π共役系高分子の溶液レーザプロセシング：異なる高分子状態のスイッチング

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(1) .

(2) . Ǹ౒ᓎ♽㜞ಽሶߩṁᶧ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣ㧦 ⇣ߥࠆ㜞ಽሶ⁁ᘒߩࠬࠗ࠶࠴ࡦࠣ Solution-Phase Laser Processing of ʌ-Conjugated Polymers: Switching between Different Molecular States ንጟ᣿ብ

(3) 㜞↰ᐢᐔ

(4) Akihiro Tomioka* and Kouhei Takada* Liquid-phase laser processing, where the laser-irradiated target material is immersed in water for cooling, has been reported as a promising processing technique for thermally fragile organic materials. Although nanometer-sized particles have been reported to be obtained with the liquid-phase laser processing, the physical property did not change because quantum-mechanical size effect does not exhibit itself in the zero-radius Frenkel excitons. In the present study, we step further to use solution droplets as a target material, “solution-phase laser processing”, where organic molecules are molecularly dispersed in organic solvent and, therefore, expected to easily alter the conformation and the energy state upon laser irradiation. Small volume organic solvent is quickly evaporated upon laser irradiation, letting the bare organic molecule placed in water and rapidly cooled. To prevent the chemical decomposition of the target S-conjugated molecule, the specimen was resonantly irradiated by a ns-pulse green laser, not by a conventional UV laser. When the solid state spin-coat film made from MEH-PPV chloroform solution was used as a irradiation target immersed in water, resulting MEH-PPV particles showed similar photoluminescence (PL) like the PL of the spin-coat film and PL of the chloroform solution, including the 0o1, 0o2 vibrational transitions: this indicates that the energy levels were not modified from the spin-coat film. In comparison, when tiny droplets of MEH-PPV chloroform solution (orange color) were suspended in water, laser irradiation gave rise to yellow MEH-PPV particles which showed 550 nm and 530 nm PL (type B), blue-shifted from the spin-coat film PL 580 nm (type A), suggesting a successful phase transition of MEH-PPV polymer to type B. Further solution-phase laser processing left the type B state unchanged. The irreversible phase transition from type A to type B suggests that the type B ground