2A15ㆃᑧ㔚ሶ⣕㔌෻ᔕࠍ೑↪ߒߚቅ┙ಽሶࠗࠝࡦߩౝㇱࠛࡀ࡞ࠡ࡯᷹ቯ㧔㚂ㇺᄢ㒮ℂᎿ*, ℂ⎇**㧕٤ᓟ⮮ၮ*㧘᧻ᧄᷕ*㧘ၔਣᤐᄦ*㧘㒙⍮ᵄᵗᰴ*㧘㑆᎑ᜏ਽*㧘↰ᴧ⡸*㧘᧲ବⴕ*, **[ߪߓ߼ߦ]
 ࠊࠇࠊࠇߪ㕒㔚ဳࠗࠝࡦ⫾Ⓧ࡝ࡦࠣࠍ↪޿ߡ㧘Ꮒᄢಽሶࠗࠝࡦߩ࡟࡯ࠩ࡯⺃⿠෻ᔕߩ᷹ⷰࠍⴕߞߡ߅ࠅ㧘ಽሶߩౝㇱࠛࡀ࡞ࠡ࡯ߩ⋧ኻ୯ࠍ᳞߼ࠆᚻᴺߦߟ޿ߡߪᣢߦႎ๔ߒߚ[1]㧚੹࿁ߪಽሶߩౝㇱࠛࡀ࡞ࠡ࡯ߩ⛘ኻ୯ࠍ᳞߼ࠆᚻᴺߦߟ޿ߡႎ๔ߔࠆ㧚ಽሶߩౝㇱࠛࡀ࡞ࠡ࡯ߪ‛ᕈࠍ⍮ࠆ਄ߢ㕖Ᏹߦ㊀ⷐߥᖱႎߢ޽ࠆ߇㧘ቅ┙⁁ᘒߦ߅ߌࠆౝㇱࠛࡀ࡞ࠡ࡯ࠍ⺞ߴࠆߎߣߪ㔍ߒ޿㧚ᦨㄭߢߪౝㇱࠛࡀ࡞ࠡ࡯ߩ᷹ቯߩߚ߼“ ㆃᑧ෻ᔕ” ߇⌕⋡ߐࠇߡ߅ࠅ㧘޿ߊߟ߆ߩ⎇ⓥᚑᨐ߇⊒⴫ߐࠇߡ޿ࠆ㧚ㆃᑧ෻ᔕߪ⛔⸘ജቇ⊛ߥㆊ⒟ߢ޽ࠆߣ⠨߃ࠄࠇߡ߅ࠅ[2]㧘ߘߩㅦᐲቯᢙߪౝㇱࠛࡀ࡞ࠡ࡯ߦࠃߞߡᡰ㈩ߐࠇߡ޿ࠆ㧚⸒޿឵߃ࠆߣ㧘ㆃᑧ෻ᔕߩㅦᐲቯᢙߪౝㇱࠛࡀ࡞ࠡ࡯ࠍ⍮ࠆߚ߼ߩࠃ޿ᜰᮡߣߥࠆ㧚ᧄ⎇ⓥߢߪ㧘శๆ෼ߦࠃࠆㆃᑧ෻ᔕࠍࡕ࠾࠲࡯ߒ㧘⫾߃ߡ޿ߚౝㇱࠛࡀ࡞ࠡ࡯(Eini)ߣๆ෼ߒߚశሶߩࠛࡀ࡞ࠡ࡯(nh!)ߩ๺ࠍ෻ᔕㅦᐲ߆ࠄ᳞߼ߚ㧚nh!ߪታ㛎ߢ᳿߼ࠆߎߣ߇
ߢ߈ࠆߩߢ㧘ᧄᴺߦࠃࠅEiniߩ⛘ኻ୯᷹ቯ߇น⢻ߢ޽ࠆ㧚
(b)

(a)

relative intensity ኻ⽎ߪࡈ࠲ࡠࠪࠕ࠾ࡦ੝㋦⽶ࠗࠝࡦ(ZnPc-)ߣߒߚ㧚࡟࡯ࠩ࡯⣕⌕ဳࠗࠝࡦḮߢ↢ᚑߒߚ⽶ࠗࠝࡦࠍ㧘࡝ࡦࠣ৻ᣇߩ⋥✢ㇱߦ౉኿ߒ⫾Ⓧߒߚ㧚ࠗࠝࡦߦࡄ࡞ࠬ࡟࡯ࠩ࡯(1.9 eV)ࠍᾖ኿ߒ㧘ࠗࠝࡦ߆ࠄ↢ᚑߒߚਛᕈ☸

55 ms
30 ms1ߘߩᓟ㧘߽߁৻ᣇߩ⋥✢ㇱߦ߅޿ߡ

30 ms
55 ms
80 ms

80 ms

10

relative intensity[ታ㛎߅ࠃ߮⚿ᨐ]

1

1

102

laser fluence (mJ/cm )

0.1

00.2

0.4

0.6

0.8

1

1.2

time after irradiation (ms)࿑㧝 ߐ߹ߑ߹ߥ⫾Ⓧᤨ㑆ߦ߅޿ߡ㧘ㆃᑧ෻ᔕߦࠃࠅ↢ᚑߒߚਛᕈ☸ሶ᷹ⷰߩ᭽ሶ㧚 (a)࡟࡯ࠩ࡯ࡈ࡞ࠛࡦࠬଐሽᕈ㧚 (b)ᷫ⴮ߩ᭽ሶ㧚ሶࠍࠗࠝࡦ౉኿஥⋥✢ㇱਅᵹߦ⸳⟎ߒߚᬌ಴ེࠍ↪޿ߡ᷹ⷰߒߚ㧚޿ߊߟ߆ߩ⫾Ⓧᤨ㑆ߦ߅޿ߡ㧘࡟࡯ࠩ࡯ᾖ኿ᓟ 20 㨪 1000 "sߦ߅ߌࠆਛᕈ☸ሶ෼㊂ࠍ࡟࡯ࠩ࡯ࡈ࡞ࠛࡦࠬߦኻߒߡਔኻᢙࡊࡠ
࠶࠻ߒߚ߽ߩࠍ࿑㧝(a)ߦ␜ߔ㧚ࠗࠝࡦߪユ኿಄ළߦࠃߞߡ㧘⫾Ⓧᤨ㑆߇ᑧ߮ࠆ߶ߤౝㇱࠛࡀ࡞ࠡ࡯ߪૐߊߥࠆ㧚ߘߩߚ߼㧘ࠗࠝࡦߩౝㇱࠛࡀ࡞ࠡ࡯߇ૐ޿߶ߤᄙశሶๆ෼ߩነਈ߇Ⴧᄢߒߡ޿ࠆ
ߎߣ߇ࠊ߆ࠆ㧚ߎࠇࠄߩࡊࡠ࠶࠻ߩ௑߈߇ㆃᑧ෻ᔕߦⷐߔࠆᐔဋశሶᢙnaveߣߔࠆ㧚߹ߚ㧘ㆃᑧ෻ᔕߩᷫ⴮I(t)㧔t: ࡟࡯ࠩ࡯ᾖ኿ᓟߩᤨ㑆㧕ࠍࡊࡠ࠶࠻ߒߚ߽ߩࠍ࿑㧝(b)ߦ␜ߔ㧚ߎߩ࿑߆ࠄ㧘ߎ
ࠇࠄߩI(t)ߪන৻ߩᜰᢙ㑐ᢙߢࡈࠖ࠶࠻ߢ߈ߥ޿ߎߣ߇ࠊ߆ࠆ㧚߹ߚ⫾Ⓧᤨ㑆㧘ߔߥࠊߜౝㇱࠛࡀ࡞ࠡ࡯ߩ㆑޿ߦࠃࠄߕI(t)߇߶ߣࠎߤᄌࠊࠄߥ޿ߎߣ߽ࠊ߆ࠆ㧚ߎࠇࠄߩ⚿ᨐߦߟ޿ߡ⠨ኤߒ㧘ౝㇱࠛࡀ࡞ࠡ࡯ߩ⛘ኻ୯ࠍ᳞߼ࠆ㧚[ౝㇱࠛࡀ࡞ࠡ࡯ߩዉ಴]ᧄ⎇ⓥߢ᷹ⷰߐࠇࠆ I(t)ߪએਅߩᑼߦࠃߞߡਈ߃ࠄࠇࠆ㧚I (t ) $ # g ( E )k ( E ) exp(%k ( E )t ) dE

