http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_11B1846.pdf

2011B1846BL47XU

ࢿ࢜ࢪ࣒☢▼ࡢ◳ X ⥺ග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ␗᪉ᛶ࡜ ᗘኚ໬
Anisotropy and Temperature-dependence of Hard X-ray Photoelectron
Spectra of Nd-Fe-B Magnets
௒⏣ ┿ a, ఀబ἞ ㎮᫛ a, ᑎᔱ ೺ᡂ a, ▮㔝 ṇ㞝 b, ຍ⏣ ኱ᫀ a, ⸨⏣ ⲁ a, Ụ⸨ ኱ᶞ a,Ώ㒊 ⱥ἞ a, ᮡᒣ Ṋᬕ c, ụỌ ⱥྖ caa
Shin Imada , Tatsuaki Isaji , Kensei Terashimaa, Masao Yanob, Hiromasa Kadaa, Akane Fujitaa, Hiroki Etoa,Eiji Watanabea, Takeharu Sugiyamac, Eiji Ikenagaca❧࿨㤋኱⌮ᕤ, b ࢺࣚࢱ⮬ື㌴, c㻔බ㈈㻕㧗㍤ᗘග⛉Ꮫ◊✲ࢭࣥࢱ࣮aRitsumeikan Univ., bTOYOTA, c JASRI/SPring-8ࢿ࢜ࢪ࣒☢▼ࡢỌஂ☢▼࡜ࡋ࡚ࡢ㧗࠸ᛶ⬟ࢆࡶࡓࡽࡋ࡚࠸ࡿᚤどⓗ࡞࣓࢝ࢽࢬ࣒ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࡣࠊ㟁Ꮚ≧ែࡢヲ⣽࡞ゎ᫂ࡀ᭷ຠ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋᮏ◊✲࡛ࡣࠊ㟁Ꮚ≧ែࡢ ᗘ౫Ꮡᛶ࡜␗᪉ᛶࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࣂࣝࢡᩄឤ◳ X ⥺ග㟁Ꮚศගࡀ࡝ࡢ⛬ᗘ᭷ຠ࠿ࢆ᳨ドࡋࡓࠋࡇࡢࡓࡵ࡟ࠊࢿ࢜ࢪ࣒☢▼ᮦ࠾ࡼࡧ Nd2Fe14B ༢⤖ᬗ࡟ࡘ࠸࡚ࠊFe 