state has lower energy than type A, which is consistent with the blue-shifted PL of type B, provided that the excited state energy is similar between the two states. Thermal annealing up to 200 oC of type A state did not give rise to type B state, which indicates that the activation potential between the two states is higher than the thermal energy at 200 oC and that only the proposed solution-phase laser processing enables the system to cross over this potential.. 1㧚ߪߓ߼ߦ ᐢ▸ߦ೑↪ߐࠇߡ޿ࠆ࡟࡯ࠩࠕࡉ࡟࡯࡚ࠪࡦ[1]ߢߪ㧘Ꮧᦸߔࠆൻቇ㊂⺰Ყߦᓥߞߡᷙว࡮ࡍ࡟ ࠶࠻ൻߐࠇߚ☳ᧃࠍᾖ኿࠲࡯ࠥ࠶࠶࠻㧔࿕૕㧕ߣߒߡ⚡ᄖࡄ࡞ࠬశࠍᾖ኿ߒ㧘᧚ᢱࠍේሶࠢ࡜ࠬ ࠲࡯ߦಽ⸃ߒߟߟ㧘⌀ⓨਛߢၮ᧼ߦၸⓍߐߖࠆ㧚⸳⸘ㅢࠅߩൻቇ㊂⺰Ყߩ⚵ᚑࠍᜬߟ࿕ṁ૕ࠍ૞ ⵾ߔࠆߎߩᚻᴺߪ㧘㜞᷷⿥વዉ૕ࠍត⚝ߔࠆ⎇ⓥߥߤߢᄢ޿ߦ೑↪ߐࠇ㧘ᄙߊߩ⍮⷗ࠍ↢ߺ಴ߒ. *ᄢ㒋㔚᳇ㅢାᄢቇ. ᄢቇ㒮Ꮏቇ⎇ⓥ⑼ 㔚ሶㅢାᎿቇኾ᡹ [email protected] !. . -1-.

(5) ߡ߈ߚ㧚ߛ߇㧘ಽሶ᭴ㅧ߇․ᕈࠍ․ᓽߠߌࠆ᦭ᯏಽሶߦߪ㧘ߎߩᚻᴺߪಽሶߩ⎕უࠍ߽ߚࠄߔߩ ߢㆡ↪ߢ߈ߥ޿㧚ߎࠇߦᦧࠊࠆᚻᴺߣߒߡㄭᐕឭ᩺ߐࠇߡ޿ࠆߩ߇㧘ᶧ⋧࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣ㧔ᶧ ⋧ LP㧕[2]ߢ޽ࠆ㧚ߎߩᣇᴺߢߪ㧘ᾖ኿࠲࡯ࠥ࠶࠶࠻㧔࿕૕㧕ࠍ᳓ਛߦᴉ߼㧔߹ߚߪ Ộߒ㧕㧘Ყ ᾲߩᄢ߈ߥ᳓ߩ಄ළലᨐߦࠃࠅ᧚ᢱߩ⎕უࠍᛥ೙ߔࠆ㧚ႎ๔଀ߢߪ㧘⏕߆ߦ࠽ࡁࠨࠗ࠭ߩᓸ☸ሶ ᒻᚑߪน⢻ߢ޽ࠆ߇㧘‛⾰ߩ‛ℂ⊛ߥ⁁ᘒᄌൻߪ⿠߈ߥ޿㧚᦭ᯏ⦡⚛ߩࡈ࡟ࡦࠤ࡞᧤❈ബ⿠ሶߢ ߪബ⿠ሶߩࡏ࡯ࠕඨᓘ߇ 0 ߢ޽ࠆߚ߼㧘㊂ሶࠨࠗ࠭ലᨐ߇ᦼᓙߢ߈ߥ޿߆ࠄߢ޽ࠆ㧚ᧄ⎇ⓥߢߪ㧘 ᧚ᢱߩ‛ℂ⊛ߥࠛࡀ࡞ࠡ࡯⁁ᘒᄌൻࠍᒁ߈⿠ߎߒߡ㧘ᣂⷙ⁁ᘒࠍ⊒⃻ߐߖࠆߚ߼㧘ಽሶ㑆ߩ⚿ว ࠛࡀ࡞ࠡ࡯ࠍ߽ߚߥ޿㧘ಽሶಽᢔ⁁ᘒߩṁᶧ⹜ᢱࠍᾖ኿࠲࡯ࠥ࠶࠶࠻ߣߒߡ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣ ࠍⴕ߁ᚻᴺ㧔ṁᶧ LP㧕[3]ࠍᣂᚻᴺߣߒߡឭ᩺ߔࠆ㧚߹ߚಽሶߩ⎕უࠍㆱߌࠆߚ߼㧘⚡ᄖశ࡟࡯ ࠩߢߪߥߊ㧘นⷞశ࡟࡯ࠩࠍᾖ኿ߔࠆ㧚ኻ⽎⹜ᢱ߇ᄢ߈ߥశๆ෼ࠍ␜ߔ✛⦡࡟࡯ࠩࠍ㜞ಽሶߦᾖ ኿ߔࠆߎߣߦࠃࠅ㧘Ǹ౒ᓎ♽ߩᒝ޿㔚ሶ࡮ᩰሶ⚿ว[4-6]ࠍㅢߓߡಽሶᝄേ߇ᒁ߈⿠ߎߐࠇ㧘ߎࠇ ߇㜞ಽሶߩࠦࡦࡈࠜࡔ࡯࡚ࠪࡦᄌൻ[7]ࠍ⺃ዉߔࠆߎߣ߇ᦼᓙߢ߈ࠆ㧚 Ყᾲߩᄢ߈ߥ᳓ߩ಄ළലᨐࠍ᦭ലߦߔࠆߚ߼㧘ಽሶಽᢔ⁁ᘒߩṁᶧ⹜ᢱࠍ᳓ߩਛߦṢਅߒ㧘 ⿥㖸ᵄಣℂߔࠆߎߣߦࠃࠅ㧘⹜ᢱṁᶧࠍᓸዊᶧṢߣߒߡ᳓ߦ Ộߒߡ߆ࠄ࡟࡯ࠩᾖ኿ࠍⴕߞߚ㧚 ࡄ࡞ࠬ࡟࡯ࠩᾖ኿ߦࠃࠆ⍴ᤨ㑆ߩടᾲߦࠃࠅ㧘ᓸዊᶧṢ߆ࠄ᦭ᯏṁᇦ߇⍴ᤨ㑆ߦ⫳⊒ߒ㧘ኻ⽎㜞 ಽሶߪਇṁṁᇦߢ޽ࠆ᳓ਛߦขࠅᱷߐࠇ಄ළ࡮ಝ㓸ߔࠆ㧚ߎߩ㓙ߩ㕖ᐔⴧ⁁ᘒߢߩಝ㓸᭽ᑼߣߒ ߡ㧘⹜ᢱ㜞ಽሶߩᣂⷙߥࠛࡀ࡞ࠡ࡯⁁ᘒ߇㆐ᚑߢ߈ࠆߩߢߪߥ޿߆ߣᦼᓙߢ߈ࠆ㧚. 2㧚⹜ᢱ૞⵾ߣ᷹ቯᣇᴺ ⹜ᢱߣߒߡᄢ߈ߥశๆ෼࡮⊒శࠍ␜ߔǸ౒ᓎ♽㜞ಽሶ poly[2-methoxy-5-(2-ethylhexyloxy)1,4-phenylenevinylene] 㧔MEH-PPV, Aldrich, Av Mn=40,000-70,000㧕ࠍ↪޿ߚ㧚MEH-PPV ߩ ࠢࡠࡠࡎ࡞ࡓ㧘ࠫࠢࡠࡠࡔ࠲ࡦ㧘ࠢࡠࡠࡌࡦ࠯ࡦ㧘߹ߚߪ࠻࡞ࠛࡦṁᶧ 200 Ǵl ࠍ 2 ml ߩ⚐᳓ 㧔MEH-PPV ߪਇṁߢ㧘߆ߟ᦭ᯏṁᇦ߽᳓ߣᷙߓࠄߥ޿㧕ਛߦṢਅߒ㧘15 ಽ⿥㖸ᵄಣℂߒߡ MEH-PPV ṁᶧߩᓸዊᶧṢࠍ᳓ਛߦဋ৻ߦಽᢔߐߖࠆ㧚⷗߆ߌߩ⦡ߪㅘ᣿ߥᯍ⦡߆ࠄ㧘శᢔੂߦ ࠃࠆỘߞߚᯍ⦡ߦᄌࠊࠆ㧚⹜ᢱߩ៊்ࠍㆱߌࠆߚ߼㧘⚡ᄖశߢߪߥߊ㧘Nd/YAG ns ࡄ࡞ࠬ࡟࡯ࠩ ߩ SHG శ㧔ᵄ㐳 532 nm, 25 mJ 5 ns pulse, 10 Hz, Minilite II, Continuum㧕ࠍ↪޿ߡ㧘 MEH-PPV ⹜ᢱࠍ 30 ಽ㑆౒㡆ബ⿠ߒߚ㧔ṁᶧ LP ಣℂ㧕㨇࿑㧝(a)㨉㧚࡟࡯ࠩᾖ኿ߦࠃࠆᾲ⊛ലᨐ. (c). (a) Nd/YAG SHG laser. Mirror Microdroplet Suspended Droplets. (b) Particle Suspension. 100Pm. ࿑㧝 (a)㜞ಽሶṁᶧߩᓸዊᶧṢࠍਇṁߥ᳓ߦ Ộߒߚ߽ߩࠍ࠲࡯ࠥ࠶࠻ߣߒߡ㧘ૐశሶ ࠛࡀ࡞ࠡ࡯ࠍ߽ߟ✛ࡄ࡞ࠬ࡟࡯ࠩࠍᾖ኿ߔࠆṁᶧ LP ಣℂߩ㈩⟎࿑㧚(b)᳓ߦ Ộߒߚ ⁁ᘒߢ↢ᚑߒߚ㜞ಽሶᓸ☸ሶߣߘߩ⿛ᩏ㔚ሶ㗼ᓸ㏜౮⌀(c)㧚ࠬࠤ࡯࡞ࡃ࡯ߪ 100Pm㧚 (d)⹜ᢱߢ޽ࠆ MEH-PPV 㜞ಽሶߩಽሶ᭴ㅧ㧚 . -2-.

