金属と多孔質シリコンの複合ナノ微粒子の作製と評価

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➨1❶ ᗎㄽ ... 1 1.1 ◊✲⫼ᬒཬࡧ┠ⓗ ... 1 1.2 ᮏㄽᩥࡢᵓᡂ ... 2 ➨2❶ ホ౯᪉ἲཬࡧ ᐃཎ⌮ ... 3 2.1 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ ... 3 2.1.1 ࡣࡌࡵ࡟ ... 3 2.1.2 ཎ⌮ ... 3 2.1.3 ᐇ㦂⣔ ... 6 2.2 ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾 ... 7 2.2.1 ࡣࡌࡵ࡟ ... 7 2.2.2 ཎ⌮ ... 8 2.3 X⥺ග㟁Ꮚศගἲ ... 10 2.3.1 ཎ⌮ ... 10 2.4 ග྾཰ ᐃ ... 12 2.4.1 ྾཰ಀᩘࡢ ᐃ ... 12 2.4.2 ᐇ㦂⣔ ... 15 2.4.3 ᣑᩓ཯ᑕἲ ... 16

2.5 Rapid Thermal Anneal (RTA) ⿦⨨ ... 17

2.5.1 ㉥እ⥺ࣛࣥࣉຍ⇕⅔ ... 17 2.5.2 ຍ⇕ヨᩱ⣔ ... 17 2.5.3  ᗘไᚚ⣔ ... 18 ➨3❶ HF/AgNO₃ΰྜᾮ୰࡛ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢ࡟ࡼࡿከᏍ㉁Si⢊ᮎࡢస〇 ... 20 3.1 ᗎㄽ ... 20 3.2 ᐇ㦂 ... 20 3.2.1 PSi/Ag」ྜᚤ⢏Ꮚࡢస〇᮲௳ ... 21 3.2.2 ౑⏝ࡋࡓヨᩱ࡜⁐ᾮ ... 211 3.2.3 ᐇ㦂ᡭ㡰 ... 221 3.2.4 ໬Ꮫ཯ᛂࣔࢹࣝ ... 222 3.3 ホ౯᪉ἲ ... 23 3.3.1 X⥺ග㟁Ꮚศගἲ(XPS) ᐃ ... 23 3.3.2 ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾(SEM) ᐃ ... 23 3.3.3 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ ... 23 3.3.4 ᣑᩓ཯ᑕ ᐃ ... 23 3.4 ᐇ㦂⤖ᯝ ... 23 3.4.1 XPS ᐃ⤖ᯝ ... 24 3.4.2 SEM ᐃ⤖ᯝ ... 26

3.4.3 ⁐፹࡟ᑐࡍࡿぶ࿴ᛶ ... 27 3.4.4 PL ᐃ⤖ᯝ ... 28 3.4.5 PL ᐃ⤖ᯝ㸦 ᗘ౫Ꮡᛶ㸧 ... 30 3.4.6 PL ᐃ⤖ᯝ㸦Ag㝖ཤ㸧 ... 32 3.4.7 PL ᐃ⤖ᯝ㸦⣸እග↷ᑕ᫬㛫౫Ꮡᛶ㸧 ... 33 3.4.8 ᣑᩓ཯ᑕ ᐃ⤖ᯝ ... 34 3.5 ⤖ㄽ ... 36 ➨ 4 ❶ HF/HNO₃ΰྜᾮ୰࡛స〇ࡉࢀࡓከᏍ㉁ Si⢊ᮎࡢᵝࠎ࡞᭷ᶵ⁐፹୰࡛ࡢⓎග≉ᛶ ... 37 4.1 ᗎㄽ ... 37 4.2 ᐇ㦂 ... 37 4.2.1 ౑⏝ࡋࡓヨᩱ࡜⁐ᾮ ... 38 4.2.2 ㉸㡢Ἴ⬺⬡Ὑί ... 38 4.2.3 స〇᪉ἲ ... 38 4.2.4 ᐇ㦂ᡭ㡰ձ㸦Si⢊ᮎ㸧 ... 38 4.2.5 ᐇ㦂ᡭ㡰ղ㸦Siᇶᯈ㸧 ... 39 4.2.6 ໬Ꮫ཯ᛂࣔࢹࣝ ... 41 4.3 ホ౯᪉ἲ ... 41 4.3.1 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ ... 41 4.4 ᐇ㦂⤖ᯝ ... 42 4.4.1 PL ᐃ⤖ᯝ ... 42 4.5 ⤖ㄽ ... 45 ➨㸳❶ HF/HNO₃ΰྜᾮ୰࡛స〇ࡉࢀࡓከᏍ㉁ Si ⢊ᮎࡢⓎග≉ᛶ࡟ᑐࡍࡿ஝⇱᪉ἲࡢᙳ 㡪 ... 46 5.1 ᗎㄽ ... 46 5.2 ᐇ㦂 ... 46 5.2.1 ౑⏝ࡋࡓヨᩱ࡜⁐ᾮ ... 46 5.2.2 స〇᪉ἲ ... 46 5.2.3 ᐇ㦂ᡭ㡰 ... 46 5.3 ホ౯᪉ἲ ... 47 5.3.1 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ ... 47 5.4 ᐇ㦂⤖ᯝ ... 48 5.4.1 PL ᐃ⤖ᯝ ... 48

➨6❶ ࣏࣮ࣛࢫࢩࣜࢥࣥᇶᯈ࡟ᑐࡍࡿ࢔ࢽ࣮ࣝฎ⌮ຠᯝ... 52 6.1 ᗎㄽ ... 52 6.2 ᐇ㦂 ... 52 6.2.1 ౑⏝ࡋࡓヨᩱ࡜⁐ᾮ ... 52 6.2.2 ㉸㡢Ἴ⬺⬡Ὑί ... 52 6.2.3 స〇᪉ἲ ... 52 6.2.4 ᐇ㦂ᡭ㡰 ... 54 6.3 ホ౯᪉ἲ ... 54 6.3.1 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ ... 54 6.3.2 FTIR ᐃ ... 54 6.4 ᐇ㦂⤖ᯝ ... 55 6.4.1 PL ᐃ⤖ᯝ ... 55 6.4.2 FTIR ᐃ⤖ᯝ ... 56 6.5 ⤖ㄽ ... 57 ➨7❶ ⤖ㄽ ... 58 ㅰ㎡ ... 60

➨

1

❶

ᗎㄽ

1.1 ◊✲⫼ᬒཬࡧ┠ⓗ   ࡇࡢᆅୖ࡛㓟⣲࡟ḟ࠸࡛㇏ᐩ࡟Ꮡᅾࡍࡿඖ⣲࡛࠶ࡿSiࡣࡑࡢ㇏ᐩࡉ࠿ࡽࠊ㠀ᖖ࡟Ᏻ౯ ࡛ྲྀࡾᘬࡁࡉࢀ࡚࠸ࡿࠋࡲࡓࠊSi ཎᏊࡣ᭱኱Ẇ࡟㟁Ꮚࢆ 8 ಶࡶࡘᏳᐃࡋࡓ༙ᑟయᮦᩱ࡛࠶ ࡿࡓࡵࠊ⌧ᅾ༙ᑟయࢹࣂ࢖ࢫࡢᮦᩱ࡜ࡋ࡚ከࡃ౑ࢃࢀ࡚࠸ࡿࠋࡋ࠿ࡋࠊᚑ᮶ࠊSi ࡣ㛫᥋㑄 ⛣ᆺࣂࣥࢻࢠࣕࢵࣉࢆࡶࡘࡇ࡜࠿ࡽⓎගᮦᩱ࡟ᛂ⏝࡛ࡁ࡞࠸࡜⪃࠼ࡽࢀ࡚ࡁࡓࠋ࡜ࡇࢁࡀࠊ ࡇࡢᐃㄝࢆࡺࡿࡀࡍᐇ㦂஦ᐇࡀࡇࡢᩘᖺ㛫࡟ḟࠎ࡜ሗ࿌ࡉࢀࠊSi ࡟࠾ࡅࡿ᭱኱ࡢᮦᩱᏛⓗ ไ⣙ࡀඞ᭹ࡉࢀࡿྍ⬟ᛶࡀ࡛࡚ࡁࡓࠋ 1, 2) ࡑࡢඛ㥑ࡅ࡜ࡋ࡚ࠊ1956 ᖺ࡟࣋ࣝ◊✲ᡤࡢUlhir ࡟ࡼࡾࠊ㝧ᴟ໬ᡂࡋࡓ Si ᇶᯈ⾲㠃࡛࣏࣮ࣛࢫᵓ㐀ࡢ☜ㄆࡀሗ࿌ࡉࢀࡓࠋ 3) ࣏࣮ࣛࢫᵓ㐀࡜ ࡣࠊᇶᯈୖ࡟↓ᩘࡢᏍࡢ㛤࠸ࡓᵓ㐀ࢆᣢࡘࠊከᏍయࡢࡇ࡜ࢆ♧ࡍࠋ  ࡉࡽ࡟ࠊ1990ᖺ࡟ࡣCanham࡟ࡼࡾ㔞Ꮚࢧ࢖ࢬຠᯝࡢྍ⬟ᛶࡀᥦၐࡉࢀࠊ࣏࣮ࣛࢫSi (PSi) ࡀᮏ᱁ⓗ࡟◊✲ࡉࢀ࡚࠸ࡃࡼ࠺࡟࡞ࡗࡓࠋ 4)

⤖ᬗSi (c-Si)ࡣࠊMOSFETࡸLSI࡜࠸ࡗࡓ༙ᑟ

య⏘ᴗࡢ௦⾲ⓗ࡞ᮦᩱ࡛࠶ࡾࠊࡑࡢࣂࣥࢻᵓ㐀ࡣࠊ㛫᥋㑄⛣ᆺࢆ᭷ࡋࠊࣂࣥࢻࢠࣕࢵࣉ(E_g)

ࡣᐊ ࡛1.11 eV࡛࠶ࡿࠋ

5)

ࡇࡢ≀ᛶ࠿ࡽࠊc-Siࢆ࣮࣋ࢫ࡜ࡋࡓⓎග⣲Ꮚࡢ◊✲࣭㛤Ⓨࡣࠊ PSi ࡢᐊ ࡛ࡢ㉥ⰍⓎගࡀ☜ㄆࡉࢀࡿ࡜ࠊPSi ࢆᛂ⏝ࡋࡓⓎගࢲ࢖࣮࢜ࢻ (Light Emission Diode : LED)ࡸගᏛ⣲Ꮚࡢ◊✲࣭㛤Ⓨࡀ㐍ࡴࡼ࠺࡟࡞ࡗࡓࠋ 6,7 ) PSiࡣᗈ࠸⠊ᅖ࡛㧗࠸ᒅᢡ⋡ ไᚚࢆࡶࡗࡓගᏛ፹㉁࡛࠶ࡾࠊග㞟✚ࡢᇶᮏせ⣲࡜ࡋ࡚᭷ຠ࡟ാࡃࡇ࡜࠿ࡽ௒ᚋࡣࠊࣔࣀ ࢩࣜࢵࢡග㞟✚࡬ࡢᒎ㛤࡜࡜ࡶ࡟ࠊPSiඹ᣺ჾ࡟࠾ࡅࡿ⮬↛ᨺฟගࡢไᚚ 8) ࠊ㠀⥺ᙧගᏛຠ ᯝ 9) ࠊගቑᖜ࡞࡝ࡢ◊✲ࡀ↔Ⅼ࡟࡞ࡿ࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋ Si ࡢ࣏࣮ࣛࢫᵓ㐀ࢆస〇ࡍࡿ࠺࠼࡛ࠊᚑ᮶ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡛ࡣฟⓎᮦᩱ࡜ࡋ࡚ Si ᇶᯈࡀ⏝࠸ࡽࢀ࡚ࡁࡓࠋࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲࡢ〇ἲࡣࠊSi ᇶᯈࢆ࢚ࢵࢳࣥࢢᾮ࡟ᾐࡍ ࡔࡅࡢࠊᇶᮏⓗ࡟ࡣ⡆༢࡞〇ἲ࡛࠶ࡿࡀࠊస〇ࡉࢀࡓPSiᒙࡢᆒ୍ᛶࡀᝏࡃࠊ෌⌧ᛶࡢၥ㢟 ࡶྵࢇ࡛࠸ࡿࠋࡇࢀࡽࡢၥ㢟Ⅼࢆ㍍ῶࡋࡓ〇ἲࡀࠊᚋ࡟ Goller ࡽ࡟ࡼࡗ࡚ᥦ᱌ࡉࢀࡓࠋࡇ ࡢ〇ἲ࡛ࡣヨᩱ࡟࣏ࣜSi⢊ᮎࢆ⏝࠸࡚PSi⢊ᮎࢆస〇ࡍࡿࠋ 10, 11) ࡇࡢ〇ἲࡢ฼Ⅼࡣࠊ⢊ᮎ ヨᩱࢆ⏝࠸ࡿࡇ࡜࡛ࠊᚑ᮶ࡢᇶᯈ࡟ẚ࡭࢚ࢵࢳࣥࢢࡉࢀࡿ⾲㠃✚ࡀ኱ࡁࡃࠊ୍ᗘ࡟኱㔞ࡢ PSiࢆస〇ࡍࡿࡇ࡜ࡀྍ⬟࡜࡞ࡿⅬ࡛࠶ࡿࠋࡋ࠿ࡋࠊከ⤖ᬗSi⢊ᮎࢆ⏝࠸ࡓ◊✲౛ࡣᑡ࡞ࡃࠊ ࡲࡓࠊస〇ࡉࢀࡓヨᩱࡢගᏛ≀ᛶ࡟ࡘ࠸࡚ࡶᮍ▱࡞㒊ศࡀከ࠸ࠋ ࡋࡓࡀࡗ࡚ᮏ◊✲࡛ࡣከ⤖ᬗࢩࣜࢥࣥ⢊ᮎࢆ⏝࠸࡚ PSi ⢊ᮎࢆస〇ࡋᵝࠎ࡞ගᏛホ౯ࢆ ┠ⓗ࡜ࡋ⾜ࡗࡓࠋ

1.2 ᮏㄽᩥࡢᵓᡂ ᮏㄽᩥࡣࠊ඲7❶࠿ࡽ࡞ࡿࠋ ➨1❶࡛ࡣࠊᗎㄽ࡛࠶ࡾࠊᮏ◊✲ࡢ⫼ᬒ࠾ࡼࡧ┠ⓗࢆ㏙࡭ࡓࠋ ➨2❶࡛ࡣࠊᮏ◊✲࡛⏝࠸ࡓࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL)ࠊX ⥺ග㟁Ꮚศග(XPS)ࠊ㉮ᰝᆺ㟁 Ꮚ㢧ᚤ㙾(SEM)ࠊ㏱㐣 ᐃࠊᣑᩓ཯ᑕ ᐃࡢᐇ㦂ཎ⌮ཬࡧࠊゎᯒ⌮ㄽࡢヲ⣽ࢆ㏙࡭ࡿࠋ ➨ 3❶࡛ࡣࠊHF/AgNO₃ΰྜᾮ୰࡛ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡟ࡼࡿከᏍ㉁Si ⢊ᮎࡢస〇᪉ ἲࡢㄝ᫂ཬࡧPL ᐃࠊXPS ᐃࠊᣑᩓ཯ᑕ ᐃࠊSEMほ ࡢゎᯒ⤖ᯝࢆ㏙࡭ࡿࠋ ➨ 4❶࡛ࡣࠊHF/HNO₃ΰྜᾮ୰࡛ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡟ࡼࡾస〇ࡋࡓ PSi⢊ᮎࡢ᭷ᶵ ⁐፹୰࡛ࡢ⃰ᗘ౫ᏑᛶࢆࠊPL ᐃࡢゎᯒ⤖ᯝࡼࡾ㏙࡭ࡿࠋ ➨ 5❶࡛ࡣࠊHF/HNO₃ΰྜᾮ୰࡛ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡟ࡼࡾస〇ࡋࡓ PSi⢊ᮎࡢ஝⇱ ᪉ἲ࡟ࡼࡿ㐪࠸ࢆࠊPL ᐃࡢゎᯒ⤖ᯝࡼࡾ㏙࡭ࡿࠋ ➨6❶࡛ࡣࠊࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡛స〇ࡋࡓPSiᇶᯈࡢ⇕࢔ࢽ࣮ࣝฎ⌮ຠᯝࢆࠊPL ᐃ ࡸFTIR ᐃࡢゎᯒ⤖ᯝࡼࡾ㏙࡭ࡿࠋ ➨7❶࡛ࡣࠊᮏ◊✲ࡢ⤖ㄽࢆ㏙࡭ࡿࠋ ཧ⪃ᩥ⊩

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Semiconductors (Kluwer Academic, Boston, 2004).

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410 (2001) 192.

