2009B1802                        BL17SUPEEM ἲ࡟ࡼࡿ㟁ụ㟁ᴟᮦᩱࡢ⾲㠃ศᯒ᪉ἲ᳨ウ㻔2㻕
Characterization of Carbon Anode Materials by PEEMᅵ஭ ᩍྐ a, すཎ ඞᾈ a, ᒣᮏ ᾈྖ a, ᑠႹ ┿ே b, ኱Ἑෆ ᣅ㞝 b
Takashi Doia, Katsuhiro Nishiharaa, Hiroshi Yamamotoa, Masato Kotsugib, Takuo Ohkochibaఫ཭㔠ᒓᕤᴗ㻔ᰴ㻕, b㻌㻔㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮ a SUMITOMO METAL INDUSTRIES, LTD., b JASRI
ࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡢ㈇ᴟᮦᩱ࡜ࡋ࡚౑⏝ࡉࢀࡿࢢࣛࣇ࢓࢖ࢺ⢊ᮎ࡟࠾࠸࡚㸪㟁ụࡢࢥࢫࢺపῶ㸪ᑑ࿨㸪ಙ㢗ᛶྥୖࡢࡓࡵ࡟㸪ᮦᩱ⾲㠃ࡢᶵ⬟໬㸪〇㐀᮲௳ࡢ᭱㐺໬ࢆ┠ᣦࡋࡓ◊✲ࡀᐇ᪋ࡉࢀ࡚࠸ࡿ㸬ࡋ࠿ࡋ㸪㈇ᴟᮦ⾲㠃ࡢศᯒᡭἲࡣ㝈ࡽࢀ࡚࠾ࡾ㸪㛤Ⓨࡢ᪉ྥᛶࢆࡘ࠿ࡳ࡟ࡃ࠸㸬ᡃࠎࡣ㸪ᒁᡤ⾲㠃ศᯒࢆᐇ᪋࡛ࡁࡿᡭἲ࡜ࡋ࡚ග㟁Ꮚ㢧ᚤ㙾㻔PEEM㻕ἲ࡟╔┠ࡋ㸪BL17SU ࡟࠾࠸࡚㸪
PEEM ἲ࡟ࡼࡿᒁᡤ C K ྾཰➃ᚤ⣽ᵓ㐀ホ౯ࡢ᭷ຠᛶࢆ᳨ウࡋࡓ㸬࣮࣮࢟࣡ࢻ㸸 PEEM㸪Li ࢖࢜ࣥ㟁ụ㸪㈇ᴟᮦᩱ㸪XANES⫼ᬒ࡜◊✲┠ⓗ㸸⎔ቃព㆑ࡢ㧗ࡲࡾ࠿ࡽ㸪㟁Ẽ⮬ື㌴⏝㏵࡞࡝࡬ࡢࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡢᒎ㛤ࡀᛴ㏿࡟⾜ࢃࢀ࡚࠸ࡿ㸬ࡑࡢࣜࢳ࣒࢘࢖࢜ࣥ㟁ụࡢ㈇ᴟᮦᩱ࡟ࡣ㸪୺࡟ࢢࣛࣇ࢓࢖ࢺ⣔⢊ᮎࡀ౑⏝ࡉࢀ࡚࠸ࡿ㸬㧗⪏ஂᛶ㸪㧗ᐜ㔞໬ࡀせồࡉࢀࡿ㒊ᮦ࡛࠶ࡿࡀ㸪⪏ஂᛶࡣ㈇ᴟᮦࡑࡢࡶࡢ࡜ࡋ࡚ࡔࡅ࡛ࡣ࡞ࡃ㸪᥋ࡍࡿ㟁ゎᾮࡢຎ໬ࢆᢚไࡍࡿࡇ࡜ࡶ㔜どࡉࢀࡿࡇ࡜࠿ࡽ㸪㈇ᴟᮦᩱ⾲㠃࡛ࡢ඘ᨺ㟁࡟࡜ࡶ࡞࠺㟁Ẽ໬Ꮫⓗ≉ᛶࡣ㔜せ࡛࠶ࡿ㸬㈇ᴟᮦ⾲㠃ࡣ㸪㟁ụࡢ඘ᨺ㟁࡟క࠸⏕ᡂࡍࡿ SEI[1]㻔Solid Electrolyte Interface㻕࡟ࡼࡾ୙ྍ㑊ⓗ࡟そࢃࢀࡿ㸬ࡇࡢ SEI ࡣ㸬㟁ᴟᮦᩱ⾲㠃࡟Ꮡᅾࡋ㸪ࣜࢳ࣒࢘࢖࢜ࣥࡢฟධࡾཱྀ࡜࡞ࡿ࡜࡜ࡶ࡟㸪㟁ゎᾮࡢศゎ཯ᛂࡢᢚไ࡟ࡶຠᯝࢆⓎ᥹ࡍࡿ࡞࡝㸪㟁ụࡢ඘ᨺ㟁≉ᛶ㸪⪏ஂᛶ࡟኱ࡁࡃᙳ㡪ࡍࡿ㸬୍᪉㸪SEI ࡣ㟁ゎᾮࡢ㑏ඖศゎ཯ᛂ࡟ࡼࡿ⏕ᡂ≀࡛࠶ࡿࡇ࡜࠿ࡽ㸪㐣๫࡞⏕ᡂ࡟࡜ࡶ࡞࠺㟁Ⲵࡢ
ᾉ㈝ࡣ୙ྍ㏫ᐜ㔞ࡢቑຍ࡜ࡶ࡞ࡿ㸬ࡼࡗ࡚㸪ࢢࣛࣇ࢓࢖ࢺ⣔㈇ᴟᮦᩱ࡜ࡋ࡚ࡣ㸪ࡑࡢ SEI ࡢᶵ⬟ྥୖ㸪⏕ᡂࡢไᚚࡀ㟁ụᛶ⬟ࡢྥୖ࡟ࡣ㔜せ࡜࡞ࡿ㸬SEI ࡢᶵ⬟㸪⏕ᡂࡢไᚚࢆ┠ᣦࡋ㸪ࢢࣛࣇ࢓࢖ࢺ⢊ᮎ࡟ᑐࡋ࡚✀ࠎࡢ⾲㠃ฎ⌮᪉ἲࡀ᳨ウࡉࢀ࡚࠸ࡿ㸬ࡋ࠿ࡋ࡞ࡀࡽ㸪⾲㠃ฎ⌮๣࡛࠶ࡿⅣ⣲ࡢศᕸ≧ἣ࡞࡝㈇ᴟᮦ⾲㠃ࡢᛶ≧࡜㟁ụ≉ᛶ࡜ࡢᑐᛂ࡞࡝⢭ᐦ࡞᳨ウࡣᅔ㞴࡞≧ἣ࡛࠶ࡗࡓ㸬⏬ᮇⓗ࡞⾲㠃ฎ⌮᪉ἲࡢ㛤Ⓨ㸪᭱㐺໬ࡢࡓࡵ࡟ࡣ㸪ࢢࣛࣇ࢓࢖ࢺ⣔⢊ᮎ⾲㠃ࡢᒁᡤศᯒ࡟ࡼࡾศᯒࡍࡿࡇ࡜ࡀᚲせ࡜ࡉࢀ࡚࠸ࡿࡀ㸪≉ᛶୖฎ⌮๣ࡢ୺ᡂศࡶⅣ⣲㸪ฎ⌮ᒙཌࡉࡶᩘ nm ௨ୗ㸪㈇ᴟᮦ⢊ᮎᚄ⮬㌟ࡶᑠࡉࡃ㸪ᩘ ȝm̿ᩘ 10ȝm ࡜࡞ࡿࡇ࡜࠿ࡽ㸪ศᯒ㞴᫆ᗘࡣ㧗ࡃ㸪᭷ຠ࡞ศᯒࡀ⾜࠼࡞࠸≧ែ࡛࠶ࡗࡓ㸬✀ࠎᡭἲࡢ᳨ウࡢ㐣⛬࡛㸪ᅗ 1 ࡟♧ࡍࡼ࠺࡟ࢢࣛࣇ࢓࢖ࢺ⢊ᮎᇶᮦ࡜⾲㠃ฎ⌮๣࡟࠾࠸࡚㸪
XANES 㻔X-ray Absorption Near Edge Structure㻕ࢫ࣌ࢡࢺࣝࡀ኱ࡁࡃ␗࡞ࡿࡇ࡜ࡀุ᫂ࡋࡓ㸬ẚ㍑࡜ࡋ
࡚㸪HOPG 㻔Highly Oriented Pyrolytic Graphite㸪㧗㓄ྥᛶ⤖ᬗᛶ㯮㖄㻕࠿ࡽࡢ XANES ࢫ࣌ࢡࢺࣝࡶ♧ࡍ㸬ࣆ࣮ࢡ A ࡣ 1s-> ʌ*㻔sp2㻕㸪C ࡣ 1s-> ı*㻔sp2㻕㸪B ࡣ୺࡟ࢢࣛࣇ࢓࢖ࢺᒙ㛫ࡢ≧ែ࡟ᑐᛂࡍࡿ[2]㸪
[3]ࣆ࣮ࢡ࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬㈇ᴟᮦ࡟౑⏝ࡉࢀࡿࢢࣛࣇ࢓࢖ࢺ⢊ᮎࡣ㸪