(6) ߩߚ߼㧘ᓸዊᶧṢਛߩṁᇦߪ⍴ᤨ㑆ߦើ⊒ߒ㧘⵻ߦߥߞߚMEH-PPV㜞ಽሶ߇᳓ߦࠃࠅᕆㅦߦ಄ ළߐࠇߡಝ㓸૕ࠍᒻᚑߔࠆߣᦼᓙߐࠇࠆ㧚Ყセߩߚ߼㧘MEH-PPVࠬࡇࡦࠦ࡯࠻⤑ࠍ᳓ਛߦᴉ߼㧘 Nd/YAG SHG laserశࠍ 30 ಽ㑆ᾖ኿ߒߚ႐ว㧔ᶧ⋧LPಣℂ㧕߽⹜ߺߚ㧚޿ߕࠇߩᚻᴺߩ႐ว߽㧘 ↢ᚑߒߚMEH-PPVᓸ☸ሶߩ Ộᶧ㨇࿑㧝(b)㨉ࠍSiၮ᧼ߦタߖߡੇ῎㧘ࠦࡦ࠻࡜ࠬ࠻ࠍᓧࠆߚ߼ Auࠍࡊ࡜࠭ࡑࠦ࡯࠻ߒߚᓟ㧘ૐടㅦ㔚࿶ 20 kVߢSEMⷰኤࠍⴕ޿㧘ᓸ☸ሶߩ↢ᚑࠍ⏕⹺ߒߚ㧚 ߹ ߚࡈࠜ࠻࡞ࡒ࠽࠶࠮ࡦࠬ㧔PL㧕ࠍ᷹ⷰߔࠆ႐วߦߪ㧘 Ộᶧࠍࠟ࡜ࠬၮ᧼਄ߦタߖߡ᳇ኒ࠴ࠚࡦ ࡃ࡯ߦ౉ࠇ㧘N2㔓࿐᳇ߢੇ῎ߒ㧘200oC߹ߢടᾲߒߡࠕ࠾࡯࡝ࡦࠣಣℂࠍⴕߞߚ㧚. 㧚ᶧ⋧࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣߣṁᶧ࡟࡯ࠩࡊࡠ࠮ ࠪࡦࠣߩᲧセ. (a). ߹ߕᲧセߩߚ߼㧘ᓥ᧪ឭ᩺ߐࠇߡ޿ࠆᶧ⋧࡟࡯ࠩࡊࡠ ࠮ࠪࡦࠣ㧔ᶧ⋧ LP㧕ᚻᴺߦࠃࠅ㧘᳓ਛߦᴉ߼ߚ MEH-PPV ࠬࡇࡦࠦ࡯࠻⤑㧔࿕૕㧕ࠍ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣߒߚ㧚Pm ࠨࠗ࠭ߩᓸ☸ሶ߇↢ᚑߒߚ߇㧘ߘߩๆ෼ࠬࡍࠢ࠻࡞࡮⊒ శࠬࡍࠢ࠻࡞ߣ߽㧘߽ߣߩࠬࡇࡦࠦ࡯࠻⤑ߩๆ෼ࠬࡍࠢ ࠻࡞࡮⊒శࠬࡍࠢ࠻࡞ߣࡇ࡯ࠢᵄ㐳ߩᄌൻߪߥ߆ߞߚ㨇࿑. (b) x0.12. 㧞(a)㨉㧚ਔ⠪ߣ߽ MEH-PPV ߩಽሶᝄേㆫ⒖ߦ઻߁ࠨࡉ ࡇ࡯ࠢࠍ߽ߟ߇㧘ߎࠇࠄߩᵄ㐳߽ᄌൻߪߥ߆ߞߚ㧚ߎࠇ ߪ㧘MEH-PPV 㜞ಽሶߩࠛࡀ࡞ࠡ࡯⁁ᘒ߇ᶧ⋧࡟࡯ࠩࡊ ࡠ࠮ࠪࡦࠣߢߪᄌൻߒߥ߆ߞߚߎߣࠍ␜ߒߡ޿ࠆ㧚 ᰴߦ MEH-PPV ߩࠢࡠࡠࡎ࡞ࡓṁᶧࠍ㧝㧜୚㊂ߩ⚐ ᳓ߦṢਅߒ㧘⿥㖸ᵄಣℂߒߡ㧘ࠢࡠࡠࡎ࡞ࡓṁᶧߩᓸዊ ᶧṢࠍ᳓ਛߦဋ৻ߦಽᢔߐߖߚᓟ㧘Nd/YAG SHG ns ࡄ ࡞ࠬ࡟࡯ࠩࠍ㧟㧜ಽ⒟ᐲᾖ኿ߒߚ㧔ṁᶧ LP㧕㧚ṁᶧ LP. (c). ಣℂߦࠃࠅ㧘ᶧ૕ߩ⷗߆ߌߩ⦡ߪᯍ⦡߆ࠄ㤛⦡ߦᄌൻߒ㧘 SEM ⷰኤߩ⚿ᨐ㧘ᢙPm ࠨࠗ࠭ߩ☸ሶߣࠨࠗ࠭ 1Pm ᧂ ḩߩᓸ☸ሶ߇ᄙᢙ↢ᚑߒߡ޿ࠆߎߣ߇್ߞߚ㨇࿑㧝(c)㨉㧚 ࿑㧞 ⊒శࠬࡍࠢ࠻࡞ߩᲧセ㧚(a)ࠢࡠࡠࡎ࡞ࡓṁᶧ߆ࠄ ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑㧔ታ✢㧕ߣᶧ⋧ LP ಣℂߒߚࠬ ࡇࡦࠦ࡯࠻⤑㧔⎕✢㧕(b)ࠬࡇࡦࠦ࡯࠻⤑㧔ታ✢㧕ߣṁᶧ LP ಣℂᓸ☸ሶ㧔ࠕ࠾࡯࡝ࡦࠣ೨㧘⎕✢㧕㧘หࠕ࠾࡯࡝ࡦ. (d). ࠣᓟ㧔ὐ✢㧘0.12 ୚ߦ❗ዊ㧕㧚ೋᦼṁᇦߪࠢࡠࡠࡎ࡞ࡓ㧚 (c)ࠢࡠࡠࡎ࡞ࡓṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑㧔ታ ✢㧕ߣṁᶧ LP ಣℂᓸ☸ሶ㧔ࠕ࠾࡯࡝ࡦࠣᓟ㧘⎕✢㧕㧚 ࠫࠢࡠࡠࡔ࠲ࡦṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑ߣṁ ᶧ LP ಣℂᓸ☸ሶ㧔ࠕ࠾࡯࡝ࡦࠣᓟ㧕ߪቢోߦ㊀ߥߞߡ ޿ࠆ㧔ὐ✢㧕㧚(d)ṁᶧߩ⊒శ㧚ታ✢ߪࠫࠢࡠࡠࡔ࠲ࡦṁ ᶧ㧘ὐ✢ߪࠢࡠࡠࡌࡦ࠯ࡦṁᶧ㧘㧝ὐ㎮✢ߪࠢࡠࡠࡎ࡞ 500. ࡓṁᶧ㧘⎕✢ߪ࠻࡞ࠛࡦṁᶧ㧚 . -3-. 550. 600. 650. 700. 750 [nm].