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➨

2

❶

ホ౯᪉ἲཬࡧ ᐃཎ⌮

2.1 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ 2.1.1 ࡣࡌࡵ࡟ ୍⯡࡟ࠊ≀㉁࡟࢚ࢿࣝࢠ࣮ࢆ୚࠼ࡿ࡜ࡑࡢ࢚ࢿࣝࢠ࣮ࡣ྾཰ࡉࢀࡿࠋࡑࡋ࡚ࡑࡢ྾཰ࡉ ࢀࡓ࢚ࢿࣝࢠ࣮ࡣࠊᵝࠎ࡞ᙧ࡛ᨺฟࡉࢀࡿࠋࡇࡢ࢚ࢿࣝࢠ࣮ࡢᨺฟࢆⓎග࡜࠸࠺ᙧ࡛⾜࠺ ⌧㇟ࡀ࣑ࣝࢿࢵࢭࣥࢫ㸦Luminescence㸧࡛࠶ࡿࠋࡇࡢ࣑ࣝࢿࢵࢭࣥࢫࡣ࢚ࢿࣝࢠ࣮ࡢ୚࠼᪉ ࡟ ࡼ ࡗ ࡚ ศ 㢮 ࡉ ࢀ ࠊ ග ࡟ ࡼ ࡾ ࢚ ࢿ ࣝ ࢠ ࣮ ࢆ ୚ ࠼ ࡓ ሙ ྜ ࡢ Ⓨ ග ࢆ ࣇ ࢛ ࢺ ࣝ ࣑ ࢿ ࢵ ࢭ ࣥ ࢫ 㸦Photoluminescence㸧࡜ゝ࠺ࠋ  ༙ᑟయ⤖ᬗ࡟࠾ࡅࡿࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫࡣࠊගࢆ↷ᑕࡍࡿࡇ࡜࡟ࡼࡗ࡚⏕ࡌࡓ㟁Ꮚ࡜ ṇᏍࡀ෌⤖ྜࡍࡿ㝿࡟ᨺฟࡉࢀࡿࠋࡇࡢ෌⤖ྜࡣ༙ᑟయ⤖ᬗ୰࡟Ꮡᅾࡍࡿ᱁ᏊḞ㝗ࡸ୙⣧ ≀ࡢᙳ㡪ࢆཷࡅࡸࡍ࠸ࡓࡵࠊᗈ࠸ព࿡࡛ࡢ”⤖ᬗ୰ࡢḞ㝗”ࢆ㧗ឤᗘ࡟᳨ฟࡍࡿࡇ࡜ࡀྍ⬟࡜ ࡞ࡿࠋࡲࡓࡇࡢᡭἲࡣ ᐃ࡟࠾࠸࡚ヨᩱࢆ◚ቯࡍࡿࡇ࡜ࡀ࡞ࡃࠊࡲࡓ≉Ṧ࡞ヨᩱ๓ฎ⌮ࡸ 㟁ᴟ௜ࡅࢆᚲせ࡜ࡋ࡞࠸࡜࠸࠺≉ᚩࡀ࠶ࡿࠋࡲࡓ୙⣧≀ࡸḞ㝗࡟㉳ᅉࡋࡓⓎගࡢᙉᗘศᕸ ࢆ ᐃࡍࡿࡇ࡜࡟ࡼࡾࠊ⤖ᬗࡢᆒ୍ᛶࡸḞ㝗ࡢศᕸ≧ἣࢆ㧗࠸ศゎ⬟࡛ホ౯ࡍࡿࡇ࡜ࡀྍ ⬟࡛࠶ࡿࠋ 2.1.2 ཎ⌮  Fig. 2.1 ࡟௦⾲ⓗ࡞ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫࡢ㐣⛬ࢆᶍᘧⓗ࡟♧ࡍࠋ (a) 㟁Ꮚ-ṇᏍ┤᥋෌⤖ྜ

E

C

D

0

D

0

D

+

D

0

A

0

E

V

(a)

(b)

(c)

(d)

(e)

(f)

Figure 2.1㻌 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫࡢ✀㢮

ບ㉳Ꮚ(free exciton:FE)࡛࠶ࡾࠊࡑࡢ෌⤖ྜࡀ⮬⏤ບ㉳ᏊⓎගࠋ (c) ᮰⦡ບ㉳Ꮚ(BE)Ⓨග ୙⣧≀࣭Ḟ㝗‽఩࡟ບ㉳Ꮚࡀᤕࡽ࠼ࡽࢀࡓ≧ែ(᮰⦡ບ㉳Ꮚ㸸bound exciton:BE)࡟࠾࠸࡚ࠊ ບ㉳Ꮚࡀ෌⤖ྜࡍࡿ㝿ࡢⓎගࠋ (d) ࢻࢼ࣮-౯㟁Ꮚᖏ㑄⛣Ⓨග ࢻࢼ࣮࡟ᤕࡽ࠼ࡽࢀࡓ㟁Ꮚ࡜౯㟁ᏊᖏࡢṇᏍࡢⓎගࠋ (e) ఏᑟᖏ-ࢻࢼ࣮㑄⛣Ⓨග ఏᑟᖏࡢ㟁Ꮚࡀ✵ࡢࢻࢼ࣮‽఩࡟ᤕࡽ࠼ࡽࢀࡿ㝿ࡢⓎගࠋ (f) ࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔(DAP)Ⓨග ࢻࢼ࣮࡟ᤕࡽ࠼ࡽࢀࡓ㟁Ꮚ࡜࢔ࢡࢭࣉࢱ࣮࡟ᤕࡽ࠼ࡽࢀࡓṇᏍ࡜ࡢ෌⤖ྜ㐣⛬࡛ࡢⓎ ගࠋ ࡑࢀࡒࢀࡢⓎග㐣⛬࡟ࡘ࠸࡚ヲࡋࡃㄝ᫂ࡍࡿࠋ  ఏᑟᖏࡢ㟁Ꮚ࡜౯㟁ᏊᖏࡢṇᏍࡢ┤᥋෌⤖ྜ࡟ࡼࡿ(a)࡜ࠊࡇࢀࡽࡢ㟁Ꮚ࡜ṇᏍࡀ⮬⏤ບ ㉳Ꮚ࡜࡞ࡗࡓ≧ែ࡛ࡢ෌⤖ྜ㐣⛬ࡢ(b)࡛ࡣࠊບ㉳Ꮚᙧᡂ࢚ࢿࣝࢠ࣮ศ(E_x)ࡔࡅ(b)ࡢⓎග࢚ࢿ ࣝࢠ࣮ࡢ᪉ࡀᑠࡉ࠸ࠋࡇࢀࡽࡢⓎග࡛ࡣࠊ㟁ᏊࠊṇᏍࠊບ㉳Ꮚࡀ㐠ື࢚ࢿࣝࢠ࣮ࢆᣢࡘࡢ ࡛ࠊࡑࢀࢆ཯ᫎࡋ࡚Ⓨගᖏᙧ≧I(hν)ࡣ㧗࢚ࢿࣝࢠ࣮ഃ࡟〈ࢆᘬࡃMaxwell-Boltzmanᆺศᕸ

( ) (

h

ν

h

ν

E

)

{

(

h

ν

E

kT

)

}

I

=

-

₀ 12

exp

-

-

₀ (2-1) ࡛୚࠼ࡽࢀࡿࠋE₀ࡣ㐠ື࢚ࢿࣝࢠ࣮ࡀ0ࡢሙྜࡢⓎග㑄⛣࢚ࢿࣝࢠ࣮࡛࠶ࡿࠋ(a)࡜(b)ࡢⓎ ගࡣࣂࣥࢻ➃Ⓨග࡜࿧ࡤࢀࠊ⤖ᬗᅛ᭷ࡢⓎග࡛࠶ࡾࠊⓎග࢚ࢿࣝࢠ࣮࠿ࡽ⤖ᬗࡢ⤌ᡂࢆồ ࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋࡲࡓࠊࣂࣥࢻ㛫Ⓨගࡣ⤖ᬗࡢࣛ࢖ࣇࢱ࢖࣒ࢆ཯ᫎࡋ࡚࠸ࡿࡢ࡛ࠊࡑࡢ ゎᯒ࠿ࡽࣛ࢖ࣇࢱ࢖࣒࡟ᙳ㡪ࢆ୚࠼࡚࠸ࡿ⤖ᬗ୰ࡢ㠀Ⓨගࢭࣥࢧ࣮ࡸ⾲㠃≧ែ࡞࡝ࢆホ౯ ࡛ࡁࡿࠋ (c)~(f)ࡣ୙⣧≀࣭Ḟ㝗‽఩ࡢ㛵୚ࡋࡓⓎග࡛࠶ࡿࠋ (c)࡛ࡣ୰ᛶࡢࢻࢼ࣮‽఩࡟ບ㉳Ꮚࡀ᮰⦡ࡉࢀ࡚࠸ࡿሙྜࢆ♧ࡋࡓࡀࠊ୰ᛶ࢔ࢡࢭࣉࢱ࣮‽ ఩ࠊ࢖࢜ࣥ໬ࢻࢼ࣮㸦࢔ࢡࢭࣉࢱ࣮)‽఩ࠊࡑࡋ࡚ࡉࡽ࡟GaP୰ࡢ❅⣲୙⣧≀ࡢࡼ࠺࡟ࢻࢼ ࣮ࡸ࢔ࢡࢭࣉࢱ࣮࡟ࡣ࡞ࡽ࡞࠸➼㟁Ꮚⓗࢺࣛࢵࣉࡢሙྜࡶ࠶ࡿࠋࡲࡓࠊ」ᩘࡢບ㉳Ꮚࡀᤊ ࠼ࡽࢀࡿࡇ࡜ࡶ࠶ࡿࠋ(c)࡛ࡣⓎග࢚ࢿࣝࢠ࣮ࡀ(b)࡜ẚ࡭ࠊບ㉳Ꮚ᮰⦡࢚ࢿࣝࢠ࣮E_BXࡔࡅᑠ ࡉࡃ࡞ࡿࠋE_BXࡣ୙⣧≀࣭Ḟ㝗ࡢ✀㢮ࠊⲴ㟁≧ែ࡟ࡼࡾ␗࡞ࡿࠋ࢖࢜ࣥ໬࢚ࢿࣝࢠ࣮ࡢ⣙1/10 ⛬ᗘ࡛࠶ࡿࡇ࡜ࡀ▱ࡽࢀ࡚࠸ࡿ(Haynes’s rule)ࠋBEⓎග࡛ࡣࠊບ㉳Ꮚࡀ୙⣧≀࡟ᒁᅾ໬ࡉࢀ ࡿࡓࡵ㐠ື࢚ࢿࣝࢠ࣮ࡣ࡞ࡃࠊⓎග⥺ࡣࢩ࣮ࣕࣉ࡟࡞ࡿࠋ(≉࡟ὸ࠸୙⣧≀࡟ࡼࡿ BE Ⓨග ࡣప ࡛㠀ᖖ࡟㗦࠸Ⓨග⥺࡜࡞ࡿࡢ࡛ࠊ୙⣧≀ࡢ༊ูࡀᐜ᫆࡟⾜࠼ࡿࡓࡵࠊ୙⣧≀ศᯒ࡟ ࡼࡃ฼⏝ࡉࢀࡿࠋ)  (d)࡛ࡢⓎග࢚ࢿࣝࢠ࣮ࡣ⚗ไᖏᖜࡼࡾࡶࢻࢼ࣮ࡢ࢖࢜ࣥ໬࢚ࢿࣝࢠ࣮ศࡔࡅᑠࡉࡃ࡞ࡿࠋ ῝࠸ࢻࢼ࣮‽఩ࡢሙྜ࡟ࡣ(e)࡟♧ࡍࡼ࠺࡟ࠊఏᑟᖏࡢ㟁Ꮚࡀ✵ࡢࢻࢼ࣮‽఩࡟ᤕࡽ࠼ࡽࢀ ࡿ㝿ࡢⓎගࡶほ ࡉࢀࡿ㸦ఏᑟᖏ㟁Ꮚ-࢔ࢡࢭࣉࢱ-ṇᏍ෌⤖ྜࠊ࢔ࢡࢭࣉࢱ-㟁Ꮚ-౯㟁Ꮚᖏ

ṇᏍ෌⤖ྜࡶᏑᅾࡍࡿ㸧ࠋࡇࢀࡽࡢⓎග࡟ࡣ⮬⏤࢟ࣕࣜ࢔ࡀྵࡲࢀࡿࡢ࡛ࠊⓎගᖏᙧ≧ࡣ (2-1)ᘧࡢMaxwell-Boltzmanᆺ࡜࡞ࡿࠋࡓࡔࡋࠊ῝࠸‽఩ࡢሙྜ࡟ࡣࠊ㟁Ꮚ-᱁Ꮚ┦஫స⏝ࡢ ࡓࡵࣇ࢛ࣀࣥࢧ࢖ࢻࣂࣥࢻ඲య࡜ࡋ࡚࢞࢘ࢫᆺࡢⓎගᖏᙧ≧࡜࡞ࡿࠋ (f)ࡢࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔(DAP)Ⓨග࡟࠾࠸࡚ࠊ✵㛫ⓗ࡟㊥㞳rࡔࡅ㞳ࢀࡓࢻࢼ࣮࡜࢔ࢡࢭ ࣉࢱࢆ⪃࠼ࡿ࡜ࠊࢻࢼ࣮࡟㟁Ꮚࡀࠊ࢔ࢡࢭࣉࢱ࡟ṇᏍࡀ࠶ࡿບ㉳≧ែ࠿ࡽࠊࡇࢀࡽ㟁Ꮚ࡜ ṇᏍࡀ෌⤖ྜࡋᇶᗏ≧ែ࡟⛣ࡿ㝿࡟ᨺฟࡍࡿගࡢ࢚ࢿࣝࢠ࣮ࡣ

(

)

r

ε

e

E

E

E

ν

h

_{G D A} 2

+

+

-=

(2-2) ࡛୚࠼ࡽࢀࡿࠋࡇࡇ࡛ࠊE_GࠊE_AࠊE_Dࡣࡑࢀࡒࢀࠊ⚗ไᖏ࢚ࢿࣝࢠ࣮ࠊ࢔ࢡࢭࣉࢱ࢖࢜ࣥ໬ 㸦άᛶ໬㸧࢚ࢿࣝࢠ࣮ࠊࢻࢼ࣮࢖࢜ࣥ໬㸦άᛶ໬㸧࢚ࢿࣝࢠ࣮࡛࠶ࡾࠊεࡣ㟼ⓗㄏ㟁⋡࡛࠶ ࡿࠋྑ㎶➨ 3 㡯ࡣᇶᗏ≧ែࡢ࢖࢜ࣥ໬ࡋࡓࢻࢼ࣮ཬࡧ࢔ࢡࢭࣉࢱ㛫࡟ാࡃࢡ࣮ࣟࣥຊࢆ⾲ ࡍࠋ㊥㞳ࡢ኱ࡁ࠸ࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔࡟ࡘ࠸࡚ࡣࠊࣇ࢓ࣥࢹ࣮ࣝ࣡ࣝࢫຊࡣ᏶඲࡟↓ど ࡛ࡁࡿࡶࡢ࡜ࡍࡿࠋࡲࡓࠊ㞄ࡾྜ࠺࣌࢔ࡢሙྜ࡛ࡶࠊࡇࡢ┦஫స⏝ࡣࡲࡔ࠿࡞ࡾᙅࡃࠊ(2-2) ᘧ࡛ࡣ⪃៖ࡋ࡚࠸࡞࠸ࠋࢻࢼ࣮࡜࢔ࢡࢭࣉࢱࡢ⤖ᬗ᱁Ꮚࡢ୰࡛༨ࡵࡿ఩⨨ࡀỴࡲࡗ࡚࠸ࡿ ࡜ࡍࡿ࡜ࠊrࡣ㐃⥆ࡋࡓ್ࢆྲྀࡾᚓࡎࠊ᱁Ꮚᐃᩘ࡟㛵㐃ࡋࡓ࡜ࡧ࡜ࡧࡢ್ࢆ࡜ࡿࡇ࡜࡟࡞ࡿ ࡓࡵࠊᨺฟࡉࢀࡿග࢚ࢿࣝࢠ࣮ࡶ୙㐃⥆࡜࡞ࡾࠊࢫ࣌ࢡࢺࣝࡣከࡃࡢ㍤⥺࠿ࡽᵓᡂࡉࢀࡿࠋ

