http://support.spring8.or.jp/Report_JSR/PDF_IAe_ALL/IAe_10B1815.pdf

2010B1815                           BL46XU㧗࢚ࢿࣝࢠ࣮ග㟁Ꮚศගἲ࡟ࡼࡿ Gd ῧຍ AlN ⷧ⭷ࡢ῝ࡉ᪉ྥࡢゎᯒDepth Analysis of the Gd Addition AlN Thin Film by Hard X-ray
Photoelectron Spectroscopyᑠᯘ ᖿᘯ a, ▼ཎ Ⴙ⏕ b, Ἠ ᏹ࿴ b, すᮏ ဴᮁ a, ⏣୰ ᐶஅ a, ౗ᒣ ┿ஓ c, ႐ከ 㝯 cMikihiro Kobayashia, Tsuguo Ishiharab, Hirokazu Izumib, Tetsurou Nishimotoa,Hiroyuki Tanakaa, Shinya Kitayamac, Takashi Kitacaa㻔ᰴ㻕࣓ࣘࢵࢡࢫ, b රᗜ┴❧ᕤᴗᢏ⾡ࢭࣥࢱ࣮, c ⚄ᡞ኱ᏛYUMEX Inc., bHyogo Prefectural Institute of Technology, cKobe Universityᡃࠎࡀ῝⣸እග※⏝⺯ගయ࡜ࡋ࡚㛤Ⓨࡋ࡚࠸ࡿ Gd ῧຍ AlN ⷧ⭷ࡣࠊ࢝ࢯ࣮ࢻ࣑ࣝࢿࢵࢭࣥࢫᐃࢆࡍࡿࡓࡵ࡟኱㟁ὶࢆ༳ຍࡍࡿ࡜Ⓨගᙉᗘࡀᛴ⃭࡟ῶ⾶ࡍࡿ⌧㇟ࡀ⏕ࡌ࡚࠸ࡿࠋࡑࡢཎᅉ࡜ࡋ࡚ࠊ㟁Ꮚࣅ࣮࣒࡟ࡼࡾ Gd ῧຍ AlN ⷧ⭷ࡀࢲ࣓࣮ࢪࢆཷࡅࡓࡇ࡜ࡀ⪃࠼ࡽࢀࡿࠋᮏሗ࿌࡛ࡣ Gdῧຍ AlN ⷧ⭷ࡢ⾲㠃࡜῝ᒙ㒊ࡢᵓᡂඖ⣲࡟ࡘ࠸࡚໬Ꮫ⤖ྜ≧ែࡢኚ໬ࢆ᫂ࡽ࠿࡟ࡍࡿࡓࡵ࡟ࠊBL46XU ࡟࡚◳ X ⥺ග㟁Ꮚศග ᐃࡋࡓ⤖ᯝࢆ㏙࡭ࡿࠋ࣮࣮࢟࣡ࢻ㸸 Gd ῧຍ AlNࠊ῝⣸እග※ࠊXAFS⫼ᬒ࡜◊✲┠ⓗ㸸ᡃࠎࡣỈ㖟ࣛࣥࣉࡢ௦᭰฼⏝ࢆ┠ⓗ࡟ࠊ❅໬࢔࣑ࣝࢽ࣒࢘㻔AlN㻕ࢆẕయ࡜ࡋ࡚ᕼᅵ㢮ඖ⣲࢞ࢻࣜࢽ࣒࢘㻔Gd㻕ࢆῧຍࡋࠊGd ࡢ f-f 㟁Ꮚ㑄⛣ࢆ฼⏝ࡋࡓỈ㖟ࣇ࣮ࣜ῝⣸እග※࡜ࡋ࡚᭷ᮃ࡞ Gd ῧຍAlN ⷧ⭷ࡢ㛤Ⓨࢆ⾜ࡗ࡚ࡁࡓ[1][2][3]ࠋࡋ࠿ࡋࠊGd ῧຍ AlN ⷧ⭷ࡣࠊ኱㟁ὶࢆ༳ຍࡍࡿ࡜࢝ࢯ࣮ࢻ࣑ࣝࢿࢵࢭࣥࢫᙉᗘࡀᛴ⃭࡟ῶ⾶ࡍࡿ⌧㇟ࡀ⏕ࡌ࡚࠾ࡾࠊࡑࡢཎᅉ࡜ࡋ࡚ࡣࠊ㟁Ꮚࣅ࣮࣒࡟ࡼࡿ⭷ࡢᦆയࢆ⪃࠼࡚࠸ࡿࠋࡑࡇ࡛ᡃࠎࡣᐇ㦂ᐊ࡛ࣞ࣋ࣝࡢ X ⥺ග㟁Ꮚศග ᐃἲ࡟ࡼࡾࠊⷧ⭷ᵓᡂඖ⣲ࡢ໬Ꮫ⤖ྜ≧ែࢆ᫂ࡽ࠿࡟ࡋࠊⓎගᙉᗘࡢ㛗᫬㛫Ᏻᐃ࡟⧅ࡀࡿᅉᏊࡢゎ᫂ࢆヨࡳ࡚ࡁࡓࠋࡑࡢ⤖ᯝࠊ㟁Ꮚࣅ࣮࣒↷ᑕᚋࡢⷧ⭷࡛ࡣࠊ㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡾ୍㒊ཎᏊࡀࡣࡌࡁ㣕ࡤࡉࢀࡓࡓ