(7) Solution-Phase Laser Procesing. ㆙ᔃಽ㔌ߦࠃࠆಽ↹ߦࠃࠅ㧘ᢙPm ࠨࠗ࠭ߩ☸ሶߪṁᶧ⁁ ᘒߣหߓశๆ෼࡮⊒శ㧔એ㒠࠲ࠗࡊ A ߣ๭߱㧕ࠍ␜ߔࠄߒ. Excited State. ޿ߎߣ㧘ࠨࠗ࠭ 1Pm ᧂḩߩᓸ☸ሶ㧔శᢔੂ᷹ቯ߆ࠄផቯߒ ߚ☸ᓘಽᏓߪනಽᢔߢ޽ࠅ㧘ᐔဋ☸ᓘߪ 200nm ߢ޽ߞߚ㧕 ߪ⍴ᵄ㐳ࠪࡈ࠻ߒߚశๆ෼࡮⊒శ㧔એ㒠࠲ࠗࡊ B ߣ๭߱㧕. PLA. PLB Ea. ࠍ␜ߔߎߣ߇್ߞߚ㨇࿑㧞(b)㨉㧚ߎࠇߪ☸ᓘ 200nm ߩᓸ☸ ሶਛߢߪ㧘MEH-PPV ߩࠛࡀ࡞ࠡ࡯⁁ᘒ߇ᄌൻߒߡ޿ࠆ㧔એ. Type A. 㒠࠲ࠗࡊ B ߩࠛࡀ࡞ࠡ࡯⁁ᘒߣ๭߱㧕ߎߣࠍ␜ߒߡ߅ࠅ㧘 ṁᶧ LP ಣℂߦࠃࠅೋᦼߩ⋡ᮡ߇㆐ᚑߢ߈ߚߎߣࠍ␜ߒߡ ޿ࠆ㧚ઁᣇ㧘ᢙPm ࠨࠗ࠭ߩ☸ሶߢߪ㧘MEH-PPV ߇ಝ㓸 ߒߡ޿ࠆߦ᜔߽ࠊࠄߕห৻ߩࠛࡀ࡞ࠡ࡯⁁ᘒࠍ␜ߔߎߣߪ㧘 ಽሶಝ㓸ߦࠃࠅࠛࡀ࡞ࠡ࡯⁁ᘒ߇ᄌൻߒߡ޿ࠆߩߢߪή ޿ߎߣࠍ␜ໂߒߡ޿ࠆ㧚MEH-PPV ߩ࠻࡞ࠛࡦṁᶧ㧔߅ࠃ ߮ߘߩࠬࡇࡦࠦ࡯࠻⤑㧕߽ࠢࡠࡠࡎ࡞ࡓṁᶧ㧔߅ࠃ߮ߘߩ ࠬࡇࡦࠦ࡯࠻⤑㧕ߣหߓ࠲ࠗࡊ A ⊒శࠛࡀ࡞ࠡ࡯ࠍ␜ߒ 㨇࿑㧞(d)㨉㧘ṁᶧ LP ಣℂߦࠃࠅ࠲ࠗࡊ B ߩࠛࡀ࡞ࠡ࡯⁁ ᘒߦォ⒖ߒߚ㧚 ࠫࠢࡠࡠࡔ࠲ࡦߢߪṁᶧ⁁ᘒߢߔߢߦ࠲ࠗࡊ B ߩ⊒శ ࠍ␜ߒ㨇࿑㧞(d)㨉㧘MEH-PPV㧝ಽሶߛߌߢ߽࠲ࠗࡊ B ߩ ࠛࡀ࡞ࠡ࡯⁁ᘒࠍขࠅ߁ࠆߎߣ߇್ߞߚ㧚ࠫࠢࡠࡠࡔ࠲ࡦ ṁᶧࠍṁᶧ LP ಣℂߒߚߣߎࠈ㧘ᓸ☸ሶߪ࠲ࠗࡊ B ࠛࡀ࡞ ࠡ࡯⁁ᘒߩ߹߹ߢ㧘ᄌൻ߇ߥ߆ߞߚ㨇࿑㧞(c)㨉㧚߹ߚ㧘ࠢ. Ground State Type B. ࿑㧟 ⋧ォ⒖ߩࠛࡀ࡞ࠡ࡯࠳ࠗࠕ ࠣ࡜ࡓ㧚ṁᶧLPಣℂߪMEH-PPV ߩ࠲ࠗࡊA⁁ᘒࠍࠃࠅၮᐩ⁁ᘒࠛ ࡀ࡞ࠡ࡯ߩૐ޿࠲ࠗࡊB⁁ᘒߦਇ นㅒ⊛ߦォ⒖ߐߖࠆ㧚ߎߩ቟ቯൻ ߪ㧘࠲ࠗࡊB⁁ᘒߩᣇ߇⍴ᵄ㐳ൻߒ ߚ⊒శࠍ␜ߔߎߣߣ㚂የ৻⽾ߒߡ ޿ࠆ㧚㧞⁁ᘒ㑆ߩᵴᕈൻࠛࡀ࡞ࠡ ࡯ߪ 200oCߢߩᾲࠛࡀ࡞ࠡ࡯kTࠃ ࠅ߽ᄢ߈޿㧚. ࡠࡠࡌࡦ࠯ࡦṁᶧߪ࠲ࠗࡊ A ߣ࠲ࠗࡊ B ߩࠛࡀ࡞ࠡ࡯⁁ ᘒߩᷙว⁁ᘒࠍ␜ໂߔࠆ⚿ᨐߣߥߞߚ㧚޿ߕࠇߩ႐ว߽৻ᐲ࠲ࠗࡊ B ߦォ⒖ߒߚ⹜ᢱࠍߐࠄߦṁ ᶧ LP ಣℂߒߡ߽㧘࠲ࠗࡊ A ߦᚯࠆߎߣߪߥ߆ߞߚ㧚ߎࠇߪ㧘࠲ࠗࡊ A ࠃࠅ߽࠲ࠗࡊ B ߩࠛࡀ࡞ ࠡ࡯⁁ᘒ㧔ၮᐩ⁁ᘒ㧕ߩᣇ߇ࠛࡀ࡞ࠡ࡯߇ૐ޿ߎߣࠍ␜ໂߒߡ޿ࠆ㨇࿑㧟㨉㧚ബ⿠⁁ᘒߩࠛࡀ࡞ࠡ ࡯ᄌൻ߇ዊߐߌࠇ߫㧘⊒శࠛࡀ࡞ࠡ࡯㧔ㆫ⒖ࠛࡀ࡞ࠡ࡯㧕߇࠲ࠗࡊ B ߩᣇ߇ᄢ߈޿ߎߣߣ㚂የ৻ ⽾ߒߡ޿ࠆߣ੔߃ࠆ㧚 ࡄ࡞ࠬ࡟࡯ࠩߦࠃࠅS౒ᓎ⚿ว߇ಾᢿߐࠇ㧘⊒శ߇⍴ᵄ㐳ൻߒߡ޿ࠆน⢻ᕈߦߟ޿ߡ‫ࡠࠢࠫޕ‬ ࡠࡔ࠲ࡦṁᶧߩ␜ߔశๆ෼࡮⊒శߣṁᶧ LP ಣℂߢᓧࠄࠇߚᓸ☸ሶߩశๆ෼࡮⊒శ߇ห৻ߢ޽ࠆ ߎߣߪ㧘ߎࠇࠄߩࠛࡀ࡞ࠡ࡯⁁ᘒ߽ห৻ߢ޽ࠅ㧘ൻቇ⊛ߥ៊்ߦ⿠࿃ߔࠆน⢻ᕈࠍุቯߒߡ޿ࠆ㧚 ಽሶ߇ࡃ࡜ࡃ࡜ߩࠫࠢࡠࡠࡔ࠲ࡦṁᶧ߇࠲ࠗࡊ B ߩࠛࡀ࡞ࠡ࡯⁁ᘒࠍߣࠆ੐ߪ㧘ߎࠇ߇ಽሶߩ㓸 วߦࠃߞߡ߽ߚࠄߐࠇࠆ⁁ᘒߢߪߥߊ㧘ࠫࠢࡠࡠࡔ࠲ࡦߩṁᇦ๺ߦࠃࠅ㧝ಽሶߩࠦࡦࡈࠜࡔ࡯ࠪ ࡚ࡦᄌൻߣߒߡ⿠߈߁ࠆ੐ࠍ␜ߒߡ޿ࠆ㧚 ࠫࠢࡠࡠࡔ࠲ࡦߩṁᇦ๺߇㧘MEH-PPV㜞ಽሶࠍ࠲ࠗࡊB቟ቯൻࠛࡀ࡞ࠡ࡯⁁ᘒߦ೔㆐ߐߖࠆ ߣ੔߃ࠆ㧚ߛ߇㧘ࠫࠢࡠࡠࡔ࠲ࡦṁᶧ߆ࠄ૞ߞߚࠬࡇࡦࠦ࡯࠻⤑ࠍ 200oC߹ߢࠕ࠾࡯࡝ࡦࠣߒߡ ࠫࠢࡠࡠࡔ࠲ࡦṁᇦࠍቢోߦ㒰෰ߒߡ߽㧘⊒శࠬࡍࠢ࠻࡞ߪ࠲ࠗࡊB߆ࠄోߊᄌൻߒߥ߆ߞߚ㧚 ߎࠇߪ㧘࠲ࠗࡊB߳ߩᄌൻ߇޿ࠊࠁࠆ‫ޟ‬ṁᇦലᨐ‫޿ߥߪߢޠ‬㧘ߟ߹ࠅṁᇦ߇ߥߊߥߞߚᓟ߽‫⛽ޟ‬ ᜬߐࠇࠆ‫ޠ‬ലᨐߢ޽ࠅ㧘㕖นㅒᄌൻߢ޽ࠆߣ੔߃ࠆ㧚 ࿑㧞ߢߪ㧘࠲ࠗࡊ B ⁁ᘒߩߤߩ⊒శࠬࡍࠢ࠻࡞߽࠲ࠗࡊ㧭⁁ᘒߩ⊒శࡇ࡯ࠢࠍ઻ߞߡ߅ࠅ㧘ߎ. . -4-.

(8) ࠇߪṁᶧ LP ಣℂ߇ਇචಽߥߚ߼࠲ࠗࡊ B ⁁ᘒߣ࠲ࠗࡊ㧭⁁ᘒߩᷙว⁁ᘒߦߥߞߡ޿ࠆ߆ࠄߛߣ ⠨߃ࠄࠇࠆ㧚੐ታࠢࡠࡠࡎ࡞ࡓṁᶧߩṁᶧ LP ಣℂᤨ㑆ࠍ⍴ߊߔࠆߣ㧘࠲ࠗࡊ㧭⁁ᘒߩ⊒శࡇ࡯ ࠢ߇ࠃࠅᄢ߈ߊߥࠅ㧘ਥߥ⊒శߣߥߞߚ㧚ߎࠇߪ࠲ࠗࡊ B ⊒శߣ࠲ࠗࡊ㧭⊒శߪ⇣ߥࠆ㔚ሶ⁁ᘒ ߦኻᔕߒߡ߅ࠅ㧘ห৻ߩ⹜ᢱਛߦᷙ࿷ߢ߈ࠆߎߣ㧘ߘߩᷙ࿷Ყߪṁᶧ LP ಣℂ᧦ઙߦࠃߞߡᄌൻ ߔࠆߎߣࠍ␜ߒߡ޿ࠆ㧚. 4㧚⊒శࠬࡍࠢ࠻࡞ߩ࠺ࠦࡦࡏ࡝ࡘ࡯࡚ࠪࡦߦࠃࠆ㔚ሶㆫ⒖ࠛࡀ࡞ࠡ࡯ߣಽሶᝄേࠛ ࡀ࡞ࠡ࡯ߩ᳿ቯ ࠲ࠗࡊ㧭⁁ᘒߣ࠲ࠗࡊ B ⁁ᘒࠍಽ㔌ߒ㧘߆ߟ⇣ߥࠆಽሶᝄേㆫ⒖߽ಽ㔌ߒߡ㧘MEH-PPV 㜞ಽ ሶ㎮ߩಽሶᝄേࠛࡀ࡞ࠡ࡯ߣǸ㔚ሶߩ㔚ሶㆫ⒖ࠛࡀ࡞ࠡ࡯ࠍ⷗Ⓧ߽ࠆߚ߼㧘࿑㧞ߩᮮゲࠍࠛࡀ࡞ ࠡ࡯ߦ឵▚ߒߚᓟ㧘⊒శࠬࡍࠢ࠻࡞ࠍ⇣ߥࠆಽሶᝄേㆫ⒖ߦ࠺ࠦࡦࡏ࡝ࡘ࡯࠻ߒߚ㧔࿑㧠㧕㧚ౕ૕ ⊛ߦߪ㧘శሶࠛࡀ࡞ࠡ࡯ E i 㧘✢᏷ 'E i ࠍ߽ߟࠟ࠙ࠬಽᏓߩᢙቇ⊛㊀⇥㧔ᑼ(1㧕㧕ߣߒߡ⊒శࠬࡍ ࠢ࠻࡞ࠍࡈࠖ࠶࠹ࠖࡦࠣߒߚ㧚. I PL ( E ). ª ( E Ei ) 2 º ¦i I i exp «« 'E 2 »» i ¼ ¬. (1). ࡠ࡯࡟ࡦ࠷ಽᏓ߽⹜ߒߚ߇㧘⊒శࠬࡍࠢ࠻࡞ࠍౣ⃻ߢ߈ߥ߆ߞߚ㧚ߎߩ੐ታߪ㧘ᡆࠗ࠰ࠪࠕ࠾ࡦ ⦡⚛ J ળว૕ߩ␜ߔశቇㆫ⒖ߩ߁ߜ㧘ࡃࡦ࠼ࠡࡖ࠶ࡊࠃࠅ߽ૐࠛࡀ࡞ࠡ࡯஥ߩ᜼േ[8,9]ߣหߓࠃ ߁ߦ㧘MEH-PPV 㜞ಽሶߩ႐ว߽㧘ಽሶᝄേߦࠃࠆ࠻࡜ࡦࠫࠚࡦ࠻ߥಽሶᄌᒻߣ޿߁േ⊛ំേ߿ 㕒⊛ᰳ㒱ߦࠃࠅ㧘⊒శㆫ⒖ߩਇဋ৻᏷߇ᡰ㈩ߐࠇߡ޿ࠆߎߣࠍ␜ໂߒߡ޿ࠆ㧚 ࿑㧠ࠍ⷗ࠆߣ㧘MEH-PPVߩࠢࡠࡠࡎ࡞ࡓṁᶧ߅ࠃ߮࠻࡞ࠛࡦṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻ ⤑ߩ␜ߔ⊒శࠬࡍࠢ࠻࡞ߪ㧘1.85eVએ਄ߩ㗔ၞߢߪ㧘ಽሶᝄേㆫ⒖ߩ 0ψ0 ㆫ⒖㧔EA0㧕㧘0ψ1 ㆫ. ⴫㧝 ⊒శࠬࡍࠢ࠻࡞ߩ࠺ࠦࡦࡏ࡝ࡘ࡯࡚ࠪࡦ ߦࠃߞߡᓧࠄࠇߚ㧘ฦಽሶᝄേㆫ⒖ߦኻᔕߔࠆ ࡇ࡯ࠢࠛࡀ࡞ࠡ࡯㧚⹜ᢱߪ MEH-PPV ࠍṁ߆. (b) solvent chloroform. 