Cⷧ࠸ࢢࣛࣇ࢓࢖ࢺࢩ࣮ࢺࢆ୸ࡵࡓ」ᩘࡢࢩ
࣮ࢺࡢ㞟ྜయࡢࡼ࠺࡞ᵓ㐀࡜⪃࠼ࡽࢀ࡚࠾㯮㖄㸦C//㸧࡞ࡿ㸬ࡇࡢࡼ࠺࡞⾲㠃࡟ࡉࡽ࡟㸪ฎ⌮๣ࡀ௜୚ࡉࢀ࡚࠸ࡿࡀ㸪㈇ᴟᮦ⾲㠃࡛ࡢ㸪➃㠃ࡸ㸪ฎ⌮๣ࡢศᕸ≧ἣࢆ᫂☜࡟ࡍࡿࡇ࡜ࡀ࡛ࡁࢀࡤ㸪㈇ᴟᮦࡢ〇㐀ᕤ⛬ࡢ᭱㐺໬㸪ᛶ⬟ྥୖ࡞࡝࡟᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬ࡇࡢࡼ࠺࡞㧗✵㛫ศゎ⬟࡛ C K ➃ X ⥺྾

Normalized absorptionࡾ㸪≉࡟ࡑࡢ➃㠃ࡀ Li+࢖࢜ࣥࡢฟධࡾཱྀ࡜AB㯮㖄㸦Cԋ㸧⾲㠃ฎ⌮๣㈇ᴟᮦ

཰ࢫ࣌ࢡࢺࣝ┦ᙜࡢࢫ࣌ࢡࢺࣝࢆᚓࡿࡇ࡜ࡢ࡛ࡁࡿᡭἲ࡜ࡋ࡚㸪㟁Ꮚ⥺ࢆ౑⏝ࡋࡓ᪉ἲࡸ㸪ᨺᑕග X ⥺ࢆ୰ᚰ࡟㐺⏝ࡉࢀࡿ
STXM[4]ࡸ PEEM ἲࡀ࠶ࡿ㸬ࡋ࠿ࡋ㸪๓⪅࡛ࡣ㸪⾲㠃ᩄឤ࡞ࢫ࣌ࢡࢺࣝࢆᚓࡿࡢࡣᅔ

285

290
295
Photon energy/eV300

㞴࡛࠶ࡾ㸪ᡃࠎࡢ┠ⓗ࡜ࡣྜ⮴ࡋ࡞࠸㸬ࡑࡇ࡛㸪PEEM ἲ࡛ࡢ᳨ウࢆ㛤ጞࡋࡓ㸬๓ᅇ
㻔2009A1757㻕࡛ࡢ᳨ウ࡛㸪PEEM ἲ࡛ࡢ༢୍⢏Ꮚࡢ C K ྾཰➃ࡢᐃࡀྍ⬟࡛࠶ࡿࡇ࡜

