2011A1683                 BL46XUᕼ㔘❅໬≀༙ᑟయ࡟࠾ࡅࡿ࢔ࢽ࣮ࣝຠᯝࡢᨺᑕගࢆ⏝࠸ࡓ◳ X ⥺ග㟁Ꮚศගἲ࡟ࡼࡿ◊✲Analysis on the annealing effect of dilute nitride semiconductors
using hard x-ray photoelectron spectroscopy▼ᕝ ྐኴ㑻, ෤㔝 ⪽, ㏆⸨ ṇᙪ
Fumitaro Ishikawa, Satoshi Fuyuno, Masahiko Kondow኱㜰኱Ꮫ኱Ꮫ㝔ᕤᏛ◊✲⛉ Graduate school of Engineering, Osaka University
 ◳ X ⥺ග㟁Ꮚศග㻔HAX-PES㻕ࢆ⏝࠸ࠊᕼ㔘❅໬≀༙ᑟయ GaInNAs ࡢඖ⣲⤖ྜ≧ែ࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋࡲࡓࠊࡑࢀࡽ⤖ྜ≧ែࡢ⇕ฎ⌮ຠᯝ࡟ࡘ࠸࡚ࡶ᳨ウࢆ⾜ࡗࡓࠋヨᩱ⾲㠃ࡼࡾࠊ14 nm῝㒊࡟ᇙࡵ㎸ࡲࢀࡓ GaInNAs ᒙ࠿ࡽࡢಙྕࢆほ ࡍࡿࡇ࡜࡛ࠊGaInNAs ࣂࣝࢡ᝟ሗࡀᨭ㓄ⓗ࡞ࢫ࣌ࢡࢺࣝࡢほ ࡟ᡂຌࡋࡓࠋほ ࡉࢀࡓ In ࡢෆẆࣆ࣮ࢡࡣࠊ⇕ฎ⌮࡟ࡼࡿ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡀほࡉࢀࠊࡑࢀࡣ⤖ྜ࢚ࢿࣝࢠ࣮ࢆῶᑡࡉࡏࡿࡶࡢࡔࡗࡓࠋᵓᡂ๭ྜᩘ%࡜ࠊ᳨ฟ㝈⏺࡟㏆࠸ N1s࿘㎶ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡶࠊほ ࡟ᡂຌࡋࡓࠋN1s ࢫ࣌ࢡࢺࣝ࡟ࡘ࠸࡚ࡶ⇕ฎ⌮࡟ࡼࡿࣆ࣮ࢡᙧ≧ࠊ఩⨨ࡢኚ໬ࡀぢࡽࢀࠊIn-N ඖ⣲⤖ྜࡀቑຍࡋࡓྍ⬟ᛶࡀ♧၀ࡉࢀࡓࠋ࣮࣮࢟࣡ࢻ㸸 