CA2282924A1 - Pellicle, method of preparing the same and exposure method - Google Patents
Pellicle, method of preparing the same and exposure method Download PDFInfo
- Publication number
- CA2282924A1 CA2282924A1 CA002282924A CA2282924A CA2282924A1 CA 2282924 A1 CA2282924 A1 CA 2282924A1 CA 002282924 A CA002282924 A CA 002282924A CA 2282924 A CA2282924 A CA 2282924A CA 2282924 A1 CA2282924 A1 CA 2282924A1
- Authority
- CA
- Canada
- Prior art keywords
- fluorine
- pellicle film
- polymer
- contained
- pellicle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 47
- 229920000620 organic polymer Polymers 0.000 claims abstract description 45
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000010408 film Substances 0.000 claims description 120
- 229920005989 resin Polymers 0.000 claims description 86
- 239000011347 resin Substances 0.000 claims description 86
- 229920000642 polymer Polymers 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 52
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 45
- 239000011737 fluorine Substances 0.000 claims description 45
- 229910052731 fluorine Inorganic materials 0.000 claims description 45
- 239000002904 solvent Substances 0.000 claims description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 239000000470 constituent Substances 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000001459 lithography Methods 0.000 claims description 13
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 230000003247 decreasing effect Effects 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000010414 supernatant solution Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 238000000206 photolithography Methods 0.000 claims description 3
- 229920003002 synthetic resin Polymers 0.000 claims description 3
- 239000000057 synthetic resin Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000006303 photolysis reaction Methods 0.000 abstract description 12
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 12
- 239000000835 fiber Substances 0.000 description 25
- -1 perfluoro Chemical group 0.000 description 20
- 239000012535 impurity Substances 0.000 description 19
- 239000000178 monomer Substances 0.000 description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229920006254 polymer film Polymers 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 229920001774 Perfluoroether Polymers 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- UJMWVICAENGCRF-UHFFFAOYSA-N oxygen difluoride Chemical compound FOF UJMWVICAENGCRF-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000005381 potential energy Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
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- 230000002950 deficient Effects 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000002557 mineral fiber Substances 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000002759 woven fabric Substances 0.000 description 2
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 1
- XLKWQAQYRNTVKF-UHFFFAOYSA-N 1,1,2,3,3,4,5-heptafluoro-5-(1,2,3,3,4,5,5-heptafluoropenta-1,4-dienoxy)penta-1,4-diene Chemical compound FC(F)=C(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)=C(F)F XLKWQAQYRNTVKF-UHFFFAOYSA-N 0.000 description 1
- JWKJOADJHWZCLL-UHFFFAOYSA-N 1,2,3,4,5,5,6,6,6-nonafluoro-1-(1,2,3,4,5,5,6,6,6-nonafluorohexa-1,3-dienoxy)hexa-1,3-diene Chemical compound FC(OC(F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F)=C(F)C(F)=C(F)C(F)(F)C(F)(F)F JWKJOADJHWZCLL-UHFFFAOYSA-N 0.000 description 1
- HXPPEBLYZOARCG-UHFFFAOYSA-N 1,2-bis(ethenoxy)-1,1,2,2-tetrafluoroethane Chemical compound C=COC(F)(F)C(F)(F)OC=C HXPPEBLYZOARCG-UHFFFAOYSA-N 0.000 description 1