ᅗ 1. ࢽ࣮ࣗࢫࣂ࡛ࣝ஦๓࡟ ᐃࡉࢀࡓྛ✀࣮࢝࣎ࣥᮦᩱࡢ㧗࢚ࢿࣝࢠ࣮ศ
ゎ⬟ C K ྾཰➃ XANES ࢫ࣌ࢡࢺࣝ㸬ࢆ☜ㄆࡋࡓ㸬௒ᅇࡣ㸪PEEM ἲ࡟ࡼࡿࢢࣛࣇ࢓࢖ࢺ⣔㈇ᴟᮦ⢊ᮎ࡬ࡢศᯒᡭἲ㐺⏝ᛶࢆ᳨ウࡍࡿࡓࡵ㸪೫ග XANES ࢆά⏝ࡋࡓ᝟ሗ㔞ࡢቑຍ㸪ࡉࡽ࡟ヨᩱỈ‽ࢆቑࡸࡋ㸪⣔⤫ⓗ࡞ᐃࢆ࠾ࡇ࡞࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓ㸬ᐇ㦂㸸ヨᩱ࡜ࡋ࡚㸪⾲㠃ฎ⌮๣࠾ࡼࡧࢢࣛࣇ࢓࢖ࢺ⢊ᮎ࠾ࡼࡧ㸪⾲㠃ฎ⌮ࡋࡓ≀ࢆ⏝ពࡋࡓ㸬ởᰁ㸪┠ⓗእ⢏Ꮚ࠿ࡽࡢࢫ࣌ࢡࢺࣝΰධࢆ㜵Ṇࡍࡿࡓࡵ⢊ᮎヨᩱࢆᗈࡃศᩓಖᣢࡋ㸪PEEM ἲ࡟࡚㸪༢୍⢏Ꮚ࡛ࡢ XANESᐃࢆ⾜ࡗࡓ㸬

ᐃࡣ㸪BL-17SU ࢆ฼⏝ࡋ㸪270eV ࠿ࡽ 320eV ࡢ⠊ᅖ᳨࡛ウࡋࡓ㸬ࡲࡓ㸪C K ྾཰➃㏆ഐࡢἼ㛗࡛㸪┤⥺೫ග㻔㌶㐨ᖹ⾜᪉ྥ㻕ࡶࡋࡃࡣ㸪෇೫ග࡟ษࡾ᭰࠼ࡓᐃࢆ⾜࠸㸪ẚ㍑ࡋࡓ㸬⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
1㸧೫ග XANES ἲ࡟ࡼࡿ⤖ᬗ᪉఩ศᕸ᳨ฟࡢྍ⬟ᛶ᳨ウ ๓㏙ࡢࡼ࠺࡟㸪㈇ᴟᮦ࡛౑⏝ࡉࢀࡿࢢࣛࣇ࢓࢖ࢺ⢊ᮎࡣ㸪ⷧ࠸ࢢࣛࣇ࢓࢖ࢺࢩ࣮ࢺࡀᢡࡾࡓࡓࡲࢀ㸪⢏Ꮚᙧ≧ࢆᙧᡂࡍࡿ≧ែࡶࡋࡃࡣ㸪」ᩘࡢࢩ࣮ࢺࡢ㞟ྜయࡢࡼ࠺࡞ᵓ㐀࡜⪃࠼ࡽࢀ࡚࠸ࡿ㸬ࡍ࡞ࢃࡕ㸪⢏Ꮚ⾲㠃࡛ࡢ୺⾲㠃ࡣ㸪ࣂ࣮ࢧࣝ㠃࠿ࡽ࡞ࡾ㸪ࡉࡽ࡟ Li+࢖࢜ࣥࡢ㏻ࡾ㐨࡛࠶ࡿࢢࣛࣇ࢓࢖ࢺࢩ࣮ࢺࡢ࢚ࢵࢪ㠃ࡀ㸪ᒁᡤⓗ࡟㢦ࢆฟࡋ࡚࠸ࡿᵓ㐀࡛࠶ࡿࡇ࡜ࡀ᝿ᐃࡉࢀ࡚࠸ࡿ㸬ࡑࡢ㸪ࢢࣛࣇ࢓࢖ࢺ⢊ᮎ⾲㠃࡟࠾ࡅࡿ㸪࢚ࢵࢪ㠃ࡢศᕸ≧ἣࡢᢕᥱࡣ㔜せ࡞ㄢ㢟࡛࠶ࡿ㸬ᒁᡤⓗ࡞㟁Ꮚᵓ㐀࡟ᩄឤ࡞೫ග XANESᐃࢆ⾜࠺ࡇ࡜࡛㸪ศᕸ≧ἣࡢᢕᥱࡀྍ⬟࠿࡝࠺࠿᳨ウࡋࡓ㸬ᅗ 2 ୰෗┿㻔a㻕㸪㻔b㻕࡟ࡣ㸪ࡑࢀࡒࢀࡢ೫ග≧ែ࡛ࡢ㸿ࣆ࣮ࢡࡢᙉᗘศᕸࢆ♧ࡍ㸬⏬ീ₇⟬ࡣ㸪TmCoCa[5]ࢆ౑⏝ࡋ㸪285㸬5eV ࡢᙉᗘࢆ 283eV ࡛ࡢᙉᗘ࡛つ᱁໬ࡋࡓ㸬୧⏬ീࡢẚ㍑࠿ࡽ㸪Ⅼ 1㸪2㸪3㸪4࡛኱ࡁࡃ㍤ᗘࡀ␗࡞ࡿࡇ࡜ࡀࢃ࠿ࡿ㸬ࡇࢀࡽࡢⅬ࡛ࡣ㸪ᵓ㐀␗᪉ᛶࢆ཯ᫎࡋ࡚࠸ࡿྍ⬟ᛶࡀ㧗࠸㸬(a)෇೫ගീ