ᕼ㔘❅໬≀༙ᑟయࠊHAXPESࠊ⤖ᬗᡂ㛗ࠊḞ㝗ࠊ⇕ฎ⌮⫼ᬒ࡜◊✲┠ⓗ㸸ᕼ㔘❅໬≀༙ᑟయࡣࠊGaAs ࡸ InP ࡜࠸ࡗࡓ III-V ᪘໬ྜ≀༙ᑟయ࡟ࠊᩘ%ࡢ❅⣲㻔N㻕ࢆῧຍࡋࡓ༙ᑟయ⤖ᬗ࡛࠶ࡿࠋᩘ㸣࡜࠸࠺ࠊᴟᑡ㔞ࡢ N ῧຍ࡟ࡼࡗ࡚ࠊ⤖ᬗࡢ཰⦰࡟ຍ࠼ࠊ≉␗࡞࢚ࢿࣝࢠ࣮ࣂࣥࢻᵓ㐀ࡢኚ໬ࡀⓎ⏕ࡋࠊࡑࢀ࡟క࠺ⓎගἼ㛗ࡢ␗ᖖ࡞㛗Ἴ㛗໬ࡀᘬࡁ㉳ࡇࡉࢀࡿࠋࡇࡢᚑ᮶࡟࡞࠸ࣂࣥࢻᵓ㐀ࡢྍኚᛶ࠿ࡽࠊྠᮦᩱ⣔ࡣࠊ᪂ᮦᩱኴ㝧㟁ụࡸ㏻ಙ⏝࣮ࣞࢨ➼ࡢḟୡ௦༙ᑟయࢹࣂ࢖ࢫᮦᩱ࡜ࡋ࡚ᮇᚅࡉࢀ࡚࠸ࡿࠋ㠀ΰ࿴ᛶࡢᙉ࠸ᮦᩱࡀΰᅾࡍࡿྠ⤖ᬗࡢᡂ㛗ࡣࠊ㧗 ᡂ㛗࡛ࡣ⤖ᬗ┦ศ㞳ࡀⓎ⏕ࡍࡿࡓࡵࠊప ᡂ㛗ࡀᚲせ࡟࡞ࡿࠋࡋ࠿ࡋ࡞ࡀࡽప ᡂ㛗࡛ࡣࠊᡂ㛗┤ᚋࡣከࡃࡢḞ㝗ࢆྵ᭷ࡋ࡚࠾ࡾࠊࡑࡢḞ㝗ᢚไ࡟⇕ฎ⌮㸦࢔ࢽ࣮ࣝ㸧ࡀᚲせ࡜࡞ࡿࠋ[1,2]ࡇࡢ࢔
ࢽ࣮ࣝࡣࠊⓎගᙉᗘࡢ኱ᖜ࡞ᨵၿ࡟ຍ࠼ࠊⓎගἼ㛗ࡢ▷Ἴ㛗໬ࢆⓎ⏕ࡉࡏࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿࠋࡇࢀࡲ࡛ࠊ࢔ࢽ࣮ࣝ࡟ࡼࡿ▷Ἴ㛗໬ࡢㄝ᫂࡜ࡋ࡚௦⾲ⓗ࡞ࡶࡢࡣࠊཎᏊ࿘㎶ࡢ III ᪘ཎᏊࡢ෌㓄ิࢆཎᅉ࡜ࡍࡿㄝ࡛࠶ࡿࠋ[3] ౛࠼ࡤ GaInNAs ࡢሙྜ࡛ࡣࠊN ཎᏊ࿘㎶࡟ Ga3In1N ࡜࠸ࡗࡓཎᏊ㓄ิࡀከࡃ࡞ࡿࡇ࡜ࡀண ࡉࢀ࡚࠸ࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ㆟ㄽࡢ⤊⤖ࢆᚓ࡚࠾ࡽࡎࠊGaࠊIn ୧᪉ࡢཎᏊ㓄ิࢆᐇ㝿࡟ ᐃࡋࡓሗ࿌࠿ࡽᐇドࡉࢀࡓ౛ࡣ࡞࠸ࠋ ௨ୖࡼࡾࠊGaInNAs ⤖ᬗ୰ࡢ N ཎᏊࡢ⤖ྜ≧ែ࡟ࡘ࠸࡚ヲ⣽࡞᳨ウࢆ⾜࠺ࡓࡵࠊᮏ◊✲࡛ࡣࠊᚑ᮶ሗ࿌ࡢ↓࠸◳ X ⥺ග㟁Ꮚศගࢆ⏝࠸࡚ࠊᕼ㔘❅໬≀༙ᑟయᵓᡂඖ⣲ࡢ⤖ྜ≧ែࢆㄪ࡭࡚࠸ࡃࠋ௨ࡗ࡚ྠ⤖ᬗ࡟࠾ࡅࡿࠊ࢔ࢽ࣮ࣝ᫬ࡢ N ࿘㎶⤖ᬗᵓ㐀࡟ࡘ࠸࡚ヲ⣽࡞᳨ウࢆ⾜࠸ࠊⓎගᙉᗘࡢᨵၿࠊ࠾ࡼࡧࠊⓎගἼ㛗▷Ἴ㛗໬࡜ࡢ┦㛵ࢆ᫂ࡽ࠿࡟ࡍࡿࡇ࡜ࢆ┠ⓗ࡜ࡋ࡚ࠊ◊✲ࢆ⾜ࡗࡓࠋᐇ㦂㸸◳ X ⥺ග㟁Ꮚศග㻔HAX-PES㻕ࢆ⏝࠸ࠊᕼ㔘❅໬≀༙ᑟయࡢࣂࣝࢡ≧ែ࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋ᭱ࡶ୺せ࡞ヨᩱࡣࠊ⾲㠃࠿ࡽ 15nm ෆ㒊࡟ᇙࡵ㎸ࡲࢀࡓ GaInNAs 㔞Ꮚ஭ᡞᵓ㐀࡛࠶ࡿࠋGaAs ᒙࡢୗ࡟ᇙࡶࢀࡓ GaInNAs ᒙࡢศᯒࢆ⾜࠺ᚲせࡀ࠶ࡿ
ࡀࠊ㏻ᖖࡢᐇ㦂ᐊග※ࢆ⏝࠸ࡓ XPS ࡛ࡣศᯒ῝ࡉࡣࡏ࠸ࡐ࠸ᩘ nm ࡛࠶ࡾࠊGaInNAs ᒙࡢศᯒࢆ㠀◚ቯ࡛⾜࠺ࡇ࡜ࡣᅔ㞴࡛࠶ࡿࠋࡼࡗ࡚ศᯒ῝ࡉࡀ
20 nm ⛬ᗘ࠶ࡿ HAXPES ࡟ࡼࡿศᯒࢆ⾜ࡗࡓࠋࡉᅗ㸯 ᐇ㦂ᴫせࡽ࡟ࠊ⇕ฎ⌮๓ᚋࡢྠヨᩱࢆẚ㍑᳨ウࡍࡿࡇ࡜࡛ࠊᵓᡂඖ⣲ࡢ⤖ྜ≧ែ࡟ࡘ࠸᳨࡚ウࢆ⾜ࡗࡓࠋᅗ㸯࡟ᐇ㦂ࡢᴫせࢆ♧ࡍࠋGa1.0N0.008As0.992 㻔14 nm㻕/Ga0.74In0.36N0.045As0.955 㻔7 nm㻕ࢆ 10 ࿘ᮇ⧞ࡾ㏉ࡋࡓ✚ᒙᵓ㐀࡜࡞ࡗ࡚࠸ࡿࠋ[4] ᚑࡗ࡚ࠊ⾲㠃࠿ࡽ 14nm ࡢ఩⨨࡟ᇙࡵ㎸ࡲࢀࡓ GaInNAs ᒙࡢಙྕࢆほ ࡛ࡁࢀࡤࠊࡑࡢ In ࠾ࡼࡧ N ࠿ࡽࡢ᝟ሗࡣࠊ⾲㠃࡟ᙳ㡪ࡉࢀ࡞࠸ෆ㒊ࡢ᝟ሗࡀᚓࡽࢀ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ⇕ฎ⌮ࡣࠊ㧗㏿ຍ⇕ฎ⌮㻔Rapid thermal annealing: RTA㻕ࢆࠊ❅⣲㞺ᅖẼ୰࡟࠾࠸࡚ 1ศ㛫ࠊ700Υ࡛⾜ࡗࡓࠋࡇࡢฎ⌮࡟ࡼࡾࠊගᏛ≉ᛶࡀ๻ⓗ࡟ᨵၿࡋࠊᡂ㛗┤ᚋ࡛ࡣほ ࡛ࡁ࡞࠿ࡗࡓᐊ ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫⓎගࡀࠊⰋዲ࡟ほ ࡛ࡁࡿࡼ࠺࡟࡞ࡿࡇ࡜ࢆࡇࢀࡲ࡛࡟☜ㄆࡋ࡚࠸ࡿࠋ[4]ᚑࡗ࡚ᮏ◊✲࡛ࡣࠊࡇࡢ⇕ฎ⌮࡟ࡼࡿⓎග≉ᛶࡢᨵၿࢆࠊඖ⣲⤖ྜ≧ែ࠿ࡽゎ᫂ࡍࡿࡇ࡜ࢆ┠ᣦࡍࠋHAX-PES ࡣࠊධᑕ X ⥺ࡢධᑕゅࡀ 10oࠊග㟁Ꮚࡢྲྀࡾฟࡋゅࡀ 80o ࡛⾜ࡗࡓࠋ⤖ᯝ࠾ࡼࡧ⪃ᐹ㸸ᅗ㸰ࡣࠊIn3d ࿘㎶ࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋIn ඖ⣲ࡣ GaInNAs ᒙ࡟ࡋ࠿Ꮡᅾࡋ࡞࠸ࡓࡵࠊࡇࡢࢫ࣌ࢡࢺࣝࡣ GaInNAs ᒙࡢ᝟ሗࢆ㑅ᢥⓗ࡟ほ ࡋ࡚࠸ࡿࠋྠࢫ࣌ࢡࢺࣝࡣࠊ⇕ฎ⌮๓ᚋ࡛ࠊ᫂☜࡟ࣆ࣮ࢡ఩⨨ࡢኚ໬ࡀほ ࡉࢀࠊ⇕ฎ⌮࡟ࡼࡗ࡚ࡑࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࡣῶᑡࡋࡓࠋࡇࢀࡽࡢ⤖ᯝࢆ㋃ࡲ
࠼ࡿ࡜ࠊN ඖ⣲࿘㎶࡛ࡢ⇕ฎ⌮࡟ࡼࡿ⤖ྜ≧ែࡢኚ໬ࡀ⪃࠼ࡽࢀࠊࡉࡽ࡟ࠊࡑࡢኚ໬ࡣ In ඖ⣲ࡢ⤖ྜ࢚ࢿࣝࢠ࣮ࢆῶᑡࡉࡏࡿ᪉ྥ࡟ാࡃࡇ࡜ࡀ♧၀ࡉࢀࡓࠋࡇࡢ⤖ᯝࡣࠊ๓㏙ࡢࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫⓎග≉ᛶࡢᨵၿ࡟ᑐࡋ࡚ࠊIn ඖ⣲࿘㎶ࡢ⤖ྜ≧ែࡀᐤ୚ࡋ࡚࠸ࡿྍ⬟ᛶࡀ⪃࠼ࡽࢀࡿࠋヲ⣽࡞⌧㇟ࡢ⌮ゎࡢࡓࡵ࡟ࡣࠊ௨㝆ࠊࡇࢀࡽࡢ⤖ᯝ࡟ᑐࡋ࡚ࡼࡾ㐍ࢇࡔ⌮ㄽ᳨ウࢆຍ࠼ࠊGaInNAs⤖ᬗ୰ࡢඖ⣲㟁Ꮚ≧ែ࡟ࡘ࠸࡚᫂ࡽ࠿࡟ࡋ࡚࠸ࡃࠋᅗ㸱ࡣࠊ௒ᅇᚓࡽࢀࡓ N1s ࿘㎶ࢫ࣌ࢡࢺ࡛ࣝ
࠶ࡿࠋ࠾ࡼࡑ 50 ᅇ⛬ᗘࡢࢫ࣌ࢡࢺࣝࢆ✚⟬ࡍࡿࡇ࡜࡛ࠊᚑ᮶୙ྍ⬟࡛࠶ࡗࡓࢫ࣌ࢡࢺࣝࡢほ ࡟ᡂຌࡋࡓࠋࡉࡽ࡟ࠊ࢔ࢽ࣮ࣝ๓ᚋ࡛ࠊ398 eV ࠾ࡼࡧ 400eV ௜㏆࡛ほ ࡉࢀࡓࣆ࣮ࢡࡢࠊᙧ≧ࠊ఩⨨ࡢኚ໬ࡀぢࡽࢀࡓࠋヨᩱ᭱ୖ㒊ࡢ GaNAs ᒙ࡟࠾ࡅࡿ❅⣲ࡢᙳ㡪ࡀ⪃࠼ࡽࢀࡿࡀࠊ༢ᒙࡢ GaNAs