- OMRPVIDAWDWSFA-UHFFFAOYSA-N 1,4-bis(ethenoxy)-1,1,2,2,3,3,4,4-octafluorobutane Chemical compound C=COC(F)(F)C(F)(F)C(F)(F)C(F)(F)OC=C OMRPVIDAWDWSFA-UHFFFAOYSA-N 0.000 description 1
- OYPIGFUBEOGSBR-UHFFFAOYSA-N 1-(1,2,2-trifluoroethenoxy)propane Chemical compound CCCOC(F)=C(F)F OYPIGFUBEOGSBR-UHFFFAOYSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- RCSKFKICHQAKEZ-UHFFFAOYSA-N 1-ethenylindole Chemical compound C1=CC=C2N(C=C)C=CC2=C1 RCSKFKICHQAKEZ-UHFFFAOYSA-N 0.000 description 1
- WDRZVZVXHZNSFG-UHFFFAOYSA-N 1-ethenylpyridin-1-ium Chemical group C=C[N+]1=CC=CC=C1 WDRZVZVXHZNSFG-UHFFFAOYSA-N 0.000 description 1
- CTXUTPWZJZHRJC-UHFFFAOYSA-N 1-ethenylpyrrole Chemical compound C=CN1C=CC=C1 CTXUTPWZJZHRJC-UHFFFAOYSA-N 0.000 description 1
- KEDSBJOHAWJRQU-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6-nonafluoro-6-(1,1,2,2,3,3,3-heptafluoropropyl)oxane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C(F)(F)C1(F)F KEDSBJOHAWJRQU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- QHVBLSNVXDSMEB-UHFFFAOYSA-N 2-(diethylamino)ethyl prop-2-enoate Chemical compound CCN(CC)CCOC(=O)C=C QHVBLSNVXDSMEB-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- MLMGJTAJUDSUKA-UHFFFAOYSA-N 2-ethenyl-1h-imidazole Chemical compound C=CC1=NC=CN1 MLMGJTAJUDSUKA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- WWJCRUKUIQRCGP-UHFFFAOYSA-N 3-(dimethylamino)propyl 2-methylprop-2-enoate Chemical compound CN(C)CCCOC(=O)C(C)=C WWJCRUKUIQRCGP-UHFFFAOYSA-N 0.000 description 1
- UFQHFMGRRVQFNA-UHFFFAOYSA-N 3-(dimethylamino)propyl prop-2-enoate Chemical compound CN(C)CCCOC(=O)C=C UFQHFMGRRVQFNA-UHFFFAOYSA-N 0.000 description 1
- DTIMPWVSTCYVIR-UHFFFAOYSA-N 3-[difluoro-[1,1,2,3,4,4-hexafluoro-2-(1,2,2-trifluoroethenyl)but-3-enoxy]methyl]-1,1,2,3,4,5,5-heptafluoropenta-1,4-diene Chemical compound FC(F)=C(F)C(F)(C(F)=C(F)F)C(F)(F)OC(F)(F)C(F)(C(F)=C(F)F)C(F)=C(F)F DTIMPWVSTCYVIR-UHFFFAOYSA-N 0.000 description 1
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- SHFGJEQAOUMGJM-UHFFFAOYSA-N dialuminum dipotassium disodium dioxosilane iron(3+) oxocalcium oxomagnesium oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Na+].[Na+].[Al+3].[Al+3].[K+].[K+].[Fe+3].[Fe+3].O=[Mg].O=[Ca].O=[Si]=O SHFGJEQAOUMGJM-UHFFFAOYSA-N 0.000 description 1
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- JCAPHLPCWXAZLG-UHFFFAOYSA-M ethenyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)C=C JCAPHLPCWXAZLG-UHFFFAOYSA-M 0.000 description 1
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
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- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000004219 molecular orbital method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- FYJQJMIEZVMYSD-UHFFFAOYSA-N perfluoro-2-butyltetrahydrofuran Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C1(F)OC(F)(F)C(F)(F)C1(F)F FYJQJMIEZVMYSD-UHFFFAOYSA-N 0.000 description 1
- YVBBRRALBYAZBM-UHFFFAOYSA-N perfluorooctane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YVBBRRALBYAZBM-UHFFFAOYSA-N 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
- G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/23—Sheet including cover or casing
- Y10T428/239—Complete cover or casing
Abstract
A pellicle that excellently transmits ultraviolet rays and, particularly, vacuum ultraviolet rays, does not lose the film thickness thereof that stems from the photolysis and, hence, exhibits excellent light resistance. The pellicle is obtained by using, as a material of pellicle film, an impurity-free organic polymer obtained by treating an organic polymer to remove at least a portion of at least any one of, preferably, a majority portion of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer. The invention further provides a method of preparing a pellicle.