2p, Nd 3d ➼ࡢෆẆ࠾ࡼࡧ౯㟁Ꮚᖏග㟁Ꮚࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ࣮࣮࢟࣡ࢻ㸸 ◳ X ⥺ග㟁Ꮚศග㻔HAXPES㻕ࠊࢿ࢜ࢪ࣒☢▼ࠊಖ☢ຊ⫼ᬒ࡜◊✲┠ⓗ㸸 ᮏ◊✲࡛ࡣࠊࢿ࢜ࢪ࣒☢▼࡟࠾ࡅࡿ⪏⇕ᛶ⬟㻔ࡘࡲࡾ㧗 ࡛༑ศ࡞ಖ☢ຊࢆᣢࡘࡇ࡜㻕ࡢⓎ⌧ᶵᵓ࡟ᑐࡍࡿࢹ࢕ࢫࣉࣟࢩ࣒࢘ῧຍࡢᙺ๭ࡢゎ᫂࡟ࠊ㟁Ꮚ≧ែࡢᐇ㦂ⓗゎ᫂ࢆ㏻ࡋ࡚ᮏ㉁ⓗ࡞㈉⊩ࢆࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋᮏ◊✲ࢢ࣮ࣝࣉ࡛ࡣࠊᮏ◊✲࡟ࡼࡗ࡚ࠊࣁ࢖ࣈࣜࢵࢻ㌴ࡢ㥑ື࣮ࣔࢱ࣮࡟฼⏝ࡉࢀࡿ㧗ᛶ⬟Ọஂ☢▼ࡢࠊ⬺ࣞ࢔࣭࢔࣮ࢫ໬࠾ࡼࡧపࢥࢫࢺ໬㛤Ⓨࡢࡓࡵࡢᣦᑟཎ⌮ࢆ☜❧ࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋ ࡇࢀࡲ࡛࡟ࠊ㌾ X ⥺ࢆ⏝࠸ࡓẚ㍑ⓗ⾲㠃ᩄឤ࡞ග㟁Ꮚศග㻔2011A1759㻕࡜◳ X ⥺ࢆ⏝࠸ࡓࣂࣝࢡᩄឤග㟁Ꮚศග㻔2011A1693㻕ࢆẚ㍑ࡋࡓࠋࡑࡢ⤖ᯝࠊ ᐃᑐ㇟࡛࠶ࡿࢿ࢜ࢪ࣒☢▼ᮦᩱࡢ◚᩿㠃
࡟ࡣ Nd ⃰ᗘࡢ㧗࠸⢏⏺┦ࡀᗈ࠸㠃✚࡛ྵࡲࢀ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡲࡓࠊ⢏⏺┦࡟ྵࡲࢀࡿ
Nd2O3 ࡢᐤ୚ࢆ Nd 3d ග㟁Ꮚࢫ࣌ࢡࢺ࡛ࣝぢ✚ࡶࡿ࡜ࠊ㌾ X ⥺ග㟁Ꮚศග࡟ẚ࡭࡚◳ X ⥺ග㟁Ꮚศග࡛ࡣࡑࡢᐤ୚ࡣᑠࡉࡃ࡞ࡿࡀࠊ↓ど࡛ࡁ࡞࠸⛬ᗘ࡟ぢࡽࢀࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋ ࡑࡇ࡛ᮏ◊✲࡛ࡣࠊ᪼ ࡟ࡼࡿ☢Ẽ␗᪉ᛶࡢపୗࡢ㉳※࡜ࡋ࡚㟁Ꮚ≧ែࡀ ᗘ࡟౫Ꮡࡋ࡚ኚ໬ࡋ࡚࠸ࡿྍ⬟ᛶࡀ࠶ࡿ࡜⪃࠼ࠊࡑࡢ᳨ドࢆヨࡳࡓࠋ୍᪉ࠊ☢Ẽ␗᪉ᛶࡢ㉳※ࢆ࡟࡞࠺࡜⪃࠼ࡽࢀࡿ㟁Ꮚ≧ែࡢ␗᪉ᛶࡢほ ࢆ┠ᣦࡋࡓᐇ㦂ࡶ⾜ࡗࡓࠋᐇ㦂㸸ᐇ㦂ࡣࣅ࣮࣒ࣛ࢖ࣥ BL47XU ࡢග㟁Ꮚศගࢫࢸ࣮ࢩࣙࣥࢆ⏝࠸࡚ 7940 