ࡵࠊAl2pࠊGd3d5/2ࠊN1s ࣆ࣮ࢡࡢᙉᗘࡀᑠࡉࡃ࡞ࡾࠊࡲࡓఱࢀࡶ㧗࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠾
ࡾࠊࡑࢀࡒࢀ໬Ꮫ⤖ྜ≧ែࡀኚ໬ࡋ࡚࠸ࡿࡇ࡜ࢆぢฟࡋࡓࠋࡋ࠿ࡋ࡞ࡀࡽࠊࡇࢀࡲ࡛౑⏝ࡋ࡚ࡁࡓᐇ㦂ᐊ⣔ࡢ XPS ࡛ࡣග㟁Ꮚࡢ⬺ฟ῝ࡉࡀᩘ nm ࡟␃ࡲࡿࡓࡵࠊᴟ⾲㠃ࡢ໬Ꮫ⤖ྜ≧ែࡢኚ໬ࡋ࠿☜ㄆ࡛ࡁ࡚࠸࡞࠸ࠋ ࡑࡇ࡛ᮏᐇ㦂࡛ࡣࠊࡼࡾ῝ᒙ㒊ࡢ᝟ሗࢆ㠀◚ቯ࡛ホ౯࡛ࡁࡿᨺᑕගࢆ฼⏝ࡋࡓ◳ X ⥺ග㟁Ꮚศගἲ㻔HAXPES㻕ࢆ⏝࠸⭷ෆ㒊ࡢ໬Ꮫ⤖ྜ≧ែࢆゎᯒࡍࡿࡇ࡜࡛ࠊ࢝ࢯ࣮ࢻ࣑ࣝࢿࢵࢭࣥࢫᙉᗘࡢ኱ᖜ࡞ῶ⾶ᶵᵓࢆ᫂ࡽ࠿࡟ࡋࠊ㧗㍤ᗘⓎගᮦᩱࡢ㛤Ⓨᣦ㔪ࢆᚓࡿࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ͒ᐇ㦂㸸ᐃヨᩱ࡛࠶ࡿ Gd ῧຍ AlN ⷧ⭷ࡣࠊ཯ᛂᛶ㧗࿘Ἴ࣐ࢢࢿࢺࣟࣥࢫࣃࢵࢱࣜࣥࢢἲ࡟ࡼࡾస〇ࡋࡓࠋ4N 㔠ᒓ Al ࢱ࣮ࢤࢵࢺୖ࡟ 3N 㔠ᒓ Gd ࢳࢵࣉࢆ㓄⨨ࡋࡓྠ᫬ࢫࣃࢵࢱࣜࣥࢢ࡛ࠊ࢔ࣝࢦࣥ❅⣲ΰྜ࢞ࢫ୰ࠊ200Υࡢ ᗘ᮲௳࡛▼ⱥ࢞ࣛࢫᇶᯈୖ࡟⭷ཌ 540 nm ⛬ᗘࡢᡂ⭷ࢆ⾜ࡗࡓࠋ㟁Ꮚࣅ࣮࣒↷ᑕᚋࡢⷧ⭷ࡣࠊຍ㏿㟁ᅽ 5 kVࠊຍ㏿㟁ὶ 200 μA ࡢ᮲௳࡛㟁Ꮚࣅ࣮࣒ࢆ↷ᑕࡋࠊ࢝ࢯ࣮ࢻ
࣑ࣝࢿࢵࢭࣥࢫᙉᗘࡀ 1/2ࠊཬࡧ 1/4 ࡟ῶ⾶ࡋࡓヨᩱࢆ‽ഛࡋࡓࠋ
㧗㍤ᗘ㹖⥺↷ᑕ࡟ࡼࡿࢳ࣮ࣕࢪ࢔ࢵࣉࢆ㜵Ṇࡍࡿࡓࡵ࡟㟁Ꮚࣅ࣮࣒↷ᑕ๓ᚋࡢヨᩱ⾲㠃࡟ࠊཌࡉ⣙ 4 nm ࡢ㔠ⷧ⭷ࢆ⵨╔ࡋ࡚ࠊCu 〇ࡢࢧࣥࣉࣝ࣍ࣝࢲ࣮࡟ᑟ㟁ᛶ࣮࢝࣎ࣥࢸ࣮ࣉ࡛ᅛᐃࡋࡓࡶࡢࢆ ᐃ࡟౪ࡋࡓࠋᐃࡣ BL46XU ࡟࠾࠸࡚༙⌫ᆺ࢔ࢼࣛ࢖ࢨ࣮㻔VG-SCIENTA 〇 R-4000㻕ࢆഛ࠼ࡓ HAXPES ᐇ㦂⿦⨨ࢆ⏝࠸ᐊ ࡟࡚⾜ࡗࡓࠋධᑕ X ⥺࢚ࢿࣝࢠ࣮ࡣ 8 keVࠊ࢔ࢼࣛ࢖ࢨ࣮ධᑕࢫࣜࢵࢺࡣ curved 0.5mmࠊࣃࢫ࢚ࢿࣝࢠ࣮ࡣ 200 eV ࡟ࡑࢀࡒࢀタᐃࡋࡓࠋࡲࡓᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࡢ࢚ࢿࣝࢠ࣮⿵ṇࡣࠊྠ᫬࡟ ᐃࡋࡓ Au4f7/2 ࣆ࣮ࢡࢆ⏝࠸࡚⾜ࡗࡓࠋIntensity (arb.units)