'Q 㩷. ߒߚೋᦼṁᇦߢಽ㘃ߒߚ㧚(a)ࠬࡇࡦࠦ࡯࠻⤑㧘 (b)ṁᶧ LP ಣℂ㧚. (a) solvent 'Q O[nm] E[eV] 'E[eV] 2.10 chloroform 0o 0㩷 590 1.93 -0.17 0o 1 642 2.09 toluene 0o 0 593 1.92 -0.17 0o 1 646 528 2.35 dichloro0.23 549 2.26 methane 0.14 2.09 0o 0 593 1.98 -0.11 0o 1 626 1.90 -0.19 653 0o 2. toluene. dichloromethane. 0o 0 0o 1 0o 2 㩷 0o 0 0o 1 0o 2 㩷 0o 0 0o 1 0o 2. . -5-. O[nm] E[eV] 'E[eV] 528 2.35 0.21 549 2.26 0.12 579 2.14 614 2.02 -0.12 639 1.94 -0.20 530 2.34 0.20 556 2.23 0.09 579 2.14 611 2.03 -0.11 653 1.90 -0.24 530 2.34 0.26 551 2.25 0.17 596 2.08 626 1.98 -0.10 653 1.90 -0.18.

(9) ⒖㧔EA1㧕[10]ߩ㧞ߟߩࠟ࠙ࠬಽᏓߩ㊀ߨวࠊߖߢࠃߊౣ⃻ߐࠇࠆߎߣ߇ࠊ߆ࠆ㧚1.8eVㄭㄝߢߩ ࠊߕ߆ߥਵ㔌ߪ㧘0ψ2 ಽሶᝄേㆫ⒖ߩࠊߕ߆ߥነਈߦࠃࠆ߽ߩߢ޽ࠈ߁ߣផኤߐࠇࠆ㧚 ߎߩ࠺ࠦࡦࡏ࡝ࡘ࡯࡚ࠪࡦ߆ࠄ㧘㧞⒳ߩࠬࡇࡦࠦ࡯࠻⤑ߣ߽㧘࠲ࠗࡊ㧭⁁ᘒߩ㔚ሶㆫ⒖ࠛࡀ࡞ࠡ ࡯ߪ 1.93eV㧘ಽሶᝄേࠛࡀ࡞ࠡ࡯ߪ 0.17eVߣ㧘ห৻ߩ୯ߣߥࠅ㧘ࠢࡠࡠࡎ࡞ࡓṁᶧ߅ࠃ߮࠻࡞ ࠛࡦṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑ਛߩMEH-PPVߪห৻⁁ᘒࠍขߞߡ޿ࠆߎߣ߇್ߞߚ㨇⴫ 1(a)㨉㧚ࠫࠢࡠࡠࡔ࠲ࡦߩṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑ߦߪ㧘EB1=2.26eV㧘EB2=2.35eVߩ㧞 ߟߩ࠲ࠗࡊB⊒శࡇ࡯ࠢ߇಴⃻ߒ㧘หᤨߦࠢࡠࡠࡎ࡞ࡓṁᶧ࡮࠻࡞ࠛࡦṁᶧߣห৻ࠛࡀ࡞ࠡ࡯ߩ. (d). (a). EB1 EA0. EA2 EA1. EA0. EB2. EA2 EA1 (e). (b). EB1. EB1 EA0 EA0 EA2 EA1. EB2. EA2EA1. EB2 (f). (c). EB1 EA0 EA2 EA1. EA1. EA0. EB2. EA2 1.8. 1.9. 2. 2.1. 2.2. 2.3. 2.4 2.5 1.8 1.9. 2. 2.1. 2.2. 2.3. 2.4 2.5 [eV]. ࿑㧠

(10) ⊒శࠬࡍࠢ࠻࡞ߩ⇣ߥࠆಽሶᝄേㆫ⒖߳ߩ࠺ࠦࡦࡏ࡝ࡘ࡯࡚ࠪࡦ㧚⇣ߥࠆಽሶᝄേ ㆫ⒖EA0㧘EA1㧘EA2߇╬ࠛࡀ࡞ࠡ࡯㑆㓒ߢਗࠎߢ޿ࠆߎߣࠍ᣿⏕ߦߔࠆߚ߼㧘ᮮゲࠍశሶ ࠛࡀ࡞ࠡ࡯ߢ⴫ߒߚ㧚ಽ㔌ߒߚฦࡇ࡯ࠢࠍ⎕✢߹ߚߪ㧝ὐ㎮✢ߢ⴫ߒߚ㧚ߎࠇࠄࠍᢙቇ⊛ ߦ㊀⇥ߒߡᓧࠄࠇߚౣ⃻ࠬࡍࠢ࠻࡞㧔ᄥ޿ታ✢㧕ߪ߶߷ቢోߦరߩ⊒శࠬࡍࠢ࠻࡞㧔ὐ✢㧕 !(d)-(f)ṁᶧLPಣℂᓸ☸ሶ㧚(a),(d)ࠢࡠࡠࡎ࡞ࡓṁᶧ߆ࠄ㧘 ߣ৻⥌ߒ㧘 (a)-(c)ࠬࡇࡦࠦ࡯࠻⤑㧘 (b),(e)ࠫࠢࡠࡠࡔ࠲ࡦṁᶧ߆ࠄ㧘(c),(f)࠻࡞ࠛࡦṁᶧ߆ࠄ૞⵾㧚. . -6-.