(GaP, ZnSe, SiC, AlSb, BP࡞࡝࡛ࡇࡢࡼ࠺࡞Ⓨගࡀほ ࡉࢀ࡚࠸ࡿ)ࠋ

ࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔Ⓨගࡣࠊᚲࡎ୍㐃ࡢ㍤⥺ࢫ࣌ࢡࢺࣝ࡜ࡋ࡚ฟ⌧ࡍࡿࢃࡅ࡛ࡣ࡞ࡃࠊ ㏻ᖖࡢ࣌࢔Ⓨග࡛ࡣrࡀ኱ࡁࡃࠊ࢚ࢿࣝࢠ࣮ᕪࡀศゎ࡛ࡁࡎ࡟୍ᮏࡢᗈ࠸್༙ᖜࢆᣢࡘⓎග ࣂࣥࢻ࡜ࡋ࡚ほ ࡉࢀࡿࡇ࡜ࡶ࠶ࡿࠋࡋ࠿ࡋࠊࡇࡢⓎගࣂࣥࢻࡶࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔Ⓨ ගࡢ࠸ࡃࡘ࠿ࡢ≉ᚩࢆᣢࡕࠊ௚ࡢ㑄⛣ᶵᵓ࡟ࡼࡿⓎගࣂࣥࢻ࡜༊ูࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ ࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔Ⓨග㸦ࣈ࣮ࣟࢻࣂࣥࢻ㸧ࡢ≉ᚩࢆࡲ࡜ࡵࡿࠋ 1) ບ㉳ගᙉᗘࢆቑࡍ࡜㧗࢚ࢿࣝࢠ࣮ഃ࡬ࢫ࣌ࢡࢺࣝࡀࢩࣇࢺࡍࡿࠋ஫࠸ࡢ㊥㞳rࡀ኱ࡁ࠸ ࣌࢔ࡣ㑄⛣☜⋡ࡀᑠࡉࡃࠊບ㉳ගᙉᗘࢆୖࡆ࡚㟁ᏊࠊṇᏍ⃰ᗘࢆቑࡋ࡚ࡶ㑄⛣㢖ᗘࡣቑ ࠼ࡎ࡟㣬࿴ࡍࡿࠋᑐࡋ࡚rࡢᑠࡉ࠸࣌࢔ࡣࠊ㟁ᏊࠊṇᏍ⃰ᗘࡢቑຍ࡜࡜ࡶ࡟㑄⛣㢖ᗘࡀ ୖࡀࡾࠊ㧗࢚ࢿࣝࢠ࣮ഃࡢⓎගࡀ┦ᑐⓗ࡟ࡑࡢᙉᗘࢆୖࡆࡿࠋ 2)  ᗘୖ᪼࡟ࡼࡾࠊὸ࠸‽఩࠿ࡽࡢ㟁ᏊࠊṇᏍࡢࣂࣥࢻ࡬ࡢ⇕ⓗບ㉳ࡀ⏕ࡌ࡚ࠊⓎගᙉᗘ ࡀୗࡀࡿࠋ 3) ⃰ᗘࡢቑຍ࡜࡜ࡶ࡟Ⓨගࣂࣥࢻࡣ㧗࢚ࢿࣝࢠ࣮ഃ࡟⛣ືࡍࡿࠋ࣌࢔ࢆᙧᡂࡍࡿ୙⣧≀⃰ ᗘࡀቑࡍ࡜ᖹᆒ࣌࢔㛫㊥㞳rࡀῶᑡࡍࡿࡓࡵࠊ(2-2)ᘧࡼࡾࣂࣥࢻࡣ㧗࢚ࢿࣝࢠ࣮ഃ࡬࡜ ືࡃࠋࡇࡢ࢚ࢿࣝࢠ࣮ࢩࣇࢺࡣẚ㍑ⓗ኱ࡁࡃࠊ୙⣧≀‽఩ࡢ࢚ࢿࣝࢠ࣮ᕪࡀ᥋㏆ࡋ࡚࠸ ࡿࢻࢼ࣮࡞࠸ࡋ࢔ࢡࢭࣉࢱࡢ໬Ꮫ✀ࡢ㐨⛬ࢆࡋࡤࡋࡤㄗࡽࡏࡿࠋ ࢻࢼ࣮-࢔ࢡࢭࣉࢱ࣌࢔Ⓨගࡣࠊࣃࣝࢫບ㉳ࡋࡓᚋࡢⓎගᙉᗘࡢῶ⾶㐣⛬࡟≉ᚩࢆᣢࡗ࡚

2.1.3 ᐇ㦂⣔

Table 2.1 PL ᐃ᮲௳

ບ㉳ග※ 㔠㛛㟁Ẽᰴᘧ఍♫ He-Cd LASER IK3302R-E Ἴ㛗 : 325 nm㸦3.81 eV㸧ࠊฟຊ : 30 mW

ࣇ࢕ࣝࢱ࣮ UTVAF-34U㸦࣮ࣞࢨ࣮┤ᚋ㸧ࠊUTF-37L㸦ศගჾ┤๓㸧 ༙ᑟయ࣮ࣞࢨ࣮ SUWTECH LASER SUWTECH LDC-2500

ศගჾ ⡿ᅜ࣮ࣟࣃ࣮ࢧ࢖࢚ࣥࢸ࢕ࣇ࢕ࢵࢡ♫〇 15 cm↔Ⅼ㊥㞳ศගჾ SP-2156-2 ࢫࣜࢵࢺᖜ input : 1 mmࠊoutput : 2 mm ᳨ฟჾ ⡿ᅜ࣮ࣟࣃ࣮ࢧ࢖࢚ࣥࢸ࢕ࣇ࢕ࢵࢡ♫〇 㧗ឤᗘ෭༷CCD᳨ฟჾ PIXIS 100B-2 He-Cd LASER 䝣䜱䝹䝍䞊 EL⣲Ꮚ 䝺䞁䝈 PC ศගჾ ᳨ฟჾ ༙ᑟయ䝺䞊䝄䞊 Figure 2.2㻌 PL ᐃᶵჾ䛾㓄⨨ᅗ

ධᑕ㟁Ꮚ⥺ ཯ᑕ㟁Ꮚ 2ḟ㟁Ꮚ 䜸䞊䝆䜵㟁Ꮚ ≉ᛶX⥺ 䜹䝋䞊䝗䝹䝭䝛䝉䞁䝇 ㏱㐣㟁Ꮚ ᩓ஘㟁Ꮚ ྾཰㟁Ꮚ ヨᩱ 2.2 ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾 2.2.1 ࡣࡌࡵ࡟

㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾 (Scanning Electron Spectroscopy ; SEM )ࡣࠊ≀య࡟⣽࠸㟁Ꮚ⥺㸦㟁Ꮚࣉࣟ ࣮ࣈ㸧ࢆ↷ᑕࡋࡓ᫬࡟Ⓨ⏕ࡍࡿ஧ḟ㟁Ꮚࡸ཯ᑕ㟁Ꮚࢆࡑࢀࡒࢀ᳨ฟჾࢆ㏻ࡋ࡚ྲྀࡾฟࡋࠊ ࣈࣛ࢘ࣥ⟶ୖ࡟ീࢆᙧᡂࡋ࡚ࠊ୺࡜ࡋ࡚ヨᩱࡢ⾲㠃ᙧయࢆほᐹࡍࡿ⿦⨨࡛࠶ࡿࠋFig. 2.3࡟ 㟁Ꮚ⥺ࢆ↷ᑕࡋࡓ᫬ࡢヨᩱ≧ែࢆ♧ࡍࠋࡇࡢ࡜ࡁࡢ≉ᚩࢆ௨ୗ࡟㏙࡭ࡿࠋ (1) ㏱㐣㟁Ꮚ ≀㉁ࢆ㏱㐣ࡋࡓ㟁Ꮚ࡛ࠊ㏱㐣㟁Ꮚ㢧ᚤ㙾࡟⏝࠸ࡽࢀࡿࠋ↷ᑕ㟁Ꮚࡀ㏱㐣࡛ ࡁࡿࡲ࡛ヨᩱࢆⷧࡃࡍࡿ࡜ࡇ࡜࡛ࠊ≀㉁ࡢෆ㒊ᵓ㐀ࡢ▱ぢࢆᚓࡿࠋࡲࡓࠊ㟁Ꮚ⥺ᅇᢡ ࢆే⏝ࡍࡿࡇ࡜࡛ࠊ⤖ᬗᵓ㐀ࡢゎᯒࡶྍ⬟࡜࡞ࡿࠋヨᩱࢆ㏱㐣ࡍࡿ㐣⛬࡛ᦆኻࡋࡓ㟁 Ꮚ⥺ࡢ࢚ࢿࣝࢠ࣮ࢫ࣌ࢡࢺࣝࡣࠊヨᩱࡢᵓᡂඖ⣲࡟౫Ꮡࡍࡿࡓࡵ࡟ࠊELLS ࡜࿧ࡤࢀ ࡿ࢚ࢿࣝࢠ࣮࢔ࢼࣛ࢖ࢨ࣮࡟ࡼࡾ⤌ᡂ࡟㛵ࡍࡿ᝟ሗࡀᚓࡽࢀࡿࠋ≉࡟ࠊ㍍ඖ⣲࡟ᑐࡋ ࡚᭷ຠ࡛࠶ࡾࠊ≉ᛶX⥺ศᯒࡢ⿵㛫ⓗ࡞ᙺ๭ࢆᢸ࠺ࠋ (2) 2ḟ㟁Ꮚ ≀㉁࠿ࡽ஧ḟⓗ࡟ᨺฟࡉࢀࡓ㟁Ꮚ࡛ࠊ⾲㠃ࡢᗄఱᏛⓗᙧ≧ࢆ཯ᫎࡍࡿࠋ (3) ཯ᑕ㟁Ꮚ ↷ᑕ㟁Ꮚ⥺ࡀ≀㉁࡟࠶ࡓࡗ࡚ᚋ᪉࡟ᩓ஘ࡉࢀࡓ㟁Ꮚ⥺࡛ࠊཎᏊ␒ྕຠᯝ࡟ ࡼࡿ⤌ᡂ᝟ሗࢆ཯ᫎࡍࡿࠋ⾲㠃ᙧయࡢ᝟ሗࡣ2ḟ㟁Ꮚ࡟ຎࡿࡀࠊ2ḟ㟁Ꮚ࡛ࡣศ࠿ࡾ ࡟ࡃ࠸ᖹᆠ࡞ヨᩱ⾲㠃ࡢพฝࢆ཯ᫎࡍࡿࠋ (4) ≉ᛶX⥺ ≀㉁࡟㟁Ꮚ⥺ࡀ↷ᑕࡉࢀࡿ࡜ࠊᵓᡂཎᏊࡢ㟁Ꮚࡀࡣࡌࡁฟࡉࢀ࡚ࠊ㟁㞳ࡍ ࡿࠋࡇࡢཎᏊࡢ㑄⛣㐣⛬࡟࠾࠸࡚X⥺ࡀⓎ⏕ࡍࡿࠋࡇࢀࡣඖ⣲≉᭷ࡢࡶࡢ࡛࠶ࡾ≉ᛶ X⥺࡜࿧ࡤࢀࠊ≀㉁ᵓᡂඖ⣲ࡢᐃ㔞ศᯒࡸᐃᛶศᯒ࡟⏝࠸ࡽࢀࡿࠋ (5) ࣮࢜ࢪ࢙㟁Ꮚ 㟁Ꮚ⥺↷ᑕ࡟ࡼࡗ࡚ບ㉳ࡉࢀࡓ㟁Ꮚࡢ㑄⛣㐣⛬࡛ࠊ≉ᛶX⥺ࡢ௦ࢃࡾ ࡟ᨺฟࡉࢀࡿࠋ࢚ࢿࣝࢠ࣮ࡀඖ⣲≉᭷ࡢࡶࡢ࡛࠶ࡾࠊୟࡘࠊᖹᆒ࢚ࢫࢣ࣮ࣉ㛗ࡀᑠࡉ ࠸ࡓࡵࠊ⾲㠃ᩘཎᏊᒙཬࡧ㍍ඖ⣲ࡢศᯒ࡟᭷ຠ࡛࠶ࡿࠋ (6) ࢝ࢯ࣮ࢻ࣑ࣝࢿࢵࢭࣥࢫ 㟁Ꮚ⥺↷ᑕ࡟ࡼࡾⓎගࡍࡿ⌧㇟ (7) ྾཰㟁Ꮚ ヨᩱ୰࡟྾཰ࡉࢀࡿ㟁Ꮚ࡛཯ᑕ㟁Ꮚ࡜⿵㛫ⓗ࡞㛵ಀ࡟࠶ࡿࠋ

2.2.2 ཎ⌮  Fig. 2.4࡟SEMࡢᴫせᅗࢆ♧ࡍࠋ㟁ᏊගᏛ⣔ࡣຍ㏿㟁ᏊࢆⓎ⏕ࡍࡿ㟁Ꮚ㖠ࠊຍ㏿㟁Ꮚࡢ᮰ ࢆ⤠ࡾ㎸ࢇ࡛⣽᮰໬ࡍࡿࣞࣥࢬ⣔ࠊヨᩱ࠿ࡽⓎ⏕ࡍࡿ 2 ḟ㟁Ꮚ࡞࡝ࢆ᳨ฟࡍࡿ᳨ฟჾ࠿ࡽ ᵓᡂࡉࢀ࡚࠸ࡿࠋ 1)  ࡲࡎࠊ㟁Ꮚ㖠ࡣࠊ࠶ࡿ࢚ࢿࣝࢠ࣮ࢆࡶࡗࡓຍ㏿㟁ᏊࢆⓎ⏕ࡉࡏࡿ※࡜࡞ࡿ㒊ศ࡛ࠊࢱࣥ ࢢࢫࢸࣥࣇ࢕࣓ࣛࣥࢺࡸ LaB₆ࣇ࢕࣓ࣛࣥࢺࢆຍ⇕ࡋ࡚㟁Ꮚࢆᨺฟࡉࡏࡿ⇕㟁Ꮚ㖠࡜ࠊᑤ≧ ࢱࣥࢢࢫࢸࣥඛ➃࡟ᙉ㟁⏺ࢆ࠿ࡅ࡚㟁Ꮚᨺฟࡉࡏࡿ㟁⏺ᨺᑕ㟁Ꮚ㖠࡜ࡀ࠶ࡿࠋࣞࣥࢬ⣔࡟ ࡣࠊ㞟᮰ࣞࣥࢬࠊᑐ≀ࣞࣥࢬࠊ㉮ᰝࢥ࢖ࣝࠊ㠀Ⅼ⿵ṇ⿦⨨࡞࡝ࡀᐇ⿦ࡉࢀ࡚࠸ࡿࠋ㞟᮰ࣞ ࣥࢬࡣ㟁Ꮚ㖠࡛Ⓨ⏕ࡋࡓ㟁Ꮚࡢ᮰ࢆ᭦࡟⣽ࡃࡍࡿࡓࡵ࡟࠶ࡿࠋᑐ≀ࣞࣥࢬࡣࠊ཰ᕪࢆᑠࡉ ࡃࡍࡿࡓࡵ࡟⏝࠸ࡿࠋ᳨ฟჾࡣ2ḟ㟁Ꮚ࡜཯ᑕ㟁Ꮚࡢ᳨ฟჾࡀ࠶ࡾࠊ2ḟ㟁Ꮚࡣ࢚ࢿࣝࢠ࣮ ࡀప࠸ࡢ࡛ࢥࣞࢡࢱ࡟ࡼࡗ࡚ᤕ⋓ࡉࢀࠊࢩࣥࢳ࣮ࣞࢱ࣮࡟ࡼࡾග㟁Ꮚ࡟ኚ᥮ࡉࢀ࡚ࠊග㟁 Ꮚቑಸ⟶࡛ಙྕቑᖜࡉࢀࡿࠋ཯ᑕ㟁Ꮚࡢ᳨ฟ࡟ࡣࠊࢩࣥࢳ࣮ࣞࢱ࠶ࡿ࠸ࡣ༙ᑟయᆺࡀ⏝࠸ ࡽࢀࡿࠋ᤼Ẽ⣔ࡣຍ㏿㟁ᏊࡀẼయᡂศ㏻㐣୰ࡢ࢚ࢿࣝࢠ࣮ᦆኻࢆᑠࡉࡃࡍࡿࡓࡵ࡟ᚲせ࡛ࠊ ࣮ࣟࢱ࣮࣏ࣜࣥࣉࠊἜᣑᩓ࣏ࣥࣉࡀ⏝࠸ࡽࢀ࡚࠸ࡿࠋ  ௨ୗ࡟SEMࡢ≉ᚩࢆࡲ࡜ࡵࡿࠋ (1) ヨᩱࡢ⾲㠃ᙧែࢆࡑࡢࡲࡲほ ࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ (2) ⤖ീࢥࣥࢺࣛࢫࢺࡢᡂᅉࡀ༢⣧࡛࠶ࡾࠊほᐹീࡢゎ㔘ࡀᐜ࡛᫆࠶ࡿࠋගࢆ⏝࠸࡚≀㉁ ࢆほ ࡋࡓሙྜ࡟㏆࠸ࡓࡵࠊ⌮ゎࡋࡸࡍ࠸ࠋ (3) ගᏛ㢧ᚤ㙾࡟ẚ࡭ࡿ࡜ࠊ↔Ⅼ῝ᗘࡀ100ಸ⛬ᗘ῝࠸ࡓࡵࠊพฝࡢ⃭ࡋ࠸ヨᩱࡢほᐹ࡟ 㐺ࡋࠊ❧యീࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋ (4) ほᐹᑐ㇟ࡢヨᩱࡀ TEMࡢࡼ࠺࡟ⷧ⭷࡛࠶ࡿᚲせࡀ࡞࠸ࡓࡵࠊࣂࣝࢡ࣭⧄⥔㉁ࡢᙧ≧ ࢆᣢࡘヨᩱࢆほᐹࡍࡿࡇ࡜ࡀ࡛ࡁࡿࠋ (5) TEM ࡟ẚ࡭࡚ࠊ኱ࡁ࡞ヨᩱࢆᢅ࠺ࡇ࡜ࡀ࡛ࡁࡿࡓࡵࠊᗈ࠸㡿ᇦ࠿ࡽࡢ▱ぢࢆᚓࡿࡇ ࡜ࡀ࡛ࡁࡿࠋ (6) ཯ᑕ㟁Ꮚࢆ⏝࠸ࢀࡤࠊ⤌ᡂࡢ㐪࠸ࢆീ࡜ࡋ࡚ᤊ࠼ࡿ஦ࡀ࡛ࡁࡿࡔࡅ࡛࡞ࡃࠊヨᩱ࠿ࡽ Ⓨ⏕ࡋࡓ✀ࠎࡢග㔞Ꮚࢆ⏝࠸࡚ࠊᵝࠎ࡞᝟ሗࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋ (7) TEM࡜ẚ㍑ࡍࡿ࡜ศゎ⬟ࡀపࡃࠊ⤖ᬗᏛⓗ࡞᝟ሗࡀᚓࡽࢀ㞴࠸ࠋ

