㧗ഴᩳ  ㍈ࢺࣔࢢࣛࣇ࢕࣮ヨᩱ࣍ࣝࢲ࣮ࡢ㛤ⓎἼከ⫄ࠊගཎᫀᑑࠊụ⏣㈼୍ࠊ୰ᓥⱥ἞㸦஑ᕞ኱Ꮫ࣭⥲⌮ᕤ㸧⏣୰ᑘᕫࠊᮾ⏣㈼஧㸦஑ᕞ኱Ꮫ࣭ᕤ㸧ᐑᓮ⿱ஓ㸦࣓ࣝࣅࣝ㸧 㟁Ꮚ⥺ࢺࣔࢢࣛࣇ࢕࣮ࡢᬑཬ࡜ᢏ⾡㛤Ⓨ࡟క࠸ࠊࡉࡲࡊࡲ࡞⤖ᬗᮦᩱ⤌⧊ࡢ ' ゎᯒࡢヨࡳࡀጞࡲࡗ࡚࠸ࡿࠋᚑ᮶ࡣᅔ㞴࡜ࡉࢀ࡚ࡁࡓᅇᢡࢥࣥࢺࣛࢫࢺ࡟ࡼࡿつ๎᱁Ꮚࢻ࣓࢖ࣥᵓ㐀ࡸ㌿఩ࡢࢺࣔࢢࣛࣇ࢕࣮ほᐹࠊ㟁Ꮚᅇᢡࢺࣔࢢࣛࣇ࢕࣮࡞࡝ࡀࡑࡢ౛࡛࠶ࡿࠋࡇࢀࡽࡢ 'ほᐹ࡛ࡣࠊᅇᢡ᮲௳ࡢ⢭ᐦ࡞ㄪᩚࡀ㔜せ࡛࠶ࡿࠋࡋ࠿ࡋࠊrq௨ୖࡢ㧗ゅᗘഴᩳࢆせࡍࡿࢺࣔࢢࣛࣇ࢕࣮⏝ࡢヨᩱ࣍ࣝࢲ࣮ࡣࠊ ㍈ഴᩳࡶࡋࡃࡣࡑࢀ࡟ヨᩱࢫࢸ࣮ࢪᅇ㌿ᶵ⬟ࡀຍࢃࡗࡓࡶࡢ࡛࠶ࡿࠋࡇࡢሙྜࠊᅇᢡ᮲௳ࡢㄪᩚ⠊ᅖࡣⴭࡋࡃ㝈ᐃࡉࢀࠊ' ほᐹࡢᡂྰࡣⷧ⭷ヨᩱࡢ⤖ᬗ᪉఩࡟ᙉࡃ౫Ꮡࡍࡿࡇ࡜࡟࡞ࡿࠋ
ᡃࠎࡣࠊ⤖ᬗᮦᩱ⤌⧊ࡢ ' ほᐹ࡟฼⏝ྍ⬟࡞㧗ഴᩳ  ㍈ヨᩱ࣍ࣝࢲ࣮ࢆ㛤Ⓨࡋࡓࠋヨᩱ࣍ࣝࢲ࣮ࡢ㛗㍈࡟ᖹ⾜࡞ ; ㍈࡟࠾࠸࡚ࠊỗ⏝ᆺ 7(0㸦)(,7(&1$,*6XSHU7ZLQ㸧࡛rqࡢ
ヨᩱഴᩳࢆ☜ಖࡋࡘࡘࠊヨᩱ୰ᚰ఩⨨࡛ ; ㍈࡜┤⾜ࡍࡿỈᖹ㍈ < ࡜ᆶ┤㍈ = ࡛ࡑࢀࡒࢀrq
ഴᩳ࡜rqᅇ㌿ࢆᐇ⌧ࡋࡓࠋࡇࢀ࡟ࡼࡾࠊ㏻ᖖࡢ  ㍈࣍ࣝࢲ࣮ࡢࡈ࡜ࡃᅇᢡ᮲௳ࡢ⢭ᐦㄪᩚࡀྍ⬟࡜࡞ࡾࠊ㌿఩⤌⧊➼ࢆᗈ࠸ഴᩳゅᗘ⠊ᅖ࡛᫂░࡟ほᐹࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡗࡓࠋ
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㸫㸫

㸫㸫㸫㸫஑ᕞ኱Ꮫ ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊࡢ⤂௓஑ᕞ኱Ꮫ ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊ ኱ᑿᓅྐᯇᮧᬗᏳ⏣࿴ᘯ⏣୰㘝ኈ஑ᕞ኱Ꮫࡢ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊࡣࠊఀ㒔࢟ࣕࣥࣃࢫ࡟  ᖺᗘ࡟᪂ࡋࡃ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ࢆタ⨨ࡋ㛫ࡶ࡞ࡃ  ᖺࢆ㏄࠼ࡲࡍࠋ
㸳ᖺィ⏬࡛ᐇ᪋ࡉࢀ࡚ࡁࡓ௜ᖏタഛࡣࠊ࣓࢜࢞ᆺ㟁Ꮚศග⿦⨨ࠊࢸࣞࣉࣞࢮࣥࢫ㐲㝸᧯స⿦⨨ࠊ࣮ࣞࢨ࣮ࣅ࣮࣒↷ᑕ⿦⨨ࠊࡑࡋ࡚᭱ᚋ࡟ඖ⣲ศᯒࠊ' ࢺࣔࢢࣛࣇ࢕⿦⨨ࡀ௜ຍࡉࢀࡿ
ࡇ࡜࡟ࡼࡾࠊࠕ㸱ḟඖࢼࣀ㉸ᵓ㐀ከඖゎᯒ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ࠖ࡜ࡋ࡚᏶ᡂࡋࡲࡋࡓࠋ
୍᪉ࠊ⟽ᓮ࢟ࣕࣥࣃࢫࡢྛ✀㟁Ꮚ㢧ᚤ㙾ࡢ⛣タ࠿ࡽ㸰ᖺ࡯࡝⤒㐣ࡋࠊఀ㒔࢟ࣕࣥࣃࢫࡢ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊࡣୡ⏺࡟㄂ࢀࡿ㟁Ꮚ㢧ᚤ㙾ඹྠ฼⏝᪋タ࡜࡞ࡾࡲࡋࡓࠋ ᙜ㉸㧗ᅽ㟁㢧ᐊࡣࠊ᭱ඛ➃㢧ᚤ⿦⨨࣭ᢏ⾡ࢆᏛෆࡢᏛ⏕࣭ᩍ⫋ဨ࡟ᥦ౪ࡋࠊ㟁Ꮚ㢧ᚤ㙾࡟ࡼࡿ≀㉁ࡢࢼࣀᵓ㐀ホ౯࡟ᚑ஦࡛ࡁࡿᢏ⾡⪅࣭◊✲⪅ࡢ⫱ᡂ࡟㈨ࡍࡿࡔࡅ࡛ࡣ࡞ࡃ◊✲⏘ᐁᏛࡢ㐃ᦠ࣭༠ຊ࡟ࡼࡿ♫఍㈉⊩ࢆ୰ᮇ┠ᶆ࡜ࡋ࡚ᥖࡆ࡚࠸ࡲࡍࠋ
ࡇࢀࡽࡢ┠ⓗࢆ㐩ࡍࡿࡓࡵ௨ୗࡢࡼ࠺࡞ᯟ⤌ࡳ࡟ࡶཧຍࡋ࡚࠾ࡾࡲࡍࠋ  ᖺᗘ࠿ࡽࢫࢱ࣮ࢺࡋࡓᩥ⛉┬ࡢࠕඛ➃◊✲᪋タඹ⏝࢖ࣀ࣮࣋ࢩࣙࣥ๰ฟ஦ᴗ࡛ࠖጤクࡉࢀࡓ஑ᕞᆅ༊ࢼࣀࢸࢡࣀࣟࢪ࣮ᣐⅬࢿࢵࢺ࣮࣡ࢡࡢ୰ᚰᶵ㛵࡜ࡋ࡚ࡢάືࡍࡿࠋ ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾㐃ᦠࢫࢸ࣮ࢩࣙࣥࢆ❧ࡕୖࡆࠊ㜰኱ࠊ໭኱ࠊྡ኱ࠊ஑኱ࠊ⏕⌮Ꮫ◊✲ᡤ࡟タ⨨ࡉࢀ࡚࠸ࡿィ㸳ᶵࡢ +9(0 ⿦⨨ࢆ඲ᅜࡢ࣮ࣘࢨ࣮࡟ඹྠ฼⏝⿦⨨࡜ࡋ࡚㛤ᨺࡍࡿࠋ ㉸㢧ᚤࣜࢧ࣮ࢳࢥ࢔㸦௦⾲⪅᱓㔝⠊அᩍᤵ㸧ࡢඖࠊ㟁Ꮚ㢧ᚤ㙾ᢏ⾡ࡢ㛤Ⓨ࣭☜❧㛵ࡍࡿ᳨ウࢆ⾜࠺ࠋ
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㸫㸫