eV ࡢ◳ X ⥺ບ㉳ග࡛⾜ࡗࡓࠋ㟁Ꮚศᯒჾࡣ VG ࢩ࢚ࣥࢱ♫〇 R4000 ࢆ⏝࠸ࡓࠋヨᩱࡣ㧗┿✵୰࡛◚᩿ࡋ࡚ᚓࡽࢀࡓΎί⾲㠃ࢆ⏝࠸ࠊ ᐃࡣᐊ ࠾ࡼࡧ୍㒊ࡢヨᩱ࡟ࡘ࠸࡚ࡣ᪼ ᫬࡟ࡘ࠸࡚ࡶ⾜ࡗࡓࠋ೫ග᪉ྥࡣ᩿ࡽ࡞࠸㝈ࡾỈᖹ೫ග࡛࠶ࡾࠊග㟁Ꮚศᯒჾࡣග࡜ྠࡌỈᖹ㠃ෆ࡟࠶ࡗ࡚ගධᑕ᪉ྥ࡜┤⾜ࡍࡿ᪉ྥ࡟࠾࠿ࢀ࡚࠸ࡿࠋᐃࡋࡓヨᩱࡣࠊ୍⯡ࡢࢿ࢜ࢪ࣒☢▼㻔NdDyFeB Ọஂ☢▼㻕ࠊDy ࢆྵࡲ࡞࠸ࢿ࢜ࢪ࣒☢▼㻔NdFeBỌஂ☢▼㻕ࠊ࠾ࡼࡧ Nd2Fe14B ༢⤖ᬗ࡛࠶ࡗࡓࠋ඾ᆺⓗ࡞ ᐃ᮲௳ࡣࠊࣃࢫ࢚ࢿࣝࢠ࣮ࢆ 200 eVࠊ࢔ࢼࣛ࢖ࢨ࣮ࡢࢫࣜࢵࢺࡣ 0.5 mm ࡜ࡋࠊศゎ⬟ࡣ⣙ 250 meV ࡛࠶ࡗࡓࠋ

ᅗ 1㸬NdDyFeB Ọஂ☢▼࠾ࡼࡧ Nd2Fe14B ༢⤖ᬗࡢ Nd 3d ග㟁Ꮚࢫ࣌ࢡࢺࣝ㻔ᕥ㻕㻌࠾ࡼࡧ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝ㻔ྑ㻕ࡢ ᗘኚ໬ࠋᐊ ௜㏆ࡢࢫ࣌ࢡࢺࣝࢆ㟷⥺ࠊ100Υ
௜㏆ࡢࢫ࣌ࢡࢺࣝࢆ㉥⥺࡛♧ࡍࠋ

ᅗ 2㸬NdDyFeB Ọஂ☢▼ࡢ Nd 3d ග㟁Ꮚࢫ࣌ࢡࢺࣝ㻔ᕥ㻕࠾ࡼࡧ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝ㻔ྑ㻕ࡢᐇ㦂㓄⨨౫Ꮡᛶࠋ೫ග᪉ྥ㻔㟁ሙ࣋ࢡࢺࣝࡢྥࡁ㻕࡜ග㟁Ꮚ᳨ฟ᪉ྥࡣྠ୍࡜ࡋࠊ㓄⨨'H' ࡛ࡣ c ㍈ࢆ೫ග᪉ྥ࡟ྥࡅࠊ㓄⨨ 'V' ࡛ࡣ c ㍈ࢆ೫ග᪉ྥ࡜ᆶ┤࡟ྥࡅࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸 ග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ ᗘ౫Ꮡᛶࡢ⤖ᯝࡢ౛࡜ࡋ࡚ࠊᅗ 1 ࡟୍⯡ࡢࢿ࢜ࢪ࣒☢▼㻔NdDyFeB Ọஂ☢▼㻕࡜ Nd2Fe14B ༢⤖ᬗ࡟ࡘ࠸࡚ࠊNd 3d ග㟁Ꮚࢫ࣌ࢡࢺࣝ࠾ࡼࡧ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝࡢ⤖ᯝࢆ♧ࡍࠋᐊ ௜㏆ࡢ ᗘ࡜ 100Υ௜㏆࡛ ᐃࢆ⾜࠸ࠊ๓⪅ࢆ㟷⥺ࠊᚋ⪅ࢆ㉥⥺࡛♧ࡋ࡚࠶ࡿࠋࡲࡎࠊ