ࢹ࢕ࢫࣉࣞ࢖ 㟁Ꮚ㖠 ㉮ᰝࢥ࢖ࣝ ᑐ≀ࣞࣥࢬ 㠀Ⅼ⿵ṇ⿦⨨ ࣇ࢕࣓ࣛࣥࢺ ࢙࣮࢘ࢿࣝࢺ ࢔ࣀ࣮ࢻ 㞟᮰ࣞࣥࢬ ஧ḟ㟁Ꮚ᳨ฟჾ ཯ᑕ㟁Ꮚ᳨ฟჾ ヨᩱ ┿✵࣏ࣥࣉ Figure 2.4㻌 SEM⿦⨨ᴫせᅗ

2.3 X⥺ග㟁Ꮚศගἲ 2.3.1 ཎ⌮ ௨ୗ࡟X⥺ග㟁Ꮚศගἲࡢཎ⌮ࢆ⡆༢࡟ㄝ᫂ࡍࡿࠋ 2) ༢Ⰽගࢆ≀㉁࡟↷ᑕࡍࡿ࡜ග㟁ຠᯝ ࡟ࡼࡾ㟁Ꮚࡀᨺฟࡉࢀࡿࠋࡇࡢ࡜ࡁ࡟Ⓨ⏕ࡍࡿ㟁Ꮚࢆග㟁Ꮚ࡜ ࠸࠺ࠋࡇࡢ㟁Ꮚࡢ࢚ࢿࣝࢠ ࣮࠾ࡼࡧᙉᗘศᕸࢆ ᐃࡍࡿ᪉ἲࡀග㟁Ꮚศගἲ࡛ࠊࣉ࣮ࣟࣈ࡟ X ⥺ࡀ⏝࠸ࡽࢀࡿ᫬ࢆX ⥺ග㟁Ꮚศගἲ࡜࠸࠺ࠋᚑࡗ࡚ࠊヨᩱࡣẼయ࣭ᾮయ࣭ᅛయࡢูࢆၥࢃ࡞࠸ࠋࡇࡢ⌧㇟ࡣḟ ᘧ࡛⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋ a b

E

=

hv

-

E

-

f

              (2.3) ࡇࡇ࡛ࠊE_aࡣⓎ⏕ࡋࡓග㟁Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࠊhvࡣධᑕࡋࡓX⥺ࡢ࢚ࢿࣝࢠ࣮ࠊE_bࡣᨺ ฟࡋࡓ㟁Ꮚࡢヨᩱ୰࡟࠾ࡅࡿ⤖ྜ㸦᮰⦡㸧࢚ࢿࣝࢠ࣮ࠊfࡣヨᩱࡢ௙஦㛵ᩘ࡛࠶ࡿࠋ㟁Ꮚࡢ 㐠ື࢚ࢿࣝࢠ࣮ࡣࣇ࢙࣑ࣝ‽఩࠿ࡽ ᐃࡍࡿ࡜≀㉁㛫ࡢẚ㍑ࡀࡋࡸࡍ࠸ࡢ࡛ࡇࡢሙྜࡣࠊ a b

E

=

hv

-

E

               (2.4) ࡜࡞ࡿࠋࡇࡢᶍᘧᅗࢆFig. 2.5࡟ ♧ࡍࠋFig. 2.5࠿ࡽࡶศ࠿ࡿࡼ࠺ ࡟ ほ   ࡉࢀ ࡓ 㟁Ꮚ ࡢ ࢚ࢿ ࣝ ࢠ࣮ ศ ᕸ ࡣ ≀㉁ ࡢ ෆẆ ࡸ ౯㟁 Ꮚ ᖏࡢ ᝟ሗࢆࡶࡗ࡚࠸ࡿࠋhv ࡀ୍ᐃ࡛ ࠶ࢀࡤ⤖ྜ࢚ࢿࣝࢠ࣮E_b ࡀồࡵ ࡽࢀࡿࠋྛ㌶㐨㟁Ꮚࡢ⤖ྜ࢚ࢿࣝ ࢠ ࣮ ࡣ ඖ⣲ ࡈ ࡜࡟ ␗ ࡞ࡿ ࠿ ࡽࠊ Ea ࢆ ᐃࡍࡿࡇ࡜࡟ࡼࡾࠊᐜ᫆ ࡟ඖ⣲ࡢྠᐃࡀྍ⬟࡜࡞ࡿࠋࡲࡓࠊ ྠ ୍ ඖ ⣲ࡢ ྠ ୍㌶ 㐨 ࡢ⤖ ྜ ࢚ࢿ ࣝࢠ࣮ࡣࠊὀ┠ࡍࡿཎᏊࡢࡲࢃࡾ ࡢ≧ែ࣭⎔ቃ࡟ࡼࡾࡑࡢ್ࡣᚤጁ ࡟ኚ໬ࡍࡿࠋࡇࡢኚ໬㔞㸦໬Ꮫࢩࣇࢺ㸧ࢆ ᐃࡍࡿࡇ࡜࡛ࠊඖ⣲ࡢ≧ែศᕸࡢྠᐃࡀྍ⬟ ࡜࡞ࡿࠋ

 XPS ᐃ࡟⏝࠸ࡽࢀࡿX⥺⟶ࡣX⥺ᅇᢡ㸦X-Ray Diffraction : XRD㸧ࡸ⺯ගX⥺ศᯒ㸦X-Ray Fluorscence : XRF㸧࡟⏝࠸ࡽࢀࡿࡑࢀ࡜ཎ⌮ⓗ࡟ࡣኚࢃࡾࡀ࡞࠸ࠋXRDࡸXRF࡛ࡣ≉ᛶX ⥺࢚ࢿࣝࢠ࣮ࡣᩘ༑ keV࡜㧗࠸ࡇ࡜ࡀせồࡉࢀࡿࡀࠊXPS ࡛ࡣᚓࡼ࠺࡜ࡍࡿ᝟ሗࡀ⾲㠃࡟ 㝈ᐃࡉࢀࡿࡓࡵᩘkeV௨ୗࡢ≉ᛶX⥺ࡀ౑⏝ࡉࢀ࡚࠸ࡿࠋ㏻ᖖࡢ⿦⨨࡛ࡣࠊᗈ࠸࢚ࢿࣝࢠ ࣮⠊ᅖ࡛ୟࡘ㧗ศゎ⬟࡛ ᐃࢆ⾜࠺ࡇ࡜ࡀせồࡉࢀࡿࡓࡵࠊAlKa࡜MgKa⥺ࡀ୍⯡ᡭ㔠࡟౑ ⏝ࡉࢀ࡚࠸ࡿࠋග※࡜ࡋ࡚MgKa࠶ࡿ࠸ࡣAlKaࡢ≉ᛶX⥺ࢆ฼⏝ࡍࡿሙྜࠊⓎ⏕ࡍࡿග㟁 Ꮚࡢ㐠ື࢚ࢿࣝࢠ࣮ࡣࡓ࠿ࡔ࠿ 1000 eV࠿ࡑࢀ௨ୗ࡜ᑠࡉ࠸ࠋᚑࡗ࡚ࠊXPS ࡛ᚓࡽࢀࡿ᝟ ሗࡢ῝ࡉࡣὸࡃࠊ10~ᩘ10Å࡛࠶ࡿࠋ  ࡲࡓࠊXPSࢆ⏝࠸࡚ヨᩱ୰ࡢྛඖ⣲ᡂศIࡢ⤌ᡂẚࢆồࡵࡿࡇ࡜ࡀྍ⬟࡛࠶ࡿࠋྛඖ⣲ࡀ ෆẆ‽఩ 䝣䜵䝹䝭‽఩ ┿✵‽఩ ග㟁Ꮚ䝇䝨䜽䝖䝹 E_b f hv hv 䩠 䩉 䩶 䨺 䩦 䩮 䨫 䩐 䩮 䨱 䩻 N(E) hv Figure 2.5 ග㟁Ꮚᨺฟ䛾ᶍᘧᅗ

῝ࡉ᪉ྥ࡟ᆒ୍࡟ศᕸࡋ࡚࠸ࡿሙྜࠊXPS ᐃ࡛ࡢࣆ࣮ࢡᙉᗘ I_iࡣࠊග࢖࢜ࣥ໬᩿㠃✚s_iࠊ ග㟁Ꮚࡢ⬺ฟ῝ࡉl_iࠊ⃰ᗘN_iࠊ⿦⨨࡟ࡼࡗ࡚ỴࡲࡿಀᩘK࡟ࡼࡾࠊ 0 i i i i i

I

=

I

s

N

l

K

(2-5) ࡛୚࠼ࡽࢀࡿࠋࡑࡇ࡛ࠊྠ୍ヨᩱࡢ␗࡞ࡗࡓᡂศI_jࡢࣆ࣮ࢡᙉᗘࡢ⤌ᡂẚ࠿ࡽࠊ i j j i i j j i i j

I

K

N

N

I

K

s l

s l

=

(2-6) ࡟ࡼࡾồࡵࡽࢀࡿࠋᐇ㦂࡟ࡼࡾࢫ࣌ࢡࢺࣝ୰ࡢྛࣆ࣮ࢡࡢ㠃✚ᙉᗘIࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ ྑ㎶ࡢࡑࡢ௚ࡢᅉᏊࡣࠊィ⟬್࠶ࡿ࠸ࡣᶆ‽ヨᩱࡢ฼⏝࡞࡝࡟ࡼࡗ࡚⤌ᡂẚࢆỴࡵࡿࡇ࡜ ࡀ࡛ࡁࡿࠋ

2.4 ග྾཰ ᐃ 2.4.1 ྾཰ಀᩘࡢ ᐃ  ࠶ࡿ≉ᐃࡢἼ㛗㸦࢚ࢿࣝࢠ࣮㸧ࡢග࡟ᑐࡋ࡚ࠊ༙ᑟయࡀ࡝ࡢࡼ࠺࡞྾཰ಀᩘ㸦absorption coefficient㸧࠶ࡿ࠸ࡣ཯ᑕ⋡㸦reflectivity㸧ࢆᣢࡘ࠿ࢆ ᐃࡍࡿࡇ࡜ࡣࠊࡑࡢ༙ᑟయࢆ⏝࠸ࡓ ගᏛ⣔ࡢタィ࡞࡝࡟ᇶᮏࢹ࣮ࢱࢆᥦ౪ࡍࡿࠋ୍᪉ࠊගࡢ྾཰ࢫ࣌ࢡࢺࣝࡸ཯ᑕࢫ࣌ࢡࢺࣝ ࡟ࡣࠊ༙ᑟయࡢ࢚ࢿࣝࢠ࣮ᖏᵓ㐀ࡀᙉࡃ཯ᫎࡉࢀ࡚࠾ࡾࠊࡑࡢ ᐃ࡟ࡼࡾ࢚ࢿࣝࢠ࣮ᖏ࡟ ᑐࡍࡿከࡃࡢᇶᮏ᝟ሗࢆᚓࡿࡇ࡜ࡀฟ᮶ࡿࠋ᪂ࡋ࠸༙ᑟయࡀ〇సࡉࢀࡓሙྜࠊ᭱ึ࡟ࠊX⥺ ᅇᢡ࡞࡝ࡢ⤖ᬗᵓ㐀ゎᯒࢆ⾜࠺࡜࡜ࡶ࡟ග྾཰ࢫ࣌ࢡࢺࣝࡢゎᯒࢆ㐍ࡵࠊࡑࡢ኱ࡲ࠿࡞࢚ ࢿࣝࢠ࣮ᵓ㐀ࢆ▱ࡿࡇ࡜ࡀ㔜せ࡛࠶ࡿࠋࡇࡢព࿡࡛ࠊ྾཰ࢫ࣌ࢡࢺࣝཬࡧ཯ᑕࢫ࣌ࢡࢺࣝ ࡢ ᐃ࡜ࡑࡢゎᯒࡣࠊගᏛ≉ᛶホ౯ࡢ୰࡛᭱ࡶᇶᮏⓗ࡞ᢏ⾡࡛࠶ࡿࠋ 3)  ༙ᑟయࡢග྾཰ࡢᶵᵓ࡟ࡣࠊ࠸ࢁ࠸ࢁ࡞ሙྜࡀ࠶ࡿࡀࠊ୺࡞ග྾཰ࡣ౯㟁Ꮚᖏ࠿ࡽఏᑟ ᖏ࡬㟁Ꮚࢆບ㉳ࡍࡿ࡜ࡁࡢᇶ♏྾཰࡛࠶ࡿࠋᇶ♏྾཰࡟ࡣࡑࢀࡀ㉳ࡇࡾጞࡵࡿ㝈⏺ගᏊ࢚ ࢿࣝࢠ࣮ࠊ㝈⏺ගἼ㛗ࡀ࠶ࡿࡀࠊࡇࡢ್ࢆ ᐃࡍࡿࡇ࡜࡟ࡼࡾࠊᇶ♏྾཰➃࢚ࢿࣝࢠ࣮࡞ ࡝ࢆồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ 4)  ගࡀ፹㉁୰ࢆ㐍⾜ࡋࡓ࡜ࡁࠊගࡢ࢚ࢿࣝࢠ࣮ࡀ྾཰ࡉࢀ࡚ගࡢᙉࡉࡀῶᑡࡋ࡚࠸ࡃ๭ྜ ࢆ྾཰ಀᩘ࡜࠸࠺ࠋ≀㉁୰ࡢ࠶ࡿⅬ࡟࠾ࡅࡿගࡢᙉᗘࢆ I₀࡜ࡋࠊගࡀ㊥㞳x ࡔࡅ㐍ࢇࡔᚋ ࡢගᙉᗘI(x)࡜ࡍࡿ࡜

( )

x

I

(

α

x

)

I

=

₀

exp

-

(2-7) ࡜᭩ࡅࡿࠋࡇࡢಀᩘαࡀ྾཰ಀᩘ࡛࠶ࡾࠊcm -1 ࡜࠸࠺༢఩࡛⾲ࡍࠋ྾཰ಀᩘࡣࠊ≀ᛶ◊✲ࡢ ሙྜࠊගࡢἼ㛗㸦࢚ࢿࣝࢠ࣮㸧ࡢ㛵ᩘ࡜ࡋ࡚ ᐃࡉࢀࠊࡇࡢ྾཰ಀᩘࡢἼ㛗㸦࢚ࢿࣝࢠ࣮㸧 ౫Ꮡᛶࢆ྾཰ࢫ࣌ࢡࢺࣝ࡜࿧ࡪࠋ  ගࡀ┿✵୰࠿ࡽ≀㉁࡟ධᑕࡍࡿሙྜࠊගࡢ୍㒊ࡣ≀㉁୰࡟౵ධࡍࡿࡀࠊṧࡾࡣ≀㉁⾲㠃 ࡛཯ᑕࡉࢀࡿࠋ཯ᑕ⋡RࡣࠊධᑕගᙉᗘI_i࡜཯ᑕගᙉᗘI_rࢆ⏝࠸࡚༢⣧࡟ i r