㸫㸫஑ᕞᆅ༊ࢼࣀࢸࢡࣀࣟࢪ࣮ᣐⅬࢿࢵࢺ࣮࣡ࢡ
㉸㢧ᚤゎᯒᨭ᥼
஑ᕞ኱Ꮫ  ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊᩥ㒊⛉Ꮫ┬࡛ࡣࠊᖹᡂ  ᖺᗘࡼࡾඛ➃◊✲᪋タ౪⏝࢖ࣀ࣮࣋ࢩࣙࣥ๰ฟ஦ᴗࢆ㛤ጞࡋࡓࠋࡑࢀࢆཷࡅ࡚ࠊబ㈡┴❧஑ᕞࢩࣥࢡࣟࢺࣟࣥග◊✲ࢭࣥࢱ࣮ࠊబ㈡኱Ꮫࢩࣥࢡࣟࢺࣟࣥගᛂ
⏝◊✲ࢭࣥࢱ࣮ࠊ໭஑ᕞ⏘ᴗᏛ⾡᥎㐍ᶵᵓ࡞ࡽࡧ࡟஑ᕞ኱Ꮫ㸦ศᏊ࣭≀㉁ྜᡂゎᯒᨭ᥼࠾ࡼ
ࡧ㉸㢧ᚤゎᯒᨭ᥼㸧ࡀ㐃ᦠࡋ஑ᕞᆅ༊ࢼࣀࢸࢡࣀࣟࢪ࣮ᣐⅬࢿࢵࢺ࣮࣡ࢡࢆᙧᡂࡋࡓࠋᮏ஦
ᴗ࡛ࡣࠊࢼࣀࢸࢡࣀࣟࢪ࣮◊✲࡟࠿࠿ࢃࡿ⏘ᐁᏛ⏺ࡢ◊✲⪅࡟ྛᶵ㛵࡟タ⨨ࡉࢀࡓ⿦⨨⩌ࡢ฼⏝㛤ᨺࢆ⾜ࡗ࡚࠸ࡿࠋ
㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ᐊ࡛ࡣࠊ㏱㐣ᆺ㟁Ꮚ㢧ᚤ㙾ࢆጞࡵ࡜ࡋ࡚ࠊヨᩱస〇ࡸࢹ࣮ࢱࡢྲྀᚓ࠾ࡼ
ࡧゎᯒ⏝ࡢ⿦⨨ࢆ㛤ᨺࡋ㉸㢧ᚤゎᯒᨭ᥼ࢆᐇ᪋ࡋ࡚࠸ࡿࠋࡉࡽ࡟ࠊᮏ஦ᴗࡢᑓ௵ࢫࢱࢵࣇࠊ
Ꮫෆࡢ◊✲⪅࡞ࡽࡧ࡟ᢏ⾡⪅࠿ࡽᵓᡂࡉࢀࡿ࣓ࣥࣂ࣮ࡀࠊᐇ㦂ィ⏬ࡢ⟇ᐃ࠿ࡽྛ⿦⨨ࡢ฼⏝᪉ἲࠊྲྀᚓࢹ࣮ࢱࡢゎᯒホ౯࡟⮳ࡿᨭ᥼ࢆ⾜ࡗ࡚࠸ࡿࠋ
ᙜᶵ㛵࡛ࡣࠊ㏱㐣㟁Ꮚ㢧ᚤ㙾ἲࡢᇶᮏⓗᡭἲ࡟ຍ࠼࡚ࠊ㧗ศゎ⬟ീほᐹࠊ࢚ࢿࣝࢠ࣮ศᩓ
ᆺ㹖⥺ศගศᯒ㸦('6㸧ࠊ㟁Ꮚ࢚ࢿࣝࢠ࣮ᦆኻศගἲ㸦((/6㸧ࠊ཰᮰㟁Ꮚ⥺ᅇᢡἲ㸦&%('㸧ࠊ ḟඖࢺࣔࢢࣛࣇ࢕࣮ࠊࡑࡢሙほᐹᐇ㦂ࡢᨭ᥼ࡢ௚ࠊ㞟᮰࢖࢜ࣥࣅ࣮࣒ヨᩱຍᕤ⿦⨨ࡸ㉸㧗ᅽ㟁Ꮚ㢧ᚤ㙾ࢆ฼⏝ࡋࡓ◊✲ᨭ᥼ࡶ⢭ຊⓗ࡟⾜ࡗ࡚࠸ࡿࠋ
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㸫㸫

㸫㸫㸫㸫

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㸫㸫

㸫㸫㸫㸫㸫㸫㸫㸫ࢩࣥࢡࣟࢺࣟࣥගศᯒࢆ⏝࠸ࡓ᭷⏣↝ࡢⓎⰍ࣓࢝ࢽࢬ࣒ࡢゎ᫂బ㈡┴❔ᴗᢏ⾡ࢭࣥࢱ࣮   ⓑ▼ᩔ๎ ྜྷ⏣⚽἞ ᑎ㷂ಙ ຾ᮌᏹ᫛
᭷⏣↝ࢆࡣࡌࡵ࡜ࡍࡿబ㈡┴㝡☢ჾࡢⓎⰍᢏ⾡ࡣࠊỤᡞ᫬௦ึᮇ࠿ࡽ୰ᮇ࡟⤒㦂๎࡜ࡋ࡚㧗ᗘ࡟☜❧ࡉࢀࡓࠋࡋ࠿ࡋࠊࡇࢀࡽࡢⓎⰍᢏ⾡ࡣ⫋ேࡢヨ⾜㘒ㄗ࡟ࡼࡿ〇㐀ᢏ⾡ࢆᇶ࡟ࡋࡓࡶ
ࡢ࡛࠶ࡾࠊⓎⰍ࣓࢝ࢽࢬ࣒࡟㛵ࡋ࡚ࡣࠊ㧗ᗘ࡞ศᯒᶵჾ࡟ࡼࡿ⛉Ꮫⓗ࡞᳨ドࡣ࡯࡜ࢇ࡝࡞ࡉ
ࢀ࡚࡞ࡃࠊ୙᫂࡞Ⅼࡀከ࠸ࠋ ᮏ◊✲࡛ࡣࠊࢩࣥࢡࣟࢺࣟࣥගࢆ฼⏝ࡋ࡚㝡☢ჾࡢⓎⰍ࣓࢝ࢽࢬ࣒ࡢゎ᫂ࢆ┠ⓗ࡜ࡋ࡚⾜࡞ࡗࡓࠋ
㝡☢ჾࡢ௦⾲ⓗ࡞ⓎⰍᮦ࡛࠶ࡿ㕲ࡣ㔙⸆ࡸୗ⤮௜ࡅࠊୖ⤮௜ࡅࡢⓎⰍᮦ࡜ࡋ࡚ᗈࡃ⏝࠸ࡽࢀࠊຍ⇕᮲௳ࡸ࢞ࢫ㞺ᅖẼ࡞࡝࡟ࡼࡾ㉥ࠊ㯤ࠊ⥳ࠊ㟷ࠊ㯮➼ࡢᵝࠎ࡞Ⰽࢆ♧ࡍࠋ௒ᅇࡣࠊ㟷Ⰽ࠿ࡽ⥳Ⰽࡲ࡛ኚ໬ࡍࡿ㟷☢㔙ࡢⓎⰍᮦ࡛࠶ࡿ㕲ࡢ≧ែࢆࢩࣥࢡࣟࢺࣟࣥග
;$)6 ࡟ࡼࡗ࡚ศᯒࡋࠊⓎⰍኚ໬࡜㕲ࡢ≧ែ㸦㕲࢖࢜ࣥࡢ≧ែ➼㸧ࡢ㛵㐃ᛶࢆㄪ࡭ࠊ㟷☢ࡢ
ⓎⰍ࣓࢝ࢽࢬ࣒ࡢᇶ♏ⓗゎ᫂ࢆヨࡳࡓࠋ
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㸫㸫

⢛᥊䊶⋡⊛
㒻⏛ེ䈱⊒⦡ᛛⴚ䈲䇮⡯ੱ䈱⹜ⴕ㍲⺋䈮䉋䉎⵾ㅧᛛⴚ䉕ၮ䈮䈚䈢䉅䈱䈪䈅䉍䇮㜞ᐲ䈭ಽᨆᯏེ䈮䉋䉎⑼ቇ⊛䈭ᬌ⸽䈲䈅䉁䉍䈭䈘䉏䈩䈇䈭䈇䇯䉲䊮䉪䊨䊃䊨䊮శಽᨆ䉕↪䈇䈢᦭↰὾䈱⊒⦡䊜䉦䊆䉵䊛䈱⸃᣿㒻⏛ེ䈱⊒⦡䉕቟ቯ䈚䈩ౣ⃻䈜䉎䈖䈫䈏น⢻䈫䈭䉎䇯㒻⏛ེ䈱⊒⦡䊜䉦䊆䉵䊛䉕⑼ቇ⊛䈮⸃᣿䈜䉎੐䉕⋡ᜰ䈜䈘䉌䈮䇮ᣂⷙ⊒⦡ᕈ㒻⏛ེ䈱㐿⊒䈮䈧䈭䈕䉎䇯

㕍⏛䈱⊒⦡Ḯ䈪䈅䉎Fe䈱⁁ᘒᄌൻ䉕䉲䊮䉪䊨䊃䊨䊮శ䈪ಽᨆ䈜䉎੐䈮䉋䈦䈩䇮㕍⏛䈱⊒⦡ᯏ᭴䉕⸃᣿䈜䉎䇯⊕⍹ᢕೣ䊶ศ↰⑲ᴦ䊶ኹ㦮 ା䊶ൎᧁብᤘ૒⾐⋵┇ᬺᛛⴚ䉶䊮䉺䊷㒻⏛ེ㉽ਛߩ⊒⦡᧚㧔㋕㧕ߩ⎇ⓥ