Description
PELLICLE, METHOD OF PREPARING THE SAME AND
EXPOSURE METHOD
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a pellicle, a method of preparing the same and an exposure method. More specifically, the invention relates to a pellicle suited for the lithography using ultraviolet rays and, particularly, vacuum,ultraviolet rays, and a method of preparing the same. The invention is further related to an exposure method by using this particular pellicle.
EXPOSURE METHOD
BACKGROUND OF THE INVENTION
1. Field of the Invention The present invention relates to a pellicle, a method of preparing the same and an exposure method. More specifically, the invention relates to a pellicle suited for the lithography using ultraviolet rays and, particularly, vacuum,ultraviolet rays, and a method of preparing the same. The invention is further related to an exposure method by using this particular pellicle.
2. Disclosure of the Prior Art In the step of photolithography, the operation is carried out to transfer by exposure a circuit pattern onto a silicon wafer coated with a resist by using a photomask or a reticle (hereinafter referred to as "mask") having the circuit pattern which comprises a deposited film such as of chromium on the surface of a glass plate or by using a reticle. In this step, when the exposure is conducted in a state where foreign matter such as dust is adhered on the circuit pattern of the mask, the foreign matter is transferred onto the wafer resulting in the formation of a defective wafer which is a defective product. When the exposure is effected by using a stepper, in particular, the chips formed on the wafer may all become defective.
Therefore, adhesion of foreign matter on the circuit pattern of the mask arouses a serious problem. In order to solve this problem, a pellicle has been developed and has been contrived in a variety of ways.
A pellicle, in general, is obtained by lining one side surface of a pellicle frame made of aluminum or the like with a transparent film of a resin such as nitrocellulose or the like, and is mounted on a mask by applying an adhesive to the other side surface thereof.
This prevents the infiltration of foreign matter from the external side. Besides, even if foreign matter happens to adhere on the pellicle film, foreign matter is transferred in a blurred state by the exposure without arousing problem.
In the processing of semiconductors, it is a tendency to use a source of light having a short wavelength in order to enhance the degree of integration by forming fine patterns. It is expected that the sources of light in the vacuum ultraviolet region (~ S 200 nm) are most promising and among them, an ArF excimer laser (~ - 193 nm) is most promising to succeed the KrF excimer laser - 248 nm) of which the market is now on the rise.
As the wavelength of the source of light becomes short, on the other hand, the energy of photon increases.
For example, the ArF excimer laser possesses the energy of as large as 6.4 eV (= 147 kcal/mol). This energy is very larger than the dissociation energy (104 kcal/mol) of the C-C bond in the organic polymer. Therefore, the polymer that absorbs light at the wavelength of the source of light easily undergoes the photolysis upon exposure to light and can no longer be used as a material of pellicle film.
On and after using the KrF lithography, therefore, there have been used fluorine-contained polymers that absorb light in relatively small amounts in the deep ultraviolet regions, such as commercially available fluorine-contained resin CYTOP (trade name) manufactured by Asahi Glass Co. and fluorine-contained resin Teflon (trade name) manufactured by du Pont Co., U.S.A.
However, even these fluorine-contained polymers absorb light in the vacuum ultraviolet region, and the thickness of the film decreases due to photolysis.
For example, the fluorine-contained resin CYTOP (film thickness of 1 um) absorbs about 0.5~ of an ArF excimer
Therefore, adhesion of foreign matter on the circuit pattern of the mask arouses a serious problem. In order to solve this problem, a pellicle has been developed and has been contrived in a variety of ways.
