価電子帯XPSおよびNEXAFSによる有機半導体の化学状態解析
ᐇ㦂␒ྕ㸸 㸰㸳㹑㸮㸮㸯 2013 ᖺᗘ ᡂᯝබ㛤↓ൾ⏝ᴗ ᡂᯝሗ࿌᭩ ̖ᩓ ࠘܇XPS ƓǑƼ NEXAFS ƴǑǔ ஊೞҞ˳ݰƷ҄ܖཞ७ᚐௌ Chemical state characterization of organic semiconductor using valence band XPS and NEXAFS ⳥㛫῟ࠊኟ┠✨ࠊᐊ㯞⾰Ꮚࠊᯇ㔝ಙஓ Jun Kikuma, Yutaka Natsume, Maiko Muro, Shinya Matsuno ᪫ᡂ㸦ᰴ㸧ᇶ┙ᢏ⾡◊✲ᡤ Analysis and Simulation Center, Asahi-KASEI Corporation 1. ᐃᐇ᪥ 2013 ᖺ 12 ᭶ 19 ᪥ 10 – 18 30 ศ (2 ࢩࣇࢺ) 㸪BL7U 2014 ᖺ 2 ᭶ 18 ᪥ 10 – 18 30 ศ (2 ࢩࣇࢺ) 㸪BL7U 2014 ᖺ 2 ᭶ 28 ᪥ 10 – 18 30 ศ (2 ࢩࣇࢺ) 㸪BL7U 2. ᴫせ ᭷ ᶵ ༙ ᑟ య ࡢ ୍ ✀ ࡛ ࠶ ࡿ 6,13-Bis(triisopropylsilylethynyl) pentacene (TIPS-Pen; Fig. 1)ࡢຍ⇕ຎࡼࡿᵓ㐀ኚࢆㄪࡿ┠ⓗ࡛ࠊຎရ࠾ࡼࡧ ᮍຎရࡢ౯㟁Ꮚᖏ XPS ࢫࢡࢺࣝཬࡧ C-K Ẇ྾➃ࡢ NEXAFS ࢫ࣌ࢡࢺ ࣝࡢ ᐃࢆ⾜࠸ࠊࢫ࣌ࢡࢺࣝࡢኚࢆ➨୍ཎᏊィ⟬ࡼࡿࢩ࣑࣮ࣗࣞࢩࣙࣥ ᇶ࡙ࡁゎ㔘ࢆ⾜ࡗࡓࠋࡑࡢ⤖ᯝࠊຍ⇕ࡼࡾ TIPS-Pen ࡢࢯࣉࣟࣆࣝᇶࡀ⬺ 㞳ࡋ࡚ OH ᇶ⨨ࡋ࡚࠸ࡿࡇࡀ♧၀ࡉࢀࡓࠋ Si 㸬⫼ᬒ◊✲┠ⓗ C C ᭷ᶵ༙ᑟయࡣࣉࣜࣥࢱࣈ࢚ࣝࣞࢡࢺࣟࢽࢡ ࢫ⏝㏵ࡋ࡚ὀ┠ࡉࢀ࡚࠸ࡿᮦᩱ࡛࠶ࡿࡀࠊ࡞ ࡛ࡶ TIPS-Pen ࡣ᭷ᶵ⁐ྍ⁐࡛࠶ࡾࠊ⡆ C C ౽࡞༳ๅᡭἲ࡛㟁Ꮚᅇ㊰ࢆస〇࡛ࡁࡿྍ⬟ᛶ Si ࡀᣦࡉࢀ࡚࠸ࡿࠋࡋࡋ࡞ࡀࡽࠊගࡸ⇕ࡼ ࡗ࡚ຎࡋࡸࡍ࠸࠸࠺ㄢ㢟ࡀ࠶ࡾࠊࡑࡢ࣓࢝ ࢽࢬ࣒ࢆ᫂ࡽࡍࡿࡇࡣᮦᩱ㛤Ⓨ࠾࠸ Fig.1 TIPS-Pen 䛾Ꮫᵓ㐀㻌 ࡚㔜せ࡛࠶ࡿࠋ ᮏㄢ㢟࡛ࡣࠊ౯㟁Ꮚᖏ࠾ࡼࡧ㠀༨᭷ࣂࣥࢻࡢᵓ㐀ࢆࠊ㌾ X ⥺ᨺᑕගࢆග※ ࡍࡿ౯㟁Ꮚᖏ XPS ࠾ࡼࡧ NEXAFS ࢆ⏝࠸࡚ᐇ㦂ⓗㄪࠊࡇࢀࡽࡘ࠸ ࡚➨୍ཎ⌮ィ⟬ࡼࡿゎ㔘ࢆ⾜࠺ࡇ࡛ࠊຎࡼࡿᏛᵓ㐀ࡢኚࢆ᫂ࡽ ࡍࡿࡇࢆ┠ⓗࡋࡓࠋ 㸬ᐇ㦂ෆᐜ ᮍຎヨᩱࡣࠊヨ⸆ࢢ࣮ࣞࢻࡢ TIPS-Pen㸦Sigma-Altrich ♫ࠊ⣧ᗘ 99㸣௨ ୖ㸧ࢆࠊຎヨᩱࡣࠊTIPS-Pen ⢊ᮎࢆ✵Ẽ୰࡛ 300Υ࡛ຍ⇕ࡋࡓࡶࡢࢆ⏝࠸ ࡓࠋྛࠎࡢ⢊ᮎࢆࢡࣟࣟ࣋ࣥࢮࣥ⁐ゎࡉࡏࠊSi ࢚࢘ࣁୖࢫࣆࣥ࢟ࣕࢫࢺ ࡋࡓࡶࡢࢆ ᐃヨᩱࡋࡓࠋ ᐃࡣ࠸ࡎࢀࡶ BL7U ࡚⾜࠸ࠊ౯㟁Ꮚᖏ XPS ࢫ࣌ࢡࢺࣝࡣࠊPhoton Energy 85eVࠊࣃࢫ࢚ࢿࣝࢠ࣮50eVࠊ⤖ྜ࢚ࢿࣝࢠ࣮ 40㹼0eV ࡢ⠊ᅖ࡛ 0.05eV ࢫࢸࢵࣉ࡛ ᐃࡋࡓࠋNEXAFS ࢫ࣌ࢡࢺࣝࡣࠊ 㟁Ꮚ㔞ἲ㸦ヨᩱ㟁ὶἲ㸧ࢆ⏝࠸ࠊPhoton Energy 280e㹼310eV ࡢ⠊ᅖ࡛ࠊ 0.1eV ࢫࢸࢵࣉ࡛⾜ࡗࡓࠋ ➨୍ཎ⌮ィ⟬ࡼࡿࣂࣥࢻィ⟬ࢯࣇࢺ࢚࢘ࡣ CASTEP㸦Accelrys ♫㸧 ࢆ⏝࠸ࠊᵓ㐀᭱㐺ࡋࡓ TIPS-Pen ࡢ⤖ᬗᵓ㐀ࡽᚓࡽࢀࡓࣂࣥࢻᵓ㐀ࢆᇶ ≧ែᐦᗘ㸦DOS㸧ࢆィ⟬ࡋࠊྛඖ⣲㌶㐨ᑐᛂࡍࡿග᩿࢜ࣥ㠃✚ࢆࡌ ࡿࡇ࡛ࠊ౯㟁Ꮚᖏࢫ࣌ࢡࢺࣝࢆᚓࡓࠋNEXAFS ࢫ࣌ࢡࢺࣝࡢィ⟬࠾࠸࡚ ࡣࠊC ཎᏊෆẆ✵Ꮝࢆᑟධࡋ࡚ィ⟬ࡋࡓࣂࣥࢻᵓ㐀ࢆᇶࠊࢫ࣌ࢡࢺࣝࢆồ ࡵࡓࠋ 㸬⤖ᯝ࠾ࡼࡧ⪃ᐹ Fig.2 ࠊຎရ࠾ࡼࡧᮍຎရࡢ౯㟁Ꮚᖏ XPS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋᮍຎ ရ࡛ࡣࠊA㹼F ࡛♧ࡍ 6 ᮏࡢࣆ࣮ࢡࡀ᫂☜᳨ฟࡉࢀ࡚࠸ࡿࠋຎရ࡛ࡣࠊ A㹼C 㡿ᇦࡢࣆ࣮ࢡࣉࣟࣇࣝࡀ᫂░࡞ࡾࠊࣆ࣮ࢡ AࠊC ࡢᙉᗘࡀῶᑡ ࡋࠊࣆ࣮ࢡ B ࡀᡂ㛗ࡋ࡚࠸ࡿࡼ࠺ぢཷࡅࡽࢀࡿࠋFig.2 ࡣࠊ㓟≧ែࢆ௬ ᐃࡋ࡚ィ⟬ࡼࡾồࡵࡓࢫ࣌ࢡࢺࣝࢆྜࢃࡏ࡚♧ࡋࡓࠋࢯࣉࣟࣆࣝᇶࡢඛ➃ ࡢ࣓ࢳࣝᇶࡀ OH ⨨ࡋࡓሙྜ㸦Model 1㸧ࠊࢯࣉࣟࣆࣝᇶࡑࡢࡶࡢࡀ OH ⨨ࡋࡓሙྜ㸦Model 2㸧ࢆẚ㍑ࡍࡿࠊࣆ࣮ࢡ B ㏆ഐࡢᙉᗘࡢቑຍࡣ ᚋ⪅ࡢࣔࢹࣝ࠾࠸࡚ほ ࡉࢀࡿࡇࡀࢃࡿࠋ Fig.2TIPS-Pen300Υ Υຎရ(a)ࠊ ࠊᮍຎရ(b) ࡢ౯㟁Ꮚᖏ XPS ࢫ ࣌ࢡࢺࣝࠊ ࠊ࠾ࡼࡧ㓟ࣔࢹࣝࢆ௬ᐃࡋࡓࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝ Fig. 3 ྛヨᩱࡢ C-K Ẇ྾➃ NEXAFS ࢫ࣌ࢡࢺࣝࢆ♧ࡍࠋ୧ヨᩱࡶ ࣌ࣥࢱࢭࣥ㦵᱁⏤᮶ࡍࡿȧ*(C=C)ࣆ࣮ࢡࡀ 285eV ㏆᫂☜᳨ฟࡉࢀ࡚ ࠸ࡿࠋຎရ࠾࠸࡚ࡣࠊ288eV ㏆ࡢȪ*(C-H)ࣆ࣮ࢡࡢᖜ࡞ῶᑡࡀぢࡽ ࢀࡓࠋィ⟬ࢫ࣌ࢡࢺࣝࡢẚ㍑ࡼࢀࡤࠊࡇࢀࡽࡢࣆ࣮ࢡࡣࢯࣉࣟࣆࣝᇶ ⏤᮶ࡍࡿ᥎ᐃࡉࢀࠊୖグࡢࢯࣉࣟࣆࣝᇶࡀ⬺㞳ࡋ࡚ࠊ㓟ࡋࡓࣔࢹࣝᩚ ྜࡍࡿࠋ ௨ୖࡢ⤖ᯝࡽࠊ౯㟁Ꮚᖏ XPS ࠾ࡼࡧ C-K Ẇ NEXAFS ࢫ࣌ࢡࢺࣝ➨୍ ཎ⌮ィ⟬ࡢ⤌ྜࡏࡼࡾࠊTIPS-Pen ࡢຍ⇕ຎక࠺ᵓ㐀ኚࢆ᥎ᐃࡍࡿࡇ ࡀ࡛ࡁࡓࠋ Fig.3TIPS-Pen300Υ Υຎရࠊᮍຎရ ࡢ C-K Ẇ NEXAFS ࢫ࣌ࢡࢺࣝ (a)ࠊ ࠊ࠾ࡼࡧྛ C ཎᏊẖࡢ NEXAFS ࢫ࣌ࢡࢺࣝࢩ࣑࣮ࣗࣞࢩࣙࣥ⤖ᯝ(b-e) ᚋࡢㄢ㢟 ᅇࠊ᭷ᶵ༙ᑟయࡢࢫࣆࣥࢥ࣮ࢺ⭷࡛Ⰻዲ࡞౯㟁Ꮚᖏ XPS ࠾ࡼࡧ NEXAFS ࢫ࣌ࢡࢺࣝࡢ ᐃࡀ࡛ࡁࡿࡇࡀࢃࡾࠊࡉࡽࠊຍ⇕ຎࡼࡿࢫ࣌ࢡࢺࣝ ኚࢆࣔࢹࣝᵓ㐀ࡢ➨୍ཎ⌮ィ⟬ࡼࡾゎ㔘࡛ࡁࡿぢ㏻ࡋࢆᚓࡓࠋᚋࠊᚤ⣽ ࡞ࢫ࣌ࢡࢺࣝኚࡘ࠸࡚ࡶࠊ⌧ᛶࢆ☜ㄆࡍࡿ࡞ࡋࡓ࠺࠼࡛ゎ㔘ࢆ㐍ࡵ࡚ ⾜ࡃࡇࡀㄢ㢟࡛࠶ࡿࠋ୍᪉ࠊ⢊ᮎヨᩱ࡛ࡣࠊᖏ㟁ࡼࡾⰋዲ࡞ࢫ࣌ࢡࢺࣝࡀ ᚓࡽࢀ࡞࠸࡞ࡢㄢ㢟ࡀ࠶ࡿࠋᚋࠊᵝࠎ࡞ᮦᩱᒎ㛤ࡋ࡚࠸ࡃୖ࡛ࡣࠊࡉࡲ ࡊࡲ࡞ᛶ≧ࡢヨᩱࢆᏳᐃࡋ࡚ ᐃ࡛ࡁࡿࢧࣥࣉࣜࣥࢢᢏ⾡ࡢ㛤Ⓨࡶᚲせ࡛࠶ ࡿࠋ
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