Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ⸃⺑ ࠢࠬ࠲ੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺߩዷᦸ ̆Ꮺ㔚ᶧṢⴣ᠄/ੑᰴࠗࠝࡦ⾰㊂ಽᨆ⸘ߩㅴዷ̆ a 㘵ፉ ༀᤨ,a,* ᐔጟ ⾫ਃ b,** ᣣᧄ㔚ሶ㧔ᩣ㧕㔚ሶశቇᯏེ༡ᬺᧄㇱ㧘EO ⽼ᄁଦㅴࠣ࡞ࡊ ޥ190-0012 ᧲੩ㇺ┙ᎹᏒᦍ↸ 2-8-3 b ጊ᪸ᄢቇࠢࡦࠛࡀ࡞ࠡ⎇ⓥࡦ࠲ ޥ400-8511 ጊ᪸⋵↲ᐭᏒᱞ↰ 4 ৼ⋡ * [email protected] ** [email protected] 㧔2008 ᐕ 2 18 ᣣฃℂ; 2008 ᐕ 4 7 ᣣឝタቯ㧕 ᦨㄭߩ㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺ㧔Time of flight secondary ion mass spectrometry, TOF-SIMS㧕ߪ㧘৻ᰴࠗࠝࡦߣߒߡ SF5+ 㧘Au3+ 㧘C60 㧗 ߣߞߚࠢࠬ࠲ࠗࠝࡦḮࠍⵝ⌕ߒߚ TOF-SIMS ߇ታ↪ൻߐࠇߡ߈ߡࠆ㧚ࠢࠬ࠲ࠗࠝࡦߪ㜞⾰㊂ੑᰴࠗࠝࡦߩ㜞₸ൻ߿㕖⎕უ ⊛ߦ᧚ᢱ㕙ࠍࠬࡄ࠶࠲ࡦࠣߔࠆߥߤߩὐࠍߒߡࠆ㧚ߒ߆ߒ↢᧚ᢱߥߤࠗࡈࠨࠗࠛ ࡦࠬ᧚ᢱಽᨆߢߪߐࠄߥࠆੑᰴࠗࠝࡦߩ㜞₸ൻ߇ⷐ᳞ߐࠇߡ߈ߡࠆ㧚ߎࠇࠄ᧚ᢱಽᨆߩߚ㧘 ᦨㄭࠃࠅࠨࠗ࠭ߩᄢ߈ߥࠢࠬ࠲ࠗࠝࡦߩ⎇ⓥ߇⋓ࠎߦⴕࠊࠇߡࠆ㧚ߎߎߢߪ㧘ᦨᣂߩᏂᄢ ࠢࠬ࠲ࠗࠝࡦ㧔Ꮺ㔚ᶧṢ㧕ࠍ↪ߚ SIMS ߩ⁁ࠍႎ๔ߔࠆ㧚 Prospects of Cluster Secondary Ion Mass spectrometry -Development of Electrospray Droplet Impact- Secondary Ion Mass SpectrometerYoshitoki Iijimaa,* and Kenzo Hiraokab,** JEOL Ltd. Electron optics Sales Division, 2-8-3 Akebono-cho Tachikawa Tokyo 190-0012 Japan b University of Yamanashi, Clean Energy Research Center, Tekeda-4 Kofu Yamanashi 400-8511 Japan * [email protected] ** [email protected] a (Received: February 18, 2008; Accepted: April 7, 2008) Time of flight type secondary ion mass spectrometry (TOF-SIMS) equipped with the cluster ion source such as SF5+, Au3+, C60 + as primary ion has been put to practical use in the last decade. Cluster ion beam has advantage of high sputtering yield and high secondary ionization yield without introducing severe damage on material surfaces. Substantial enhancement of secondary ion yield for bio-molecules is strongly demanded, and consequently, use of giant cluster ions for SIMS is attracted very recently. In this paper, the development of SIMS with the giant cluster ions (water droplet cluster) is reported. Copyright (c) 2008 by The Surface Analysis Society of Japan 214 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 1. ߪߓߦ 㘧ⴕᤨ㑆ဳੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺ㧔Time of flight secondary ion mass spectrometry, TOF-SIMS㧕ߪ 1980 ᐕೋ㗡ߦ㐿⊒ߐࠇ㧘ᓥ᧪ߩ SIMS㧔࠳ࠗ࠽ࡒ࠶ࠢ SIMS,D-SIMS㧕ߣห᭽ߥේሶ⁁ࠗࠝࡦߦട߃㧘ࡈ ࠣࡔࡦ࠻ࠗࠝࡦ㧘⣕㔌ᡆૃಽሶࠗࠝࡦ㧘ߐࠄߦࠝ ࠧࡑࠗࠝࡦߥߤಽሶ᭴ㅧࠍᤋߒߚᖱႎࠍᓧࠆߎ ߣ߇ߢ߈ࠆߎߣ߆ࠄ㧘ඨዉ᧚ᢱ߆ࠄ㜞ಽሶ᧚ᢱ㧘 ࠗࡈࠨࠗࠛࡦࠬ᧚ᢱߥߤߩಽ㊁߹ߢᐢߊ↪ߐࠇ㧘 ⋉ߥ⚿ᨐ߇ᓧࠄࠇߡ߈ߡࠆ[1,2]㧚 SIMS ࠍ X ✢శ㔚ሶಽశᴺ㧔XPS㧕߿ࠝࠫࠚ㔚 ሶಽశᴺ㧔AES㧕ߥߤߩ㕙ಽᨆᴺߣᲧߴߚᤨߩ㐳 ᚲߪ㧘㕙ᓸ㊂ర⚛ߩ㜞ᗵᐲ᷹ቯ㧘ಽሶ᭴ㅧᖱႎߩ ᷹ቯ㧘ߐࠄߦ AES ߦߪഠࠆ߇ XPS ࠍ࿁ࠆࠨࡉࡒ ࠢࡠࡦ㗔ၞߩࠗࡔࠫࡦ᷹ࠣቯ߇น⢻ߢࠆὐ[3,4]㧘 ߐࠄߦ⹜ᢱಣℂήߒߦ᷹ቯ߇ߢ߈ࠆὐ╬ߢࠆ㧚ߎ ߩߚᯏൻว‛⭯⤑㧘㜞ಽሶඨዉ᧚ᢱߥߤ ᐢ᧚ᢱಽ㊁ߦട߃㧘ᦨㄭߢߪක⮎↢᧚ᢱߣ⸒ߞ ߚࠗࡈࠨࠗࠛࡦࠬ᧚ᢱߦ߽㧘TOF-SIMS ߩᔕ↪ಽ ㊁߇৻Ბߣᐢ߇ߞߡ߈ߡࠆ㧚 ߎࠇ߹ߢߪ㧘SIMS ߩ৻ᰴബḮߣߒߡߩࠗࠝࡦ ࡆࡓߣߒߡනේሶࠗࠝࡦࠍ↪ࠆࠗࠝࡦࠛ࠶࠴ࡦ ࠣᴺ㧔Ꮧࠟࠬࠗࠝࡦ߿㉄⚛ࠗࠝࡦ㧕߇৻⥸⊛ߦ↪ ߐࠇߡࠆ㧚ߎߩᣇᴺߢߪ৻ᰴ☸ሶࠗࠝࡦ߇࿕ౝ ㇱߦᢙ 10nm ⒟ᐲଚߒ㧘㕙ߩߺߥࠄߕ㧘㕙ਅ ጀߩ⚵❱߹ߢ⎕უߔࠆߚ㧘㕖⎕უߢ㕙ጀᢙේ ሶಽሶጀߩᷓߐᣇะᖱႎࠍᓧࠆߎߣߪ࿎㔍ߢࠆ㧚 ߃߫㧘ᯏൻว‛ߢߪ㉄⚛ߩᒁ߈ᛮ߈ᔕ߇⊒↢ ߒ㧘ࠣࡈࠔࠗ࠻ൻ߇ㅴⴕߒ㧘ߐࠄߦ㧘ࠗࠝࡦᾖ ߦࠃࠆ㕙ߩ⨹ࠇߩ⊒↢㧘ߘࠇߦߣ߽ߥ߁ᬌାภ ߩᒝᐲߩᷫዋ߇ߎࠅ㧘ቯߒߡ㜞ᗵᐲߢ SIMS ಽ ᨆࠍⴕ߁ߎߣ߇ߢ߈ߥ㧚ߎߩ㗴ࠍ⸃ߔࠆߚ ߩ⎇ⓥ߇ᢙᄙߊⴕࠊࠇߡࠆ㧚 ߎߩઍ⊛ᛛⴚߣߒߡࠢࠬ࠲ࠗࠝࡦࠍ৻ᰴബ Ḯߣߒߡ↪ࠆᣇᴺ߇ࠆ=5-7?㧚ࠢࠬ࠲ࠗࠝ ࡦࠍ᧚ᢱ㕙ߦⴣ᠄ߒߚ㓙ߩ․ᓽߣߒߡ㧘㧔1㧕⹜ᢱ 㕙ߦⴣ⓭ߔࠆ㓙ߦಽⵚߔࠆߚฦේሶಽሶߚ ࠅߩࠛࡀ࡞ࠡ߇ዊߐߊߥࠅ㧘ࡒࠠࠪࡦࠣࠍᛥ㧘 㧔2㧕ࠬࡄ࠶࠲ࡦࠣ₸߇⪺ߒߊ㜞㧘 㧔3㧕㜞⾰㊂ੑ ᰴࠗࠝࡦߩ㜞₸ൻ㧘㧔4㧕᧚ᢱ㕙ߩᐔṖൻ㧘ߥߤ ߇ࠆ[8]㧚ߎࠇࠄߩࠢࠬ࠲ࠗࠝࡦⴣ᠄ᤨߩ․ᓽ ߪᓥ᧪ᣇᴺߢ㗴ߣߥߞߡࠆ㗄ࠍ⸃ߔࠆߎߣ ߇ߢ߈ࠆᣂߒᚻᴺߣߒߡᦼᓙߐࠇߡࠆ㧚ߎߩߚ ࠢࠬ࠲ࠗࠝࡦࠍ↪ߒߚ SIMS ߪ 1989 ᐕ߆ࠄ ⎇ⓥ߇ᧄᩰൻߒߚ㧚৻ᰴࠗࠝࡦߣߒߡ Cs+(CsI)n [8]㧘 SF5+ [6,9]㧘Au+㧘Au2+㧘Au3+ [10-13]ࠍ↪ࠆ⎇ⓥ߆ ࠄᆎ߹ࠅ㧘ᦨㄭߢߪᶧ㊄ዻḮ߆ࠄߐࠇࠆ Bi ࠢࠬ࠲[14]߿ C60+ࠍ↪ߚࠢࠬ࠲SIMS ߇ ߒߡࠆ[15-19]㧚ߎࠇࠄએᄖߦ߽ Ar ࠢࠬ࠲ ߥߤߩࠟࠬࠢࠬ࠲ࠗࠝࡦࠍ SIMS ߦ↪ߚ⎇ⓥ ᚑᨐ߽ႎ๔ߐࠇߡ߈ߡࠆ[20]㧚ߎߩࠃ߁ߥࠢࠬ ࠲ࠗࠝࡦࠍ৻ᰴࠗࠝࡦߣߒߡ↪ࠆߎߣߦࠃࠅᡆ ૃಽሶࠗࠝࡦߥߤߩᯏಽሶࠗࠝࡦߩੑᰴࠗࠝࡦൻ ല₸߇ᄢߦᡷༀߐࠇߡ߈ߡࠆ[21]㧚 Fig. 1 ߦ Garrison ࠄ߇ⴕߞߚ 15 keV ߩ Ga+߮ C60+ࠗࠝࡦࠍ Ag(111)㕙ߦኻߒ 90qߢߒߚ㓙ߩ ⴣ⓭⽎ߩಽሶേജቇࠪࡒࡘ࡚ࠪࡦࠍ␜ߔ[22]㧚 Ga+ࠗࠝࡦߢߪࠗࠝࡦ߇⹜ᢱਅㇱ߹ߢଚߒ㧘⹜ᢱ ౝㇱ᭴ㅧࠍ⎕უߒ㧘ߐࠄߦ㕙߆ࠄߩ⣕㔌ේሶᢙ߇ ዋߥߎߣࠍ␜ߒߡࠆ㧚৻ᣇ㧘C60+ࠗࠝࡦߩ႐ว ߪࠢࠬ࠲ࠗࠝࡦⴣ᠄ߩὐߢࠆ㕙߆ࠄߩ⣕ 㔌ේሶᢙ߇ᄙߎߣ߇ಽ߆ࠆ㧚ߒ߆ߒ C60+ࠗࠝࡦߢ ߽߹ߛ⹜ᢱౝㇱ᭴ㅧߩ⎕უ㧘ࠢ࠲ࠅ߳ߩේሶ ၸⓍ߇␜ߐࠇߡࠆ㧚ߎߩ⽎߇⊒↢ߔࠆߎߣߪ㜞 ಽሶ߿↢᧚ᢱ߳ߩㆡᔕߪ࿎㔍ߢࠆߎߣ߇ߡข ࠇࠆ㧚ᓥߞߡ㧘ߢ߈ࠆߛߌᄢ߈ߥࠢࠬ࠲ࠗࠝࡦ Fig. 1 Snapshots from a molecular dynamics computer simulation of 15 keV C60 and 15 keV Ga + bombardment of Ag metal [22] (Reprinted with permission from Anal. Chem. 2005, 77, 143A-149A. Copyright 2005 American Chemical Society). 215 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ࠍ↪ࠆ SIMS ⵝ⟎ߩ㐿⊒߇᳞ࠄࠇߡࠆ㧚 ߹ߢ㐿⊒ߐࠇߚࠢࠬ࠲SIMS ߦ߅ߡᦨ߽ ᄢ߈ߥ৻ᰴࠗࠝࡦ㧔ࠢࠬ࠲ࠗࠝࡦ㧕ࠍ↪ߒߚ ߩ߇ Mahoney ࠄߦࠃࠆ Massive Cluster Impact (MCI) ߢࠆ[23-26]㧚ߎߩ MCI ߩේℂߪ 1.5 M ߩ㈶㉄ࠕࡦ ࡕ࠾࠙ࡓࠍṁ⸃ߒߚࠣࡦࠍ⌀ⓨਛߢ㕒㔚႐ྃ 㔵ߒ㧘⾰㊂߇⚂ 109u ߢ⚂ 200 ଔߦᏪ㔚ߒߚᏂᄢࠣ ࡦࠢࠬ࠲ࠗࠝࡦࠍ⊒↢ߐߖ㧘ߎࠇࠍടㅦ㔚 15 kV ߢ⹜ᢱ㕙ࠍⴣ᠄ߔࠆ߽ߩߢࠆ㧚ߎߩᚻᴺ ࠍ↪ߡ Fabris ࠄߪࡑ࠻࠶ࠢࠬήߒߢಽሶ㊂⚂ 30,000 ߩ࠲ࡦࡄࠢ⾰ಽሶߩᬌߦᚑഞߒߚႎ๔ࠍ ⴕߞߚ㧚ߒ߆ߒ㧘ߎߩ MCI ࠍ↪ࠆᣇᴺߪ৻ᰴࠗࠝ ࡦߦ㔍ើ⊒ᕈߩࠣࡦࠍ↪ߒߡࠆߚ㧘⍴ ᤨ㑆ߢࠗࠝࡦടㅦ㔚ᭂߥߤ߇ᳪᨴߐࠇߡߒ߹߁ᰳὐ ࠍߒߡࠆ[27]㧚 ᦨㄭ Fujiwara ࠄߪᏂᄢಽሶߢࠆ㊄ዻࠢࠬ࠲ ㍲ߩࠗࠝࡦࡆࡓḮࠍឭ᩺ߒ㧘ࠨࠗ࠭ߩߘࠈߞߚ ࠢࠬ࠲ࠗࠝࡦࠍᓧߡࠆ[28-31]㧚↪ߚ㊄ዻ㍲ ߪ Ir4(CO)12㧔ಽሶ㊂ 1104.9㧕ߢ㧘࿕⁁ߩ㊄ዻࠢ ࠬ࠲㍲ࠍ⌀ⓨਛߢ⪇㧘㔚ሶⴣ᠄ᴺߢࠗࠝࡦ ൻߒ㧘ᢙ keV ߩࠛࡀ࡞ࠡߢടㅦߒ⹜ᢱ㕙ࠍⴣ᠄ ߔࠆ㧚ߎߩᣇᴺߩὐߪࠢࠬ࠲ࠨࠗ࠭ߩᓮ߇ ኈᤃߢ㧘ߐࠄߦ㔚ሶⴣ᠄ᴺࠍ↪ߡࠆߚࠗࠝࡦ Ḯߩࠦࡦࡄࠢ࠻ൻ߇น⢻ߣߥࠆὐߢࠆ㧚 ߎࠇࠄࠢࠬ࠲ࠗࠝࡦࡆࡓࠍ↪ߚ SIMS ߩ ․ᓽߪᓥ᧪ߩනේሶࠗࠝࡦࡆࡓ SIMS ߦᲧߴ⹜ᢱ 㕙߆ࠄߩੑᰴࠗࠝࡦ⊒↢ല₸߇㜞ߊ㧘㜞ᗵᐲߢߩ ᷹ቯࠍน⢻ߣߒߡࠆὐߢࠆ㧚ߐࠄߦ㧘ߎࠇࠄߩ ࠢࠬ࠲ࠗࠝࡦࠍ߁ߣ㧘ේሶࠗࠝࡦߦᲧߴߡ㧘 ⣕㔌ല₸߇㕖✢ᒻ⊛ߦჇᄢߒ㧘ౝㇱߩ៊்߽ᄢߦ シᷫߐࠇࠆߎߣ߇␜ߐࠇߡࠆ㧚ߒ߆ߒ㧘⹜ᢱ㕙 ᢙಽሶጀߩߺࠍ⣕㔌ߐߖࠆߎߣߪ࿎㔍ߢ㧘߹ߚ㧘ⴣ ᠄ߐࠇࠆ⹜ᢱጀߩෘߐߪ㧘ᢙ 10 ේሶಽሶጀߦ߮㧘 㕙ਅጀ⚵❱ߩ⎕უ߇ㅴߎߣ߇⸘▚ࠪࡒࡘ ࡚ࠪࡦߦࠃߞߡࠄ߆ߦߐࠇߡࠆ㧚 ᦨㄭ㧘Hiraoka ࠄߪࠛࠢ࠻ࡠࠬࡊߢ⊒↢ߐߖ ߚᏪ㔚ᶧṢ㧔ࠢࠬ࠲ࠗࠝࡦ㧕ࠍ↪ߔࠆ SIMS ࠍ 㐿 ⊒ ߒ 㧔 Electrospray Droplet Impact SIMS, EDI-SIMS㧕㧘Ꮺ㔚ᶧṢⴣ᠄ߢ⹜ᢱ߇ోߊ៊்ࠍฃߌ ߕ㧘⣕㔌ߔࠆಽሶጀߩෘߐ߇ᢙಽሶጀߦ㒢ࠄࠇߡ ࠆߎߣࠍ␜ߒ㧘㜞ᗵᐲߢ SIMS ಽᨆ߇ߢ߈ࠆߎߣࠍ ␜ߒߚ[32-35]㧚ߎߩ Hiraoka ࠄ߇㐿⊒ߒߚᣇᴺߪ㧘 ᢙ kV ߩ㜞㔚ࠍශടߒߚ㊄ዻࠠࡖࡇߦ㈶㉄ ᳓ṁᶧࠍㅍᶧߒ㧘᳓ṁᶧࠍ㕒㔚႐ྃ㔵ߐߖࠆߎߣߢ㧘 Ꮺ㔚ߒߚᓸ⚦ᶧṢࠬࡊࠍ⊒↢ߐߖ㧔ࠛࠢ࠻ࡠ ࠬࡊߣ߁㧕 㧘↢ᚑߒߚᏪ㔚ᶧṢࠍᄢ᳇߆ࠄ⌀ ⓨߦࠨࡦࡊࡦࠣߒ㧘ࠗࠝࡦࠟࠗ࠼ߢ⾰㊂ㆬߒߚ ߩߜ㧘10 kV ߢടㅦߒߡ㧘࿕㕙ࠍࠬࡄ࠶࠲ࠛ࠶ ࠴ࡦࠣߔࠆ߽ߩߢࠆ㧚ߐࠄߦ㧘ߎߩᣇᴺߪ Mahoney ࠄߩᚻᴺߣ⇣ߥࠅ᳇ൻߒ߿ߔᶧࠍ↪ࠆߚ㧘 㔚ᭂߩᳪᨴࠍ↢ߓߥߊᏂᄢࠢࠬ࠲ࠗࠝࡦࠍ⊒↢ ߢ߈ࠆὐ߽ࠆ㧚 ᧄႎ๔ߢߪߎߩᏪ㔚ᶧṢⴣ᠄ᴺࠍ↪ߚ TOF-SIMS㧔ᧄⓂߢߪ EDI-SIMS ߣ⸥ㅀ㧕ߦߟߡ⸃ ⺑ߒ㧘 ࠢࠬ࠲ࠗࠝࡦࠍ↪ߚ TOF-SIMS ߩ⁁㧘 ᧪ዷᦸߦߟߡ⸥ㅀߔࠆ㧚 2. Ꮺ㔚ᶧṢⴣ᠄/SIMS (EDI-SIMS)ⵝ⟎ Fig. 2 ߦᏪ㔚ᶧṢⴣ᠄/SIMS(EDI-SIMS)ⵝ⟎ߩ ᔨ࿑ࠍ␜ߔ[32,33]㧚ᢙ kV ߩ㜞㔚ࠍශടߒߚ㊄ዻ ࠠࡖࡇߦ㈶㉄᳓ṁᶧࠍㅍᶧߒ㧘᳓ṁᶧࠍ㕒㔚 ႐ྃ㔵ߐߖࠆߎߣߢ㧘Ꮺ㔚ߒߚᓸ⚦ᶧṢࠬࡊࠍ ⊒↢ߐߖ㧔ࠛࠢ࠻ࡠࠬࡊߣ߁㧕 㧘↢ᚑߒߚᏪ 㔚ᶧṢࠍᄢ᳇߆ࠄ⌀ⓨߦࠨࡦࡊࡦࠣߔࠆ㧚ࠝ ࡈࠖࠬ㧔400 PmI㧕߆ࠄ⌀ⓨਛߦዉ߆ࠇߚᏪ㔚ᶧṢ ߪ྾㊀ᭂࠗࠝࡦࠟࠗ࠼ߦㆇ߫ࠇ㧘ߎߩࠗࠝࡦࠟࠗ࠼ ਛᔃㇱߦ᧤ߐࠇࠆ㧚ࠗࠝࡦࠟࠗ࠼ㇱߪ࠲ࡏಽሶ ࡐࡦࡊ㧔ឃ᳇ㅦᐲ 230l /s㧕ߢᏅേឃ᳇ߐࠇࠆ㧚m/z ୯ߩಽᏓ߆ࠄߥࠆᏪ㔚☸ሶߪࠗࠝࡦࠟࠗ࠼ߢ⾰㊂ㆬ ߒߚߩߜ㧔m/z ߇ 10,000~50,000 ߩ▸࿐ߩᏪ㔚☸ሶ㧕 㧘 10 kV ߢടㅦߒߡ㧘࿕㕙ࠍࠬࡄ࠶࠲ࠛ࠶࠴ࡦࠣ ߔࠆ㧚⹜ᢱㇱߩࠅߩ⌀ⓨᐲߪ~10-4 Pa ߢ㧘ࠛ࠶࠴ ࡦࠣᤨߩ⌀ⓨᐲߪ㨪10-2 Pa ߢࠆ㧚Ꮺ㔚ߒߚ᳓Ṣߪ㧘 ⌀ⓨߦዉߐࠇࠆߣ㧘᳇ൻᾲߢᕆ಄ߐࠇ㧘⚂ 20%ߩ ⾰㊂ࠍᄬߞߚᶧṢߣߥࠅ㧘ߘߩᓟ㧘߶ߣࠎߤ⾰㊂ࠍ ᷫߓࠆߎߣߥߊ㧘⌀ⓨਛࠍャㅍߐࠇ⹜ᢱ㕙ࠍⴣ᠄ ߔࠆߩߢࠆ㧚ⴣ⓭ᓟ㕙߆ࠄ⊒↢ߔࠆੑᰴࠗࠝࡦ ࠍ╙ੑߩࠗࠝࡦࠟࠗ࠼ߢ᧤ߒߚᓟ㧘⋥ဳ㘧ⴕᤨ Fig. 2 Schematic diagram of the electrospray droplet impact (EDI) secondary ion mass spectrometer [32]. 216 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 㑆⾰㊂ಽᨆ⸘ߢಽ㔌⸘᷹ߢ߈ࠆࠃ߁ߦ㈩⟎ߒߡ ࠆ㧚හߜ㧘Fig. 2 ߦ␜ߔࠃ߁ߦ EDI-SIMS ⵝ⟎ߪᏂ ᄢࠢࠬ࠲ࠗࠝࡦḮࠍⵝ⌕ߒߚ᭴ᚑߣߥߞߡࠆ㧚 ᰴߦ㧘ߎߩ EDI-SIMS ߢߩᏪ㔚ᶧṢ㧔ࠢࠬ࠲ ࠗࠝࡦ㧕ߩ⾰㊂㧘ଔᢙߪߤߩߢࠆ߆㧘ߐࠄߦ⹜ ᢱ㕙ߣߩⴣ⓭⽎ߪߤ߁ߥߩ߆㧘ߦߟߡ⸥ㅀߔ ࠆ㧚 ߪߓߦᏪ㔚ᶧṢ㧔ࠢࠬ࠲ࠗࠝࡦ㧕ߩ⾰㊂߅ ࠃ߮ଔᢙߢࠆ߇㧘ࠛࠢ࠻ࡠࠬࡊߢ↢ᚑߔࠆ Ꮺ㔚ᶧṢߪ㧘ᶧṢߩ㕙ᒛജߣᶧṢߦ߹ࠇࠆㆊ ࠗࠝࡦห჻ߩ⊒ജ߇ߟࠅวߞߚ⁁ᘒ㧘හߜࠢࡠ ࡦᢺജߦࠃࠆᶧṢߩಽⵚᭂ㒢ߦㄭߩߢ㧘Rayleigh ߩᶧṢಽⵚᭂ㒢ߩ㑐ଥᑼ(1)ߢ␜ߔߎߣ߇ߢ߈ࠆ㧚 Z 8S e J H 0 R 3 (1) ߎߎߢ㧘Z ߪᏪ㔚ᶧṢߩଔᢙ㧘R ߪᶧṢඨᓘ㧘Jߪ᳓ ߩ㕙ᒛജ㧔7210-3 Jm-2㧕㧘Hߪ⺃㔚₸㧔8.9u10-12 C2J-1m-1㧕㧘e ߪ㔚᳇⚛㊂㧔1.610-19 C㧕ߢࠆ㧚 (1)ᑼࠃࠅ⾰㊂ߪᢙ 100 ਁ߆ࠄ 1000 ਁ(u)㧘㔚⩄㊂ ߪ 70 ߆ࠄ 300 ଔߣ⸘▚ߢ߈ࠆ㧚100 ߩࡊࡠ࠻ࡦࠍ ᶧṢߩ႐ว㧘[(H2O)90000㧗100H]100+ߢߔߎߣ߇ ߢ߈㧘100 ଔߦᏪ㔚ߒߡ㧘ߎߩᶧṢࠍ 10 kV ߦടㅦ ߔࠆߣ㧘ᓧࠄࠇࠆᶧṢߩㆇേࠛࡀ࡞ࠡߪ 100 ਁ eV ߣᄢ߈ߥ୯߇␜ߐࠇࠆ㧚ߎߩᤨߩࠢࠬ࠲ࠗࠝࡦ ߩㅦᐲߪ~12 km/s ߢ㖸ㅦ㧔~10 km/s㧕ࠍ߃ߡࠆ㧚 ߹ߚ㧘ߎߩᶧṢߩ⋥ᓘߪ~10 nm ߢࠆߎߣ߇᳞ࠄ ࠇࠆ[32]㧚 ߎߩᏂᄢࠢࠬ࠲ࠗࠝࡦߣ᧚ᢱ㕙ߣߩⴣ⓭ ⽎ߦߟߡ⸥ㅀߔࠆ㧚ߎߩⴣ᠄ᤨߩㅦᐲߪ㖸ㅦࠍ ߃ࠆ߽ߩߢࠆߚ㧘ᶧṢ߇᧚ᢱ㕙ࠍⴣ᠄ߔࠆ㓙㧘 ⴣ⓭⇇㕙ߦⴣ᠄ᵄ߇⊒↢ߔࠆ㧚ߎߩ⚿ᨐ㧘⇇㕙ߦ↢ ߓࠆ⥃⇇⁁ᘒ߇ᒻᚑߐࠇ㧘ᓥ᧪ታߐࠇߥ߆ߞߚ ᢙಽሶጀෘߐߦ㒢ቯߐࠇߚ㜞㧘㜞᷷ൻቇ⽎ 㧔ࠗࠝࡦൻߣ⣕㔌㧕߇߈ࠆ㧚Fig. 3 ߦߎߩⴣ⓭ ⽎ࠍߔ࿑ࠍ␜ߔ㧚࿑ߦ␜ߔࠃ߁ߦࠢࠬ࠲☸ሶ ߦ߹ࠇࠆ⚂ 10 ਁߩ᳓ಽሶߪหㅦᐲ㧘หᣇะߢ᧚ ᢱ㕙ߦⴣ⓭ߔࠆ㧚ⴣ⓭ߩ⍍㑆㧘⇇㕙ߢࠦࡅࡦ ࠻ߥⴣ⓭߇↢ߓࠆ㧚ߎߩᏪ㔚ᶧṢⴣ᠄ߢ⹜ᢱಽሶߩ 㔚ሶ⁁ᘒ߇ᄢ߈ߥ៨േࠍฃߌ㧘㔚ሶബ⁁ᘒߣߥࠆ㧚 ߎߩബ⁁ᘒߩ✭ㆊ⒟ߢࠗࠝࡦൻ㧘ಽሶߩಽ⸃ߥ ߤߩ᭽ࠆߔ↢⊒߇⽎ߥޘ㧚ੑᰴࠗࠝࡦߩ⊒↢߽ߎ ߩ✭ㆊ⒟ߩ৻⽎ߢࠆߣ⠨߃ࠄࠇࠆ[36]㧚 3. ᷹ቯ⚿ᨐ 3.1. 㕙ᷡᵺലᨐ㧔ಽሶࡌ࡞ࠛ࠶࠴ࡦࠣ㧕 Ꮺ㔚ᶧṢ(ࠢࠬ࠲ࠗࠝࡦ)ⴣ᠄ᴺߩ․ᓽߩ৻ߟ ߪᓥ᧪ߩනේሶࠗࠝࡦߩࠬࡄ࠶࠲ࠛ࠶࠴ࡦࠣᴺ߿ ߹ߢႎ๔ߐࠇߡࠆࠢࠬ࠲ࠗࠝࡦߩࠬࡄ࠶࠲ ࠛ࠶࠴ࡦࠣᴺߦᲧߴߡ㧘ᭂߡ࠰ࡈ࠻ߦ㧘ߒ߆߽㧘 ࠊߕ߆ᢙಽሶጀߩෘߐߢ࿕⹜ᢱ㕙ಽሶ߇ࠬࡄ࠶ ࠲ࠛ࠶࠴ࡦࠣߢ߈ࠆὐߢࠆ㧚ߒ߆߽㧘⣕㔌ߔࠆ⹜ ᢱߩਅጀߩಽሶߪ߶ߣࠎߤ៊்ࠍฃߌߥ㧚Fig. 4 ߪ㧘1 nmol㧔⹜ᢱߩ⤑ෘ㧦⚂ 100 ಽሶጀ㧕ߩ FK-506 㧔⮎‛ߩ৻⒳㧕ࠍ㊄ዻၮ᧼ߦႣᏓੇ῎ߒ㧘ߎࠇࠍ EDI-SIMS ߢಽᨆߒߚ⚿ᨐߢࠆ[33]㧚Fig. 4(a)ߪ㧘 Ꮺ㔚ᶧṢⴣ᠄ߢ↢ᚑߒߚࠗࠝࡦࠍ⾰㊂ಽᨆߒߚ߽ߩ ߢࠆ㧚FK-506 ಽሶߩಽሶ㊂㑐ㅪࠗࠝࡦ߇᷹ⷰߐࠇ ߡࠆ㧚 ߎߩࠗࠝࡦߩᒝᐲߪ㧘1 ᤨ㑆એߦࠊߚߞߡ㧘ᄌ ൻ߇᷹ⷰߐࠇߡߥ㧚ߎࠇߪ㧘Ꮺ㔚ᶧṢ㧔ࠢࠬ ࠲ࠗࠝࡦ㧕ߩࠛ࠶࠴ࡦࠣߢߪ⹜ᢱ߇ోߊ៊்ࠍฃ ߌߥߎߣ㧔⎕უߐࠇߡ↢ߓߚ㊀ว‛ߩ⫾Ⓧ߇⊝ή㧕 㧘 ߅ࠃ߮⣕㔌ߔࠆಽሶጀߩෘߐ߇ᢙಽሶጀߦ㒢ࠄࠇߡ ࠆ߆ࠄߢࠆ㧚Fig. 4(b)ߪ㧘FAB (fast atom bombardment) ㌂ࠍ↪ߡ㧘5 keV ߩ Xe ේሶߢ⹜ᢱࠍⴣ ᠄ߒߚ⋥ᓟߩࡑࠬࠬࡍࠢ࠻࡞ߢࠆ㧚FK506 ߩሽ ࠍ␜ߔಽሶࠗࠝࡦߪ᷹ⷰߐࠇߥ㧚Fig. 4(c)ߪ㧘FAB ⴣ᠄㐿ᆎ 10 ⑽ᓟߩࡑࠬࠬࡍࠢ࠻࡞ߢࠆ㧚㕖Ᏹߦᒝ ᰴ↢ᚑࠗࠝࡦ㧔ࠤࡒࠞ࡞ࡁࠗ࠭㧕߇ࠇ㧘߹ߚ FK506 ߩੑᰴࠗࠝࡦାภ߇ᒙߊ᷹ⷰߐࠇࠆ㧚Fig. 4(d) ߪ㧘FAB ᷹ቯ㐿ᆎ 20 ⑽ᓟߩ SIMS ࠬࡍࠢ࠻࡞ߢࠆ㧚 FK506 ߩ㕙߇⎕უߐࠇ㧘Xe ේሶⴣ᠄ߦࠃࠅ↢ᚑߒ ߚ㊀ว‛ߢ㕙߇ⷒࠊࠇࠆߚ㧘FK-506 ߩੑᰴࠗࠝ ࡦାภ߇ᶖ߃㧘ࠤࡒࠞ࡞ࡁࠗ࠭ᒝᐲ߽ᷫዋߒߡࠆ 㧔㊀ว‛߇⣕㔌ߒߦߊߚ㧕㧚Fig. 4(e)ߪ㧘FAB ᷹ ቯࠍ⚳ੌߒ㧘ౣ߮Ꮺ㔚ᶧṢࠛ࠶࠴ࡦࠣࠍ㐿ᆎߒߚߣ ߈ߩ SIMS ࠬࡍࠢ࠻࡞ߢࠆ㧚Fig. 4(a)ߣหߓ SIMS ࠬࡍࠢ࠻࡞߇ౣ↢ߐࠇߡࠆ㧚ߎࠇߪ㧘⹜ᢱ㕙ࠍ Droplet 12km/s Coherent disintegration Shockwave Desorption/ioni formation zation Fig.3 Surface collision conception diagram of electrospray droplet [36]. 217 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ⷒߞߡߚ㊀ว‛߇߉ขࠄࠇߡ㧘ਅጀߩᣂߒ⹜ ᢱ㕙߇ౣ↢ߒߚߚߢࠆ㧚ߎߩ⚿ᨐ㧘Ꮺ㔚ᶧṢ㧔ࠢ ࠬ࠲ࠗࠝࡦ㧕ࠛ࠶࠴ࡦࠣᴺߪ㧘ಽሶࡌ࡞ߢ㧘 ᯏ‛⹜ᢱߩ㕙ࠍࠛ࠶࠴ࡦࠣߔࠆ㧔surface cleaning effect㧕ߎߣ߇ಽ߆ࠆ㧚 3.2. Layer by Layer ࠛ࠶࠴ࡦࠣߦࠃࠆᷓߐᣇะಽᨆ Fig. 5 ߦࠣࡒࠪࠫࡦߣࡉࠫࠠ࠾ࡦࠍ 10 ಽሶ ጀߕߟⓍጀߐߖߡ㧘ߎࠇࠍᏪ㔚ᶧṢ㧔ࠢࠬ࠲ࠗ ࠝࡦ㧕ߢࠛ࠶࠴ࡦࠣߒߚ႐วߩ㧘ਔൻว‛ߦ↱᧪ߔ ࠆಽሶ㊂㑐ㅪࠗࠝࡦ㧔ࡊࡠ࠻ࡦൻߐࠇߚಽሶ㧘MH+㧕 ߩࠗࠝࡦᒝᐲߩ᷹ቯᤨ㑆ଐሽᕈ㧔Depth profile㧕ࠍ␜ ߔ[36]㧚↪ߚⓍጀ⹜ᢱߪ㧘ႣᏓੇ῎ߐߖߚࡉࠫ ࠠ࠾ࡦߩߦࠣࡒࠪࠫࡦṁᶧࠍႣᏓߒ㧘⋥ߜߦ⌀ ⓨਛߢᕆㅦੇ῎ߐߖߚ߽ߩߢࠆ㧚㕙ᵴᕈ㧔⇹᳓ ᕈ㧕ߢࠆࠣࡒࠪࠫࡦ߇ጀߦ㧘㕙ᵴᕈߩࠃࠅ ૐࡉࠫࠠ࠾ࡦ߇ਅጀߣߥࠆ⤑߇ᒻᚑߐࠇࠆ㧚Fig. 5 ߦ߅ߡ㧘ࠛ࠶࠴ࡦࠣᤨ㑆ߩჇടߦ㧘ጀߩ ࠣࡒࠪࠫࡦ↱᧪ߩੑᰴࠗࠝࡦᒝᐲ߇ᷫዋߒ㧘৻ᣇ㧘 ਅጀߩࡉࠫࠠ࠾ࡦ↱᧪ߩੑᰴࠗࠝࡦᒝᐲ߇Ⴧടߒ ߡࠆ㧚ߎߩᤨߩࠛ࠶࠴ࡦࠣ࠻ߪ 2 ಽሶ/min.ߣ Ⓧ߽ࠄࠇࠆ㧚ਔ⹜ᢱࠍቢోߦ 2 ጀߦಽ㔌ߐߖߚⓍ ጀ⹜ᢱᚑ߇࿎㔍ߢࠆߚ㧘Depth profile ߩಽ⸃ ⢻ߪᖡ߇㧘ߒ߆ߒ㧘ߎߩ⚿ᨐߪᏪ㔚ᶧṢ㧔ࠢࠬ ࠲ࠗࠝࡦ㧕ࠛ࠶࠴ࡦࠣᴺߢߪ㧘ਅጀಽሶߦࠛ࠶࠴ ࡦࠣࠃࠆ៊்߇ήߊ㧘ᯏ‛⹜ᢱ㕙߇ᢙಽሶጀߩ ෘߐߢࠛ࠶࠴ࡦࠣߐࠇߡࠆߎߣࠍ⍎ߦ␜ߒߡ ࠆ㧚 3.3. 