A pellicle, in general, is obtained by lining one side surface of a pellicle frame made of aluminum or the like with a transparent film of a resin such as nitrocellulose or the like, and is mounted on a mask by applying an adhesive to the other side surface thereof.
This prevents the infiltration of foreign matter from the external side. Besides, even if foreign matter happens to adhere on the pellicle film, foreign matter is transferred in a blurred state by the exposure without arousing problem.
In the processing of semiconductors, it is a tendency to use a source of light having a short wavelength in order to enhance the degree of integration by forming fine patterns. It is expected that the sources of light in the vacuum ultraviolet region (~ S 200 nm) are most promising and among them, an ArF excimer laser (~ - 193 nm) is most promising to succeed the KrF excimer laser - 248 nm) of which the market is now on the rise.
As the wavelength of the source of light becomes short, on the other hand, the energy of photon increases.
For example, the ArF excimer laser possesses the energy of as large as 6.4 eV (= 147 kcal/mol). This energy is very larger than the dissociation energy (104 kcal/mol) of the C-C bond in the organic polymer. Therefore, the polymer that absorbs light at the wavelength of the source of light easily undergoes the photolysis upon exposure to light and can no longer be used as a material of pellicle film.
On and after using the KrF lithography, therefore, there have been used fluorine-contained polymers that absorb light in relatively small amounts in the deep ultraviolet regions, such as commercially available fluorine-contained resin CYTOP (trade name) manufactured by Asahi Glass Co. and fluorine-contained resin Teflon (trade name) manufactured by du Pont Co., U.S.A.
However, even these fluorine-contained polymers absorb light in the vacuum ultraviolet region, and the thickness of the film decreases due to photolysis.
For example, the fluorine-contained resin CYTOP (film thickness of 1 um) absorbs about 0.5~ of an ArF excimer
3 laser beam of an oscillation wavelength of 193 nm, and loses light resistance to a large extent compared with when it is irradiated with the KrF excimer laser beam.
OBJECTS AND SUMMARY OF THE INVENTION
The object of the present invention therefore is to provide a pellicle that excellently transmits ultraviolet rays and, particularly, vacuum ultraviolet rays, does not lose the film thickness thereof that stems from the photolysis and, hence, exhibits excellent light resistance, and a method of producing the same.
Another object of the present invention is to provide an exposure method, which, even when ultraviolet rays are used and, particularly, vacuum ultraviolet rays are used, does not cause the pellicle to lose light resistance that stems from the photolysis and, hence, makes it possible to form vivid and fine patterns by the lithography for relatively extended periods of time.
According to the present invention, there is provided a pellicle film obtained by using, as a material of pellicle film, an impurity-free organic polymer obtained by treating an organic polymer to remove at least a portion of or, preferably, a majority portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer.
According to the present invention, there is further provided a method of preparing a pellicle film by conducting the operation for obtaining an impurity-free organic polymer by removing at least a portion of or, preferably, a majority portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer, by using a filter that exhibits the adsorbing action based on the zeta potential.
According to the present invention, there is further
OBJECTS AND SUMMARY OF THE INVENTION
The object of the present invention therefore is to provide a pellicle that excellently transmits ultraviolet rays and, particularly, vacuum ultraviolet rays, does not lose the film thickness thereof that stems from the photolysis and, hence, exhibits excellent light resistance, and a method of producing the same.
Another object of the present invention is to provide an exposure method, which, even when ultraviolet rays are used and, particularly, vacuum ultraviolet rays are used, does not cause the pellicle to lose light resistance that stems from the photolysis and, hence, makes it possible to form vivid and fine patterns by the lithography for relatively extended periods of time.
According to the present invention, there is provided a pellicle film obtained by using, as a material of pellicle film, an impurity-free organic polymer obtained by treating an organic polymer to remove at least a portion of or, preferably, a majority portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer.