(1)㧘

10 7

ߎߎߢ g(E)ߪ࡟࡯ࠩ࡯ᾖ኿ᓟߩౝㇱࠛࡀ࡞ࠡ࡯ಽᏓ㧘E ߪౝㅦᐲቯᢙߣಽᏓ㑐ᢙߩࠛࡀ࡞ࠡ࡯ଐሽᕈࠍ೎ㅜ⸘▚ߔࠆߎߣߦࠃࠅ㧘ታ᷹ߩ I(t)ࠍౣ⃻ߔࠆౝㇱࠛࡀ࡞ࠡ࡯ࠍ᳞߼ࠆ㧚k(E)ߩ⷗Ⓧ߽ࠅߪෳ⠨ᢥ₂[3]ߩᚻ㗅ߦᓥߞߚ㧚ZnPc-ߩㅦᐲቯᢙߩ▚಴ߩߚ߼ߦ㧘ਛᕈZnPcߩ㔚ሶⷫ๺ജ(3.5 eV [4])㧘ၮ

10 5

10 4

10 3

ḰᝄേࠍၮߦᓧࠄࠇߚᲧᾲ(1.2×10-2 eV/K [5])㧘߅ࠃ߮ᐞ૗᭴
ㅧ߆ࠄ⷗Ⓧ߽ߞߚ㔚ሶઃ⌕ߩᢿ㕙Ⓧ(100 Å2)ࠍ↪޿ߚ㧚g(E)ࠍ᳞߼ࠆߚ߼㧘߹ߕశๆ෼೨ߩಽᏓࠍࡏ࡞࠷ࡑࡦಽᏓ߆ࠄ▚

0

0.2

0.4

0.6

0.8

1

relative intensity ೋᦼ㧔శๆ෼೨㧕᷷ᐲ 1500 K ߦߟ޿ߡ I(t)ࠍ⸘▚ߒߚ⚿ᨐ

1.2

࿑㧞 ೋᦼ᷷ᐲ 1500 K ߢࠪࡒࡘ࡟࡯࠻ߒ
ߚ I(t)ߩᦛ✢ߣฦࠛࡀ࡞ࠡ࡯ᚑಽߩነਈ㧚

500 K
700 K
900 K
1100 K
1300 K
1500 Knశሶㆊ⒟ߘࠇߙࠇߩಽᏓࠍ⿷ߒวࠊߖࠆߎߣߦࠃߞߡ g(E)ሶๆ෼ߔࠆ⏕₸)ࠍ৻ቯ(0.5)ߣߒߚ㧚1time after irradiation (ms)಴ߒߚ㧚ߘߩᓟ㧘ߎߩಽᏓࠍၮߦnశሶๆ෼ᓟߩಽᏓࠍ᳞߼㧘
ࠍ⷗Ⓧ߽ߞߚ㧚੹࿁ߩࠪࡒࡘ࡟࡯࡚ࠪࡦߢߪPn+1 /Pn (Pn: nశ

17 eV18 eV
19 eV
20 eVI(t)
14 eV
15 eV
16 eV

10 6intensity (arb.)ㇱࠛࡀ࡞ࠡ࡯㧘k(E)ߪㆃᑧ෻ᔕߩㅦᐲቯᢙࠍ⴫ߔ㧚ߎߎߢ㧘

0.1

ࠍ࿑㧞ߦ␜ߔ㧚ߎߎߢߪ㧘․ቯߩౝㇱࠛࡀ࡞ࠡ࡯ߦߟ޿ߡߩ
0ߺ⸘▚ࠍⴕߞߚ㧚ߎߩ࿑߆ࠄૐ޿ౝㇱࠛࡀ࡞ࠡ࡯ߩᚑಽ㧘଀

0.2

0.4

0.6

0.8

1

1.2

time after irradiation (ms)߃߫࿑ਛ 14 eV ߩᚑಽߪ㧘࿑ߢ␜ߐࠇߚᤨ㑆▸࿐ߦ߅޿ߡ I(t)ߦ߶ߣࠎߤነਈߒߡ޿ߥ޿ߎߣ߇ࠊ߆ࠆ㧚߹ߚ࡟࡯ࠩ࡯ᾖ኿
ᓟᢙ 10 "s ߦ߅޿ߡߪታ㛎⊛ߥ೙⚂ߦࠃࠅਛᕈ☸ሶࠍ᷹ⷰߔ