㜞ᗵᐲ᷹ቯ ⹜ᢱߣߒߡ 100 pmol ߩࡈࡦࠍᏪ㔚ᶧṢࠢ ࠬ࠲ࠗࠝࡦࠛ࠶࠴ࡦࠣߒߚᤨߩ SIMS ࠬࡍࠢ࠻ ࡞ࠍ Fig. 6 ߦ␜ߔ[36]㧚ਛᕈಽሶߢࠆࡈࡦߩ ᱜ⽶ࠗࠝࡦ C60r߇หߓᒝᐲߢ᷹ⷰߐࠇߡࠆߎߣ ߇␜ߐࠇߡࠆ㧚ߎߩ⚿ᨐߪ㧘Ꮺ㔚ᶧṢ㧔ࠢࠬ࠲ ࠗࠝࡦ㧕ⴣ᠄ߦࠃࠅ㧘ⴣ⓭⇇㕙ߢ㔚ሶബࠗࠝࡦ ൻ⽎߇ߎߞߡࠆߎߣࠍ␜ߔ㧚▚ߦࠃࠇ߫㧘 ⴣ⓭⇇㕙ߦ߅ߡ㧘ᢙਁ᳇㧘ᢙ 1000oC ߩⴣ᠄ᵄ߇ ⊒↢ߒ㧘ߎߩ⚿ᨐ㧘⇇㕙ߦ↢ߓࠆ⥃⇇⁁ᘒ߇ᒻᚑ ߐࠇ㧘ᓥ᧪ታߐࠇߥ߆ߞߚᢙಽሶጀෘߐߦ㒢ቯߐ ࠇߚ㜞㧘㜞᷷ൻቇ⽎㧔ࠗࠝࡦൻߣ⣕㔌㧕߇ ߈ࠆ㧚⣕㔌ߔࠆಽሶጀ߇ࠊߕ߆ᢙಽሶጀߦ㒢ࠄࠇ Fig. 4. EDI and FAB TOF-SIMS spectra from 1 nmol of dry FK506. (a):EDI-SIMS spectrum, (b):FAB-SIMS spectrum, (c):FAB-SIMS spectrum at 10 s after FAB gun ignition, (d):FAB-SIMS spectrum at 20 s after FAB gun ignition, (e):EDI-SIMS spectrum after the sample was irradiated by FAB gun for 20 s [33],[36]. Relative intensity 100 䂹[Gramicidin S + H]+ 䃂[Bradykinin + H]+ 80 60 40 20 0 0 2 4 6 Time (min) Fig. 5. Depth profile of EDI-SIMS [36]. 218 8 10 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ࠆߩߪ㧘ⴣ᠄ᵄ⊒↢ߩ⋥ᓟߦߎࠆ᳓ߩ᳇ൻߦࠃࠆ ᕆㅦ಄ළ⽎ߦ࿃ߔࠆ㧚ߎߩߚ㧘ᾲಽ⸃ߒᤃ ↢⹜ᢱߦ߅ߡ߽㧘ࡈࠣࡔࡦ࠹࡚ࠪࡦߥߒߢ㧘 ಽሶ㊂㑐ㅪੑᰴࠗࠝࡦ߇᷹ⷰߐࠇࠆߩߢࠆ㧚 Fig. 7 ߦᓥ᧪ᴺߩ TOF-SIMS㧘MALDI (matrix assisted laser desorption ionization)-TOF-MS [37,38]ߥߤ ߢߪ᷹ቯ࿎㔍ߣߐࠇߡࠆ㗻ᢱ㧔☳ᧃ㧕ࠍ EDI-SIMS ߢ᷹ቯߒߚ⚿ᨐࠍ␜ߔ[32]㧚⹜ᢱߩ㗻ᢱߩ☳ᧃߪ㊄ ዻၮ᧼ߦᡂࠅߟߌߚߩߺߢ㧘⹜ᢱਛߦࠗࠝࡦൻࠍ ᡰᜬߔࠆ‛⾰ߪߒߡߥ㧚Fig. 7 ߦ␜ߔࠃ߁ ߦᱜ⽶ࠗࠝࡦࡕ࠼ߢ㧘ᒝಽሶ㊂㑐ㅪࠗࠝࡦ߇ 㜞ᗵᐲߢᬌߐࠇߡࠆ㧚ߎߩࠃ߁ߦ㧘ṁᇦߦ㔍ṁ ᕈߩ⛘✼⹜ᢱߦኻߒߡ߽㧘EDI-SIMS ߢߪ㧘ࡑ࠻ ࠶ࠢࠬߥߒߢᭂߡኈᤃߦ㧘ߒ߆߽⍴ᤨ㑆ߢಽሶ ㊂㑐ㅪࠗࠝࡦ߇᷹ⷰߐࠇࠆ㧚࿑ߩ⹜ᢱߩ SIMS ࠬࡍ ࠢ࠻࡞᷹ቯߪᢙಽ㧔2~3 ಽ⒟ᐲ㧕ߢࠆ㧚ߎߩ⚿ᨐ ࠃࠅ EDI-SIMS ߪࡑ࠻࠶ࠢࠬήߒߦ㜞ᗵᐲߢ᷹ቯ ߢ߈ࠆߎߣ߇␜ߐࠇࠆ㧚 3.4. ⹜ᢱ៊்シᷫ Fig. 8 ߦ 10 fmol㧔1000 ಽߩ 1 ಽሶጀ⋧ᒰ㧕ߩࠣ ࡒࠪࠫࡦ⹜ᢱࠍ EDI-SIMS ߢ᷹ቯߒߚ⚿ᨐࠍ␜ߔ [32,36]㧚࿑ߦ␜ߔࠃ߁ߦ㧘ಽሶ㊂㑐ㅪࠗࠝࡦ[M+H]+ ߇ S/N=30 ߢ᷹ⷰߐࠇ㧘30 ಽએߦࠊߚߞߡ[M+H]+ ࠪࠣ࠽࡞߇᷹ⷰߐࠇࠆ㧚ߎߩࠃ߁ߥᏪ㔚ᶧṢ㧔ࠢ ࠬ࠲ࠗࠝࡦ㧕ⴣ᠄ੑᰴࠗࠝࡦ⾰㊂ಽᨆᴺߩ㜞ᗵ ᐲᕈ⢻ߪ㧘ⴣ⓭⇇㕙ߦ߅ߌࠆ⹜ᢱࠗࠝࡦߩ⌀ⓨ߳ߩ ⣕㔌ല₸߇ᭂߡ㜞ߎߣߦ࿃ߔࠆ㧚 Fig. 9 ߦࠣࡒࠪࡦ S ࠍ㊄ዻၮ᧼ߦ 1 ML㧔ಽሶ ጀ㧕㧘10 ML㧘100 ML ဋ৻ߦႣᏓߒ㧘Ꮺ㔚ᶧṢ㧔ࠢ ࠬ࠲ࠗࠝࡦ㧕ⴣ᠄ߢࠣࡒࠪࡦ S ߩಽሶࠗࠝࡦ ᒝᐲߩᾖᤨ㑆ଐሽࠍ␜ߔ[32,33,36]㧚Ꮺ㔚ᶧṢࠢ ࠬ࠲ࠗࠝࡦᾖߢ⹜ᢱ㕙ߦ៊்ࠍฃߌࠆߣ㧘ಽ ⸃↢ᚑ‛߇⹜ᢱ㕙ߦၸⓍߒ㧘ߘߩ⚿ᨐಽሶࠗࠝࡦ ାภᒝᐲ߇ᷫዋߔࠆ㧚ߒ߆ߒ Fig. 9 ߦ␜ߔࠃ߁ߦ 10 ML㧘100 ML ߩ⤑ෘ⹜ᢱߢߪ 5 ಽ㑆ࠛ࠶࠴ࡦࠣߢ߽ ାภᒝᐲ߇ᷫዋߒߡߥ⚿ᨐࠍ␜ߒߡࠆ㧚ߎࠇ ߪᏪ㔚ᶧṢࠢࠬ࠲ࠗࠝࡦᾖߦࠃࠅ⹜ᢱ㕙߇ ៊்ࠍฃߌߡߥ⚿ᨐߢࠆ㧚100 ML ߩାภᒝᐲ ߇ 10 ML ߩ⚿ᨐࠃࠅૐߩߪ৻࿁ߩࠛ࠶࠴ࡦࠣߢ⣕ 㔌ߔࠆಽሶጀߩෘߐ߇ 10 ML ࠃࠅ⭯ߎߣࠍ␜ߒߡ ࠆ㧚1 ML ߩ႐ว㧘⹜ᢱߩඨಽ߇ࠛ࠶࠴ࡦࠣߦࠃࠅ 㒰ߐࠇߚߚ㧘ᒝᐲ߇ᷫዋߒߡࠆ㧚ߎࠇࠄߩ⚿ ᨐࠃࠅᏪ㔚ᶧṢࠢࠬ࠲ࠗࠝࡦߢߩࠛ࠶࠴ࡦࠣᴺ Fig. 8. EDI-SIMS spectrum of 10 fmol gramicidin [36]. Fig. 6. EDI-SIMS spectra of C60 sample [36]. Counts Molecular-related ion intensity vs time 350000 300000 250000 200000 150000 100000 50000 0 100pmol (~10ML) 1nmol (~100ML) 10pmol (~1ML) 0 Fig. 7. EDI-SIMS of pigment [32]. 