I

I

R =

(2-8) ࡜ᐃ⩏ࡉࢀࡿࠋ  ග㸦㟁☢Ἴ㸧ࡣࠊ≀㉁ࡢෆ㒊ࠊእ㒊ࢆၥࢃࡎ㟁☢ἼࡢMaxwell᪉⛬ᘧ࡟ࡼࡾグ㏙ࡉࢀࡿࠋ 㟁ሙࠊ☢ሙࠊ㟁ὶ࡞࡝ࡢほ ࡟࠿࠿ࡿᕧどⓗ≀⌮㔞࡜ࠊᅛయࡢᚤどⓗ㸦ཎᏊⓗ㸧ᛶ㉁ࡢᶫ Ώࡋࢆࡍࡿࡢࡀ“ㄏ㟁⋡”࡜“ఏᑟ⋡”࡛࠶ࡿࠋ༙ᑟయࡢගᏛ≉ᛶࡢᢕᥱ࡟ࡣࠊࡇࢀࡽࡢ㔞࡜྾ ཰ಀᩘࠊ཯ᑕ⋡࡜ࡢ㛵㐃ࢆ⌮ゎࡍࡿࡇ࡜ࡀ㔜せ࡜࡞ࡿࠋ  ☢Ẽⓗຠᯝࢆᢅࢃ࡞࠸࡜ࡍࡿ࡜ࠊMaxwellࡢ᪉⛬ᘧࡣ 㼞㼛㼠

H

=

J

+

¶

D

¶

t

(2-9) 㻌 㼞㼛㼠

H

=

J

+

¶

D

/

¶

t

(2-10) 㼐㼕㼢

B

=

0

(2-11) 㻌 㼐㼕㼢 e D=r (2-12)  ࡛୚࠼ࡽࢀࡿࠋࡇࡇ࡛ࠊE㸪D㸪H㸪Bࡣࡑࢀࡒࢀࠊ㟁ሙࠊ㟁᮰ᐦᗘࠊ☢ሙࠊ☢᮰ᐦᗘ࡛࠶ ࡾࠊρ_e㸪Jࡣࠊ㟁Ⲵᐦᗘࠊ㟁ὶᐦᗘࢆ⾲ࡍࠋࡲࡓࠊ࣮࣒࢜ࡢἲ๎ࢆ௬ᐃࡍࡿ࡜

E

σ

J =

(2-13) ࡀᡂ❧ࡍࡿࠋࡇࡇ࡛ࠊσࡣ㟁Ẽఏᑟᗘ࡛࠶ࡿࠋ(2-9)-(2-12)ᘧ࠿ࡽE࡟㛵ࡍࡿἼື᪉⛬ᘧ

0

0 2 2 2 2

₌

¶

¶

-¶

¶

-Ñ

t

E

σ

μ

t

E

c

k

E

e (2-14) ࡀᑟࡁ࠿ࢀࡿࠋࡇࡇ࡛ࠊk_eࡣ≀㉁ࡢẚㄏ㟁⋡ࠊμ₀ࡣ┿✵ࡢ㏱☢⋡࡛࠶ࡿࠋࡲࡓcࡣࠊ 0 0

μ

ε

c =

(2-15) ε0ࡣ┿✵ࡢㄏ㟁⋡࡛࠶ࡾࠊ┿✵୰ࡢග㏿࡟➼ࡋ࠸ࠋ྾཰ಀᩘࠊ཯ᑕ⋡࡟ᑐࡍࡿ࢚ࢿࣝࢠ࣮ศ ᩓࢆồࡵࡿࡓࡵ࡟ࠊἼື࣋ࢡࢺࣝkࠊ᣺ືᩘωࢆᣢࡘ㟁ゎ࣋ࢡࢺࣝἼEࢆ⪃࠼ࡿࠋ

{

ik

r

ω

t

}

E

E

=

₀

exp

×

-

(2-16) ࡇࢀࢆἼື᪉⛬ᘧ㸦2-14㸧࡟ධࢀࡿ࡜ࠊ

( )

2 1 0

÷÷

ø

ö

çç

è

æ

+

=

ωε

σ

i

k

c

ω

ω

k

_e (2-17) ࡀᚓࡽࢀࠊࡇࡇ࡛」⣲ᒅᢡ⋡Nࢆ 2 1 0

÷÷

ø

ö

çç

è

æ

+

=

ωε

σ

i

k

N

_e (2-18) ࡟ࡼࡾᑟධࡍࡿࠋ  ᕧどⓗ࡞ ᐃ࡟ࡼࡾほ ࡉࢀࡿගᏛⓗᛶ㉁ࡣࠊ」⣲ᒅᢡ⋡ N ࢆ౑ࡗ࡚⾲ࡉࢀࡿࠋ」⣲ㄏ 㟁⋡ࡣࠊ」⣲ᒅᢡ⋡࡜ྠࡌࡃᢅࢃࢀࡿ㔞࡛࠶ࡾࠊ 2

N

ε º

(2-19) ࡛⾲ࡉࢀࡿࠋ 」⣲ᒅᢡ⋡ࢆᐇᩘ㒊n࡜⹫ᩘ㒊k࡟ศࡅࠊz᪉ྥ࡟ఏ᧛ࡍࡿἼࢆ⪃࠼ࠊ

ik

n

N

=

+

(2-20) ࡜࠾ࡃ࡜㸦2-16㸧ࡣ

÷

ø

ö

ç

è

æ-×

þ

ý

ü

î

í

ì

÷

ø

ö

ç

è

æ

-=

c

z

ω

k

t

c

nz

ω

i

E

E

₀

exp

exp

(2-21) ࡜᭩ࡃࡇ࡜ࡀ࡛ࡁࡿࠋࡇࢀ࡜(2-7)ࡢẚ㍑࠿ࡽ

c

ω

k

α

=

2

(2-22) ࡜ࠊ྾཰ಀᩘࡣkࢆ⏝࠸࡚⾲ࡍࡇ࡜ࡀ࡛ࡁࡿࠋNࢆᒅᢡ⋡ࠊkࢆᾘ⾶ಀᩘ࡜࿧ࡪࠋ

 ཯ᑕ⋡ࡶn࡜kࢆ⏝࠸࡚⾲ࡍࡇ࡜ࡀ࡛ࡁࠊFig. 2.6ࡢࡼ࠺࡟z᪉ྥ࡟㐍ࡴἼࡀz=0࡟⾲㠃 ࢆᣢࡕࠊz>0࡟Ꮡᅾࡍࡿ≀㉁࡟ᆶ┤࡟ධᑕࡋࡓ࡜ࡍࡿ࡜ࠊ㏱㐣ἼE_t࡜཯ᑕἼE_rࡢz=0࡟࠾ ࡅࡿቃ⏺᮲௳ r i t

E

E

E

=

+

(2-23)

dz

dE

dz

dE

dz

dE

_{t i r}

+

=

(2-24) ࡼࡾࠊ

ik

n

ik

n

N

N

E

E

i r

+

+

+

-=

+

-=

1

1

1

1

(2-25) ࢆᚓࡿࡇ࡜ࡀ࡛ࡁࡿࠋගᙉᗘࡣ㟁ሙ᣺ືࡢ஧஌࡛࠶ࡿ࠿ࡽࠊ཯ᑕ⋡Rࡣ

(

)

(

)

2 2 2 2 2

1

1

1

1

k

n

k

n

N

N

R

+

+

+

-=

+

-=

(2-26) ࡜ࠊ」⣲ᒅᢡ⋡ࢆ⏝࠸࡚᭩ࡃࡇ࡜ࡀ࡛ࡁࡿࠋ  ༙ᑟయࡢ྾཰ಀᩘࢆồࡵࡿ᭱ࡶ୍⯡ⓗ࡞᪉ἲࡣࠊⷧ⭷ࡲࡓࡣ㠀ᖖ࡟ⷧࡃࡋࡓᮦᩱࢆ㏱㐣 ࡍࡿගࡢᙉࡉࠊ⾲㠃࡛཯ᑕࡍࡿගࡢᙉࡉࢆ┤᥋ ᐃࡍࡿ᪉ἲ࡛࠶ࡿࠋ྾཰ಀᩘαࠊཌࡉdࢆ ᣢࡘᖹ⾜∧⤖ᬗ࡟ගࡀᆶ┤ධᑕࡋࡓሙྜࡢ㏱㐣⋡T_mࠊ཯ᑕ⋡R_mࡣࠊᖸ΅ࢆ↓どࡋ࡚

(

)

(

)

(

α

d

)

R

d

α

R

T

_m

2

exp

1

exp

1

2 2

-=

(2-27) ㏱㐣Ἴ ධᑕἼ

E

_i

=

E

_i0

exp

{

iω

(

z/c

-

t

)

}

཯ᑕἼ

E

r

=

E

r0

exp

{

-iω

(

z/c

+

t

)}

0 = Z Z

)}

/

{exp(

exp

z 0

N

c-t

E

E

t

=

i Figure 2.6㻌ᆶ┤ධᑕගࡢ㏱㐣࡜཯ᑕ

(

)

{

T

α

d

}

R

R

_m

=

1

+

_m

exp

-

(2-28) ࡛ࠊ୚࠼ࡽࢀࡿࠋࡇࡇ࡛ࠊR ࡣᘧ(2-27)࡛୚࠼ࡽࢀࡿ༙↓㝈ࡢཌࡉࢆᣢࡘヨᩱࡢ཯ᑕ⋡࡛࠶ ࡿࠋ ᐃࡋࡓ㏱㐣⋡T_mࠊ཯ᑕ⋡R_m࠿ࡽ྾཰ಀᩘࢆồࡵࡿ࡟ࡣࠊᘧ(2-27)㸪(2-28)ࢆ⏝࠸࡚ィ ⟬ᘧ࡛㏫⟬ࡍࡿ᪉ἲࡀ࡜ࡽࢀ࡚࠸ࡿࡀࠊR ࡀ཯ᑕ⋡ ᐃ࡞࡝࡟ࡼࡾồࡵࡽࢀࡿሙྜ࡟ࡣᘧ (2-27)ࡼࡾゎᯒⓗ࡟ᐜ᫆࡟ồࡵࡿࡇ࡜ࡀ࡛ࡁࡿࠋ  ౯㟁Ꮚᖏࡢ᭱኱࡜ఏᑟᖏࡢ᭱ᑠࡢ㛫ࡢ㑄⛣ࡀጞࡲࡾࠊᇶ♏྾཰➃ࡢᙉᗘࡣ౯㟁Ꮚᖏࡢ᭱ ኱ཬࡧఏᑟᖏࡢ᭱ᑠࡀࣈࣜࣘ࢔ࣥࢰ࣮ࣥࡢྠࡌⅬ࡛⏕ࡌࡿ࠿࡝࠺࠿࡟ࡼࡾࠊྠࡌἼᩘ࣋ࢡ ࢺࣝࡢࣂࣥࢻ㛫㑄⛣ࡣ┤᥋࡜ྡ࡙ࡅࡽࢀ࡚࠾ࡾࠊᇶ♏྾཰➃ࡀ┤᥋㑄⛣࡛ྜ࠺ࡶࡢࡣ┤᥋ ྾཰➃ࢆᣢࡘ࡜ゝࢃࢀࡿࠋ 2.4.2 ᐇ㦂⣔  ග྾཰ ᐃ㸦 ᗘ౫Ꮡ≉ᛶ㸧࡟⏝࠸ࡓ ᐃ⿦⨨ࡢᴫ␎ᅗࢆFig. 2.7࡟♧ࡍࠋග※࡟ࣁࣟࢤ ࣥࣛࣥࣉࢆ⏝࠸ࠊගࢆࣞࣥࢬ࡟㏻ࡋ࡚ヨᩱ఩⨨࡛᭱ࡶ 㞟ගࡍࡿࡼ࠺࡟⣔ࢆ㓄⨨ࡋࡓࠋヨᩱ ࢆ㏱㐣ࡋࡓගࢆࣇ࢛ࢺ࣐࡛ࣝཷගࡋࡓࠋගࡢ㏱㐣⋡ Tࢆ ᐃࡍࡿࡇ࡜࡛ࠊ཯ᑕ⋡R࡜ヨᩱ ࡢཌࡉ dࢆ⏝࠸࡚ᘧࡢィ⟬࠿ࡽ྾཰ಀᩘ α ࢆồࡵࡓࠋヨᩱࡣࢡࣛ࢖࢜ࢫࢱࢵࢺෆ࡟ࢭࢵࢺ ࡋ ᗘኚ໬ࢆ࠿ࡅࡓࠋ

Harogen lamp

Pin hole

Cryostat

Lens

Sample

Chopper

Photomultiplier

Monochromator

Lock-in

Amplifier

Computer

Figure 2.7㻌ග྾཰ ᐃ⿦⨨

2.4.3 ᣑᩓ཯ᑕἲ ⢊ᮎࡸ㠃ࡢ⢒࠸ヨᩱࡢ྾཰ࢫ࣌ࢡࢺࣝࢆ ᐃࡍࡿ㝿࡟ࡣᣑᩓ཯ᑕἲࡀ⏝࠸ࡽࢀࡿࠋගࡀ ⢊ᮎヨᩱ࡟ධᑕࡍࡿ࡜ෆ㒊࡛཯ᑕࠊᒅᢡࠊ྾཰ࢆ⧞ࡾ㏉ࡋࡓᚋ࡟ᣑᩓ཯ᑕග࡜࡞ࡗ࡚ࡶ࡝ ࡗ࡚ࡃࡿࠋ ࡑࡢ㝿ࠊᐇ㦂ⓗ࡟ᚓࡽࢀࡿᣑᩓ཯ᑕ⋡R_dࡼࡾ྾཰ಀᩘα࡟㛵ࡍࡿ᝟ሗࢆᚓࡽࢀࡿࡓࡵ࡟ ࡣࢡ࣮࣒࣋ࣝ࢝ࣥࢡࡢᘧࡀ⏝࠸ࡽࢀࡿࠋࡇࡇ࡛ࠊ㹱ࡣᩓ஘ಀᩘ࡛࠶ࡿࠋᬑ㏻log f(R_d)㹼 logα ࡜࠾࠸࡚ゎᯒࡉࢀࡿࠋ

)

(

2

)

1

(

2

Rd

f

s

R

R

=

=

-

a

ᣑᩓ཯ᑕࢆ ᐃࡍࡿ࡟ࡣ✚ศ⌫ࢆࡶࡘ MgO ࡲࡓࡣBa₂SO₄ࡢ⢊ᮎࡀ඲㠃࡟୍ᵝ࡟ሬᕸࡉ ࢀ࡚࠾ࡾࠊෆ㒊࡛ධᑕගࡀ᏶඲ᣑᩓ≧ែ࡟࡞ࡿࡼ࠺࡟࡞ࡗ࡚࠸ࡿࠋ

ᣑᩓ཯ᑕ㠃

ධᑕ❆

ヨᩱ

ග᳨▱ჾ

Figure 2.8 ✚ศ⌫

2.5 Rapid Thermal Anneal (RTA) ⿦⨨  ᐇ㦂࡟⏝࠸ࡓ࢔ࢽ࣮ࣝ⿦⨨ࡢཎ⌮࡟ࡘ࠸࡚㏙࡭ࡿࠋ 2.5.1 ㉥እ⥺ࣛࣥࣉຍ⇕⅔ ຍ⇕⅔ࡣࠊ㉥እ⥺ࣛࣥࣉࢆᨺ≀཯ᑕ㠃ࣜࣇࣞࢡࢱ࣮ࡢ↔Ⅼ࡟ᅛᐃࡋ࡚㉥እ⥺ගࢆ୪⾜࡟ ཯ᑕࡉࡏࡿຍ⇕᪉ᘧ࡛࠶ࡿࠋࣛࣥࣉࡣ㏆㉥እ⥺ࣛࣥࣉ (100 V-1kW / ᮏ)ࢆ౑⏝ࡋ࡚࠸ࡿࠋ㉥ እ⥺ࣛࣥࣉࡣࠊ▼ⱥ࢞ࣛࢫࢳ࣮ࣗࣈ࡟ᑒධࡉࢀ࡚࠸ࡿࡓࡵࠊⓎ⇕య࠿ࡽࡢ࢞ࢫⓎ⏕ࡀ࡞ࡃࠊ ࢡ࣮ࣜࣥ࡞ຍ⇕ࡀฟ᮶ࡿࠋࡲࡓࠊ⅔యࡣ࢔࣑ࣝࢽ࣒࢘〇࡛ࠊ㧗 ࡲ࡛ࡢຍ⇕࡟⪏࠼ࡽࢀࡿ ࡼ࠺࡟Ỉ෭༷ࡋ࡚࠸ࡿࠋ 2.5.2 ຍ⇕ヨᩱ⣔ ヨᩱ⣔ࡣ㏱᫂▼ⱥ〇࢞ࣛࢫ⟶ࡢ୧➃ࡢ“O ࣜࣥࢢ”ࡼࡾẼᐦࢩ࣮ࣝࡋ࡚Ỉ෭࢔࣑ࣝࢽ࣒࢘ ྜ㔠〇ࣇࣛ ࣥࢪ࡟ᅛᐃࡍࡿࠋヨᩱࡣࠊ⛣ືࣇࣛࣥࢪࡢ㏱᫂▼ⱥ〇࢞ࣛࢫ࣍ࣝࢲ࣮ୖ࡟ࢭࢵ ࢺࡋࠊ㏱᫂▼ⱥ〇࢞ࣛࢫ⟶ෆ࡟཰⣡ࡉࢀࠊ㏱᫂▼ⱥ〇࢞ࣛࢫ⟶ࡢእഃࡢ㉥እ⥺ࣛࣥࣉ࡟ࡼ ࡾ㍽ᑕຍ⇕ࡉࢀࡿࠋ