XAFSࠪࡦࠢࡠ࠻ࡠࡦశࠍ೑↪ߒߚ⊒⦡ᯏ᭴ߩ⸃᣿

ࠟ࡜ࠬਛߩFeߩ⁁ᘒ㧔ଔᢙߩᄌൻ╬㧕⊒⦡᧚䈫䉧䊤䉴䋨㉽䋩䈱⋧੕૞↪

⎇ⓥౝኈ㽲

⎇ⓥౝኈ㽳

㕍⏛䈲䇮὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈱㆑䈇䈮䉋䈦䈩䇮⊒⦡䈏ᄌൻ䈜䉎䇯㕍⏛䈲䇮ၮ␆㉽䈱⚵ᚑ䈱㆑䈇䈮䉋䈦䈩䇮⊒⦡䈏ᄌൻ䈜䉎䇯

䋨㉄ൻ䋩

䋨ㆶర䋩
ㆶర䉧䉴Ớᐲ

Ớ
䋳䋫

Mg♽㉽

Ba♽㉽

Fe䈱ଔᢙᄌൻ䋿䌤゠㆏䈱ㆫ⒖䈱䉣䊈䊦䉩䊷ᄌൻ䋿

䋲䋫

Fe

Ca♽㉽

㉽ਛ䈱⊒⦡ᚑಽ䈪䈅䉎Fe䈱৻ㇱ䈏䇮ㆶర὾ᚑ䈮䉋䈦䈩䋳ଔ䈎䉌䋲ଔ䈮ᄌൻ䈜䉎䈖䈫䈪䇮㤛⦡䈎䉌㕍䋨✛䋩⦡䈮ᄌൻ䈜䉎䈫䈇䉒䉏䈩䈇䉎䇯㉽⚵ᚑ䈱䉝䊦䉦䊥࿯㘃㊄ዻ䈱ᄌൻ䈮䉋䈦䈩䇮Fe䈱ଔᢙᄌൻ䉇䇮䋳d゠㆏䈱㔚ሶ䈱ㆫ⒖䉣䊈䊦䉩䊷䈱ᄌൻ䈪䇮⊒⦡䈏㤛✛⦡䈎䉌㕍⦡䈮ᄌൻ䈜䉎䋿䋿὾ᚑᤨ䈱ㆶరỚᐲ䈱ᄌൻ䈮䉋䉎Fe䈱⁁ᘒᄌൻ䋨ଔᢙ䋩䉕
XAFS᷹ቯ䈮䉋䈦䈩⺞䈼䉎ၮ␆㉽䈱⚵ᚑ䈱㆑䈇䈮䉋䉎Fe䈱⁁ᘒᄌൻ䋨ଔᢙ䋩䉕XAFS᷹ቯ䈮䉋䈦䈩⺞䈼䉎

ታ㛎ᣇᴺ὾ᚑ᧦ઙ෸䈶㉽⚵ᚑ䈱㆑䈇䈮䉋䉎⊒⦡䈱ᄌൻ⹜㛎↪ၮ␆㉽㉄⚛Ớᐲ⸘ᜰ␜୯

䇼MG䇽

0.3(K2O Na2O) 0.4CaO 0.3MgO

0.5Al2O3 5SiO2

䇼CA䇽

0.3(K2O Na2O) 0.7CaO

0.5Al2O3 5SiO2

䇼BA䇽

0.3(K2O Na2O) 0.7BaO

0.5Al2O3 5SiO2

㶎ฦ㉽⮎䈮䈲Fe2O3䉕䈠䉏䈡䉏䋲wt%ᷝട䇯䉝䊦䉦䊥࿯㘃㊄ዻ䉕ᄌൻ䈘䈞䈩䈇䉎䇯䋨ઁ䈱ൻቇ⚵ᚑ䈲ห䈛䋩
Fe2O3䉕ᷝട䈚䈭䈇㉽䈲䇮䈇䈝䉏䉅ή⦡ㅘ᣿䈭䉧䊤䉴䇯

1%

0%

-0.2%

-0.5%

-1.0%

-2.0%

-3.0%

-4.0%

-5.0%

MG

㉽
⹜
ᢱ

䋳⒳㘃䈱㉽⮎䉕⚛὾䈐㒻᧼䈮䈠䉏䈡䉏ᣉ㉽䈚䇮䈖䉏䉌䉕ㆶర䉧䉴Ớᐲ䉕ᄌൻ䈘䈞䋱䋳䋰䋰͠䈪὾ᚑ䈚䇮⹏ଔ↪⹜ᢱ䉕૞⵾䈚䈢䇯CABA

੹࿁䈲䇮㕍⏛䈱⊒⦡䊜䉦䊆䉵䊛䉕⸃᣿䈜䉎䈢䉄䈮䇮㉄ൻ䃁὾ᚑ᧦ઙ䉇㉽⚵ᚑ䈱⇣䈭䉎ฦ⒳㕍⏛㉽⹜ᢱ䈱⦡Ꮕ᷹ቯㆶర䉧䉴Ớᐲ䈏㜞䈒䈭䉎䈖䈫䈪㤛⦡ĺ㕍⦡䈮ᄌൻ䇯ㆶర䉧䉴Ớᐲ䈏㜞䈇䈾䈬⦡䈱ᓀᐲ䈏㜞䈒䈭䉎䇯
䌍䌧䇮Ca䇮Ba䈫ේሶ䈏ᄢ䈐䈒䈭䉎䈾䈬䇮㤛✛ĺ㕍䈮ᄌൻ䇯䃁⊒⦡Ḯ䈪䈅䉎㕍⏛㉽ਛ䈱㋕䈱⁁ᘒᄌൻ䋨ଔᢙ╬䋩䉕䌘䌁䌆䌓ಽᨆ䈮䉋䈦䈩⸃ᨆ㸫㸫ㆶర

XAFS᷹ቯ⚿ᨐ䋨䋱䋩 ㆶర䉧䉴Ớᐲ䈱ᓇ㗀

XAFS᷹ቯ⚿ᨐ䋨䋱䋩

1.4

2008.8.21

N

R

dE

DW

CA OF 1%

2.9 㫧 0.5

1.88 㫧 0.02

7.3 㫧 2.7

0.07㫧 0.03

CA -0.2%

2.6 㫧 0.3

1.90 㫧 0.01

7.8 㫧 1.9

0.07 㫧 0.02

CA -2%

2.5 㫧 0.4

1.90 㫧 0.01

8.3 㫧 2.3

0.07 㫧 0.02

CA -4%

2.3 㫧 0.3

1.89 㫧 0.01

8.3 㫧 2.4

0.05 㫧 0.03

Normalized absorption

1.2
1
0.8

FeO
(Fe2+)

0.6

CA -0.2%
CA OF 1%
CA -2%

Fe2O3(Fe3+)

0.4
0.2

CA -4%
FeO

0

Fe2O3

-0.2
7100

7110

7120

7130

7140

Energy (eV)䊶὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈏㜞䈇⹜ᢱ䈏䇮Fe䈱XANES(X✢ๆ෼┵᭴ㅧ) 䈱┙䈤਄䈏䉍䈏ૐ䉣䊈䊦䉩䊷஥䈮䉒䈝䈎䈮䉲䊐䊃䈚䈩䈇䉎䇯䊶ઁ䈱䋲⹜ᢱ䋨Mg♽,Ba♽䋩䈪䉅ห䈛௑ะ䈪䈅䈦䈢䇯

EXAFS䈱⸃ᨆ⚿ᨐ䈪䉅䇮὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈏㜞䈇⹜ᢱ䈱ᣇ䈏䇮㓞ធේሶᢙ䋨㉄⚛䈫઒ቯ䈚䈢႐ว䋩䈏ᷫዋ䈜䉎௑ะ䈏䈪䈢䇯䋨Fe2O3ĺ)H2䋩

὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈏㜞䈇⹜ᢱ䋨䉋䉍㕍䈇㉽䋩䈏䇮Fe䈱䋲ଔ䈱⁁ᘒ䈮ㄭ䈒䈭䈦䈩䈇䉎䇯㉽ਛ䈱Fe䈲ㆶర὾ᚑ䈮䉋䈦䈩䇮ଔᢙ䈏ᄌൻ䈚䈩䈇䉎䈫ᕁ䉒䉏䉎䇯䉁䈫䉄

XAFS᷹ቯ⚿ᨐ䋨䋲䋩
1.4ห৻䈱㉽⚵ᚑ䈱႐ว㕍⏛㉽䈲䇮὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈏ᄢ䈐䈒䈭䉎੐䈮䉋䈦䈩䇮⊒⦡䈏㤛⦡㸢㕍䋨✛䋩⦡䈮ᄌൻ䈜䉎䇯
XAFS᷹ቯ䈱⚿ᨐ䈎䉌䇮㕍⏛㉽ਛ䈱Fe䈲䇮὾ᚑᤨ䈱ㆶర䉧䉴Ớᐲ䈏ᄢ䈐䈒䈭䉎੐䈮䉋䈦䈩ଔᢙ䈏䋲ଔ䈎䉌䋳ଔ䈮ᄌൻ䈚䈩䈇䉎䈫ᕁ䉒䉏䉎䇯䈖䉏䈏䇮㕍⏛㉽⊒⦡䈱ᄌൻⷐ࿃䈫ᕁ䉒䉏䉎䇯㕍⏛㉽䋨ၮ␆㉽䋩䈱䉝䊦䉦䊥࿯㘃㊄ዻ䉕ᄌൻ䈘䈞䈢႐วේሶ㊂䈏ᄢ䈐䈒䈭䉎䈮ᓥ䈇䇮⊒⦡䈏㤛✛⦡ĺ㕍✛⦡䈮ᄌൻ䈜䉎䇯
XAFS᷹ቯ䈱⚿ᨐ䈎䉌䇮㕍⏛㉽䈱⊒⦡䈲⊒⦡Ḯ䈪䈅䉎Fe䈱䈢䈣න䈭䉎ଔᢙᄌൻ䈱䉂䈏⊒⦡䉕ᡰ㈩䈚䈩䈇䉎䈱䈪䈲䈭䈒䇮Fe䈱㔚ሶ㈩⟎䈱䇮䈬䈱゠㆏䈱㔚ሶ䈏⒖േ䋨ㆫ⒖䋩䈚䈢䈎╬䈱⁁ᘒ䉕฽䉄䈢ⶄว⊛䈭ⷐ⚛䈮䉋䈦䈩ᄌൻ䈚䈩䈇䉎䈫ᕁ䉒䉏䉎䇯