1 2 3 Time (min) 4 5 Fig. 9 Irradiation time dependence of molecular-related ion intensity [32],[36]. 219 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ߪ⹜ᢱᢙಽሶጀߩෘߐߦኻߒ៊்߇↢ߓߥߎߣ߇ ಽ߆ࠆ㧚 4㧚߹ߣ Ꮺ㔚ᶧṢ㧔ࠢࠬ࠲ࠗࠝࡦ㧕ࠛ࠶࠴ࡦࠣᴺࠍ↪ ߚ EDI-SIMS ߩⷐ߅ࠃ᷹߮ቯࠬࡍࠢ࠻࡞ࠍ߽ߣ ߦߘߩ․ᓽࠍ⸥ㅀߒߚ㧚ߎࠇࠄࠍ߹ߣࠆߣએਅߩ ㅢࠅߦߥࠆ㧚 ԘEDI ᴺߪࠗࠝࡦടㅦ♽㔚ᭂ╬ࠍ৻ಾᳪᨴߒߥᏂ ᄢࠢࠬ࠲ࠗࠝࡦ⊒↢ᴺߢࠆ㧔⌀ⓨਛߢቢో ᳇ൻߒ㧘ࡔࡕലᨐ߇⊒↢ߒߥ㧕㧚 ԙᯏ‛⹜ᢱߩ㕙ㄭறᢙಽሶጀࠍਅጀಽሶߦ៊் ࠍਈ߃ߕߦㆬᛯ⊛ߦ⣕㔌ߢ߈ࠆ㧚 Ԛⴣ᠄⇇㕙ߦ߅ߡ⊒↢ߔࠆⴣ᠄ᵄߦࠃߞߡ࿕ 㕙ಽሶ߇ࠗࠝࡦൻߐࠇࠆ㧚 ԛ⹜ᢱ㕙߆ࠄߐࠇࠆੑᰴࠗࠝࡦߩାภᒝᐲߪ ቯߢ㧘ࡑ࠻࠶ࠢࠬήߒߢ߽㜞ᗵᐲߢ᷹ቯߐ ࠇࠆ㧚 Ԝ㕙ᢙಽሶጀߩߺ߇⣕㔌ߔࠆߩߢ᷹ⷰߐࠇࠆࠗࠝ ࡦ߇ሽಽሶߦࠃߞߡᓇ㗀ࠍฃߌߦߊ㧚 ԝ৻ᰴࡆࡓ☸ሶߦࠃࠆ⹜ᢱ㕙߳ߩੑᰴᳪᨴ߇ߥ 㧚 ߎߩࠃ߁ߦ EDI-SIMS ߪ߹ߢႎ๔ߐࠇߡࠆࠢ ࠬ࠲ࠗࠝࡦࠍⵝ⌕ߒߚ TOF-SIMS ߦᲧߴᄙߊߩ ⋉ߥ․ᓽࠍߒߡ߅ࠅ㧘ᓟߩᏂᄢࠢࠬ࠲ࠗ ࠝࡦࠍ↪ࠆ TOF-SIMS ⵝ⟎㧘ಽᨆᛛⴚߩ⊒ዷߦ⽸ ₂ߢ߈ࠆࠗࠝࡦḮߦᚑࠅᓧࠆߣ⸒߃ࠆ㧚 ৻ᣇ㧘৻⥸ߦࠢࠬ࠲ࠗࠝࡦߩᰳὐߣߒߡߘߩ ࠨࠗ࠭߇නේሶࠗࠝࡦ㧔Cs+ߥߤ㧕ߦᲧߴ⪺ߒߊᄢ߈ ߥὐߢࠆ㧚ߎߩߚੑᰴࠗࠝࡦߩ᷹ቯ߿ᓸዊㇱ ᷹ቯߢߪනේሶࠗࠝࡦࠍ↪ߚ TOF-SIMS ߦߪഠߞ ߡࠆߎߣ߇ᜰ៰ߐࠇߡ߈ߡߚ㧚ㄭᐕ Au3+߿ Bi3+ ߥߤߪ Ga+ ߦᢜߔࠆ㕙ಽ⸃⢻߇ᓧࠄࠇࠆࠃ߁ߦ ߥߞߡࠆ㧚ߒ߆ߒ㧘Ꮺ㔚ᶧṢߢߪઁߩࠢࠬ࠲ ࠗࠝࡦߦᲧߴࠇ߫㕙ಽ⸃⢻ߪ⪺ߒߊഠߞߡࠆ㧚 ᓟߐࠄߦࠗࠝࡦశቇ♽ᛛⴚߩㅴᱠߢㄭ᧪ಽሶࠗ ࡔ ᷹ࠫ ቯࠍ น ⢻ߣ ߔࠆ Ꮒ ᄢࠢ ࠬ ࠲ ࠗ ࠝࡦ TOF-SIMS ߇⊓႐ߔࠆߎߣࠍᦼᓙߒߚ㧚 5. ෳ⠨ᢥ₂ [1] A. 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Mass Spectrom. 2, 151 (1988). ᩏ⺒ࠦࡔࡦ࠻ ᩏ⺒⠪ 2. ⮮ේᐘ㓶㧔↥ᬺᛛⴚ✚ว⎇ⓥᯏ᭴㧕 ᧄ⸃⺑ߩਥ㗴ߢࠆ̌EDI-SIMS̍ߪ㧘ᣣᧄ⊒ߩ↹ ᦼ⊛ߥ⎇ⓥᚑᨐߢࠅ㧘㕙ಽᨆ╬ߦ߅ߡ㧘ᓟ ߩ⊒ዷ߇㕖Ᏹߦᦼᓙߐࠇࠆ㊀ⷐߥᛛⴚߣ⠨߃߹ߔ㧚 ᧄ⸃⺑ߪ㧘̌EDI-SIMS̍ߩේℂ߿ᦨㄭߩ⎇ⓥᚑᨐ╬ ࠍ߹ߣߚ߽ߩߢ㧘ᧄࠫࡖ࠽࡞㧔JSA㧕ߩ⺒⠪ߦ ߣߞߡ㧘㕖Ᏹߦ⋉ߥ⺰ᢥߣߥࠆ߽ߩߣ⠨߃߹ߔ㧚 㨇ᩏ⺒⠪ 2-1㨉 ޟ1. ߪߓߦ ╙ߩޠ4 ࡄࠣࡈߦ߅ߡ㧘 ᧚ࠍࡦࠝࠗ࠲ࠬࠢ ޟᢱ㕙ߦⴣ᠄ߒߚ㓙 ߩ․ᓽߣߒߡ㧘(1)⹜ᢱ㕙ߦ㧘(2)㧘(3)㧚ޠ ߣ㧘ࠢࠬ࠲ࠗࠝࡦߩ․ᓽࠍߍࠄࠇߡ߹ߔ߇㧘 ᒁ↪ᢥ₂ࠍㅊടߐࠇߚᣇ߇⦟ߣᕁࠊࠇ߹ߔ㧚․ߦ㧘 ੩ㇺᄢቇࠍਛᔃߣߒߡⴕࠊࠇߡࠆ̌ࠟࠬࠢࠬ ࠲ࠗࠝࡦࡆࡓ̍ࠍ↪ߚ⎇ⓥᚑᨐߪ㧘ᤚ㕖㧘ᒁ ↪ߔߴ߈ߛߣᕁ߹ߔ㧚 㨇⪺⠪㨉 ߏᜰ៰ߩㅢࠅߦᒁ↪ᢥ₂ࠍㅊടߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-2㨉 ߹ߚ㧘⸥▎ᚲߢ㧘(ޟ2) ࠬࡄ࠶࠲ࡦࠣ₸߇⪺ ߒߊ㜞㧘හߜ㧘㜞⾰㊂ੑᰴࠗࠝࡦߩ㜞₸ൻߣޠ ࠅ߹ߔ߇㧘̌ࠬࡄ࠶࠲ࡦࠣ₸߇㜞ߎߣ̍ߣ㧘 ̌㜞⾰㊂ߩੑᰴࠗࠝࡦߩ₸߇㜞ߎߣ̍ߪ㧘ᔅߕ ߒ߽⥄ߩ㑐ଥߢߪߥߣᕁ߹ߔߩߢ㧘ᄙዋ㧘ᢥ ┨ࠍୃᱜߒߡ㗂ߚᣇ߇⦟ߣᕁࠊࠇ߹ߔ㧚 㨇⪺⠪㨉 ߏᜰ៰ߩ㗄ࠍ〯߹߃ᢥ┨ࠍ⸓ᱜߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-3㨉 หߓࡄࠣࡈߢ㧘SIMS ߦ߅ߌࠆฦ⒳ࠢࠬ࠲ ࠗࠝࡦࡆࡓߩ⚫ࠍߐࠇߡ߹ߔ߇㧘̌ࠟࠬࠢ ࠬ࠲ࠗࠝࡦࡆࡓ̍ࠍ SIMS ߦ↪ߚ⎇ⓥᚑᨐ߽㧘 ㅊടߒߡᒁ↪ߐࠇߚᣇ߇⦟ߣᕁࠊࠇ߹ߔ㧚 㨇⪺⠪㨉 ᒁ↪ᢥ₂ࠍㅊടߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-4㨉 ޟ1㧚ߪߓߦߩޠᓟࠈ߆ࠄ 3 ⇟⋡ߩࡄࠣࡈߢ㧘 ߒ߆ߒޟ㧘⹜ᢱ㕙ᢙಽሶጀߩߺࠍ⣕㔌ߐߖ ࠆߎߣߪ࿎㔍ߢ㧘߹ߚ㧘ⴣ᠄ߐࠇࠆ⹜ᢱጀߩෘߐߪ㧘 ᢙ 10 ේሶಽሶጀߦ߮㧘㕙ਅጀ⚵❱ߩ⎕უ߇ㅴ ߎߣ߇⸘▚ࠪࡒࡘ࡚ࠪࡦߦࠃߞߡࠄ߆ߦߐ ࠇߡࠆ㧚߇ߔ߹ࠅߣޠ㧘ߎߩ⸘▚ࠪࡒࡘ࡚ࠪ ࡦߦ㑐ߔࠆᒁ↪ᢥ₂ࠍᧄᢥਛߦ⸥ߒߡ㗂ߚᣇ߇ ⦟ࠃ߁ߦᕁࠊࠇ߹ߔ㧚 㨇⪺⠪㨉 ᒁ↪ᢥ₂ࠍㅊടߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-5㨉 ޟ2. Ꮺ㔚ᶧṢⴣ᠄/SIMS (EDI-SIMS) ⵝ⟎ ╙ߩޠ1 221 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 ࡄࠣࡈߦ߅ߡ ޟᏪ㔚ߒߚ᳓Ṣߪ㧘⌀ⓨ ߦዉߐࠇࠆߣ㧘᳇ൻᾲߢᕆ಄ߐࠇ㧘⚂ 20%ߩ⾰㊂ ࠍᄬߞߡ᳖Ṣߣߥࠅ㧘⸥߁ߣޠㅀ߇ࠅ㧘 ᶧṢ߇᳖ߦߥࠆߣ⸥ㅀߐࠇߡ߹ߔ߇㧘⪺⠪╬ߦࠃ ࠆઁߩ⺰ᢥ[ᵻᎹ㧘㧘ᐔጟ, J. Mass. Spectrom. Soc. Jpn. 55, 127 (2007).]