ヨ ᩱ Ỉ ෭ 䝏 䜵 䞁 䝞

䞊

෭༷Ỉධཱྀ

┿✵ᘬ䛝ཱྀ

㐽

⇕

ᯈ

ヨᩱ⣔ほᐹ❆

䝃 䞁 䝥 䝹 䝩 䝹 䝎

䞊

෭༷Ỉฟཱྀ

ヨᩱ⛣ື䝣䝷䞁䝆

⇕ 㟁 ᑐ ᤄ ධ

ཱྀ

㉥ እ ⥺ 䝷 䞁 䝥 ຍ ⇕

⅔

ຍ

⇕

ヨ

ᩱ

⣔

O

䝸䞁䜾

ヨ ᩱ ⛣ ື 䝣 䝷 䞁

䝆

㍈䝇䝑䝖䝟䞊

Figure 2.9 ヨᩱ⣔䛾ᵓ㐀

2.5.3  ᗘไᚚ⣔ PIDไᚚࢆ⏝࠸࡚ ᗘࢥࣥࢺ࣮ࣟࣝࡋ࡚࠸ࡿࠋࡑࡢPIDไᚚ࡟ࡘ࠸࡚ㄝ᫂ࡍࡿࠋ ㄪ⠇⣔ࡣFig. 2.9࡟♧ࡍࡼ࠺࡟ධฟຊࡢᕪࢆྲྀࡾฟࡍാࡁࢆࡍࡿࠋㄪ⠇⣔ࡢఏ㐩㛵ᩘࡣᅗ࠿ ࡽࠊ

)

1

1

(

)

(

_DS IS p PID

T

T

K

s

G

=

+

+

࡛⾲ࡏࡿࠋࡇࡇ࡛ࠊTI ࡣ✚ศ᫬㛫ࠊTD ࡣᚤศ᫬㛫࡛࠶ࡿࠋࡇࡢఏ㐩㛵ᩘࢆぢࡿ࡜ࠊධฟ ຊࡢᕪࠊࡘࡲࡾ೫ᕪ࡟ẚ౛ࡍࡿ㡯ࠊ೫ᕪࡢ✚ศ࡟ẚ౛ࡍࡿ㡯ࠊ೫ᕪࡢᚤศ࡟ẚ౛ࡍࡿ㡯ࡢ ୕ࡘࡢ࿴࠿ࡽ࡞ࡿࠋࡑࡇ࡛ࡑࢀࡒࢀࡢ㡯ࢆẚ౛ (Proportional) ືసࠊ✚ศ (Integral) ືసࠊ ᚤศ (Derivative) ືస࡜࠸࠺ࠋࡇࡢㄪ⠇⣔ࡣࡋࡓࡀࡗ࡚ࠊPIDືసࢆ⾜࠺ࠋࡲࡓࡇࡢㄪ⠇⣔ ࢆPIDㄪ⠇⣔࡜࠸࠺ࠋ  ḟ࡟ࠊྛືసࡢㄝ᫂ࢆࡍࡿࠋ 㸦1㸧ẚ౛せ⣲ ⌧ᅾࡢ೫ᕪ࡟ᛂࡌ࡚ࠊಟṇືసࢆ⾜࠺ࡀ࢜ࣇࢭࢵࢺࡀṧࡿࠋ 㸦2㸧✚ศせ⣲ 㐣ཤࡢ೫ᕪࢆ✚ศࡋ࡚࢜ࣇࢭࢵࢺࢆྲྀࡾ㝖ࡁࠊࢮࣟ࡟࡞ࡿࠋ 㸦3㸧ᚤศせ⣲ ᛂ⟅ࡀ㏿ࡃ࡞ࡿࡀࣀ࢖ࢬ࡟ᙅ࠸ࡢ࡛࠶ࡲࡾࣃ࣓࣮ࣛࢱࢆᙉࡵ࡞࠸ࠋ

G

_c

(s)

G

_p

(s)

C(s)

R(s)

+

-G

_PID

(s)

ㄪ⠇⣔

G

_c

(s)

G

_p

(s)

C(s)

R(s)

+

-G

_PID

(s)

ㄪ⠇⣔

Figure 2.10㻌  ᗘไᚚ⣔

ཧ⪃ᩥ⊩ 1. ᳃⏣Ύ୕㸸㉮ᰝᆺࣉ࣮ࣟࣈ㢧ᚤ㙾ࡢࡍ࡭࡚㸦ᕤᴗㄪᰝ఍ࠊ1992㸧 2. ⃝⏣Ⴙ㑻㸸X⥺ග㟁Ꮚศගἲ㸦୸ၿᰴᘧ఍♫ࠊ1998㸧 3. Ἑᮾ⏣ 㝯㸸༙ᑟయホ౯ᢏ⾡ ⏘ᴗᅗ᭩㸦1989㸧. 4. P.Y.࣮ࣘ㸪M.࢝ࣝࢻࢼ㸦ⴭ㸧 ᮎඖ ᚭ㸪຾ᮏ ಙ࿃㸪ᒸ Ὀኵ㸪኱ᡂ ㄔஅຓ㸦ヂ㸧㸸 ༙ᑟయࡢᇶ♏ ࢩࣗࣉ࣮࣭ࣜࣥ࢞ࣇ࢙࢔࣮ࣛࢡᮾி

➨

3

❶

HF/AgNO

₃

ΰྜᾮ୰࡛ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢ࡟ࡼࡿ

ከᏍ㉁

Si

⢊ᮎࡢస〇

3.1 ᗎㄽ ᮏ❶࡛ࡣࠊከ⤖ᬗࢩࣜࢥࣥ⢊ᮎࢆฟⓎᮦᩱ࡜ࡋ࡚⏝࠸ࠊ㓟໬๣࡟◪㓟㖟ࢆ౑⏝ࡍࡿࡇ࡜ ࡛ࠊ㖟࡜ࢩࣜࢥࣥ(Si)ࡢ」ྜᚤ⢏Ꮚࡢ⡆ ౽࡞〇ἲ࡟ࡘ࠸࡚ሗ࿌ࡍࡿࠋSi ᇶᯈࡣࠊHF/HNO₃ ΰྜᾮ୰࡛ࢫࢸ࢖࢚ࣥࢵࢳࣥࢢࢆࡍࡿࡇ࡜࡛㛫౽࡟࣏࣮ࣛࢫࢩࣜࢥࣥ㸦PSi㸧ࡢస〇ࡀྍ⬟ ࡛࠶ࡿࡇ࡜ࢆSarathyࡽࡣሗ࿌ࡋࡓࠋ 1) Suemuneࡽࡶࠊࣇ࢛ࢺ࢚ࢵࢳࣥࢢἲ㸦He - Ne laser ↷ᑕୗ࡟࠾ࡅࡿHF⁐ᾮ୰࡛ࡢ࢚ࢵࢳࣥࢢ㸧࡟ࡼࡾࠊⓎගࡍࡿPSiࡢᙧᡂࢆ♧ࡋࡓࠋ 2) ࡲࡓࠊ ㏆ᖺࠊMetal Assissted Electroless Etching࡜࿧ࡤࢀࡿ㔠ᒓ࢖࢜ࣥࢆྵࡴᵝࠎ࡞㓟໬๣࡛࢚ࢵࢳ ࣥࢢࢆ⾜࠺ᡭἲ࡟ࡼࡾࠊSiࢼࣀ࣡࢖࣮ࣖࡸPSi࡞࡝ࡢࢼࣀᵓ㐀ࢆస〇ࡍࡿ◊✲ࡀ┒ࢇ࡟⾜ࢃ ࢀ࡚࠸ࡿࠋ 3~10) ᮏ◊✲࡛ࡣࠊࣇࢵ㓟࡜◪㓟㖟ࡢΰྜᾮࢆ⏝࠸ࡓࠊࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲ࡟ ࡼࡿࠊከ⤖ᬗSi⢊ᮎ࠿ࡽPSi࡜㖟ࡢ」ྜᚤ⢏Ꮚ㸦PSi/Ag」ྜᚤ⢏Ꮚ㸧ࡢస〇ࢆヨࡳࠊࡑࡢ ≀ᛶホ౯ࢆ⾜࠺ࡇ࡜ࢆ┠ⓗ࡜ࡋࡓࠋ 3.2 ᐇ㦂 3.2.1 PSi/Ag」ྜᚤ⢏Ꮚࡢస〇᮲௳ PSi࡜㖟ࡢ」ྜᚤ⢏Ꮚࢆస〇ࡍࡿ࡟࠶ࡓࡾᵝࠎ࡞᮲௳࡛ヨᩱస〇ࢆ⾜ࡗࡓࠋTable 3.1࡟స 〇᮲௳ࢆ♧ࡍࠋ™ࡣⓎගࡢ☜ㄆࡀ࡛ࡁ࡞࠿ࡗࡓࡶࡢࠊ ڹࡣ࡜ࡇࢁ࡝ࡇࢁᚤᙅ࡞Ⓨගࡢ☜ㄆ ࡀ࡛ࡁࡓࡶࡢࠊۑࡣᆒ୍࡞Ⓨගࡢ☜ㄆࡀ࡛ࡁࡓࡶࡢࢆ⾲ࡍࠋ࢚ࢵࢳࣥࢢ⤊஢ᚋࡢ஝⇱᪉ἲ ࡛⮬↛஝⇱࡛ࡣࠊⓎගࡢ☜ㄆࡀ࡜ࢀࡓࡶࡢ࡛ࡶ ࠊ┿✵஝⇱ࢆ⾜࠺࡜Ⓨගࡋ࡞࠸ヨᩱࡀぢࡽ ࢀࡓࠋࡇࢀࡣࠊ⮬↛஝⇱࡛ࡣࠊ┿✵஝⇱࡜ࡣ㐪࠸ࠊ஝⇱㐣⛬࡟࠾࠸࡚ࡶ Siෆ㒊࡛ࡣࠊ࢚ࢵ ࢳࣥࢢࡀ㐍ࢇ࡛࠾ࡾࠊࡑࢀࡀヨᩱ⾲㠃࡟ᙳ㡪ࢆ࠶ࡓ࠼࡚࠸ࡿࡢ ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ ᮏ◊✲࡛ࡣࠊࡇࡢ୰࡛ࡶࡶࡗ࡜ࡶᏳᐃࡋࡓⓎගࡢ෌⌧ᛶࡀ࡜ࢀࡿࡇSi 1.0 gࡢ᮲௳࡛స〇ࡋ ࡓヨᩱ࡟ࡘ࠸࡚ヲࡋࡃㄪ࡭ࡓࠋ Table 3.1 PSi/Ag」ྜᚤ⢏Ꮚࡢస〇᮲௳ Si⢊ᮎ (g) 0.3 0.5 1.0 1.5 ࢚ࢵࢳࣥࢢ᫬㛫 (min) 180 180 ~ 360 60 10 ~ 50 AgNO3 (g/L) 3 ~ 12 12 ~ 33 3 ~ 37 12 ~ 40 ⮬↛஝⇱ ڹ ™ ۑ ڹ ┿✵஝⇱ ™ ™ ™ ™

3.2.2 ౑⏝ࡋࡓヨᩱ࡜⁐ᾮ  ౑⏝ࡋࡓヨᩱࡣࠊከ⤖ᬗSi⢊ᮎ㸦VESTACERAMC♫〇㸧࡛ࠊ⢏Ꮚࡢᖹᆒ⢏ᚄࡣ4 μm࡛ ࠶ࡿࠋᐇ㦂ࡣࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲࢆ⏝࠸ࠊ⁐ᾮ࡟ࡣࠊ◪㓟㖟࡜ᘮ໬Ỉ⣲㓟㸦50 %㸧࡜⬺ ࢖࢜ࣥỈࡢΰྜᾮࢆ⏝࠸ࡓࠋస〇᮲௳ࡣTable 3.2࡟♧ࡋࡓࠋ 3.2.3 ᐇ㦂ᡭ㡰  ௨ୗࡢࡼ࠺࡞ᐇ㦂ᡭ㡰࡛⾜ࡗࡓࠋ 㸦1㸧HF㸦50 %㸧࡜⬺࢖࢜ࣥỈࡢయ✚ẚ3㸸7㸦24ml㸸56 ml㸧ࡢΰྜᾮࢆࢸࣇࣟࣥ〇ࡢᐜ ჾ࡟ධࢀΰࡐࡿࠋ 㸦2㸧◪㓟㖟5 gࢆ⬺࢖࢜ࣥỈ20 mlࡢ๭ྜ࡛⁐࠿ࡋ◪㓟㖟Ỉ⁐ᾮࢆస〇ࡍࡿࠋ 㸦2㸧ΰྜᾮࡢධࡗࡓᐜჾ࡟Si⢊ᮎࢆ1.0 gධࢀࡿࠋ 㸦3㸧◪㓟㖟Ỉ⁐ᾮࢆࣆ࣌ࢵࢺࢆ⏝࠸࡚ΰྜᾮ࡟⁲ୗࡍࡿࠋ10 min࡛ࡑࢀࡒࢀࡢ⃰ᗘ࡟㐩 ࡍࡿࡼ࠺࡟⁲ୗࡍࡿࠋ㔞ࢆ᫬㛫࡟ᑐࡋ࡚➼ศࡋ࡚ᑡ㔞ࡎࡘධࢀࡓࠋ 㸦4㸧◪㓟㖟ࡢ⃰ᗘࡣࠊ3㹼37 g/Lࡢ⠊ᅖ࡛ኚ໬ࡉࡏࡓࠋ㸦◪㓟㖟Ỉ⁐ᾮࡢ㔞ࠊ1 ml㹼14 ml㸧 㸦5㸧࢚ࢵࢳࣥࢢ᫬㛫ࡣ60 min࡜ࡋ࢚ࢵࢳࣥࢢ᏶஢ᚋࠊ⢊ᮎࢆℐ⣬ୖ࡟ྲྀࡾࠊࢻࣛࣇࢺෆ ࡛⮬↛஝⇱ࡉࡏࡿࠋ஝⇱᫬㛫ࡣ⣙㸯᪥࡜ࡋࡓࠋ Table 3.2 స〇᮲௳ ヨᩱ ከ⤖ᬗࢩࣜࢥࣥ⢊ᮎ(1.0 g) ࢚ࢵࢳࣥࢢᾮ HF(50 %)㸸(AgNO₃)㸸H₂O㸻3㸸7 AgNO3⃰ᗘ 3~37 g/L ࢚ࢵࢳࣥࢢ᫬㛫 60 min ᐇ㦂 ᗘ 30 Υ  ࢚ࢵࢳࣥࢢࢆ⾜࠺㐣⛬࡛ὀពࡋ࡞ࡅࢀࡤ࠸ࡅ࡞࠸Ⅼ࡜ࡋ࡚ࠊࢩࣜࢥࣥ⢊ᮎࢆ⁐ᾮ࡟ධࢀ ࡓ┤ᚋࡣࠊࢩࣜࢥࣥ⢊ᮎࡀ␯Ỉᛶࡢࡓࡵࣅ࣮࣮࢝⾲㠃࡟ᾋࡁୖࡀࡗ࡚ࡃࡿࠋࡑࡇ࡟ࠊ㓟໬ ๣࡛࠶ࡿ◪㓟㖟Ỉ⁐ᾮࢆᚎࠎ࡟ຍ࠼࡚ࢩࣜࢥࣥ࡜཯ᛂࡉࡏࡿࡇ࡜࡛ࠊࢩࣜࢥࣥ࡟㖟ࡀ௜╔ ࡋぶỈᛶ࡟࡞ࡾࣅ࣮࣮࢝ࡢᗏ࡟ỿẊࡋ࡚࠸ࡃࠋࡑࡢ㝿ࠊࢩࣜࢥࣥࢆ‶㐢࡞ࡃ࢚ࢵࢳࣥࢢᾮ ࡜཯ᛂࡉࡏࡿࡓࡵࠊ࢚ࢵࢳࣥࢢࡢ᭱୰ࡣᖖ࡟⢊ᮎ࡜࢚ࢵࢳࣥࢢᾮࢆΰࡐ⥆ࡅࡿᚲせࡀ࠶ࡿࠋ ࡲࡓࠊࢩࣜࢥࣥࡀ࢚ࢵࢳࣥࢢࡉࢀ ỿẊࡋጞࡵࡿ࡜ሢࡢࡼ࠺࡟⢊ᮎࡀᐦ࡟࡞ࡗ࡚ࡃࡿࡢ࡛₽ ࡍࡼ࠺࡟ࡋ࡚࠿ࡁΰࡐࡓࠋࡇࡢసᴗࡀࠊస〇᫬㛫ࡸPSiࡢᆒ୍ᛶ࡞࡝࡟ᙳ㡪ࡋ࡚ࡁ࡚ࡋࡲ࠺ ࡢ࡛ࠊ୍ᐃࡢ࣮࣌ࢫࢆᏲࡿᚲせࡀ࠶ࡿࠋ ᮏ◊✲ࡢࢫࢸ࢖࢚ࣥࢵࢳࣥࢢἲࡢᐇ㦂ᴫ␎ᅗࢆFig. 3.1࡟♧ࡋࡓࠋ࠶ࡿ⛬ᗘࡢ᫬㛫ΰࡐ⥆