2008.8.21 data

Normalized absorption

1.2
1
0.8

CA -0.2%

0.6
0.4

MG -0.2%

0.2

BA -0.2%

0
-0.2
7100

7110

7120

7130

7140

Energy (eV)Normalized absorption

1.4

2008.8.21 data

1.2

੹ᓟ䈱⸘↹

1
0.8
0.6

CA -2%⃻Ბ㓏䈪䈲䇮㕍⏛㉽䈱⦡ᄌൻ䈫Fe䈱⁁ᘒᄌൻ䈱㑐ㅪᕈ䉕⷗䈇䈣䈚䈩䈲䈇䈭䈇䇯੹ᓟ䇮὾ᚑᤨ䈱㔓࿐᳇᧦ઙ䉕ᄌൻ䈘䈞䈩૞⵾䈚䈢⹜ᢱ䈱XAFS᷹ቯ䋨エ䌘䈱XAFS᷹ቯ╬䋩䉕➅䉍㄰䈚ⴕ䈇䇮㉽ਛ䈱㋕䈱ଔᢙ䇮㔚ሶ⁁ᘒ╬ᄌൻ䈫㉽䈱⦡ᄌൻ䈱㑐ㅪᕈ䉕⸃᣿䈚䈩䈇䈒䇯䉁䈢䇮㋕㉽䈮㒢䉌䈝㌃㉽╬䈱ઁ⦡㉽䈱⊒⦡ᯏ᭴䉕⸃᣿䈚䈩䈇䈒䇯MG -2%

0.4
0.2

BA -2%
0
-0.2
7100

7110

7120

7130

7140

⻢ㄉ

Energy (eV)䉋䉍㕍⦡䈏ᒝ䈇⹜ᢱ䋨BA㉽䋩䈏䇮Fe䈱XANES䈱┙䈤਄䈏䉍䈏㜞䉣䊈䊦䉩䊷஥䈮䉲䊐䊃䈚䈩䈇䉎䇯䉋䉍㕍⦡䈏ᒝ䈇⹜ᢱ䈱ᣇ䈏Fe䈱ଔᢙ䈏䋳ଔ䈮ㄭ䈒䈭䈦䈩䈇䉎䇯ĺ੍ᗐ䈫ㅒ䈱⚿ᨐ䇯੹࿁䈱⎇ⓥ䉕ㅴ䉄䉎䈮䈅䈢䉍䇮਻Ꮊ䉲䊮䉪䊨䊃䊨䊮శ⎇ⓥ䉶䊮䉺䊷䈱೽ᚲ㐳䈱ᐔ੗᳁䇮䉫䊦䊷䊒㐳䈱ጟፉ᳁䇮⎇ⓥຬ䈱⍹࿾᳁䇮㓈⼱᳁䉕䈲䈛䉄਻Ꮊ䉲䊮䉪䊨䊃䊨䊮శ䉶䊮䉺䊷䈱⡯ຬ䈱ᣇ䇱䈮䈲䇮ᄙᄢ䈭䈗ᜰዉ䇮䈗දജ䉕㗂䈐䉁䈚䈢䇯㸫㸫

Ni induced crystallographic stability of Cu6Sn5 for Pb-free solder
K. Nogita1, S. D. McDonald1, S. Suenaga2, T. Nishimura2,
R. Ohtani3 and K. Sumitani3
The University of Queensland1, Nihon Superior Co. Ltd.2, SAGA Light Source3

Cu6Sn5 is a promising intermetallic compound in structural and functional lead-freesolder joints. Cu6Sn5 has been reported to exist in two crystal structures with an allotropictransformation from monoclinic Ș'-Cu6Sn5 at temperatures lower than 186ºC tohexagonal Ș-Cu6Sn5 at higher temperatures. We recently discovered that the hexagonal
structure of Cu6Sn5 in the presence of trace Ni additions forms (Cu,Ni)6Sn5 which isstable down to room temperature[1]. This report further confirms the phase stabilising
effect of Ni on Cu6Sn5 and the mechanisms of this discovery by synchrotron base powder
X-ray diffraction with Rietveld refinement analysis using Cu6-xNixSn5 (x=0, 0.5, 1, 1.5
and 2) samples with three different thermal annealing conditions.
[1] K. Nogita and T. Nishimura, Scripta Materialia 59 (2008) 191-194.
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㸫㸫

㸫㸫

$J&X ඹ࢖࢜ࣥ஺᥮ἲ࡟࠾ࡅࡿ࣍࢘ࢣ࢖㓟࢞ࣛࢫࡢ╔Ⰽᶵᵓ⚟ᒸ┴ᕤᴗᢏ⾡ࢭࣥࢱ࣮࣭㜰ᮏᑦᏕ㸪㸦ᰴ㸧ࢡࣛ࢖࣑ࣥࢢ࣭℈ᆅಙගᶵ⬟ᛶ࢞ࣛࢫࡢタィࢆ┠ⓗ࡜ࡋ࡚ࠊ࢖࢜ࣥ஺᥮ἲࢆ⏝࠸࢞ࣛࢫᵓ㐀୰࡟஧ࡘࡢ␗࡞ࡿ㔠ᒓ࢖࢜ࣥࢆྠ᫬࡟ᑟධࡋࠊࡑࢀࡒࢀࡢ┦஫స⏝࡟ࡼࡿᙧែኚ໬࡟ࡘ࠸᳨࡚ウࡋࡓࠋᮏ◊✲࡛ࡣ࣍࢘ࢣ࢖㓟࢞ࣛࢫ 3\UH[ ᇶᯈࢆᑐ㇟࡜ࡋࠊ$Jࠊ&Xࠊ࠾ࡼࡧࡑࡢΰྜᮦࢆ⏝࠸࡚࣮࣌ࢫࢺሬᕸЍ⇕ฎ⌮࡟ࡼࡿ✀ࠎࡢ࢖࢜ࣥ஺᥮ࢆ⾜࠸ヨᩱࢆㄪ〇ࡋࡓࠋࡇࢀ࡟ࡘ࠸࡚ࠊ྾ගᗘ
ᐃࠊࢩࣥࢡࣟࢺࣟࣥග࡟ࡼࡿ ;$1(6ᐃࠊ7(0 ほᐹࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊ⇕ฎ⌮᮲௳࡟ࡼࡿᙳ㡪ࡣ࠶ࡿࡶࡢࡢࠊ$J ༢⊂ᑟධࡋࡓሙྜࠊࣉࣛࢬࣔࣥ྾཰
࡟ࡼࡾ㔠ᒓࢥࣟ࢖ࢻ⏕ᡂࡀ☜ㄆࡉࢀࡿࡢ࡟ᑐࡋࠊ&X༢⊂࡛ࡣ୺࡟㸯౯ࡢ࢖࢜ࣥ྾཰ࡀ᳨ฟࡉࢀࠊ&X࢖࢜
ࣥ࡜ࡋ࡚Ꮡᅾࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ$J ࡜&X ࡀΰᅾࡋࡓඹ࢖࢜ࣥ஺᥮ࢆ⾜࠺࡜ࠊ㔠ᒓ $J ࡟ࡼࡿࣉࣛࢬࣔࣥ྾཰㔞ࡀⴭࡋࡃቑ኱ࡋࡓࠋࡇࡢ࡜ࡁࡢ࢞
ࣛࢫ୰ࡢ &X ࡣࠊᅗ࡟♧ࡍࡼ࠺࡟㸰౯࢖࢜ࣥࡀ୺య࡛
࠶ࡾࠊ$J ࡀᑟධࡉࢀࡿࡇ࡜࡛ 5HGR[ ࡀ㉳ࡇࡗ࡚࠸ࡿ
ࡇ࡜ࡀ᫂ࡽ࠿࡜࡞ࡗࡓࠋࡍ࡞ࢃࡕࠊ$J&X ඹ࢖࢜ࣥ஺
᥮ࢆ⾜࠺࡜ࠊ࢞ࣛࢫ୰ࡢ &X ࢖࢜ࣥࡣ㓟໬ࡉࢀ࡚㸰౯࡟࡞ࡿ࡜࡜ࡶ࡟ࠊ$J ࢖࢜ࣥࡢ㑏ඖࡀ㐍ࡴࡓࡵࠊ$J ࢥᅗ Cu ࡢ XANES ࢫ࣌ࢡࢺࣝ
㸦Cu,Cu2O,CuO ࡣᶆ‽ヨ⸆㸧ࣟ࢖ࢻ㔞ࡀቑ኱ࡍࡿࡶࡢ࡜⪃࠼ࡽࢀࡿࠋ
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㸫㸫