ߩ p. 128 ߦߪ㧘᳖̌ߦߪߥࠄߥ ̍ߣ⸥ㅀߐࠇߡ߹ߔ㧚⺒⠪߇ᷙੂߒߡߒ߹߁ߣ ⠨߃ࠄࠇ߹ߔߩߢ㧘ᢥ┨╬ߩୃᱜ߽ߡ㧘ߏᬌ⸛ ߒߡ㗂ߌࠇ߫ᐘߢߔ㧚 㨇⪺⠪㨉 ߏᜰ៰ߩߣ߅ࠅ᳖Ṣߦߪߥࠅ߹ߖࠎ㧚ᧄᢥࠍୃᱜ ߚߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-6㨉 Fig. 2 ࠍ↪ߡታ㛎ⵝ⟎ߩ⺑ࠍߐࠇߡ߹ߔ߇㧘 Ꮕߒᡰ߃ߥߌࠇ߫㧘⌀ⓨࡐࡦࡊߩឃ᳇ㅦᐲ߿㧘ฦㇱ ߦ߅ߌࠆౖ̌ဳ⊛ߥࠟࠬജ̍ߦ㑐ߔࠆᖱႎ߽⸥タ ߒߡ㗂ߌࠇ߫㧘⺒⠪ߦߣߞߡߪ⋉ߛߣᕁࠊࠇ߹ߔ㧚 ߹ߚ㧘ᄢ᳇߆ࠄᏅേឃ᳇ࠍߔࠆࠊߌߢߔߩߢ㧘 ಽᨆ⹜ᢱઃㄭߩࠟࠬᚑಽߪ㧘̌ⓨ᳇㧔N2 ߿ O2㧕̍ߣ ̌᳓̍߇ᄙߣᕁ߁ߩߢߔ߇㧘EDI-SIMS ࠍታᣉਛ ߦ߅ߌࠆ㧘ಽᨆ⹜ᢱઃㄭߦ߅ߌࠆⓨ᳇ߣ᳓ߩ̌ಽ Ყ̍ߪ㧘ߤߩ⒟ᐲߢߒࠂ߁߆㧫㧔̪ ࠺࠲߇ή႐ ว߿㧘Ꮕߒᡰ߃ࠆ႐วߪ㧘⸥ㅀߒߡ㗂߆ߥߊߡ߽⚿ ᭴ߢߔ㧚㧕 㨇⪺⠪㨉 ߏᜰ៰ߩ▎ᚲ㧘ୃᱜ߅ࠃ߮⌀ⓨᐲߥߤ⸥ߒ߹ߒ ߚ㧚 㨇ᩏ⺒⠪ 2-7㨉 (1)ᑼ㧔Rayleigh ࡒ࠶࠻ߩᑼ㧕ࠍ↪ߚ⺑ㇱಽ ߦ㑐ߒߡߢߔ߇㧘ᱷᔨߥ߇ࠄ㧘ℂ⸃ߔࠆߩ߇㔍ߒ ߣᕁࠊࠇ߹ߔ㧚̌EDI-SIMS̍ߦ߅ߡ㧘Ꮺ㔚ᶧṢߩ ࠨࠗ࠭߿ଔᢙߩⓍࠅߪ㧘㕖Ᏹߦ㊀ⷐߥὐߛߣᕁ ߹ߔߩߢ㧘߽߁ዋߒ⺑ࠍㅊടߐࠇߚᣇ߇⦟ࠃ߁ ߦᕁࠊࠇ߹ߔ㧚ߥ߅㧘ߎߩὐߦ㑐ߒߡߪ㧘⪺⠪╬ߦ ࠃࠆઁߩ⺰ᢥ[ᵻᎹ㧘㧘ᐔጟ, J. Mass. Spectrom. Soc. Jpn. 55, 127 (2007).]ߩ p. 129 ߦ߅߈߹ߒߡ㧘㕖Ᏹߦ ⚦ߥ⺑߇ߥߐࠇߡ߹ߔߩߢ㧘ߎߩ⺰ᢥࠍᒁ↪ ᢥ₂ߦㅊടߒߡ㗂ߌࠇ߫㧘⺒⠪ߦ߽⋉ߛߣᕁࠊࠇ ߹ߔ㧚 㨇⪺⠪㨉 ᒁ↪ᢥ₂ࠍട߃߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-8㨉 (1)ᑼߩᓟߦ㧘 ޟ100 ߩࡊࡠ࠻ࡦࠍᶧ Ṣ ߩ ႐ ว 㧘 [(H2O)90000+100H]100+ ߢ ߔ ߎ ߣ ߇ ߢ ߈㧘 ⸥߁ߣޠㅀ߇ࠅ߹ߔ㧚ߎߩൻቇᑼߦ ࠃࠇ߫㧘Ꮺ㔚ᶧṢߪ㧘᳓㧔H2O㧕ߣࡊࡠ࠻ࡦ㧔H+㧕 ߩߺࠍߎߣߦߥࠅ߹ߔ㧚৻ᣇ㧘̌EDI-SIMS̍ߢ ߪ㧘㈶㉄ࠍ᳓ߦṁ߆ߒߚṁᶧࠍ↪ߡ߹ߔ߇㧘Ꮺ 㔚ᶧṢਛߦ߅ߌࠆ̌㈶㉄ᚑಽ̍ߪήⷞߢ߈ࠆߩߢߒࠂ ߁߆㧫 ߃߫㧘̌EDI-SIMS̍ߢߪ㧘⾰㊂ಽᨆಽ㊁ߢ↪ ࠄࠇࠆ ESI-MS ߣᲧߴߡ㧘ᩴ㆑ߦ㜞Ớᐲ㧔~1 M = 1 mol/Litter㧕ߢ㈶㉄ࠍ᳓ߦṁ⸃ߐߖߡ߹ߔ㧚᳓ 1 ࠶࠻࡞ߦ㈶㉄ࠍ 1 mol ࠍṁ߆ߒߚ႐ว㧔=1 M㧕ߦ ߪ㧘㈶㉄ߩỚᐲߪᢙࡄࡦ࠻ߦߥࠆ߽ߩߣ⠨߃ࠄ ࠇ߹ߔ㧚߽ߜࠈࠎ㧘ࠛࠢ࠻ࡠࠬࡊߦࠃߞߡ㓁 ࠗࠝࡦࠍᄙߊᏪ㔚ᶧṢࠍ↢ᚑߔࠆࠊߌߢߔ߇㧘 ߎࠇߛߌỚᐲ߇㜞᧦ઙߢߔߣ㧘↢ᚑߐࠇߚᏪ㔚ᶧ Ṣਛߦ߽㧘㈶㉄߇ߐࠇࠆߣᕁࠊࠇࠆߩߢߔ߇㧘 㑆㆑ߢߒࠂ߁߆㧫 㨇⪺⠪㨉 ߏᜰ៰ߩㅢࠅߢߔ㧚 㨇ᩏ⺒⠪ 2-9㨉 ޟ2. Ꮺ㔚ᶧṢⴣ᠄/SIMS (EDI-SIMS) ⵝ⟎ᦨߩޠ ᓟߩࡄࠣࡈߦ߅ߡ㧘⚿ߩߎޟᨐ㧘⇇㕙 ߦ↢ߓࠆ⥃⇇⁁ᘒᒻᚑߐࠇ㧘ᓥ᧪ታߐࠇߥ߆ߞ ߚᢙಽሶጀෘߐߦ㒢ቯߐࠇߚ㜞㧘㜞᷷ൻቇ ⽎㧔ࠗࠝࡦൻߣ⣕㔌㧕߇߈ࠆ㧚Fig. 3.ߦߎߩⴣ⓭ ⽎ࠍߔ࿑ࠍ␜ߔ㧚⸥߁ߣޠㅀ߇ࠅ߹ ߔ㧚⺒⠪ߩ┙႐ߣߒߡߪ㧘̌⥃⇇⁁ᘒߩᒻᚑߦࠃ ࠆࡔࠞ࠾࠭ࡓ̍ߦ㑐ߒߡ㧘ࠃࠅ⚦ߦ⍮ࠅߚߣᕁ ߁ߩߢߔ߇㧘߽ߒᧄࡔࠞ࠾࠭ࡓ╬ࠍ⚦ߦ⺰ߓߚ⺰ ᢥ╬߇ߏߑ߹ߒߚࠄ㧘ᒁ↪⺰ᢥߦㅊടߒߡ㗂ߌࠇ ߫㧘⺒⠪ߣߒߡߪ㕖Ᏹߦࠅ߇ߚߢߔ㧚 㨇⪺⠪㨉 ᒁ↪ᢥ₂ࠍㅊടߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-10㨉 Fig. 4 ߪ㧘⪺⠪ࠄߩߩ⺰ᢥ㧔Ref. 30㧕ߩ⚿ᨐࠍ ᒁ↪ߒߚ߽ߩߣᕁࠊࠇ߹ߔ߇㧘ᧄᢥߥࠄ߮ߦ࿑ߩ ࠠࡖࡊ࡚ࠪࡦਛߦ㧘ᒁ↪ߒߚᢥ₂ࠍ⸥タߒߡ㗂ߚ ᣇ߇⦟ߣᕁࠊࠇ߹ߔ㧚 㧔߹ߚ㧘Fig. 4 એᄖߩ㧘ߘߩઁߩታ㛎⚿ᨐߦ㑐ߒ ߹ߒߡ߽㧘ઁߩࠫࡖ࠽࡞╬ߢ⊒ᷣߺߩ⚿ᨐߪ㧘 ᒁ↪ᢥ₂ࠍᧄᢥߥࠄ߮ߦ࿑ߩࠠࡖࡊ࡚ࠪࡦਛߦ⸥タ ߒߡ㗂ߚᣇ߇ࠃߣᕁࠊࠇ߹ߔ㧚㧕 㨇⪺⠪㨉 ᒁ↪ᢥ₂ࠍㅊടߒ߹ߒߚ㧚 222 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 㨇ᩏ⺒⠪ 2-11㨉 ޟ3.1. 