C

Normalized intensity

ABⅬ㸲(b)┤⥺೫ගീ

Ⅼ㸱
Ⅼ㸰
Ⅼ㸯

285

290

295

300

Photon energy/eVᅗ 2. ྑ෗┿ྛ㒊࠿ࡽ TmCoCa ࢆ⏝࠸࡚ᢳฟࡉࢀࡓ C K ➃ XANES ࢫ࣌ࢡࢺࣝ㸬෇೫ගീ࡜┤⥺೫ගീ࡜ࡢẚ㍑࡛㸪┤⥺೫ගീ࡛ࡢ㍤Ⅼ࠿ࡽᢳฟࡋࡓ㸬ࡑࢀࡒࢀࡢⅬ࠿ࡽࡢࢫ࣌ࢡࢺࣝࢆ෌ᗘ TmCoCa[5]ࢆ⏝࠸࡚ᢳฟࡋࡓ㸬ࡑࢀࡒࢀࡢࢫ࣌ࢡࢺࣝࢆᅗ
2 ᕥᅗ࡟♧ࡍ㸬 ࠸ࡎࢀࡢⅬ࠿ࡽࡢࢫ࣌ࢡࢺࣝࡶࣆ࣮ࢡ C ᵓ㐀ࢆ᭷ࡍࡿࠋࡉࡽ࡟ࠊⅬ 1 ࠿ࡽࡢࢫ࣌ࢡࢺࣝࡣࣆ࣮
ࢡ B ࡢᵓ㐀ࢆ᭷ࡋ࡞࠸ࡀ㸪௚ࡢ 3 Ⅼ࡟࠿ࡽࡢࢫ࣌ࢡࢺࣝࡣࣆ࣮ࢡ B ᵓ㐀ࢆ᭷ࡋࡓࢫ࣌ࢡࢺࣝࡀᚓ
ࡽࢀࡓ㸬ᅗ 1 ࡢࢫ࣌ࢡࢺࣝࢆཧ⪃࡟ࡍࡿ࡜ࠊࣆ࣮ࢡ B ཬࡧࣆ࣮ࢡ C ࢆ᭷ࡍࡿⅬ 2㸫4 ࡣࠊࢢࣛࣇ
࢓࢖ࢺ࢚ࢵࢪ㠃ࡀ㟢ฟࡋࡓ㒊఩࡛࠶ࡿྍ⬟ᛶࡀ㧗࠸࡜ุ᩿࡛ࡁࡿ㸬೫ග XANES ἲࢆά⏝ࡍࡿࡇ࡜࡛㸪㈇ᴟᮦ༢୍⢏Ꮚ࡛ࡢ Li+࢖࢜ࣥࡢฟධࡾཱྀ࡜࡞ࡿ࢚ࢵࢪ㒊ࡢศᕸ≧ែࡢほᐹࡀྍ⬟࡜࡞ࡿྍ⬟ᛶࡀ㧗࠸㸬௒ᅇࡣ㸪୍᪉ྥࡢ೫ග