㸫㸫㌾ X ⥺ศගࢫ࣌ࢡࢺࣝ

ᐃ⿦⨨⏝⏕యヨᩱᐃࢩࢫࢸ࣒ࡢ㛤Ⓨ࡜⤖ᯝ㏕ᕝ Ὀᖾࠊᯇᑿ ಟྖࠊᰩᓮ ᩄࠊ⬥⏣ ஂఙ㸦⚟ᒸ኱⌮㸧࠙ᗎㄽࠚᡃࠎࡣࠊࡇࢀࡲ࡛࡟኱Ẽᅽୗ࡛ࡶᐃྍ⬟࡞⏕యヨᩱᐃࢩࢫࢸ࣒㸦௨ୗࠊ⁐ᾮࢭࣝࢩࢫࢸ࣒㸧ࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓࠋᮏ◊✲ࡢ┠ⓗࡣࠊ᪂ࡓ࡟㛤Ⓨࡋࡓ⏕యヨᩱࡢ࢖࣓࣮ࢪࣥ
ࢢᐃ࡟ࡶᑐᛂྍ⬟࡞⁐ᾮࢭࣝࢩࢫࢸ࣒࡟ࡼࡿ

ᐃࢆ⾜࠸ࠊᚓࡽࢀࡓ⤖ᯝࢆࡶ࡜࡟ᮏ⿦⨨ࡢᛶ⬟ホ౯ཬࡧሷ໬ࢼࢺ࣒ࣜ࢘Ỉ⁐ᾮ୰ࡢࢼࢺ࣒ࣜ࢘࢖࢜ࣥ࿘ࡾࡢỈ࿴ᵓ㐀࡟ࡘ࠸࡚ DV-XD
ศᏊ㌶㐨ィ⟬ἲࢆ⏝࠸࡚ゎᯒࢆ⾜࠺ࡇ࡜࡛࠶ࡿࠋ
࠙ᐇ㦂ࠚᐃ᪋タ㸸SAGA-LS BL-12 ( ᐃྍ⬟㡿ᇦ㸸⣙ 40 ~ 1500 eV )࣭

ᐃࢩࢫࢸ࣒࣭

ᐃ⿦⨨㸸⏕యヨᩱᐃヨᩱ㸸NaCl ⢊ᮎ࣭Ỉ⁐ᾮ(5.0~1.0mol/l) (Na K-edge)ࠊMgCl2 ⢊ᮎ࣭Ỉ⁐ᾮ (5.0~0.5mol/l) (Mg K-edge)ࠊࣁ࢖ࢻࣟ࢟ࢩ࢔ࣃࢱ࢖ࢺ Ca10(PO4)6(OH)2ࠊ࢘ࢧࢠࡢ㦵(CaLII,III-edge)࠙⤖ᯝ࡜⪃ᐹࠚNaClࠊMgCl2 ࡟ࡘ࠸࡚ᅛయ⢊ᮎ࡜⣙ 5.0~1.0mol/l Ỉ⁐ᾮࡢ Na-KࠊMg-K
XANES ࢫ࣌ࢡࢺࣝ

ᐃࢆ⾜ࡗࡓ⤖ᯝࠊࡑࢀࡒࢀࡢヨᩱࡢᅛయ࡜Ỉ⁐ᾮ࠿ࡽᚓࡽࢀࡿ

XANES ࢫ࣌ࢡࢺࣝࡢ㛫࡟㢧ⴭ࡞㐪࠸ࢆ☜ㄆࡋࡓࠋࡑࡢ⤖ᯝࠊ᪂つࡢ⁐ᾮࢭࣝࢩࢫࢸ࣒࡟࠾
࠸࡚ࠊ⁐ᾮヨᩱ୰ࡢ㍍ඖ⣲ࡢ XANES ࢫ࣌ࢡࢺࣝ

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ᐃࡀ༑ศྍ⬟࡛࠶ࡿࡇ࡜ࡀ☜ㄆࡉࢀࡓࠋ

㸫㸫ᨺᑕග ;$)6ᐃ࡟ࡼࡿ %D7L2 ࢼࣀ⢏Ꮚࡢᐊ⤖ᬗ໬ᣲືゎᯒ㸦⚟ᒸ┴ᕤᢏࢭ㸧‫ྜྷ⸨ۑ‬ᅜᏕ࣭∾㔝᫭ஂ࣭᭷ᮧ㞞ྖ࣭ᒣୗὒᏊ
㸦஑ᕤ኱ᕤ㸧ୗᒸᘯ࿴㸦஑ᕞࢩࣥࢡࣟࢺࣟࣥග◊ࢭ㸧ᒸᓥᩄᾈ
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%D7L2 ࡣ௦⾲ⓗ࡞ㄏ㟁యᮦᩱ࡛࠶ࡿࡀࠊ㏆ᖺᚤ⢏໬ࡀồࡵࡽࢀ࡚࠸ࡿࠋࡇࢀ࡟ᑐࡋᡃࠎࡣࠊ
%D ࡜ 7L ࡢ࢔ࣝࢥ࢟ࢩࢻΰྜ⁐ᾮ࡟ప࡛ỈࢆῧຍࡋࡓᚋࠊΥ⛬ᗘࡢᗘ࡛⇍ᡂฎ⌮ࡍࡿࠊ㧗⃰ᗘࢰࣝࢤࣝἲ࡜࿧ࡤࢀࡿ᪉ἲ࡛ %D7L2 ࢼࣀ⢏Ꮚࢆྵࡴࢤࣝ≧≀ࢆྜᡂࡋ࡚࠸ࡿ  ࠋࡇ
ࡢ %D7L2 ప ⤖ᬗ໬ᣲື࡟ࡘ࠸᳨࡚ウࡍࡿࡓࡵࠊ⤖ᬗ໬๓ DJLQJK ࡢࢤࣝࠊ⤖ᬗ໬ᚋ
DJLQJK ࡢࢤࣝ࡜ࠊᕷ㈍ %D7L2 ⢊ᮎ㸦ሜ໬Ꮫᕤᴗओ〇ࡢ %7㸧࡟ࡘ࠸࡚ࠊ7L. ➃ࡢ
;$1(6 ࡜ %D/Ϫ➃ࡢ (;$)6ᐃࢆᐇ᪋ࡋࢫ࣌ࢡࢺࣝࢆẚ㍑ࡋࡓࠋ࠸ࡎࢀࡢ

ᐃࡶࠊ6$*$/6 ࣅ࣮࣒ࣛ࢖ࣥࢆ౑⏝ࡋ㏱㐣ἲ࡛⾜ࡗࡓࠋ7L. ➃ࡢ ;$1(6 ࢫ࣌ࢡࢺࣝ࡟࠾࠸࡚ࠊ࢚࣮ࢪ
ࣥࢢ Kࡢࢫ࣌ࢡࢺࣝ࡟ࡣࠊH9 ௜㏆࡟ࣉ࢚ࣜࢵࢪࣆ࣮ࢡ࡜ࠊ㹼H9 ࡟ࣈ࣮ࣟࢻ
࡞ࣆ࣮ࢡࡀぢࡽࢀࡓࠋ࢚࣮ࢪࣥࢢ᫬㛫ࡢᘏ㛗࡟క࠸ࠊH9 ௜㏆࡟㗦࠸ࣆ࣮ࢡࡀ⌧ࢀࠊ࢚࣮ࢪࣥࢢ K ࡛ࡣ඲యⓗ࡞࣌ࢡࢺࣝࡢᙧ≧ࡀᕷ㈍ %D7L2 ⢊ᮎࡢࡶࡢ࡜㢮ఝࡋࡓࡶࡢ࡜࡞ࡗ
ࡓࠋ%D/Ϫ➃ࡢ (;$)6 ࢫ࣌ࢡࢺࣝࡶ࢚࣮ࢪࣥࢢ᫬㛫ࡢᘏ㛗࡟క࠸ࠊᕷ㈍ရ %D7L2 ⢊ࡢࢫ࣌ࢡࢺࣝᙧ≧࡟㏆࡙ࡃ஦ࡀ☜ㄆࡉࢀࠊ㧗⃰ᗘࢰࣝࢤࣝἲ࡛ྜᡂࡋࡓ %D7L2 ࡀᕷ㈍ရ࡜ྠᵝࡢࢫ࣌ࢡࢺࣝᙧ≧ࢆ♧ࡍࡇ࡜ࡀุࡗࡓࠋ
࠙ㅰ㎡ࠚᮏ◊✲ࡢ୍㒊ࡣ 1('2 ᢏ⾡㛤Ⓨᶵᵓᖹᡂ  ᖺᗘ⏘ᴗᢏ⾡◊✲ຓᡂ஦ᴗࡢຓᡂࢆཷࡅ
࡚ᐇ᪋ࡋࡓࡶࡢ࡛ࡍࠋ
࠙ཧ⪃ᩥ⊩ࠚ ᱓ཎㄔ಴⏣ዉὠᏊ⥴᪉㐨ᏊᒣୗὒᏊ᭷ᮧ㞞ྖ ࢭ࣑ࣛࢵࢡࢫ
>@  
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㸫㸫

% ࢻ࣮ࣉ㉸ࢼࣀᚤ⤖ᬗࢲ࢖ࣖࣔࣥࢻỈ⣲໬࢔ࣔࣝࣇ࢓ࢫ࣮࢝࣎ࣥ⭷ࡢ๰〇࡜ࡑࡢኴ㝧㟁ụ࡬ࡢᛂ⏝኱᭤᪂▮ ྜྷṊ๛ Ọ㔝ᙲ ཎṊႹ ኱㇂ுኴ ℩ᡞᒣᐶஅ ᑠᯘⱥ୍ Ọᒣ㑥ோ ஑ᕞ኱⥲⌮ᕤ ᭷᫂㧗ᑓ ஑ᕞࢩࣥࢡࣟࢺࣟࣥග◊✲ࢭࣥࢱ࣮ ஑ᕞ኱㝔ᕤࡣࡌࡵ࡟㸸㉸ࢼࣀᚤ⤖ᬗࢲ࢖ࣖࣔࣥࢻ 81&' Ỉ