䝦䝷

HF/H

2

O/AgNO

3

, Si

Si

⢊ᮎ

AgNO3

AgNO3

䜢ᑡ㔞䛪䛴㏣ຍ

Figure 3.1 ᐇ㦂ᴫ␎ᅗ

ℐ㐣

 3.2.4 ໬Ꮫ཯ᛂࣔࢹࣝ  ࢚ࢵࢳࣥࢢ୰ࡢ໬Ꮫ཯ᛂࢆ௨ୗ࡟♧ࡍࠋFig. 3.2࡟໬Ꮫ཯ᛂࣔࢹࣝࢆ♧ࡍࠋ Si + 2H2O 㸩 nh + → SiO2 + 4H + (4㸫n) e − , SiO2 + 6HF → H2 SiF6 + 2H2O, Ag+ + e- → Ag0 h+࡜e -ࡣࠊࡑࢀࡒࢀ࣮࣍ࣝ࡜㟁Ꮚ࡛࠶ࡿࠋSiཎᏊࡀ࣮࣍ࣝࡢᤕ⋓ࠊ㟁ᏊࡢὀධࠊỈ⣲ࡢᨺ ฟࡢ཯ᛂ㐣⛬ࢆ㎺ࡿ࡜⪃࠼ࡽࢀࡿࠋ࢚ࢵࢳࣥࢢᾮ୰࡟ྵࡲࢀࡿ㖟࢖࢜ࣥࡀ㑏ඖࡋࠊࢩࣜࢥ ࣥ⤖ᬗࡢ⾲㠃ࡀ໬Ꮫ㓟໬ࡉࢀࡿࠋࡑࢀ࡜ྠ᫬࡟ ࠊ㖟ࡀᯒฟࡋࢩࣜࢥࣥ⢊ᮎ࡟௜╔ࡍࡿࠋḟ ࡟ࠊࡇࡢ⤖ᬗ⾲㠃ࡢ㓟໬⭷ (SiO₂) ࡀ࢚ࢵࢳࣥࢢᾮ୰ࡢHF ᡂศ࡛㝖ཤࡉࢀࡿࠋࡇࡢ㐣⛬ࡀ ⧞ࡾ㏉ࡋ࡚㐍⾜ࡍࡿࡇ࡜࡛ࠊ⤖ᬗ⾲㠃ࡀพฝ࡜ࡋࡓ㖟࡜ࢩࣜࢥࣥࡢ」ྜయࡀฟ᮶ࡿ࡜⪃࠼ ࡽࢀࡿࠋ

Ag

+

Si

e

-Si

Ag

+

Si

Ag

0

HF

Si

O

Ag

0

Si

h

+

H

2

SiF

6

Ag

+

_Ag

+ Figure 3.2 ໬Ꮫ཯ᛂࣔࢹࣝ

3.3 ホ౯᪉ἲ

3.3.1 X⥺ග㟁Ꮚศගἲ(XPS) ᐃ

XPS (ULVAC-PHI Model 5600 spectrometer) ᐃࡣࠊX⥺ග※ࢆMg Ka (1253.6 eV)࡜ࡋࠊヨ ᩱ࡟ᑐࡋ࡚ࠊSi2p㌶㐨ࢫ࣌ࢡࢺࣝ࡜Ag3d㌶㐨ࢫ࣌ࢡࢺࣝࢆ ᐃࡋࡓࠋ  3.3.2 ㉮ᰝᆺ㟁Ꮚ㢧ᚤ㙾(SEM) ᐃ  ⾲㠃≧ែࢆぢࡿࡓࡵ࡟ࠊྛಸ⋡࡛SEMほ ࢆ⾜ࡗࡓࠋ ᐃࡣࠊJSM6330F㸦᪥ᮏ㟁Ꮚ㸧ࢆ ⏝࠸ࡓࠋ          3000 ಸ 10000 ಸ 15000 ಸ 30000 ಸ 3.3.3 ࣇ࢛ࢺ࣑ࣝࢿࢵࢭࣥࢫ(PL) ᐃ  స〇ࡋࡓヨᩱ࡟ࡘ࠸࡚ࠊḟࡢ᮲௳࡛PL ᐃࢆ⾜ࡗࡓࠋ ບ㉳ග※     㸸He-Cd Laser (

l

=

325 nm )

Laser๓ࡢFilter 㸸UTVAF-34 U (㏱㐣㡿ᇦ 280 ~ 380 nm ) ศගჾ๓ࡢFilter 㸸UTF-37 L (㐽᩿㡿ᇦ370 nm ௨ୗ) ศගჾࢫࣜࢵࢺ 㸸0.025 mm  ᐃ ᗘ 㸸ᐊ ࠊ20㹼300 K CCD detector ᗘ 㸸㸫75 Υ 3.3.4 ᣑᩓ཯ᑕ ᐃ స〇ࡋࡓヨᩱ࡟ࡘ࠸࡚ࠊḟࡢ᮲௳࡛ᣑᩓ཯ᑕ ᐃࢆ⾜ࡗࡓࠋ ഃග࣮ࣔࢻ    㸸%R ࣞࢫ࣏ࣥࢫ    㸸Fast  ᐃ⠊ᅖࡣ    㸸250㹼1500 nm ࢹ࣮ࢱྲྀࡾ㎸ࡳ㛫㝸㸸2.0 nm  ᐃࡍࡿ㝿࡟Fig. 3.3 ࡢࡼ࠺࡟ࠊヨᩱࢆ▼ⱥᇶᯈ࡛ ᣳࡴࡼ࠺࡟ࡋࠊ࿘ࡾࢆ࢝ࣉࢺࣥࢸ࣮ࣉ࡛そ࠸⟽≧࡟㛢 ࡌ㎸ࡵ࡚ ᐃࢆ⾜ࡗࡓࠋ

0

5

10

15

20

25

30

35

40

0

1

2

3

4

5

In

te

n

s

it

y

(a

rb

.

u

n

it

s)

(g/L)

114

112

110

108

106

0

1

2

3

4

In

te

n

s

it

y

(a

rb

.

u

n

it

s)

Binding energy (eV)

3.4 ᐇ㦂⤖ᯝ

3.4.1 XPS ᐃ⤖ᯝ

Fig. 3.4ࡣࠊస〇ࡋࡓヨᩱࡢSi2pࡢXPSࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋFig. 3.5ࡣࢫ࣌ࢡࢺࣝࡢ࣓࢖ ࣥࡢࣆ࣮ࢡᙉᗘࢆ◪㓟㖟ࡢ⃰ᗘ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓࢢࣛࣇ࡛࠶ࡿࠋ

ᅗࡼࡾࠊከᑡࡢࡤࡽࡘࡁࡣ࠶ࡿࡀࠊ◪㓟㖟⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀࠊࢩࣜࢥࣥ࠿ࡽࡢࢩࢢࢼ ࣝࡀῶᑡࡋ࡚࠸ࡃᵝᏊࡀࢃ࠿ࡿࠋ

Figure 3.5 ࣆ࣮ࢡᙉᗘࡢኚ໬ Figure 3.4 ;36  ᐃ⤖ᯝ㸦Si2P㸧

0

1

2

3

4

5

In

te

n

s

it

y

(a

rb

.

u

n

it

s)

385

380

375

370

365

360

355

0

1

2

3

4

5

In

te

n

s

it

y

(a

rb

.

u

n

it

s)

Binding energy (eV)

Fig. 3.6ࡣࠊస〇ࡋࡓヨᩱࡢAg3dࡢXPSࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋᕥഃࡢࣆ࣮ࢡࡣ3d_3/2ࠊྑഃ ࡢࣆ࣮ࢡࡣ3d_5/2࠿ࡽࡢࢩࢢࢼࣝࢆ♧ࡍࠋFig. 3.7ࡣࠊ3d_5/2ࣆ࣮ࢡࡢᙉᗘࢆ◪㓟㖟ࡢ⃰ᗘ࡟ᑐ ࡋ࡚ࣉࣟࢵࢺࡋࡓࢢࣛࣇ࡛࠶ࡿࠋᅗࡼࡾࠊ◪㓟㖟⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀࠊ࠶ࡿ⛬ᗘࡲ࡛ࡣ ẚ౛ࡋ࡚㖟࠿ࡽࡢࢩࢢࢼࣝࡀቑຍࡋࠊ35 g/Lࢆ㐣ࡂࡓ࠶ࡓࡾ࠿ࡽࠊᛴ⃭࡟㖟ࡢࣆ࣮ࢡࡀቑຍ ࡋ࡚࠸ࡿᵝᏊࡀࢃ࠿ࡿࠋ ௨ୖࡢ⤖ᯝ࠿ࡽࠊ࢚ࢵࢳࣥࢢᾮࡢቑຍ࡟ᚑࡗ࡚ࠊSiࡀ࢚ࢵࢳࣥࢢࡉࢀࠊAgࡀᯒฟࡋ࡚࠸ ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡿࠋࡲࡓࠊࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡ఩⨨ࡢࢩࣇࢺࡣࠊXPS ࡢග㟁Ꮚᨺฟ࡟క ࠺ヨᩱ⾲㠃ࡢࢳ࣮ࣕࢪ࢔ࢵࣉࡢᙳ㡪࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ Figure 3.6 XPS ᐃ⤖ᯝ㸦Ag3d㸧

3.4.2 SEM ᐃ⤖ᯝ

0.5 μ m

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

Figure 3.8㻌SEM⏬ീ

Fig. 3.8ࡣࠊHF࡜AgNO₃ࡢΰྜ⁐ᾮ࡛స〇ࡋࡓヨᩱࡢSEM⏬ീ࡛࠶ࡿࠋ(a)ࠊ(e)ࡣSi⢊ ᮎࡢSEM⏬ീࠊ(b)ࠊ(f)ࡣ◪㓟㖟⃰ᗘ17 g/L࡛ࢫࢸ࢖࢚ࣥࢵࢳࣥࢢࡋࡓPSi⢊ᮎࡢSEM⏬ ീࠊ(c)ࠊ(g)ࡣ33 g/Lࠊ(d)ࠊ(h)ࡣ37 g/L࡛స〇ࡉࢀࡓヨᩱ࡛࠶ࡿࠋࡑࢀࡒࢀᕥഃࡢᅗࡀపಸ ⋡ࠊྑഃࡢᅗࡀ㧗ಸ⋡ࢆ♧ࡍࠋ ࡲࡎࠊ(b)ࠊ(f)ࡢヨᩱ࡛ࡣࠊ⾲㠃࡟ᚤ⢏Ꮚ≧ࡢࡶࡢࡀ௜╔ࡋ࡚࠸ࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋ(c)ࠊ (g)ࡢヨᩱ࡛ࡣࠊᚤ⢏Ꮚ≧ࡢࡶࡢࡀࠊࡉࡽ࡟ᐦᗘࡀ㧗ࡃ௜╔ࡋ࡚࠸ࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋ(d)ࠊ (h)ࡢヨᩱ࡛ࡣࠊฝพ࡜ࡋࡓ⭷ࡢࡼ࠺࡞ࡶࡢࡀᙧᡂࡋ࡚࠸ࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋ 11) 3.4.1 ࡢXPS  ᐃ⤖ᯝ࡜↷ࡽࡋྜࢃࡏࡿ࡜ࠊ⾲㠃࡟௜╔ࡋ࡚࠸ࡿࡶࡢࡣࠊAg࡛࠶ࡿ࡜⪃ ࠼ࡽࢀࡿࠋࡲࡓࠊࡇࢀࡽࡢSEM⏬ീ࠿ࡽ௜╔ࡋ࡚࠸ࡿ㖟ᚤ⢏Ꮚࡢࢧ࢖ࢬࡣࠊ◪㓟㖟ࡢ⃰ᗘ ࡟ᙉࡃ౫Ꮡࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ 3.4.3 ⁐፹࡟ᑐࡍࡿぶ࿴ᛶ Fig. 3.9ࡣࠊSi⢊ᮎࢆ◪㓟㖟ࢆྵࡴHFỈ⁐ᾮ࡛ࢫࢸ࢖࢚ࣥࢵࢳࣥࢢࡋࡓヨᩱ࡜◪㓟ࢆྵ ࡴHFỈ⁐ᾮ࡛࢚ࢵࢳࣥࢢࡋࡓヨᩱࡢ⁐፹࡜ࡢぶ࿴ᛶࢆẚ㍑ࡋࡓ෗┿࡛࠶ࡿࠋᕥ࠿ࡽ◪㓟㖟 ࡛స〇ࡋࡓヨᩱࢆỈࠊ࢔ࢭࢺࣥࠊ࣓ࢱࣀ࣮ࣝࠊ ࢺࣜࢡ࢚ࣟࣟࢳࣞࣥ࡟ ศᩓࡉࡏࡓࡶࡢࠊ◪ 㓟࡛స〇ࡋࡓヨᩱࢆࠊࡑࢀࡒࢀࡢ⁐፹࡟ศᩓࡉࡏࡓࡶࡢ࡟࡞ࡿࠋ  ◪㓟࡛స〇ࡋࡓヨᩱࡣࠊ↓ᴟᛶ⁐፹࡛࠶ࡿࢺࣜࢡ࢚ࣟࣟࢳࣞࣥ࡟ࡣࡼࡃศᩓࡍࡿࡀࠊᴟ ᛶࢆᣢࡘ࢔ࢭࢺࣥ࡜࣓ࢱࣀ࣮࡛ࣝࡣⱝᖸ ศᩓ࡟೫ࡾࡀ࠶ࡿࡼ࠺࡟ぢ࠼ࡿࠋࡉࡽ࡟ᴟᛶࡢᙉ ࠸Ỉ࡛ࡣศᩓࡋ࡞࠸ࡇ࡜ࡀࢃ࠿ࡿ ࠋ୍᪉ࠊ◪㓟㖟࡛స〇ࡋࡓヨᩱࡣ࡝ࡢ⁐፹࡟ᑐࡋ࡚ࡶࡼ ࡃศᩓࡋ࡚࠸ࡿࡇ࡜ࡀࢃ࠿ࡿࠋ  ࡇࢀࡽࡢ⁐፹࡟ᑐࡍࡿぶ࿴ᛶࡢ㐪࠸ࡣࠊPSi⢊ᮎࡢ⾲㠃≧ែࡀస〇᪉ἲ࡟ࡼࡗ࡚␗࡞ࡗ࡚ ࠸ࡿࡓࡵ࡟⏕ࡌ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ  Figure 3.9