(11) ࠲ࠗࡊ㧭⊒శࡇ࡯ࠢEA0㧘EA1㧘EA2߽ዊߐ޿ߥ߇ࠄ౒ሽߒߡ޿ࠆߎߣ߇ࠊ߆ߞߚ㧚EB1ߣEB2ߩࡇ ࡯ࠢ㑆㓒ߪ 0.09eVߢ㧘࠲ࠗࡊ㧭⁁ᘒߩಽሶᝄേ㑆㓒 0.17eVࠃࠅ߽ዊߐߊ㧘࠲ࠗࡊB⊒శEB1㧘EB2 ߇࠲ࠗࡊ㧭⊒శߣߪ⇣ߥࠆ⿠Ḯࠍ߽ߟߎߣࠍ␜ໂߒߡ޿ࠆ㧚 ṁᶧLPಣℂᓟߩ⊒శࠬࡍࠢ࠻࡞ࠍ࠺ࠦࡦࡏ࡝ࡘ࡯࠻ߒߚ⚿ᨐߪ㧘ࠢࡠࡠࡎ࡞ࡓṁᶧ㧘࠻࡞ࠛࡦ ṁᶧ߅ࠃ߮ࠫࠢࡠࡠࡔ࠲ࡦṁᶧߩ޿ߕࠇ߆ࠄ૞⵾ߒߚ႐ว߽ห৻ߩ࠲ࠗࡊB⊒శࠛࡀ࡞ࠡ࡯EB1㧘 EB2ࠍ␜ߒ㨇⴫ 1(b)㨉㧘ᱷሽߔࠆᒙ޿࠲ࠗࡊ㧭⊒శࡇ࡯ࠢߣߩ㧡ᚑಽߩ㊀ߨวࠊߖߣߒߡరߩ⊒శ ࠬࡍࠢ࠻࡞ࠍᔘታߦౣ⃻ߢ߈ߚ㨇࿑㧠(d)-(f)㨉㧚࿑㧠߆ࠄ್ᢿߔࠆߣ㧘࠺ࠦࡦࡏ࡝ࡘ࡯࠻ߒߡ᳞߼ ߚ⊒శᒝᐲߩᲧ I A1 / I A0 㧘 I A 2 / I A0 ߪ಴⊒ṁᶧߩ⒳㘃ߦࠃߞߡᄌേߒߡ޿ࠆ㧚ߛ߇㧘หߓࠫࠢࡠ

(12) . !"#$%&'()* ࡠࡔ࠲ࡦṁᶧ߆ࠄ૞⵾ߒߚࠬࡇࡦࠦ࡯࠻⤑ߣṁᶧLPಣℂᓸ☸ሶߪ߶߷หߓ⊒శᒝᐲᲧࠍ +,-./ 012 3456789:;< => ?,@A4BCDEF4 ␜ߔ㧚ߎߩ੐ታߪ㧘㧔㧝㧕MEH-PPV ಽሶߦ߅ߌࠆ㔚ሶ࡮ᩰሶ⋧੕૞↪߇ṁᇦߩ⒳㘃ߦࠃߞߡ㍈ᢅ GH)7-/I>0J2+,GH ?K>L"MNOPQRST7-/'(UDV7* ߦᄌൻߔࠆ੐㧘ߛ߇㧔㧞㧕ߎߩᄌൻߪṁᇦ๺߇⫳⊒ߒߚᓟ߽‫⸥ޟ‬ᙘ‫ࠆࠇߐޠ‬੐㧘ࠍ␜ໂߒߡ޿ࠆ㧚 ߎߩ‫⸥ޟ‬ᙘ‫ޠ‬ലᨐࠍ߽ߚࠄߔ୥⵬ߩ৻ߟߪ MEH-PPV 㜞ಽሶߩࠦࡦࡈࠜ࡯࡚ࠪࡦߢ޽ࠆ㧚߽ߣ߽ ߣṁᇦߦṁߌߥ޿ PPV 㜞ಽሶࠍṁᇦߦนṁߦߥࠆࠃ߁㧘㧞୘ߩᭂᕈ஥㎮ࠍઃടߒߚߩ߇ MEH-PPV ߢ޽ࠅ㧘ߎࠇࠄߩᭂᕈ஥㎮߇૞ࠆ㔚⇇㧔ዪᚲ႐㧕ߩਛߦ MEH-PPV ಽሶߪ⟎߆ࠇߡ޿ ࠆ㧚MEH-PPV 㜞ಽሶ㧔޽ࠆ޿ߪߘߩ஥㎮㧕ߩ᛬ࠇᦛ߇ࠅᣇ㧔ࠦࡦࡈࠜ࡯࡚ࠪࡦ㧕߇ᄌࠊࠆߣ㧘 ߎߩዪᚲ႐߇ᄌࠊࠆߩߢ㧘MEH-PPV 㜞ಽሶߩ⟎߆ࠇߡ޿ࠆ㧔㔚᳇⊛㧕ࠛࡀ࡞ࠡ࡯Ḱ૏߇ᄌൻߔ ࠆߣ⠨߃ࠄࠇࠆ㧚ߎߩࠃ߁ߥࡔࠞ࠾࠭ࡓߦࠃࠅ㧘MEH-PPV 㜞ಽሶ㧔޽ࠆ޿ߪߘߩ஥㎮㧕ߩࠦࡦ ࡈࠜ࡯࡚ࠪࡦᄌൻ߇࠲ࠗࡊ㧭ߣ࠲ࠗࡊ B ߩၮᐩ⁁ᘒࠛࡀ࡞ࠡ࡯ߩᄌൻࠍ߽ߚࠄߔߣ⺑᣿ߢ߈ࠆ㧚㔚ሶ࡮ᩰሶ⋧੕૞↪ߩᒝߐߦߟ޿ߡ߽ዪᚲ႐ߦၮߠߊ⺑᣿߇น⢻ߢ޽ࠆ㧚හߜ㧘MEH-PPV ಽሶ ߩǸ㔚ሶ߇Ǹ౒ᓎ㎮ߦᴪߞߡ㧔శቇ⊛ᝄേᢙߢ㧕ᝄേߒߡ޿ࠆബ⿠⁁ᘒ߆ࠄၮᐩ⁁ᘒߦㆫ⒖ߔࠆ ߣ߈㧘Ǹ౒ᓎ㎮ߩિ❗ᝄേࠍ⺃ዉߒߡࠛࡀ࡞ࠡ࡯ߩ৻ㇱࠍᝄേࡕ࡯࠼ߦਈ߃ࠆ⏕₸㧔㔚ሶ࡮ᩰሶ ⋧੕૞↪ߩᒝߐ㧕߽㧘ߎߩ MEH-PPV 㜞ಽሶ㧔޽ࠆ޿ߪߘߩ஥㎮㧕ߩࠦࡦࡈࠜ࡯࡚ࠪࡦߦᡰ㈩ߐ ࠇߡ޿ࠆߣ⷗ߥߔߩߪᅷᒰߥ⠨߃ߢ޽ࠈ߁㧚. ߹ߣ߼ Ǹ౒ᓎ♽㜞ಽሶṁᶧߩᓸዊᶧṢࠍਇṁߥ᳓ߦ Ộߒ㧘శሶࠛࡀ࡞ࠡ࡯ߩዊߐߥ✛ࡄ࡞ࠬ࡟࡯ࠩ ߢ౒㡆ബ⿠ߔࠆߣ޿߁㧘ᣂⷙߥṁᶧ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣᚻᴺࠍ㐿⊒ߒߚ㧚࿕૕ࠍ࠲࡯ࠥ࠶࠻ߣߔ ࠆᓥ᧪ߩ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣߢߪ㜞ಽሶߩ‛ℂ⁁ᘒᄌൻࠍ⿠ߎߖߥ޿߇㧘ᧄᚻᴺߦࠃߞߡᓧࠄࠇ ߚ㜞ಽሶߩᓸ☸ሶߪ⊒శ߇⍴ᵄ㐳ࠪࡈ࠻ߒ㧘㜞ಽሶߩ⋧ォ⒖ࠍ㆐ᚑߢ߈ߚ㧚ߎߩ⋧ォ⒖ߪਇนㅒ ߢ㧘ߐࠄߥࠆ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣ߿ 200oC߳ߩࠕ࠾࡯࡝ࡦࠣߢߪరߩ⁁ᘒߦᚯࠄߥ߆ߞߚ㧚ᓧࠄ ࠇߚᓸ☸ሶߩၮᐩ⁁ᘒߪరߩ⁁ᘒࠃࠅࠛࡀ࡞ࠡ࡯⊛ߦ቟ቯൻߒ㧘ബ⿠⁁ᘒߩࠛࡀ࡞ࠡ࡯ᄌൻ߇ዊ ߐ޿ߣߔࠇ߫㧘ߎࠇߪ⊒శ߇⍴ᵄ㐳ࠪࡈ࠻ߒߚߎߣߣ㚂የ৻⽾ߒߡ޿ࠆ㧚ࠕ࠾࡯࡝ࡦࠣߩ⚿ᨐߪ ߎߩ⋧ォ⒖ߩᵴᕈൻࠛࡀ࡞ࠡ࡯߇ 200oCߢߩᾲࠛࡀ࡞ࠡ࡯ࠃࠅᄢ߈޿੐ࠍ␜ߒ㧘ಽሶಽᢔ⁁ᘒࠍ ࠲࡯ࠥ࠶࠻ߣߔࠆṁᶧ࡟࡯ࠩࡊࡠ࠮ࠪࡦࠣߩߺ߇㧘ೋᦼṁᇦߩ⒳㘃ߦࠃࠄߕห৻ߩ‛ℂ⁁ᘒ߳ߣ ⋧ォ⒖ߐߖࠆߩߦ᦭ലߢ޽ࠆߎߣࠍ␜ߒߡ޿ࠆ㧚. ⻢ㄉ ᳇ኒടᾲ࠴ࠚࡦࡃ࡯ߩ೑↪ߦߟ޿ߡᧄቇᄢ㊁ትੱᢎ᝼ߦ㧘ṁᶧ࠮࡞ಽశశᐲ⸘ߩ೑↪ߦߟ޿ߡ ᧄቇḡญት᣿ಎᢎ᝼ߦ㧘శᢔੂࠍ↪޿ߚᓸ☸ሶߩ☸ᓘಽᏓ᷹ቯߦߟ޿ߡᧄቇ᭑ᧄඳⴕᢎ᝼ߦ㧘߅. . -7-.