Temperature (K)
600

500

400

300

QP ௨ୗࡢࢲ࢖ࣖࣔࣥࢻࢼࣀᚤ⤖ᬗࢆỈ⣲໬࢔ࣔࣝࣇ࢓ࢫ࣮࢝࣎ࣥࡀྲྀࡾᅖࡴᵓ㐀ࢆࡶࡘ᪂つᮦᩱ࡛࠶ࡿ㸬81&'D&+ ࡣ࢔ࣔࣝࣇ࢓ࢫ࣮࢝࣎ࣥ࡜ከ
⤖ᬗࢲ࢖ࣖࣔࣥࢻࡢⰋ࠸Ⅼࢆేࡏᣢࡘ≉ᚩࢆ᭷ࡋ࡚࠾ࡾ㸪◳㉁⓶⭷ࡢࡳ࡞ࡽࡎ༙ᑟయ࡜ࡋ࡚ࡶ⯆࿡
῝࠸>@㸬ᡃࠎࡣ௒ᅇ㸪ሗ࿌౛ࡀᩘᑡ࡞࠸ 81&'D

Conductivity (S/cm)⣲໬࢔ࣔࣝࣇ࢓ࢫ࣮࢝࣎ࣥ D&+ ΰ┦⭷ࡣ㸪⢏ᚄ
100‫ غ‬B 13at.%
ٟ B 7at.% B 3at.%ً non–doped&+ ࡢ S ᆺ໬ࢆ࣎ࣟࣥῧຍ࡟ࡼࡾヨࡳ㸪⭷ᵓ㐀ࢆヲ⣽࡟ホ౯ࡋ㸪ኴ㝧㟁ụ࡬ࡢᛂ⏝ࢆ᳨ウࡋࡓ㸬

10

–1

2

ᐇ㦂᪉ἲ࡜⤖ᯝ⪃ᐹ㸸⭷స〇࡟ࡣ࣮ࣞࢨ࣮࢔ࣈࣞ

3

–1

4

1000/T (K )Fig. 1 Change in the electrical conductivityof UNCD/a-C:H films for the Boron content▼ⱥᇶᯈࢆ౑⏝ࡋ㸪Ỉ⣲ᅽ 3D㸪ᇶᯈ ᗘ  in the film.
࣮ࢩࣙࣥἲࢆ⏝࠸ࡓ㸬ᇶᯈ࡟ࡣ &]6L  ᇶᯈ㸪
q& ࡛ᡂ⭷ࡋࡓࢱ࣮ࢤࢵࢺ࡟ࡣ࣎ࣟࣥࡀࢻ࣮ࣉࡉ
ࢀࡓࢢࣛࣇ࢓࢖ࢺࢆ౑⏝ࡋࡓ㸬స〇ࡋࡓ⭷ࡢᵓ㐀ホ౯ࢆ ; ⥺྾཰ᚤ⣽ᵓ㐀 1(;$)6 㸪ග㟁Ꮚศග

ᐃ ;36 㸪⭷୰ࡢ㟁Ẽఏᑟ≉ᛶࡣ 9DQGHU3DXZ ἲ࡟ࡼࡗ࡚ホ౯ࡋ㸪ఏᑟᆺࡣ⇕㉳㟁ຊ࡟ࡼࡗุู࡚ࡋࡓ㸬ᅗ  ࡟࣎ࣟࣥࢻ࣮ࣉ㔞ࡢ␗࡞ࡿ 81&'D&+ ⭷ࡢ㟁Ẽఏᑟᗘࡢ ᗘ౫Ꮡᛶࢆ♧ࡍ㸬ࢻ࣮ࣉ㔞࡟ᛂࡌ࡚ఏᑟᗘࡀቑࡋ㸪࢟ࣕࣜ࢔⃰ᗘไᚚࡀྍ⬟࡛࠶ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓ㸬ఏᑟᗘࡀ 7  ࡟ẚ౛ࡍࡿࡇ࡜࠿ࡽ㸪࢟ࣕࣜ࢔ఏᑟ࡟ࡣ࣍ࢵࣆࣥࢢఏᑟࡀᨭ㓄ⓗ࡜⪃࠼ࡽࢀࡿ㸬ࡑࡢ௚ヲ⣽ࡣⓎ⾲ᙜ᪥ሗ࿌ࡍࡿ㸬>@7<RVKLWDNHHWDO-SQ-$SSO3K\V/  
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1䋮INTRODUCTION

2䋮Experimental⿥䊅䊉ᓸ⚿᥏䉻䉟䊟䊝䊮䊄/᳓⚛ൻ䉝䊝䊦䊐䉜䉴䉦䊷䊗䊮ᷙ⋧⤑䋨UNCD/a-C:H䋩䊧䊷䉱䊷䉝䊑䊧䊷䉲䊢䊮(PLD)ᴺ

Rotate᳓⚛ൻ䉝䊝䊦䊐䉜䉴䉦䊷䊗䊮䈏☸ᓘ10nmએਅ䈱䉻䉟䊟䊝䊮䊄ᓸ⚿᥏䉕ข䉍࿐䉃ᣂ᧚ᢱ䉻䉟䊟䊝䊮䊄⁁὇⚛
DLC (a-C:H)⿥䊅䊉ᓸ⚿᥏
䉻䉟䊟䊝䊮䊄
UNCD

ᄙ⚿᥏䉻䉟䊟䊝䊮䊄

ᒻᘒ

㕖᥏⾰

䊅䊉ᓸ⚿᥏

ᄙ⚿᥏

න⚿᥏

⇣⒳ၮ᧼䈻䈱
ᚑ㐳

䃁ኈᤃ

䂾น⢻

䂦࿎㔍

㬍ᭂ䉄䈩࿎㔍

᷷ᐲ቟ቯᕈ

㬍

䂾

䃁

䃁

䊋䊮䊄䉩䊞䉾䊒

< 5.5 eV

5.5 eV ?

5.5 eV

5.5 eV

⛘✼ᕈ

䂾

䂾

䃁

䃁

⤑䈱ᐔṖᕈ

䃁

䃁

㬍

䃁

ᾲવዉᐲ

㬍

䂾

䃁

䃁

ㅘㆊᕈ

䂾

䂾

䃁

䃁

H2 53.3 Pa

Wavelength : 193nm
Energy: 100mJ
Irradiation area: 2mm2
Repetition Rate: 50Hzන⚿᥏䉻䉟䊟䊝䊮䊄

Target( Graphite )Lens

Excimer Laser (ArF)
1 nm

45 q
Thin film
Substrate㔚ሶ✢࿁᛬䊌䉺䊷䊮䈫䉻䉟䊟䊝䊮䊄111䊥䊮䉫䈱৻ㇱ䈱࿁᛬శ䉕↪䈇䈢ᥧⷞ㊁TEM௝UNCD/a-C:H㜞ಽ⸃⢻TEM௝

T. Hara et.al Diamond Relat. Mater.15(2006)649

䉝䊝䊦䊐䉜䉴䉦䊷䊗䊮

UNCD/a-C:H

NCDᄙ⚿᥏䊶න⚿᥏䉻䉟䊟䊶 ᚑ⤑䈏ኈᤃ
䊶 B䊄䊷䊒䈪pဳൻ䊶 N䊄䊷䊒䈪nဳൻ
䊶 variable Eg䊶 ⤑⴫㕙䈏ᭂ䉄䈩Ṗ䉌䈎䊶 ᚑ⤑䈏ኈᤃ䊶 ᭂ䉄䈩ᄢᄢ䈐䈭 ๆ෼ଥᢙ䊶 ⤑⴫㕙䈏ᭂ䉄䈩Ṗ䉌䈎䊶 N䊄䊷䊒䈪nဳൻ䋧䉨䊞䊥䉝Ớᐲ೙ᓮ

䊶 B䊄䊷䊒䈪p
ဳൻ䋧䉨䊞
䊥䉝Ớᐲ೙
ᓮ
䊶 N䊄䊷䊒䈪n
ဳൻ䋧䉨䊞
䊥䉝Ớᐲ೙
ᓮ

䊶 ⓥᭂ䈱䊪䉟䊄䉩䊞䉾䊒ඨዉ૕䊶B䊄䊷䊒䈪pဳൻ䋧䉨䊞䊥䉝Ớᐲ೙ᓮવዉဳ೙ᓮ䋧䉨䊞䊥䉝Ớᐲ೙ᓮ䈏䈪䈐䉏䈳䋬ᄢ䈐䈭ๆ෼ଥᢙ䉕᦭䈜䉎ᣂⷙ䉝䊝䊦䊐䉜䉴♽ඨዉ૕᧚ᢱ
䈫䈚䈩⥝๧ᷓ䈇䋮䊶 䊐䉜䉶䉾䊃䋧☸⇇䊶 ๆ෼ଥᢙ䈏ዊ䈘䈇䊶䊓䊁䊨ᚑ㐳䈏࿎㔍
䊶Nဳൻ䈏࿎㔍

UNCD/a-C:H䈱B䊄䊷䊒䈮䉋䉎pဳൻ䈫ᄥ㓁㔚ᳰᔕ↪䈻䈱น⢻ᕈ䉕ត䉎?