XAFS ࡋ࠿ᐃ࡛ࡁ࡞࠿ࡗࡓࡀ㸪೫ග᪉ྥࡢᅇ㌿㸪ࡶࡋࡃࡣ㸪ヨᩱࢆᅇ㌿ࡉࡏࡿࡇ࡜࡛㸪ࡉࡽ࡟᭷⏝࡞᝟ሗࡀᚓࡽࢀࡿࡇ࡜ࡀᮇᚅ࡛ࡁࡿ㸬2㸧⾲㠃ฎ⌮๣ࡢศᕸ≧ἣࢢࣛࣇ࢓࢖ࢺ⾲㠃࡟Ꮡᅾࡍࡿ⾲㠃ฎ⌮๣ࡢศᕸ≧ἣゎᯒࡶ㔜せ࡞ㄢ㢟࡛࠶ࡿ㸬ᅗ 3 ࡟♧ࡍࢫ࣌ࢡࢺࣝࡣ㸪ฎ⌮๣௜╔㔞ࢆኚ໬ࡉࡏࡓ⢏Ꮚࡢ PEEM ീ࠿ࡽ㸪௦⾲⠊ᅖࡢ XANES ࢫ࣌ࢡࢺࣝࢆ
TmCoCa[5]ࢆ౑⏝ࡋ࡚ᢳฟࡋࡓ㸬≉࡟ὀ┠ࡋ࡚࠸ࡿࡢࡣ㸪ࣆ࣮ࢡ C ࡛࠶ࡿ㸬ෑ㢌㏙࡭ࡓࡼ࠺࡟㸪ࣆ࣮ࢡ C ࡣ㸪⾲㠃ฎ⌮๣࡛ࡣฟ⌧ࡋ࡞࠸㸬ฎ⌮㔞࡟ᚑ࠸㸪ࣆ࣮ࢡ C ࡀᑠࡉࡃ࡞ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡓ㸬௒ᅇࡢᐃ࡛ࡣ㸪512X512 ࡛ࡢど㔝࡛ᐃࡋࡓ㸬ࡑࡢྛⅬ࠿ࡽࡢ඲ࢫ࣌ࢡࢺ࡛ࣝࣆ࣮ࢡ C ࡢᙉᗘศᕸࢆぢࡿࡇ࡜࡛㸪࠶ࡿ⛬ᗘฎ⌮๣ࡢศᕸ≧ἣࡀᢕᥱ࡛ࡁࡿࡢ࡛ࡣ࡞࠸࠿࡜⪃࠼࡚࠸ࡿ㸬ṧᛕ࡞ࡀࡽ㸪ࡲࡔ඲Ⅼ࠿ࡽࡢࢫ࣌ࢡࢺࣝࢆゎᯒࡋࡁࢀ࡚࠾ࡽࡎ㸪⤖ㄽࡣᚓࡽࢀ࡚࠸࡞࠸㸬௒ᚋ᳨ウࢆ㐍ࡵ࡚࠸ࡁࡓ࠸㸬