(13) ਎⹤ߦߥࠅ߹ߒߚ㧚ᧄ⎇ⓥߩ৻ㇱߪᢥㇱ⑼ቇ⋭⑼ቇ⎇ⓥ⾌⵬ഥ㊄ၮ⋚(C)ߩᡰេ㧘৻ㇱߪቇౝᄢቇ 㒮ୃ჻⺖⒟⎇ⓥ⾌ߩᡰេࠍฃߌߡታᣉߒߚ㧚. ෳ⠨ᢥ₂ 1) T. Lucatorto and M. D. Graef, “Laser Ablation and Desorption”, in “Experimental Methods in the Physical Sciences” vol 30, ed., R. F. Haglund and J. C. Miller, Academic Press (1997). 2) D. Bauerle, “Liquid-Phase Deposition, Electroplating Laser Processing and Chemistry”, Chap. 11, Springer-Verlag (2011). 3) K. Takada and A. Tomioka, “Solution-Phase Laser Processing of S-Conjugated Polymers: Switching Between Different Molecular States”, J. Phys.: Conf. Ser., 358 012012 1-7 (2012). 4) M. Liess, S. Jeglinski, Z. V. Vardeny, M. Ozaki, K. Yoshino, Y. Ding and T. Barton, “Electroabsorption spectroscopy of luminescent and nonluminescent Ǒ-conjugated polymers”, Phys. Rev. B., 56, 15712-15724 (1997). 5) S. Abe, “Exciton vs Interband Absorption in Peierls Insulators”, J. Phys. Soc. Jpn., 58, 62 -65 (1989). 6) T. Ogawa, and T. Takagahara, “Optical absorption and Sommerfeld factors of one-dimensional semiconductors: An exact treatment of excitonic effects”, Phys. Rev. B, 44, 8138-8156 (1991). 7) J. Zhang, Z. Wang and T. Kobayashi, “Vibrational fine structures revealed by the real-time vibrational phase and amplitude in MEH-PPV using few cycle pulses”, Phy. Rev. B, 77, 153202 1-4 (2008). 8) A. Nabetani, H. Tamaru, A. Tomioka, T. and K. Miyano, “Optical properties of two-dimensional dye aggregate”, J. Chem. Phys., 102, 5109-5117 (1995). 9) A. Tomioka and K. Miyano, “Numerical study of excitons in a two-dimensional organic dye aggregate”, Phys. Rev. B, 54, 2963-2967 (1996). 10) K. Pickler, D. A. Halliday, D. D. C. Bradley, P. L. Burn, R. H. Friend and A. B. Holmes, “Optical spectroscopy of highly ordered poly(p-phenylene vinylene)”, J. Phys.: Condens. Matter, 5, 7155 -7172 (1993).. . -8-.

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