䊶 䉨䊞䊥䉝Ớᐲ䈱೙ᓮ䈏䈪䈐䈭䈇䋨⛘✼ᕈ䋩䊶 ૐ䈇᷷ᐲ቟ቯᕈ

᭴ㅧ⹏ଔ
X✢ๆ෼ᓸ⚦᭴ㅧ(NEXAFS)SAGA-LS BL12శ㔚ሶಽశ᷹ቯ(XPS)䊧䊷䉱䊷䊤䊙䊮ಽశశᐲ⸘
䊐䊷䊥䉣ᄌ឵⿒ᄖಽశశᐲ⸘(FTIR)㔚᳇વዉ․ᕈ
Van der Pauwᴺ
વዉဳ್೎
ᾲ⿠㔚ജᴺ

⋡⊛

Base vacuum < 10-4 Pa

Substrate temperature
550 qC

TargetSubstrate

Graphite

QuartzBoron-doped Graphiten-Si(100)

ᧂ⍮䈱‛ᕈ

C1s

B/C ratio

O1s
Boron contents in films (at. %)10O(Auger)
B1s

800

HOPG 45°

600

400

200

QRQ±GRSHG

5

0
0

0

5
10
15
Boron contents in targets (at. %)Binding energy (eV)⤑ਛ䈻䈱B䊄䊷䊒㊂䈏㗼⪺䈮ჇടB/C 䋽

81&'D±&+Intensity (arb.unit)20

1kV 0.2min.

280
B (10at.%) doped

B䊄䊷䊒UNCD/a-C:H

Barea/BP + Carea/CPɽB䈮⿠࿃䈜䉎䊏䊷䉪䈏287.5eVઃㄭ䈮಴⃻280䉺䊷䉭䉾䊃䊷⤑㑆䈪⚂30%䊨䉴

290

540

Conductivity[S/cm]

0

Temperature (K)
300

±

±

n-Si(100)ၮ᧼਄䈮䊓䊁䊨ᚑ㐳䈚䈢p-UNCD⤑䈱I-V․ᕈ
±

3

p-UNCD
4

5

10- in the dark±

0.0003

٨ B 13at.% doped
ٌ B 7at.% doped‫ ع‬B 3at.% doped‫غ‬QRQ±GRSHG

n-Si(100)- under illumination
0.0002

Al electrode0.0001

0.22
0.24
1/4
±
(1/T) (K )10of D(BD_004_b)
vs. hQ
Plot ofPlot
D vs.hQ

7

10

0
±

±

0
Voltage (V)

1

6

10

䊗䊨䊮䊄䊷䊒㊂䉕਄᣹‫ غ‬B 13at.%
ٟ B 7at.%3䌾6eV䈮䈍䈇䈩ๆ෼ଥᢙ106(cm-1)

1010⤑ਛ䈱㔚᳇વዉᐲ䈏਄᣹

±
3

10

±

2

5

10

4

 B 3at.%ً undoped10⺞ᩏਛ

Pd electrodeactivationenergy95meV=100m(eV)1000/T

0.2

ʋ*C C䈱৻ㇱ䈏ʍ*CB䈮⟎឵?

-1Conductivity (S/cm)

0330

6䋮Hetero Junction

Temperature [K]
340
240

2

±

320

0

Current (A)

400

±

500

lnǻ(ohm cm )

600

10

440

310

Photon energy (eV)

0

10

300

D [cm ]

600
400
200
Binging energy (eV)5䋮Conductivity measurement

10

ʋ*C C䈏non-dope UNCD䈮Ყ䈼䈩ዊ䈘䈇

SR

Current (A)

800

330

ʍ*CC 䈏 ʍ*CH, ʋ*C{C 䈫Ყ䈼䈩ᄢ䈐䈇

B (20at.%) doped

1kV 5.0min.

1000

300
310
320
Photon energy (eV)UNCD/a-C:H䈱․ᓽ

Barea/BP

1kV 1.5min.

O1s 䈲⤑⴫㕙䈱ਇ⚐‛290[S. Ohmagari, T. Yoshitake, A. Nagano, S. AL-Riyami, R. Ohtani, H. Setoyama,
E. Kobayashi, and K. Nagayama, Jornal of Nanomaterials, article in press]

1kV 0.5min.

1kV 2.5min.

81&'D±&+B (5at.%) doped

287.5

Barea, Carea : Total area of Boron and Carbon
BP, CP : Photoionization energy ( MgKɲ line )O1s 䈲Ar+䉴䊌䉾䉺䈪ᶖṌ

QRQ±VSW

Intensity (arb.unit)

Intensity (arb.unit)± B 20at.% target± B 10at.% target± B 5at.% target

Intensity (arb.unit)

(a)

1000

ʍ*

ǻ*C=C

ʋ*
15

ǻ*C҂C

4䋮Near-edge X-ray absorption Fine Structure
Ǹ*C=C
ǻ*CH
Ǹ*C҂C
ǻ*&±&

3䋮X-ray photoemission spectroscopy3±

1000/T (K )4±䉨䊞䊥䉝Ớᐲ೙ᓮ䈏น⢻䉨䊞䊥䉝વዉ䈮䈲䊖䉾䊏䊮䉫વዉ䈏ᡰ㈩⊛㸫㸫

0Voltage (V)

1

1

2

3
4
5
Photon energy [eV]6

7

T. Yoshitake et al. Jpn. J. Appl. Phys. 46, L936 (2007)

UNCD⭯⤑䈲ᄥ㓁㔚ᳰ䈱⍴ᵄ㐳஥䈱ๆ෼ጀ䈫䈚䈩᦭ᦸྠ㍈ᆺ䜰䞊䜽䝥䝷䝈䝬䜺䞁䛻䜘䜛㉸䝘䝜ᚤ⤖ᬗ䝎䜲䝲䝰䞁䝗/Ỉ⣲໬䜰䝰䝹䝣䜯䝇䜹䞊䝪䞁⭷䛾๰〇䛸䛭䛾ᙧᡂᶵᵓⰼ⏣㈼ᚿ 1䠈୰ᕝ ඃ 1䠈すᒣ㈗ྐ 2䠈ྜྷ⏣ᬛ༤ 1䠈ྜྷṊ ๛ 1䠈኱㇂ுኴ 3䠈㝮㇂࿴Ⴙ 3䠈ᒸᓥᩄᾈ 3䠈℩ᡞᒣᐶஅ 3䠈ᑠᯘⱥ୍ 3䠈Ọᒣ㑥ோ 21஑኱㝔⥲⌮ᕤ䠈2 ஑኱㝔ᕤ䠈3 ஑ᕞ䝅䞁䜽䝻䝖䝻䞁ග◊✲䝉䞁䝍䞊ྠ㍈ᆺ䜰䞊䜽䝥䝷䝈䝬䜺䞁䜢⏝䛔䛯䜰䞊䜽䝥䝷䝈䝬ἲ䛻䞁 (UNCD/a-C) ⭷䛾๰〇䜢ヨ䜏䛯䠊䜎䛯䠈䛭䛾ᙧᡂᶵᵓ䛻㛵䛧䛶⪃ᐹ䜢⾜䛳䛯䠊స〇䛧䛯⭷䛾ᵓ㐀ホ౯䛿䠈䝅䞁䜽䝻䝖䝻䞁ග (஑ᕞ䝅䞁䜽䝻䝖䝻䞁ග◊✲䝉䞁䝍䞊BL12, 15)䜢⏝䛔䛯⢊ᮎ X ⥺ᅇᢡ (XRD)䠈ග㟁Ꮚศග (XPS) 䛻䜘䜚⾜䛳䛯䠊స〇䛧䛯⭷䛾 X ⥺ᅇᢡ䝟䝍䞊䞁䜢 Figure 1 䛻♧䛩䠊Diamond-111, 220 ᅇᢡ䝸䞁䜾䛜ほ 䛥䜜䠈స〇䛧䛯

Intensity (arb. unit)䜘䜚㉸䝘䝜ᚤ⤖ᬗ䝎䜲䝲䝰䞁䝗/Ỉ⣲໬䜰䝰䝹䝣䜯䝇䜹䞊䝪

1
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1
1
1
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D

30

40

0
2
2
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D

0
2
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ai
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⭷୰䛻 UNCD ⤖ᬗ䛜⏕ᡂ䛧䛶䛔䜛䛣䛸䛜ศ䛛䜛䠊ᅇᢡ䝢䞊䜽䛾್༙ᖜ䛛䜙 UNCD ⤖ᬗ䛾⢏ᚄ䛿⣙ 2 nm 䛸ぢ✚䜒䜙䜜䛯䠊䜎䛯䠈〇⭷୰䛻Ⓨ⏕䛩䜛䝥䝷䝈䝬䝥䝹䞊䝮䜢ほ䛧䠈UNCD ᙧᡂᶵᵓ䛻㛵䛧䛶⪃ᐹ䜢⾜䛳䛯䠊䛭䛾௚䛾⤖ᯝ䛸⪃ᐹ䛿Ⓨ⾲ᙜ᪥䛻ሗ࿌䛩䜛䠊

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0

10

20

50

60

70

2ǰ (deg)

Figure 1 : X-ray diffraction pattern ofthe deposited film, which was measured
with 12-keV synchrotron radiation. The
inset shows Debye-Scherrer rings takenwith an imaging plate.