࿑㧟 ࠪࡒࡘ࡟࡯࡚ࠪࡦ߆ࠄᓧࠄࠇߚ I(t)ߩೋᦼ᷷ᐲଐሽᕈ㧚ࠆߎߣ߇ߢ߈ߕ㧘ߎߩߎߣߪ࿑ਛ 19 eV ࠃࠅ㜞޿ࠛࡀ࡞ࠡ࡯ߩᚑಽߪ߶߷᷹ⷰਇน⢻ߢ޽ࠆߎߣࠍᗧ๧ߔࠆ㧚ߎࠇࠄߩ⚿ᨐࠃࠅ㧘㒢ࠄࠇߚᤨ㑆▸࿐㧔࡟࡯ࠩ࡯ᾖ኿ᓟ 20 㨪 1000 "s㧕ߦ߅ߌࠆਛᕈ☸ሶ෼㊂ࠍ⺞ߴࠆߎߣߪ㧘15 ߆ࠄ 18 eV ߩౝㇱࠛࡀ࡞ࠡ࡯ࠍᜬߟᚑಽࠍㆬᛯ⊛ߦ᷹ⷰߒߡ޿ࠆߣ޿߃ࠆ㧚ߐ߹ߑ߹ߥೋᦼ᷷ᐲߦኻߒߡ㧘I(t)ࠍ⸘▚ߒߚ⚿ᨐࠍ࿑㧟ߦ␜ߔ㧚I(t)ߪೋᦼ᷷ᐲߦ߶ߣࠎߤଐሽߖߕ㧘ታ᷹ߩ I(t)ߦ⫾Ⓧᤨ㑆ଐሽᕈ߇⷗ࠄࠇߥ߆ߞߚߣ޿߁⚿ᨐࠍౣ⃻ߒߡ޿ࠆ㧚߹ߚ㧘ਛᕈ☸ሶߩ࡟࡯ࠩ࡯ࡈ࡞ࠛࡦࠬଐሽᕈࠍ޿ߊߟ߆ߩೋᦼ᷷ᐲߦ߅޿ߡ⸘▚ߒߚ⚿ᨐ㧘ታ㛎ߢ↪޿ߚ࡟࡯ࠩ࡯ࡈ࡞ࠛࡦࠬߩ▸࿐ౝߦ߅޿ߡ㧘ਔኻᢙࡊࡠ࠶࠻ߦ߅ߌࠆ௑߈߇߶߷⋥✢ߦߥࠅ㧘ೋᦼ᷷ᐲߩ㆑޿ߦࠃࠅ௑߈߇⇣ߥࠆߎߣ߽ࠊ߆ߞߚ㧚 એ਄ߩ⚿ᨐ߆ࠄ㧘᷹ⷰน⢻ߥౝㇱࠛࡀ࡞ࠡ࡯▸࿐(Eobs)ߦ೔㆐ߒߚࠗࠝࡦߩߺࠍᧄታ㛎ߢߪ᷹ⷰߒߡ޿ࠆߎߣ߇ࠊ߆ࠆ㧚ᓥߞߡ㧘࿑㧝(a)ߦ␜ߐࠇߚታ㛎⚿ᨐߣએਅߩᑼ߆ࠄౝㇱࠛࡀ࡞ࠡ࡯ߩ⛘ኻ୯ࠍ᳞߼ࠆߎߣ߇಴᧪ࠆߣ⠨߃ࠄࠇࠆ㧚

Eini(eV) = 16.5 – naveh!

(2)㧘

ߎߎߢ 16.5 eVߣ޿߁୯ߪࠪࡒࡘ࡟࡯࡚ࠪࡦࠃࠅᓧࠄࠇߚEobsߩਛᄩߩ୯ߢ޽ࠆ㧚(2)ᑼߦߪr1.5eVߩ⺋Ꮕ߇ሽ࿷ߔࠆ߇㧘Einiࠍቯ㊂⊛ߦ᳞߼ࠆߎߣ߇ߢ߈ߚ㧚[ෳ⠨ᢥ₂][1] M. Goto et al., Chem. Phys. Lett. 460, 46 (2008).
[2] E.E.B. Campbell and R.D. Levine, Annu. Rev. Phys. Chem. 51, 65 (2000).
[3] J.U. Andersen et al., J. Phys. B: At. Mol. Opt. Phys. 35, R1 (2002).
[4] T. G. Gantchev et al., Radiat. Phys. Chem. 72, 367 (2005).
[5] Z. Liu et al., Spectochmica. Acta. A 67, 1232 (2007).