Intensity (arb.units)⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸
ᅗ 1 ࡟㟁Ꮚࣅ࣮࣒↷ᑕ๓ᚋ࡟࠾ࡅࡿ Gd ῧຍ AlN ⷧ⭷ࡢ N1s ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᅗ୰ࡢ after 㻔1㻕ࡣࠊ㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡾ᭱ึࡢⓎගᙉᗘ࠿ࡽ 1/2 ࡲ࡛ᙉᗘࡀῶ⾶ࡋࡓヨᩱ࡛ࠊafter 㻔2㻕 ࡣࠊ1/4
ࡲ࡛ᙉᗘࡀῶ⾶ࡋࡓヨᩱ࡛࠶ࡿࠋ㟁Ꮚࣅ࣮࣒↷ᑕᚋࡢⷧ⭷࡛ࡣࠊ㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡾ N ཎᏊࡀᢤࡅࡓࡓࡵ࡟ࠊࣆ࣮ࢡᙉᗘࡀᑠࡉࡃ࡞ࡗ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࣆ࣮ࢡ఩⨨ࡣప࢚ࢿࣝࢠ࣮ഃ
࡟ࢩࣇࢺࡋ࡚࠾ࡾࠊࣆ࣮ࢡ఩⨨ࡀ㧗࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡓᐇ㦂ᐊ⣔ XPS ᐃࡢ⤖ᯝ࡜ࡣ
㏫᪉ྥ࡟ࣆ࣮ࢡࡀࢩࣇࢺࡋ࡚࠸ࡿࠋ

N1s
䠉before䠉after (1)䠉after (2)




405400395390
Binding Energy (eV)
ᅗ 1㸬㟁Ꮚ⥺↷ᑕ๓ᚋ࡟࠾ࡅࡿ Gd ῧຍ AlN ⷧ⭷ࡢ N1s ࢫ࣌ࢡࢺࣝ

ᅗ 2 ࡟♧ࡋࡓ Al2sࠊཬࡧᅗ 3 ࡟♧ࡋࡓ Gd3d ࢫ࣌ࢡࢺࣝࡶྠᵝ࡟ࠊ㟁Ꮚࣅ࣮࣒↷ᑕᚋࡢࣆ࣮ࢡᙉᗘࡣᑠࡉࡃ࡞ࡗ࡚࠾ࡾࠊࣆ࣮ࢡ఩⨨ࡣᐇ㦂ᐊ⣔ XPS ᐃ࡛ࡣ㧗࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡓ
ࡢ࡟ᑐࡋ࡚ࠊHAXPES ᐃ࡛ࡣప࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡓࠋࡇࢀࡽࡢኚ໬ࡀࠊ㟁Ꮚࣅ࣮࣒ບ㉳ࡢ㝿࡟ Gd ῧຍ AlN ⷧ⭷࠿ࡽⓎ⏕ࡍࡿ࢝ࢯ࣮ࢻ࣑ࣝࢿࢵࢭࣥࢫᙉᗘࡀపୗࡍࡿཎᅉ࡜㛵ಀࡀ࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ

Al 2s
䠉before䠉after (1)䠉after (2)