㸫㸫Near-Edge X-ray Absorption Fine-Structure and X-ray Photoemission
Spectroscopies of Nitrogen-doped Ultrananocrystalline
Diamond/Hydrogenated Amorphous Carbon Films
S. Al-Riyami, S. Ohmagari, T. Yoshitake, R. Ohtani1, H. Setoyama1, E. Kobayashi1,and K. Nagayama
Kyushu University, 1SAGA-LS
Nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenated amorphous carbon (a-C:H)
composite films were deposited on Si substrates at a substrate temperature of 550 qC by pulsed laser
deposition using a graphite target. The ambient pressure was fixed to be 53.3 Pa and the nitrogenationof the films was controlled by the inflow ratio between the hydrogen and nitrogen gases. The
chemical bonding structure was studied by near-edge X-ray absorption fine-structure (NEXAFS) and
X-ray photoemission spectroscopy (XPS). The sp3/(sp3+sp2) ratio of the 9.7 at.% nitrogen-doped films
was estimated to be 59 % from the peak decomposition of the XPS spectrum as shown in Fig. 1. The
full-width at half-maximum of the sp3 peak was 0.9 eV. This small value is specific to UNCD/a-C:H
films.(1) The NEXAFS spectra showed that the S* peaks shift toward higher energies with the increasein the nitrogen content. Further details will be shown in the presentation.
3

sp = 59 %N 9.7 at. %FWHM = 0.9 eVIntensity (arb.unit)

Intensity (arb.unit)

N 6.4 at. %
3

sp

sp

C–O /C–N

2

C=O

N 4.8 at. %N 1.5 at. %non doped UNCD

HOPG angle 45'

292

290

288

286

284

282

280

280

290

300

310

320

330

Binding energy (eV)Binding energy (eV)Fig. 1 Typical XPS Spectrum of nitrogen-doped films.
films

Fig. 2 NEXAFS spectra of nitrogen-doped UNCD/a-C:H(1) T. Yoshitake, A. Nagano, S. Ohmagari, M. Itakura, N. Kuwano, R. Ohtani, H. Setoyama, E. Kobayashi, and K. Nagayama: Jpn. J.
Appl. Phys. 48 (2009) 020222.

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Experimental

RotatePulsed Laser Deposition (PLD)
Wavelength : 193nm
Energy: 100mJ
Irradiation area: 2mm2
Repetition Rate: 50Hz

Background and Aim
It has been known that nitrogen-doping for diamond is ineffective for realizing n-typeconduction because nitrogen in diamond forms a deep donor level. For amorphous
carbon, the electrical conductivity is difficult to be controlled although the n-typeconduction is realized, by the nitrogen-doping. On the other hand, it has recently beenreported that nitrogen-doped ultrananocrystalline diamond (UNCD)/hydrogenatedamorphous carbon (a-C:H) composite films possess n-type conduction with highelectrical conductivities [1]. The nitrogen-doping effects on UNCD/a-C:H , which areapparently different from those on diamond and amorphous carbon, are of interest fromphysical viewpoint. In this study, the chemical bonding structures of nitrogen-doped
UNCD/a-C:H films were investigated by near-edge X-ray absorption fine-structure(NEXAFS) and X-ray photoemission spectroscopy (XPS).

N2+H2 53.3 Pa
Target( Graphite )Lens

Excimer Laser (ArF)

45 q
Thin film
Substrate
Base vacuum < 10-4 Pa

Structural evaluation
NEXAFS
SAGA-LS BL12
XPS and SR-PES
Raman spectroscopy
FTIR
Electrical conductivity
Van der Pauw method

XPS C1s survey spectrum of non doped UNCD and nitrogen ±doped UNCD

Substrate temperature 550 qC

Substrate
Targetn-Si(100)

NEXAFS spectra of nitrogen-doped UNCD/a-C:H films

C1s

C1s

V*

S*

N 9.7 at.%

NEXAFS spectrum :¾ The S* peak was broadened with
the nitrogen content.
¾ The V*C
C peak was broadenedwith the nitrogen content. Thismight be due to the overlapping of
V*C
N peak whose position isextremely close to that of V*C
C peak.

O1s
N 6.4 at.%

N1s

N 4.8 at.%Intensity (arb.unit)

Intensity [arb.unit]

QuartzGraphitenon doped UNCD

N 1.5 at.%non doped UNCD

N 1.5 at.%

N 4.8 at.%
N 6.8 at.%

HOPG (45' )N 9.7 at. %600
Binding energy (eV)

200

280

290

Typical XPS C1s Spectrum of nitrogen-doped films

2&±2&±1

290

288
286 284
Binding energy (eV)

sp

282

N 6.4 at. %3

sp = 61.3 %FWHM =0.9 eVIntensity (arb.unit)

Intensity (arb.unit)

292

3

sp

280292320

330

N 4.8 at. %3

N 1.5 at. %sp = 62.3 %FWHM =0.91eV3

sp&±2&±1

290

310

Typical XPS C1s Spectrum of nitrogen-doped films

288
286
284
Binding energy (eV)

2

sp

282

Intensity (arb.unit)

N 9.7 at. %3

sp = 59 %FWHM =0.9 eV

300

Binding energy (eV)&±2&±1

292

290

3

sp = 65 %FWHM = 0.9 eV

3

sp

2

sp

Intensity (arb.unit)

1000

3

sp

2

sp
&±2&±1280

㸫㸫

288 286 284
Binding energy (eV)282

280 292290

288 286 284 282
Binding energy (eV)280

Estimation of sp2 and sp3 value by NEXAFS or XPS

Summary :1. From the decomposition of the XPS spectrum:sp 2 %The sample

sp3 %Nitrogen at. %NEXAFS

XPS

XPS

9.7

53

41

59

6.4

51.3

38.7

61.3

4.8

51

37.7

62.3

1.5

46

35

65

0

58

32

68

¾ The sp3/ (sp3+sp2) value of the non-doped films was estimated to be 68 %[2].
¾ It gradually decreased with the nitrogen content in the films.
¾ The full-width at half-maximum of the sp3 peak was 0.9 eV. The small value isspecific to UNCD/a-C:H films [3].
2. From the NEXAFS spectrum :¾ The S* peak was broadened with the nitrogen content.
¾ The V*CC peak was broadened with the nitrogen content. This might be due tothe overlapping of V*CN peak whose position is extremely close to that of
V*CC peak.

References:[1] S. Bhattacharyya, O. Auciello, J. Birrell, J. A. Carlisle, L. A Curtiss, A. N.Goyette, D. M.
Gruen, A. R. Krauss, J. Schulueter, A. Sumant, and P. Zapol, Appl.Phys. Lett. 79, 1441(2001).
[2] T. Yoshitake, A. Nagano, M. Itakura, N. Kuwano, T. Hara, and K. Nagayama: Jpn. J. Appl.
Phys. 46 (2007) L936.
[3] T. Yoshitake, A. Nagano, S. Ohmagari, M. Itakura, N. Kuwano, R. Ohtani, H. Setoyama, E.
Kobayashi, and K. Nagayama: Jpn. J. Appl. Phys. 48 (2009) 020222.

sp2 values were increased with increasing nitrogen contents㸫㸫

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ෆࡢCa࢖࢜ࣥ࡜㔠ᒓ࢖࢜ࣥࡢ⨨᥮ࡸࠊ࢔ࣃࢱ࢖ࢺࡢ⁐ゎ࡟ࡼࡗ࡚౪⤥ࡉࢀࡿࣜࣥ㓟࡟ࡼࡗ࡚㔠ᒓ࢖࢜ࣥࡀ㞴⁐ゎᛶࡢᒙ࡬࡜ྲྀࡾ㎸ࡲࢀࡿࡓࡵ㉳ࡇࡿࠋᮏ◊✲࡛ࡣ࢔ࣃࢱ࢖ࢺ̾Pb㛫┦஫స⏝࡟ࡼࡿ཯ᛂ⏺㠃㏆ഐࡢࢼࣀࢫࢣ࣮ࣝ⌧㇟ࢆゎ᫂ࡍࡿࡓࡵࠊpH = 5.0ࠊᐊࠊ◪㓟㖄⁐ᾮ୰㸦2 mM㸧࡛ྜᡂ⢊ᮎHAP ࡜༢⤖ᬗࡢኳ↛ࣇࣝ࢜ࣟ࢔ࣃࢱ࢖ࢺ
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ࢀࡿࡇ࡜ࡀ᫂ࡽ࠿࡟࡞ࡗࡓࠋࡲࡓࠊࡑࡢᒙ࡟࠾࠸࡚Ca̾Pb࢖࢜ࣥ஺᥮ᶵᵓࡀ㉳ࡇࡗ࡚࠸࡞࠿
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(Pb5(PO4)3OH, HPY)࡛࠶ࡿ࡜ྠᐃࡉࢀࡓࠋࡇࡢHPY࡟ࡣ␗࡞ࡿ㸰ࡘࡢ⏕ᡂ࣓࢝ࢽࢬ࣒ࡀࡳ
ࡽࢀࡓࠋ୍ࡘࡣࠊHAPࡢ⁐ゎ࡟ࡼࡗ࡚཯ᛂ⁐ᾮ඲యࡀHPY࡟ᑐࡋ࡚㣬࿴≧ែ࡟࡞ࡗࡓࡓࡵ
HAPୖ࡟HPYࡀ⏕ᡂࡍࡿ࣓࢝ࢽࢬ࣒ࠊࡶ࠺୍ࡘࡣࠊHAP ࡢ⾲㠃࡛HAPࡢ⁐ゎࡢᚋ༶ᗙ࡟
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