Nd2Fe14B ༢⤖ᬗࡢ Nd 3d ග㟁Ꮚࢫ࣌ࢡࢺ࡛ࣝࡣࠊNdDyFeB Ọஂ☢▼࡟ࡳࡽࢀࡿ㓟໬ࡢᙳ㡪࡜⪃࠼ࡽࢀࡿᵓ㐀㻔EB = 983 eV ௜㏆㻕࡟ᑐᛂࡍࡿᵓ㐀ࡀ↓ど࡛ࡁࡿ࡯࡝ᑠࡉ࠸ࠋ ᗘࢆୖࡆ࡚ࡶࠊNd2Fe14B༢⤖ᬗࡢሙྜࡣ㓟໬࡟ࡼࡿᵓ㐀ࡀ࡯࡜ࢇ࡝ᡂ㛗ࡋ࡞࠸ࡀࠊNdDyFeB Ọஂ☢▼࡛ࡣ㓟໬࡟ࡼࡿᵓ㐀ࡀࢃࡎ࠿࡟ቑ኱ࡋ࡚࠸ࡿࠋᚋ⪅ࡢ㉳※࡟ࡘ࠸࡚ࡣࠊ⾲㠃ࡢ㓟໬ࡀ┿✵୰ࡢṧ␃࢞ࢫࡢࡓࡵ࡟㐍ࢇࡔࡢ࠿ࠊ࠶ࡿ࠸ࡣ⾲㠃௜㏆ࡢ≀㉁ࡀ᪼ ࡟కࡗ࡚ఱࡽ࠿ࡢኚ໬ࢆ㉳ࡇࡋࡓ࠿ࠊࡲࡓࡣヨᩱୖࡢᐃ࣏࢖ࣥࢺࡀࡎࢀࡓࡓࡵ࡜࠸ࡗࡓྍ⬟ᛶࡀ࠶ࡿࠋNd 3d ࢫ࣌ࢡࢺࣝࡀ࡯࡜ࢇ࡝ኚ໬ࡋ࡞࠿ࡗࡓNd2Fe14B ༢⤖ᬗࡢሙྜࡣࠊ౯㟁Ꮚᖏග㟁Ꮚࢫ࣌ࢡࢺࣝࡢ ᗘኚ໬ࡣ࡯࡜ࢇ࡝ほ ࡉࢀ࡞࠿ࡗࡓࠋ
ࡇࡢࡇ࡜࠿ࡽࠊNd2Fe14B ༢⤖ᬗࡢ౯㟁Ꮚᖏ㟁Ꮚ≧ែࡢᐊ ࠿ࡽ 100Υ࡟࠿ࡅ࡚ࡢኚ໬ࡣࠊ௒ᅇࡢᐃ⢭ᗘࡼࡾࡶᑠࡉ࠸࡜⪃࠼ࡽࢀࡿࠋ୍᪉ࠊNdDyFeB Ọஂ☢▼ࡢ౯㟁Ꮚᖏග㟁Ꮚࢫ࣌ࢡࢺࣝࡣࠊ
ᗘୖ᪼࡟కࡗ࡚ 5 eV ௜㏆ࡢࣆ࣮ࢡࡀ㧗⤖ྜ࢚ࢿࣝࢠ࣮ഃ࡟ࢃࡎ࠿࡟⛣ືࡋ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀ
ࡽ Nd 3d ࢫ࣌ࢡࢺࣝࡀ ᗘኚ໬ࡋ࡚࠸ࡿࡇ࡜ࢆ⪃࠼ࡿ࡜ࠊࡇࡢࢫ࣌ࢡࢺࣝኚ໬ࡣ⾲㠃௜㏆ࡢఱࡽ࠿ࡢኚ໬࡟ࡼࡿྍ⬟ᛶࡀ࠶ࡿࡢ࡛ࠊ㟁Ꮚ≧ែࡢᮏ㉁ⓗ࡞ኚ໬ࢆ཯ᫎࡋ࡚࠸ࡿ࡜ࡣ⤖ㄽ࡙ࡅࡽࢀ࡞࠸ࠋ ḟ࡟⤖ᬗ᪉ྥ౫Ꮡᛶࡢ ᐃ⤖ᯝࡢ౛࡜ࡋ࡚ࠊᅗ 2 ࡟ NdDyFeB Ọஂ☢▼ࡢࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡢ
⤖ᯝࢆ♧ࡍࠋࡇࢀࡽࡢ ᐃ࡟࠾࠸࡚ࡣࠊ೫ග᪉ྥ㻔㟁ሙ࣋ࢡࢺࣝࡢྥࡁ㻕࡜ග㟁Ꮚほ ᪉ྥࡣྠ୍࡜
