜⪃࠼࡚࠸ࡿࠋཧ⪃ᩥ⊩㸸[1] Y. Yamazaki, R. Hernandez-Sanchez, S.M. Haile, Chem. Mater. 21 2755 㻔2009㻕.
[2] Y. Yamazaki, R, Hernandez-Sanchez, S.M. Haile, J. Mater. Chem. 20 8158 㻔2010㻕.
[3] A.K. Azad, C. Savaniu, S. Tao, S. Duval, et al., J. Mater. Chem. 18 3414 㻔2008㻕.
[4] S. Imashuku, T. Uda, Y. Awakura, Electrochem. Solid St. 10 B175 㻔2007㻕.