㕙ᷡᵺലᨐޟߡ߅ߦޠ⣕㔌ߔࠆ ಽሶጀߩෘߐ߇ᢙಽሶጀߦ㒢ࠄࠇߡࠆ߆ࠄߢ ࠆ㧚ߔ߹ࠅߣޠ㧚⺒⠪ߩ┙႐߆ࠄߚߒ߹ߔߣ㧘 ޟᢙಽሶጀ̌ߩޠᢙ ̍ߩᗧ߇ᦌᤒߦᕁࠊࠇ߹ߔ㧚 ߽ߒ㧘Ꮕߒᡰ߃ߥࠇ߫㧘ޟ2~3 ಽሶጀ߆ߩߥޠ㧘 ࠆߪޟ5~6 ಽሶጀ߆ߩߥޠ㧘ౕ⊛ߦ⸥ㅀߒߡ㗂 ߌࠇ߫⦟ࠃ߁ߦᕁࠊࠇ߹ߔ㧚 㨇⪺⠪㨉 ᛠីߢ߈ࠆ▸࿐ߢౕ⊛ߥᢙ୯ࠍ⸥ㅀߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-12㨉 ޟ3.2. Layer by Layer ࠛ࠶࠴ࡦࠣߦࠃࠆᷓߐᣇะ ಽᨆߡ߅ߦޠ㧘ޟDepth profile ߩಽ⸃⢻ߪਔ⹜ᢱ ࠍቢోߦ 2 ጀߦಽ㔌ߐߖߚⓍጀ⹜ᢱᚑߪ࿎㔍ߢ ࠆߚᖡ߇㧘ߔ߹ࠅߣޠ㧚৻⥸⊛ߦ㧘SIMS ╬ߢᷓߐᣇะߩಽ⸃⢻ࠍ⺞ߴࠆ႐วߦߪ㧘ࠊࠁࠆ ࠫ࠶ࠛޟലᨐ߇ޠᷓೞߥ㗴ߦߥࠆߚ㧘ᵈᗧ߇ᛄ ࠊࠇࠆߩߢߔ߇㧘Fig. 5 ߦ߅ߡߪ㧘ࠫ࠶ࠛޟലᨐޠ ࠍ㒰ߔࠆࠃ߁ߥಣℂߪߥߐࠇߡࠆߩߢߒࠂ߁ ߆㧫 㨇⪺⠪㨉 ࠛ࠶ࠫലᨐ㒰ಣℂߪߒߡ߅ࠅ߹ߖࠎ㧚 㨇ᩏ⺒⠪ 2-13㨉 หߓߊ Fig. 5 ߦ㑐ߒߡߢߔ߇㧘ᾖ 1 ಽᓟ㧘ߟ߹ ࠅ̌㕙ㄭற̍ߩ᷹ቯߦ߅ߡ㧘㧔10 ಽሶጀߛߌਅ ጀߦሽߔࠆ㧕ࡉࠫࠠ࠾ࡦߦ࿃ߔࠆାภ߇ขᓧ ߐࠇߡࠆߎߣ߇ࠊ߆ࠅ߹ߔ㧚৻ᣇ㧘ᧄ⸃⺑ߢߪ㧘 EDI ߩ㐳ᚲߣߒߡ㧘ޟ⣕㔌ߔࠆಽሶጀߩෘߐ߇ᢙಽ ሶጀߦ㒢ࠄࠇߡࠆߣޠਥᒛߐࠇߡ߹ߔ㧚ᓥߞߡ㧘 න⚐ߦ⠨߃߹ߔߣ㧘Fig. 5 ߩ⚿ᨐߣ⍦⋫ߔࠆࠃ߁ߦ ⠨߃ࠄࠇ߹ߔ㧚ߘߎߢ㧘⚛ᧉߥ⾰ߢ⺈ߦᕟ❗ߢߔ ߇㧘ߎߩὐߦ㑐ߒ߹ߒߡ߽㧘㧔ᧄᢥਛߦ⸥タߐࠇߡ ࠆࠃ߁ߥ㧕̌ Ⓧጀ⹜ᢱߩ㗴 ̍ߛߌߢ⺑ߢ߈ ࠆߣ⠨߃ߡ⦟ߩߢߒࠂ߁߆㧫 㨇⪺⠪㨉 ߏᜰ៰ߩὐߢߔ߇㧘᷹ቯߦ↪߹ߒߚ⹜ᢱߦ㗴 ߇ࠆߣ⸒߃߹ߔ㧚ߎࠇࠄ⹜ᢱߩⓍጀ᭴ㅧߪᱷᔨߥ ߇ࠄ⏕ߪߒߡ߹ߖࠎ㧚 㨇ᩏ⺒⠪ 2-14㨉 Fig. 6 ߩ⺑ߦ߅ߡ㧘ޟ⣕㔌ߔࠆಽሶጀ ߇ࠊߕ߆ᢙಽሶጀߦ㒢ࠄࠇࠆߩߪ㧘ⴣ᠄ᵄ⊒↢ߩ⋥ ᓟߦߎࠆ᳓ߩ᳇ൻߦࠃࠆᕆㅦ಄ළ⽎ߦ࿃ߔ ࠆ㧚߇ߔ߹ࠅߣޠ㧘ઁߩ⺰ᢥ[Ref. 31 ߿㧘 ⸥ߩᵻᎹ╬, J. Mass. Spectrom. Soc. Jpn. 55, 127 (2007).ߩ p. 134 ]ߢߪ㧘ޟၮ᧼ߦⴣ⓭ߒߚ᳓Ṣߩᄢㇱ ಽߪ᳇ൻߖߕ㧘ࡒࠢࡠߥࠢࠬ࠲ࠗࠝࡦߣߒߡ㘧 ᢔߔࠆߎߣ߇ࠊ߆ߞߡࠆ㧚⸥ߣޠㅀߐࠇߡ߹ߔ㧚 ⺒⠪ߣߒߡߪ㧘ᷙੂߒߡߒ߹߁ߣᕁ߁ߩߢߔ߇㧘ߤ ߜࠄ߇ᱜߒߩߢߒࠂ߁߆㧫 㨇⪺⠪㨉 ᓟ⠪ߦ⸓ᱜୃᱜߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-15㨉 ޟ3.3. 㜞ᗵᐲ᷹ቯᦨߩޠᓟߢ㧘⹜߽߆ߒޟ ᢱߩ SIMS ࠬࡍࠢ࠻࡞᷹ቯߪࠊߕ߆ᢙಽߢࠆߎߣ ࠍ␜ߒߡࠆ㧚߇ߔ߹ࠅߣޠ㧘໊⓭ߥᗵߓ ߇ࠅ㧘ᱷᔨߥ߇ࠄ⦟ߊℂ⸃ߢ߈߹ߖࠎߢߒߚ㧚߽ ߒ㧘ࠃࠈߒߌࠇ߫㧘߽߁ዋߒ⺑ࠍㅊടߒߡ㗂ߌ߹ ߖࠎߢߒࠂ߁߆㧫 㨇⪺⠪㨉 ୃᱜߒ߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-16㨉 Fig. 9 ߦ߅ߡ㧘100 ML ࠃࠅ߽ 10 ML ߩାภߩ ᣇ߇ᄢ߈⚿ᨐߣߥߞߡ߹ߔ㧚߽ߒ㧘ߎߩὐߦ㑐 ߒߡ㧘⠨߃ࠄࠇࠆℂ↱╬߇ߏߑ߹ߒߚࠄ㧘ᢎ߃ߡ 㗂ߌࠇ߫ࠅ߇ߚߢߔ㧚 㨇⪺⠪㨉 ℂ↱ࠍട߃߹ߒߚ㧚 㨇ᩏ⺒⠪ 2-17㨉 ޟ4. ߹ߣᦨߩޠᓟߩࡄࠣࡈߦ߅ߡ㧘৻ޟ ᣇ㧘ࠢࠬ࠲ࠗࠝࡦߩᰳὐߪߘߩࠨࠗ࠭߇නේሶ ࠗࠝࡦ㧔Cs+ߥߤ㧕ߦᲧߴ⪺ߒߊᄢ߈ߥὐߢࠆ㧚ޠ ߣࠅ߹ߔ߇㧘̌ࠢࠬ࠲ࠗࠝࡦߩࠨࠗ࠭̍ߣ ߁ߩߪ㧘ࠗࠝࡦ⥄ߩࠨࠗ࠭ࠍᗧߔࠆߩߢߒࠂ߁ ߆㧫ߘࠇߣ߽㧘ࠗࠝࡦࡆࡓߣߒߡߩ̌ࡆࡓᓘ̍ ߩߎߣࠍᜰߔߩߢߒࠂ߁߆㧫㧔ᢥ⣂߆ࠄߔࠆߣ㧘ࡆ ࡓᓘߩߎߣࠍᗧߒߡࠆࠃ߁ߦᕁࠊࠇࠆߩߢߔ ߇㧚㧕 ߹ߚ㧘ߎߎߢ߁̌ࠢࠬ࠲ࠗࠝࡦ̍ߣߪ㧘ᧄ ⸃⺑ߩਥ㗴ߢࠆ̌Ꮺ㔚ᶧṢ̍ߩߎߣࠍᜰߔߩߢߒࠂ ߁߆㧫ߘ߁ߢࠇ߫㧘ౕ⊛ߦ㧘Ꮺ㔚ᶧṢߣ⸥ㅀߒ ߡ㗂ߚᣇ߇㧘⺋⸃߇ήߊ㧘⦟ࠃ߁ߦᕁࠊࠇ߹ߔ㧚 㨇⪺⠪㨉 ߏᜰ៰ߩ▎ᚲୃᱜߒ߹ߒߚ㧚 223 Journal of Surface Analysis Vol.14, No. 3 (2008) pp. 214-224 㘵ፉༀᤨઁ㩷 䉪䊤䉴䉺䊷ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ዷᦸ㵪Ꮺ㔚ᶧṢⴣ᠄/ੑᰴ䉟䉥䊮⾰㊂ಽᨆ⸘䈱ㅴዷ㵪 㨇ᩏ⺒⠪ 2-18㨉 หߓߊ㧘ޟ4. ߹ߣᦨߩޠᓟߩࡄࠣࡈߦ߅ ߡ㧘ߚߩߎޟੑᰴࠗࠝࡦߩ᷹ቯ߿ᓸዊㇱ᷹ቯߢ ߪනේሶࠗࠝࡦࠍ↪ߚ TOF-SIMS ߦߪഠߞߡ ࠆ㧚߇ߔ߹ࠅߣޠ㧘ࠢࠬ࠲ࠗࠝࡦߩ႐วߢ߽㧘 Au3+߿ Bi3+ߢߪ㧘Ga+╬ߣห᭽ߦ㕙ಽ⸃⢻ߦఝࠇߚ᷹ ቯ߇น⢻ߢߔ㧚ᓥ߹ߒߡ㧘⸥ߩᢥ┨ߪ㧘⺋⸃ࠍ ߊߩࠃ߁ߦᕁࠊࠇ߹ߔߩߢ㧘ᢥ┨ߩୃᱜ╬ߩ ߏᬌ⸛ࠍߒߡ㗂ߌࠇ߫ᐘߢߔ㧚 㨇⪺⠪㨉 ୃᱜߒ߹ߒߚ㧚 224
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