ࡋࠊヨᩱࡢ⤖ᬗ᪉ྥࡔࡅࢆኚ໬ࡉࡏࡓࠋc ㍈ࡀ೫ග᪉ྥ࡜୍⮴ࡋ࡚࠸ࡿሙྜ㻔configuration 'H'㻕࡜ c㍈ࡀ೫ග᪉ྥ࡜ᆶ┤ࡢሙྜ㻔configuration 'V'㻕࡟ࡘ࠸࡚ ᐃࡋࡓࠋࡑࡢ㝿ࠊྠࣟࢵࢺࡢヨᩱࢆ⏝࠸ࠊ◚᩿㠃ࡀග㟁Ꮚ᳨ฟ᪉ྥ࡟࡯ࡰᆶ┤࡟࡞ࡿࡼ࠺࡟ࠊ๓⪅ࡣ c ㍈࡟ᆶ┤࡞㠃࡛◚᩿ࡋࠊᚋ⪅ࡣ c ㍈
࡟ᖹ⾜࡞㠃࡛◚᩿ࡋࡓࠋNd 3d ࢫ࣌ࢡࢺࣝࡣࠊ㓄⨨'H'࡟ẚ࡭࡚'V'ࡢ᪉ࡀ㓟໬ࡢᙳ㡪࡜ぢࡽࢀࡿᡂศࡀᙉ࠸ࠋࡘࡲࡾࠊ◚᩿⾲㠃࡟ṧࡿ࡜⪃࠼ࡽࢀࡿ⢏⏺⤌⧊ࡀࠊ◚᩿㠃࡟ c ㍈ࡀᆶ┤࡞ሙྜ㻔'H'㻕࡜◚᩿㠃ෆ࡟ c ㍈ࡀ࠶ࡿሙྜ㻔'V'㻕࡛␗࡞ࡗ࡚࠸ࡿྍ⬟ᛶࡀ♧၀ࡉࢀࡿࠋࡇࡢࡓࡵࠊ⤖ᬗ᪉ྥࡢ㐪࠸࡟ࡼࡗ࡚ぢࡽࢀ࡚࠸ࡿ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝࡢኚ໬ࡣࠊ㟁Ꮚ≧ែࡢ␗᪉ᛶࡔࡅࢆ཯ᫎࡋ࡚࠸ࡿ࡜ࡣ⤖ㄽ࡙ࡅࡽࢀ࡞࠸ࠋ ௨ୖࡢࡼ࠺࡟ࠊ㟁Ꮚ≧ែࡢ ᗘ౫Ꮡᛶ࡜␗᪉ᛶࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࣂࣝࢡᩄឤ◳ X ⥺ග㟁Ꮚศගࢆ⏝࠸ࡿ㝿࡟ࠊࢿ࢜ࢪ࣒☢▼≉᭷ࡢࠕ⢏⏺┦ࠖࡢཌࡉࡀ◳ X ⥺ග㟁Ꮚศගࡢࣉ࣮ࣟࣈ῝ࡉࡢᩘศࡢ୍⛬ᗘ࡛࠶ࡿࡓࡵࠊ◳ X ⥺ග㟁Ꮚศග࡛ࡶ↓ど࡛ࡁ࡞࠸ࡇ࡜ࡀၥ㢟࡜࡞ࡿࡇ࡜ࡀ᫂ࡽ࠿࡟
࡞ࡗࡓࠋࡘࡲࡾࠊ ᗘࡸ⤖ᬗࡢ◚᩿᪉ྥࢆኚ࠼ࡓ㝿࡟ࠊ ᐃࡋࡓ࠸ ᗘ౫Ꮡᛶࡸ᪉ྥ౫Ꮡᛶ࡜ࠊ⢏⏺┦ࡢཌࡉࡸ㓟໬≧ែࡀ␗࡞ࡿ࡜࠸ࡗࡓኚ໬ࡢᙳ㡪ࢆ࠸࠿࡟ࡋ࡚༊ูࡍࡿ࠿࡜࠸࠺ㄢ㢟ࢆゎỴࡍࡿᚲせࡀ࠶ࡿࠋ௒ᚋࡢ᳨ウ㸸 Ọஂ☢▼ᮦᩱࡀ୺┦࡜⢏⏺┦࠿ࡽᡂࡿከ┦⣔࡛࠶ࡿࡇ࡜࠿ࡽࠊ᮲௳ࢆኚ࠼࡚ ᐃࡋࡓ㝿࡟ ᐃ㡿ᇦࡢ໬Ꮫⓗ⤌ᡂࡢ㐪࠸ࡢࡓࡵ࡟㟁Ꮚ≧ែࡢ㐪࠸ࢆᢳฟ࡛ࡁ࡞࠸ሙྜࡀከ࠸ࡇ࡜ࡀࢃ࠿ࡗࡓࠋ௒ᚋࡉࡽ࡟␗࡞ࡿ⤌ᡂࡸసᡂ᮲௳ࡢヨᩱ࡟ࡘ࠸࡚ࠊࡼࡾヲ⣽࡞ᐇ㦂ࢆ⾜࠺ࡇ࡜ࢆ㏻ࡋ࡚ࠊ㟁Ꮚ≧ែࢆࡁࡕࢇ࡜ゎ᫂ࡍࡿࡇ࡜࡛ࠊỌஂ☢▼ᛶ⬟ࡢⓎ⌧ᶵᵓࢆ᫂ࡽ࠿࡟ࡍࡿᚲせࡀ࠶ࡿࠋ≉࡟ࠊ㟁Ꮚ≧ែࡢ␗᪉ᛶࡸ ᗘ౫Ꮡᛶ࡟ࡘ࠸࡚ࡣࠊᇶᮏ࡜࡞ࡿ༢⤖ᬗヨᩱ࡟ࡘ࠸࡚ࠊග㟁Ꮚศගࡔࡅ࡛࡞ࡃෆẆ྾཰ศගࡶྵࡵ࡚ᵝࠎ࡞ ᐃࢆ⾜ࡗ࡚ࠊ࡝ࡢ ᐃࡀ᭷ຠ࠿ࢆ᳨ウࡍࡿᚲせࡀ࠶ࡿࠋ