124
122
120
118
116

Binding
Energy(eV)ᅗ 2㸬㟁Ꮚ⥺↷ᑕ๓ᚋ࡟࠾ࡅࡿ Gd ῧຍ AlN ⷧ⭷ࡢ Al2s ࢫ࣌ࢡࢺࣝ


Intensity (arb.units) 
Gd 3d5/2 䠉before䠉after (1)䠉after (2)






1200
1190
1180
Binding
Energy(eV)ᅗ 3㸬㟁Ꮚ⥺↷ᑕ๓ᚋ࡟࠾ࡅࡿ Gd ῧຍ AlN ⷧ⭷ࡢ Gd3d ࢫ࣌ࢡࢺࣝᡃࠎࡣᐇ㦂⤖ᯝࡼࡾࠊ┿✵୰࡛㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡗ࡚ヨᩱ⾲㠃ࡣ㑏ඖࡉࢀࠊࡑࡢᚋࠊ኱Ẽ୰࡟ྲྀࡾฟࡋࡓ᫬࡟ࠊヨᩱࡢᴟ⾲㠃ࡔࡅࡀ㓟໬ࡉࢀࡓ࡜࠸࠺ᶵᵓࢆ⪃࠼࡚࠸ࡿࡀࠊࡑࡢ௚࡟ࡶヨᩱ⾲㠃ࡢᖏ㟁࡟ࡼࡿᙳ㡪ࡸ௚ࡢᅉᏊࡶ⪃࠼ࡽࢀࠊヲ⣽࡟ࡘ࠸࡚ࡣ௒ᚋࡉࡽ࡟ㄪᰝࡀᚲせ࡛࠶ࡿࠋ௒ᅇ HAXPES ᐃ࡟ࡼࡾࠊ㟁Ꮚࣅ࣮࣒↷ᑕࢆཷࡅࡓ Gd ῧຍ AlN ῝⣸እ⺯ගⷧ⭷࡟ࡘ࠸࡚ࠊᐇ㦂ᐊ⣔ XPS ᐃ࡛ࡣᚓࡽࢀ࡞࠿ࡗࡓ▱ぢࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡓࠋ௒ᚋࡢㄢ㢟㸸௒ᚋࠊ㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡾヨᩱࡢ XPS ࢫ࣌ࢡࢺࣝࡀ࡝ࡢࡼ࠺࡟ኚ໬ࡍࡿ࠿ࢆヲ⣽࡟ㄪ࡭ࠊヨᩱຎ໬ࡢཎᅉ࡜㧗㍤ᗘ໬ࡢせᅉࢆࡉࡽ࡟ㄪᰝࡍࡿᚲせࡀ࠶ࡿࠋᮏᐇ㦂ࡢ⤖ᯝ࠿ࡽࠊ㟁Ꮚࣅ࣮࣒↷ᑕ࡟ࡼࡗ࡚ⷧ⭷ࡣ㑏ඖࡉࢀࠊࡑࡢᚋࠊᴟ⾲㠃ࡢࡳࡀ㓟໬ࡉࢀࡓ࡜࠸࠺ᶵᵓࢆ⪃ᐹࡋ࡚࠸ࡿࡀࠊ௒ᅇࡢ ᐃ࡛ࡣᖏ㟁㜵Ṇ⏝࡟⵨╔ࡋࡓ㔠ⷧ⭷ࡀཌ࠿ࡗࡓࡓࡵࠊฟᑕゅ౫Ꮡᛶࡢ ᐃࡀ࡛ࡁ࡞࠿ࡗࡓࠋḟᅇࡣ㔠ⷧ⭷ࡢཌࡉࢆ 1㹼4 nm ࡢ⠊ᅖෆ࡛ኚ࠼ࡓヨᩱࢆ‽ഛࡋࠊග㟁Ꮚࡢฟᑕゅᗘ౫Ꮡᛶࡢ ᐃ࡟ࡼࡾ⭷ཌ᪉ྥ࡛ࡢྛᵓᡂඖ⣲ࡢ໬Ꮫ≧ែศᯒࢆ⾜࠸ࠊຎ໬ᶵᵓࡢጇᙜᛶࢆ᳨ウࡋࡓ࠸ࠋཧ⪃ᩥ⊩㸸[1] T. Kita et al., Appl. Phys. Lett., 93, 21190,㻌㻔2008㻕.
[2] S.Kitayama et al., IOP Conf. Series: Materials Science and Engineering, 1, 012001, 㻔2009㻕.
[3]ᑠᯘᖿᘯ௚, ᖹᡂ 22 ᖺᗘ SPring-8 㔜Ⅼ⏘ᴗ฼⏝ㄢ㢟ᡂᯝሗ࿌᭩, 㻔2010A1711㻕.