ᒙ࡟࠾ࡅࡿ HXPES ᐃ࡛ࡣࠊ⇕ฎ⌮๓ᚋ࡛ᵓᡂඖ⣲ࡢ Ga ࡸ As ࡟࠾ࡅࡿࣆ࣮ࢡࡢ᫂☜࡞ኚ໬ࡣᚓࡽࢀ࡞࠿ࡗࡓࠋᚑࡗ࡚௒ᅇᚓࡽࢀࡓ⤖ᯝࡣࠊGaInNAs 㔞Ꮚ஭ᡞᒙ୰ࡢ N ඖ⣲࡟࠾ࡅࡿࠊN ࿘㎶ࡢ⤖ྜ≧ែࡀኚ໬ࡋ࡚࠸ࡿࡇ࡜ࢆ♧ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ๓㏙ࡢ In3d ௜㏆ࡢ⤖ᯝ࡟ࠊࡇࡇ࡛ᚓ
ࡽࢀࡓ N ࿘㎶ࡢ᝟ሗࢆຍ࠼࡚⪃ᐹࢆ㐍ࡵࡿࡇ࡜࡛ࠊ≉࡟ከࡃ㆟ㄽࡢ࠶ࡿ In-N ⤖ྜࡢ≧ែ࡟ࡘ࠸࡚
᝟ሗࡀᚓࡽࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ[3]ᚑ᮶ࡣ X ⥺྾཰ᚤ⣽ᵓ㐀 ᐃ࡟ࡼࡗ࡚ࡢࡳࡇࢀࡽ⤖ྜ≧ែࡢゎᯒࡀ࡞ࡉࢀ࡚ࡁࡓࡀࠊ௒ᅇᚓࡽࢀࡓࢫ࣌ࢡࢺࣝࢆヲ⣽࡟ゎᯒࡍࡿࡇ࡜࡛ࠊᚑ᮶ࡢ㆟ㄽࢆ⿵᏶ࡋࠊ᪂ࡓ࡞▱ぢࡀᚓࡽࢀࡿࡶࡢ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ௒ᚋࡢㄢ㢟㸸 ௒ᅇࡣࠊ࠾ࡼࡑ༙᪥ࡢ✚⟬ࢆ⾜࠺ࡇ࡜࡛ࠊᅗ㸯࡟♧ࡍ N1s ࿘㎶ࢫ࣌ࢡࢺࣝࡢほ ࡟ᡂຌࡋࡓࠋ❅⣲࿘㎶ࡢ⤖ྜ≧ែࡢゎᯒ࡟㔜Ⅼࢆ⨨ࡃᮏ◊✲࡟࠾࠸࡚ࠊ㠀ᖖ࡟㈗㔜࡞⤖ᯝࢆᚓࡿࡇ࡜ࡀฟ᮶ࡓࠋࡋ࠿ࡋ࡞ࡀࡽྠࢫ࣌ࢡࢺࣝ࡟⨨࠸࡚ࡶࠊ௚ࡢࢫ࣌ࢡࢺࣝ࡜ẚ㍑ࡍࡿ࡜ࠊඖ⣲ࡢ⤯ᑐ㔞ࡢᑠࡉࡉࡶ
࠶ࡾࠊS/N ẚࡢⰋዲ࡞ࢫ࣌ࢡࢺࣝ࡜ࡣゝ࠸㞴ࡃࠊྍ⬟࡛࠶ࢀࡤࡉࡽ࡞ࡿࢫ࣌ࢡࢺࣝࣀ࢖ࢬࡢῶᑡ࡟ࡼࡾࠊࡼࡾヲ⣽࡞᳨ウࡀ㐙⾜࡛ࡁࡿࡇ࡜ࡀᮃࡲࡋ࠸ࠋ

ᅗ㸰 In3d ࿘㎶ࢫ࣌ࢡࢺࣝ

ᅗ㸱 N1s ࿘㎶ࢫ࣌ࢡࢺࣝ

ཧ⪃ᩥ⊩㸸
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