ABC

ฎ⌮㔞ከ

Normalized absorption

ฎ⌮㔞୰

ฎ⌮㔞ᑡ

ᮍฎ⌮

285

290
295
Photon energy/eV300

ᅗ 3. ྛฎ⌮ᚋࡢ㈇ᴟᮦࡢ PEEM ീ࠿ࡽ௵ព࡟ᢳฟࡋࡓ⠊ᅖ࠿ࡽࡢ XAFS ࢫ࣌ࢡࢺࣝ㸬ࡲ࡜ࡵ࡜௒ᚋࡢㄢ㢟㸸┠ⓗ࡜ࡋࡓ㸪1)┤⥺೫ගά⏝ࡋ࡚ࡢ㸪㈇ᴟᮦ⾲㠃࡛ࡢ࢚ࢵࢪ㠃ศᕸホ౯᭱⤊ⓗ࡟ࡣ㸪ูἲ࡛ࡢẚ㍑ࡶᚲせ࡜ࡣ⪃࠼ࡿࡀ㸪෇೫ගീ࡜┤⥺೫ගീࢆẚ㍑ࡋ㸪┤⥺೫
ගീ࡛ࡢ㍤Ⅼࢫ࣌ࢡࢺࣝ࠿ࡽ㸪࢚ࢵࢪ㠃࡟≉ᚩⓗ࡞ࢫ࣌ࢡࢺࣝࡀᚓࢀࡽ࡚࠾ࡾ㸪 ᐃᡭἲ࡜ࡋ࡚ࡣ࠿࡞ࡾ᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿ㸬2)ฎ⌮๣ࡢศᕸ≧ἣฎ⌮๣㔞࡟ᛂࡌࡓ࣮ࣜࢬࢼࣈࣝ࡞ࢫ࣌ࢡࢺࣝኚ໬ࡣᚓࡽࢀࡓ㸬ࡋ࠿ࡋ㸪ࡲࡔ㸪ᒁᡤゎᯒ࡟ᣢࡕ㎸ࡵ࡚࠾ࡽࡎ㸪ࢹ࣮ࢱฎ⌮ἲ㸪࢔ࣝࢦࣜࢬ࣒ྵࡵ࡚௒ᚋ᳨ウࡋࡓ࠸㸬ࡇࢀࡲ࡛㸪㈇ᴟᮦ࡞࡝࣮࢝࣎ࣥᚤ⣽⢏Ꮚࡢศᯒࡣ㸪㟁Ẽ໬Ꮫⓗ࡞ᡭἲࡸ࣐ࣛࣥᩓ஘ศගἲ㸪
XPS(ග㟁Ꮚศගἲ)࡛ࡢ࣐ࢡࣟ࡞ホ౯㸪ࡶࡋࡃࡣ TEM(㏱㐣㟁Ꮚ㢧ᚤ㙾)㸪AFM(ཎᏊ㛫ຊ㢧ᚤ㙾)ࡸ STXM[4](㉮ᰝᆺ㏱㐣 X ⥺㢧ᚤ㙾)࡛ࡢᒁᡤホ౯ࡀ୺࡟ᐇ᪋ࡉࢀ࡚ࡁࡓ㸬๓⪅ࡢ࣐ࢡࣟホ౯࡛ࡣ㸪㠃ෆ࡛ࡢẚ㍑ⓗᗈ࠸(ᩘ࣑ࢡࣟࣥ࠿ࡽ࣑ࣜ)ᖹᆒⓗ࡞㔞ࡢࡳࡀᚓࡽࢀ㸪࢚ࢵࢪ㠃ࡢ✵㛫ⓗ࡞ศᕸࡣ୙
࡛᫂࠶ࡿ㸬୍᪉㸪ᚋ⪅࡛ࡣ㸪ศᯒど㔝ࡀ nm ࣮࢜ࢲ࣮ࡢᒁᡤ࡜࡞ࡾ㸪⢏Ꮚ඲య࡛ࡢ࢚ࢵࢪ㠃ࡢศᕸ≧ἣࡢ᳨ウࡣᅔ㞴࡛࠶ࡿ㸬ࡉࡽ࡟ TEM ࡸ STXM ࡔ࡜⾲㠃ศᯒ࡜ࡣゝ࠼ࡎ㸪௒ᅇ᳨ウࡋࡓ㸪
PEEM ἲࢆ⏝࠸࡚ࡢ㸪೫ග XANESᐃే⏝ࡋ࡚ࡢศගศᯒࡣ㸪ࡕࡻ࠺࡝୍⢏Ꮚࢆど㔝࡟࠸ࢀࡓ᫬㸪⏬⣲࠶ࡓࡾࡢศゎ⬟ࡀ 40nm ⛬ᗘ࡜࡞ࡾ㸪ࡲࡉ࡟᭱㐺࡞ศᯒ᪉ἲ࡛࠶ࡿ࡜࠸࠼ࡿ㸬ཧ⪃ᩥ⊩㸸[1] E. Peled, J. Electrochem. Soc, 126, 2047 㻔1979㻕.
[2] D. A. Fischer, R. M. Wentzcovitch, R. G. Carr, A. Continenza, A. J. Freeman, Physical Review B,
44㻔1991㻕1427.
[3] P. E. Baston, Physical Review B, 48㻔1993㻕2608.
[4] S. Wirick, G. J. Flynn, L. P. Keller, S. A. Sandford, M. E. Zolensky, K. Nakamura Messenger, C.
Jacobsen, 39th Lunar and Planetary Science Conference, 㻔2008㻕1450.
[5] T. Matsushita, http://kabuki.spring8.or.jp/Members/matusita/index_html