HNO

䠏

㻌

Ỉ㻌

䜰䝉䝖䞁㻌

䝯䝍䝜䞊䝹㻌

䝖䝸䜽䝻

AgNO

䠏

㻌

Ỉ㻌

䜰䝉䝖䞁㻌

䝯䝍䝜䞊䝹㻌

䝖䝸䜽䝻

3.4.4 PL ᐃ⤖ᯝ

Fig. 3.10ࡣࠊHF࡜AgNO₃ΰྜᾮ࡟࠾ࡅࡿᵝࠎ࡞◪㓟㖟⃰ᗘ࡛స〇ࡋࡓPSi⢊ᮎࡢPL 

ᐃ⤖ᯝ࡛࠶ࡿࠋᅗࡼࡾࠊ◪㓟㖟⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀ࡚Ⓨගᙉᗘࡀቑຍࡋࠊ9 g/L࡛᭱኱್ ࢆᣢࡘࡇ࡜ࢆ☜ㄆࡋࡓࠋࡲࡓࠊ◪㓟㖟ࡢ⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀ࡚ࠊⓎගࣆ࣮ࢡࡢࣈ࣮ࣝࢩ ࣇࢺࡀ☜ㄆ࡛ࡁࡿࠋ Fig. 3.11ࡣࠊFig. 3.10ࡢPLࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡᙉᗘࢆ◪㓟㖟ࡢ⃰ᗘ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋ ࡓࢢࣛࣇ࡛ࠊFig. 3.12ࡣࢫ࣌ࢡࢺࣝࡢࣆ࣮ࢡἼ㛗ࢆ◪㓟㖟ࡢ⃰ᗘ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓࢢࣛ ࣇ࡛࠶ࡿࠋ Fig. 3.11࠿ࡽࠊ◪㓟㖟ࡢ⃰ᗘࡀ9 g/Lࢆ㐣ࡂࡓ࠶ࡓࡾ࠿ࡽⓎගᙉᗘࡀῶᑡࡋ࡚࠸ࡁ37g/L ࡛᏶඲࡟ᾘගࡍࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊ ࡇࢀࡽࡢ ᙉᗘࡢ᭱኱್࡟࡞ࡿ◪㓟㖟 ࡢ⃰ᗘࡣࠊస〇᪥࡟ࡼࡗ࡚ࠊࡤࡽࡘࡁࢆぢࡏࡿࡇ࡜ࡀࢃ࠿ࡗࡓࠋࡇࢀࡣࠊస〇᪥ࡢ‵ᗘࡸ Ẽ ࡟ᙳ㡪ࡉࢀࡿ࡜⪃࠼ࡽࢀࡿࠋ ࡓࡔࡋࠊ᏶඲࡟ᾘගࡍࡿヨᩱࡣࠊస〇᪥࡟ࡼࡽࡎྠࡌ⃰ ᗘ࡜࡞ࡗࡓ ࠋࡇࡢࡇ࡜ࡣࠊస〇ࡉࢀࡓヨᩱࡢ≧ែࡣྠࡌ࡛࠶ࡿࡀࠊヨᩱࡢ཰⋡ࡀ␗࡞ࡿࡢ ࡛ࡣ࡞࠸࠿࡜⪃࠼ࡽࢀࡿࠋ Fig. 3.12࠿ࡽࡣࠊ◪㓟㖟ࡢ⃰ᗘࡀቑຍࡍࡿ࡟ࡘࢀ࡚Ⓨගࣆ࣮ࢡࡢࣈ࣮ࣝࢩࣇࢺࡀ☜ㄆ࡛ࡁ ࡿࠋ ࡇࢀࡽࡢ⤖ᯝࡣࠊᐃᛶⓗ࡟ࡣࠊ࣏࣮ࣛࢫࢩࣜࢥࣥࡢᏍࡢࢧ࢖ࢬࡢቑຍ࡟ࡼࡿࠊෆ㒊ࡢᚤ ⣽ᵓ㐀ࡢࢧ࢖ࢬࡢῶᑡࢆ཯ᫎࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋ

400

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AgNO₃ concentration [g/L]

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3 6 9 12 15 17 20 23 25 28 30 33 35 37

(a)

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Figure 3.10 PL ᐃ⤖ᯝ Figure 3.11 ࣆ࣮ࢡᙉᗘࡢኚ໬

0

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3.4.5 PL ᐃ⤖ᯝ㸦 ᗘ౫Ꮡᛶ㸧 Fig. 3.13ࡣ◪㓟㖟⃰ᗘ28 g/L࡛స〇ࡉࢀࡓPSi࡟࠾࠸࡚ࠊ ᗘࢆ20㹼300 K࡛ኚ໬ࡉࡏࡓ ࡜ࡁࡢPL ᐃ⤖ᯝࢆ♧ࡍࠋFig. 3.14ࡣࠊ௨๓ᙜ◊✲ᐊ࡛ሗ࿌ࡉࢀࡓ㝧ᴟ໬ᡂἲ࡛స〇ࡋࡓ PSiᇶᯈࡢ ᗘ౫Ꮡࡢࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋヨᩱ࠿ࡽ50 K௨ୗ࡛≉ᚩⓗ࡞Ἴᙧࡀぢࡽࢀࡓࠋ Fig. 3.15ࡣࠊFig. 3.14ࡢ50 K௨ୗࡢࢫ࣌ࢡࢺࣝࢆᣑ኱ࡋࡓࡶࡢࢆ♧ࡍࠋ㝧ᴟ໬ᡂ࡛స〇ࡉ ࢀࡓヨᩱ࡛ࡣప ࡟࡞ࡿ࡟ࡘࢀ」ᩘࡢࢹ࢕ࢵࣉࢆ☜ㄆࡋࡓࠋࡇࢀࡣࠊPSi⭷࡟ࡼࡿගࡢᖸ΅ ࡸࠊPSi⾲㠃ࡢ྾╔≀㉁ࡀᙳ㡪ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡋ࠿ࡋ࡞ࡀࡽࠊPSi⢊ᮎ࡛ࡣ ᗘኚ ໬࡟ࡼࡿ≉ᚩⓗ࡞ኚ໬ࡣ☜ㄆࡉࢀ࡞࠿ࡗࡓࠋࡇࡢཎᅉ࡟ࡘ࠸࡚ࡣ୙᫂࡞ࡓࡵࠊࡼࡾヲ⣽࡞ ᐇ㦂ࡀᚲせ࡛࠶ࡿࠋFig. 3.16ࡣࠊࣆ࣮ࢡᙉᗘࢆ ᗘ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓᅗ࡛࠶ࡿࠋFig. 3.17 ࡣࠊࣆ࣮ࢡἼ㛗ࢆ ᗘ࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓᅗ࡛࠶ࡿࠋFig. 3.16࠿ࡽ ᗘࡀప ࡟࡞ࡿ࡟ࡘ ࢀࠊⓎගᙉᗘࡀቑຍࡋ࡚࠸ࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋ Figure 3.13 PSi⢊ᮎ㸦 ᗘ౫Ꮡᛶ㸧

Wavelength (nm)

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50 K Figure 3.14 PSiᇶᯈ㸦 ᗘ౫Ꮡᛶ㸧

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Figure 3.16 ࣆ࣮ࢡᙉᗘ

115 110 105 100 95 AgNO₃ HNO₃

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SiO2 Si Si-Ag 400 500 600 700 800 900 AgNO₃ HNO 3

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㽢

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㽢

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㽢

1.6

3.4.6 PL ᐃ⤖ᯝ㸦Ag㝖ཤ㸧  Fig. 3.18ࡣࠊ㓟໬๣ࡢ◪㓟㖟⃰ᗘࢆࡑࢀࡒࢀ9 g/L, 20 g/L, 30 g/L, ࡜ࡋ࡚స〇ࡋࡓࡶࡢ࡜ࠊ స〇ᚋ◪㓟࡟ₕࡅ㖟ࢆ㝖ཤࡋࡓࡶࡢࡢPLࢫ࣌ࢡࢺࣝࢆẚ㍑ࡋࡓᅗ࡟࡞ࡿࠋᅗࡼࡾ㖟ࢆ㝖ཤ ࡋࡓᚋࡢヨᩱࡢ᪉ࡀࠊⓎගᙉᗘࡀᙉࡃࢫ࣌ࢡࢺࣝࡀࣈ࣮ࣝࢩࣇࢺࡋ࡚࠸ࡿࡢࡀ☜ㄆ࡛ࡁࡿࠋ  Fig. 3.19ࡣࠊFig. 3.18ࡢヨᩱࡢXPS ᐃ⤖ᯝ࡟࡞ࡿࠋᅗ࠿ࡽࠊSiO₂ࡢ㔞ࡀ㖟㝖ཤ๓࡜㝖

ཤᚋ࡛ࠊቑຍࡋ࡚࠸ࡿࡢࡀ☜ㄆ࡛ࡁࡿࠋࡇࡢ⤖ᯝࡼࡾPLࢫ࣌ࢡࢺࣝࡢࣈ࣮ࣝࢩࣇࢺࡣࠊ㓟 ໬⭷ࡢቑຍࡀࠊᐤ୚ࡋ࡚࠸ࡿ࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊFig. 3.19࡟ぢࡽࢀࡿ99 eV௜㏆ࡢࣆ࣮ࢡ ࡣᩥ⊩ࡼࡾSi-Ag࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ 12) Figure 3.18 PL ᐃẚ㍑ Figure 3.19 XPS ᐃẚ㍑

3.4.7 PL ᐃ⤖ᯝ㸦⣸እග↷ᑕ᫬㛫౫Ꮡᛶ㸧

Fig. 3.20ࡣࠊస〇ࡋࡓヨᩱ࡟⣸እග㸦He-Cd࣮ࣞࢨ࣮㸧325 nmࢆ↷ᑕࡋࠊPLࢫ࣌ࢡࢺࣝ ࡢࣆ࣮ࢡᙉᗘࢆᶓ㍈᫬㛫࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓࢢࣛࣇ࡛࠶ࡿࠋ ࡓࡔࡋࠊගࢆ↷ᑕࡋ࡚࠸࡞ ࠸≧ែࡢᙉᗘ࡛つ᱁໬ࢆ⾜ࡗࡓࠋFig. 3.21ࡣࠊࣆ࣮ࢡἼ㛗ࢆᶓ㍈᫬㛫࡟ᑐࡋ࡚ࣉࣟࢵࢺࡋࡓ ࢢࣛࣇ࡛࠶ࡿࠋ

Fig. 3.20ࡢHe-Cd࣮ࣞࢨ࣮ࢆ↷ᑕࡋ࡚࠿ࡽ25 secࡲ࡛ࡢࢢࣛࣇ࡟ὀ┠ࡍࡿ࡜ࠊ◪㓟㖟࡛ స〇ࡋࡓヨᩱࡣࠊ◪㓟࡛స〇ࡋࡓヨᩱ࡟ẚ࡭ᙉᗘࡢῶᑡࡀ⦆ࡸ࠿࡞ࡢࡀࢃ࠿ࡿࠋࡲࡓࠊ25 sec ࠿ࡽ300 secࡲ࡛ࡢ⤒㐣᫬㛫ࢆẚ㍑ࡍࡿ࡜ࠊ඲࡚ࡢヨᩱࡀྠࡌࡼ࠺࡟ῶᑡࡋ㣬࿴࡟ྥ࠿ࡗ࡚ ࠸ࡿᵝᏊࡀ☜ㄆ࡛ࡁࡿࠋ⣸እග↷ᑕ᫬㛫ࡢቑຍ࡟క࠸ࠊPLᙉᗘࡀῶᑡࡍࡿࡢࡣࠊගࢆ↷ᑕ ࡍࡿࡇ࡜࡟ࡼࡗ࡚ࠊ⾲㠃ࡢỈ⣲ཎᏊࡀኻࢃࢀࠊ 13) ྠ᫬࡟⾲㠃ࡢ㓟໬ࡀಁ㐍ࡉࢀࡿࡇ࡜࡟ࡼࡿ PSi ⾲㠃࡜㓟໬⭷ࡢ⏺㠃࡟㠀Ⓨග୰ᚰࡀ⏕ᡂࡉࢀ࡚࠸ࡿࡓࡵ࡛࠶ࡿ࡜⪃࠼ࡽࢀࡿࠋ 14) ࡲࡓࠊ ◪㓟㖟࡛స〇ࡋࡓヨᩱࡀࠊ◪㓟࡛స〇ࡋࡓヨᩱࡼࡾࡶ࣮ࣞࢨ࣮࡟ࡼࡿຎ໬ࡀᑡ࡞࠸ࡢࡣࠊ ◪㓟㖟࡛స〇ࡋࡓヨᩱ࡟ࡣࠊከᏍ㉁ࢩࣜࢥࣥ⾲㠃࡟Si-H࡟㍑࡭࡚Ᏻᐃ࡞Si-Ag⤖ྜࡀᏑᅾ ࡋ࡚࠸ࡿࡓࡵ࡜⪃࠼ࡽࢀࡿࠋ 15) Fig.3.21ࡼࡾࠊ◪㓟࡛స〇ࡋࡓヨᩱࡣⱝᖸࡢࣈ࣮ࣝࢩࣇࢺࡋ ࡚࠸ࡿࡢ࡟ᑐࡋࠊ◪㓟㖟࡛స〇ࡋࡓヨᩱࡣ஧ࡘ࡜ࡶࣞࢵࢻࢩࣇࢺࡋ࡚࠸ࡿ⤖ᯝ࡟࡞ࡗࡓࠋ Figure 3.20 PLࣆ࣮ࢡᙉᗘẚ㍑ Figure 3.21 PLࣆ࣮ࢡἼ㛗ẚ㍑ 0 50 100 150 200 250 300 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 AgNO₃ AgNO 3_HNO3 HNO₃ P L i n te n s it y ( n o rm a li z e d ) Time (sec) 0 50 100 150 200 250 300 620 630 640 650 660 670 680 690 700 710 720 730 AgNO₃ AgNO₃_HNO₃ HNO₃ W a v e le n g th ( n m ) Time (sec)

3.4.8 ᣑᩓ཯ᑕ ᐃ⤖ᯝ Fig. 3.22 ࡣࠊ཯ᑕ⋡ ᐃ⤖ᯝࡢࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ୍␒ୖࡢࢫ࣌ࢡࢺࣝࡣࠊ◪㓟㖟⃰ᗘ 37 g/Lࡢヨᩱࢆ✵Ẽ୰࡛ ᐃࡋࡓࢫ࣌ࢡࢺ࡛ࣝ࠶ࡿࠋ400 nm௜㏆࡟ࠊ཯ᑕ⋡ࡢพࡳࡀぢࡽ ࢀࡿࠋ Fig. 3.23ࡣࠊᩥ⊩࡟ሗ࿌ࡉࢀࡓ⾲㠃ࡀࢫ࣒࣮ࢫ࡞㖟ⷧ⭷࡜ࣛࣇࢿࢫࡢ࠶ࡿ㖟ࡢ཯ᑕࢫ࣌ࢡ ࢺ࡛ࣝ࠶ࡿࠋ 16) ࣛࣇࢿࢫࡢ࠶ࡿ㖟ⷧ⭷࡟ࡣࠊ400 nm௜㏆࡟཯ᑕ⋡ࡢพࡳࡀぢࡽࢀࠊࡇࢀࡣ 㖟ⷧ⭷ࡢ⾲㠃ࣉࣛࢬࣔࣥඹ㬆࡟ࡼࡿ྾཰࡜⪃࠼ࡽࢀ࡚࠸ࡿࠋᮏ◊✲࡛ࠊ37 g/Lࡢヨᩱ࡟ほ  ࡉࢀࡓพࡳࡀࠊ⾲㠃ࣉࣛࢬࣔࣥ࡟ࡼࡿ྾཰࠿࡝࠺࠿ࢆ☜࠿ࡵࡿࡓࡵࠊỈ୰࡛ࡢ཯ᑕ⋡ࢆ  ᐃࡋࡓࠋୖ࠿ࡽ஧␒┠ࡢࢫ࣌ࢡࢺࣝࡀࠊỈ୰࡛ࡢ཯ᑕ⋡ࡢࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᅗࡼࡾࠊ✵ Ẽ୰࡜ẚ㍑ࡋ࡚ࠊพࡳࡀ㛗Ἴ㛗ഃ࡟ࢩࣇࢺࡋ࡚࠸ࡿࡇ࡜ࡀ☜ㄆ࡛ࡁࡿࠋ ⾲㠃ࣉࣛࢬࣔࣥ࡟ࡼࡿ྾཰ࡢࠊඹ㬆Ἴ㛗ࡣࠊ௨ୗࡢᘧ࡛୚࠼ࡽࢀࡿࠋ 17)                                      (3-1) ࡇࡇ࡛ࠊ sp w ࡣ⾲㠃ࣉࣛࢬࣔࣥࡢඹ㬆࿘Ἴᩘࠊ p w ࡣࣉࣛࢬ࣐࿘Ἴᩘࠊemࡣ፹㉁ࡢㄏ㟁⋡࡛ ࠶ࡿࠋࡇࡢᘧ࡛⾲ࡉࢀࡿࡼ࠺࡟ࠊ࿘ࡾࡢ፹㉁ࡢㄏ㟁⋡࡟౫Ꮡࡋࠊㄏ㟁⋡ࡀ㧗ࡃ࡞ࡿ࡜ࠊ ⾲ 㠃ࣉࣛࢬࣔࣥࡢඹ㬆୍ࡣࠊప࢚ࢿࣝࢠ࣮ഃ࡟ࢩࣇࢺࡍࡿࠋࡇࢀࡣࠊほ ࡉࢀࡓพࡳࡢἼ㛗 ࡢኚ໬࡜୍⮴ࡋ࡚࠸ࡿࡢ࡛ࠊࡇࡢพࡳࡣࠊ⾲㠃࡟ᯒฟࡋࡓ㖟ᚤ⢏Ꮚࡢ⾲㠃ࣉࣛࢬࣔࣥ࡟ࡼ ࡿ྾཰࡜⪃࠼ࡽࢀࡿࠋࡲࡓࠊ⾲㠃ࣉࣛࢬࣔࣥࡢ྾཰ࡀ㉳ࡁࡿἼ㛗ࡣ௨ୗࡢᘧ sp R D ࡛୚࠼ࡽ ࢀࡿࠋ 16) (3-2) ࡇࡇ࡛ࠊ

d

ࡣࣛࣇࢿࢫࡢ஧஌್ࠊ 1

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Figure 3.22 ྾཰ ᐃ⤖ᯝ