According to the present invention, there is further provided a method of preparing a pellicle film by conducting the operation for obtaining an impurity-free organic polymer by removing at least a portion of or, preferably, a majority portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer, by using a filter that exhibits the adsorbing action based on the zeta potential.
According to the present invention, there is further
4 provided a pellicle film in which the contents of trace amount-metal components in the impurity-free organic polymer are not larger than 1 ppm, respectively.
According to the present invention, it is desired that the organic polymer is a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components and, particularly, is a fluorine-contained resin comprising carbon (C), fluorine (F) and oxygen (O) only as chief constituent components.
According to the present invention, there is provided an exposure method by using the pellicle film in the lithography that uses a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nm.
As an embodiment, the invention is further concerned with a pellicle film comprising a fluorine-contained resin which contains carbon (C) and fluorine (F) as chief constituent components, the fluorine resin being treated with a soluble solvent.
It is desired that the fluorine-contained resin treated with the soluble solvent is obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated.
As a preferred embodiment, the thus obtained fluorine-contained resin contains metal components in amounts of not larger than 1 ppm, respectively.
It is further desired that the fluorine-contained resin used in this embodiment is treated with a soluble solvent to remove at least part of high molecular components from the fluorine-contained resin.
The pellicle films obtained by the above-mentioned various embodiments are suppressed from being subjected to the photolysis even when they are used for the lithography using ultraviolet rays as a source of light for exposure, and exhibit durability that could not be obtained so far.
That is, another embodiment of the present invention is to provide a novel pellicle film simultaneously satisfying the following conditions (a) to (c):
According to the present invention, it is desired that the organic polymer is a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components and, particularly, is a fluorine-contained resin comprising carbon (C), fluorine (F) and oxygen (O) only as chief constituent components.
According to the present invention, there is provided an exposure method by using the pellicle film in the lithography that uses a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nm.
As an embodiment, the invention is further concerned with a pellicle film comprising a fluorine-contained resin which contains carbon (C) and fluorine (F) as chief constituent components, the fluorine resin being treated with a soluble solvent.
It is desired that the fluorine-contained resin treated with the soluble solvent is obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated.
As a preferred embodiment, the thus obtained fluorine-contained resin contains metal components in amounts of not larger than 1 ppm, respectively.
It is further desired that the fluorine-contained resin used in this embodiment is treated with a soluble solvent to remove at least part of high molecular components from the fluorine-contained resin.
The pellicle films obtained by the above-mentioned various embodiments are suppressed from being subjected to the photolysis even when they are used for the lithography using ultraviolet rays as a source of light for exposure, and exhibit durability that could not be obtained so far.
That is, another embodiment of the present invention is to provide a novel pellicle film simultaneously satisfying the following conditions (a) to (c):
5 (a) when an ArF excimer laser beam (~1 - 193 nm) is irradiated under the following conditions, the total dosage before the thickness of the film is decreased by 5 manometers (nm) is not smaller than 1420 joules/square centimeter (J/cmz), preferably, from 1420 to 28400 joules/square centimeter (J/cm2) and, particularly preferably, from 1420 to 14200 joules/square centimeter ( J/cm2 ) , ArF excimer laser beam irradiation conditions:
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate of 20 L/min., (b) the pellicle film comprises a fluorine-contained resin comprising carbon (C) and fluorine (F), or further oxygen (O), as chief constituent components; and (c) the pellicle film has a thickness of from 0.1 to 10 microns (um).
These pellicle films are suited for the exposure method in the lithography using a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 manometers (nm), and exhibit excellent light resistance that was not obtained so far.
The pellicle film of the present invention contains impurities in decreased amounts, exhibits excellent transmission property for the ultraviolet rays and particularly for the vacuum ultraviolet rays, suppresses the reduction in the thickness caused by the photolysis, and exhibits excellent light resistance.
The method of the present invention removes
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate of 20 L/min., (b) the pellicle film comprises a fluorine-contained resin comprising carbon (C) and fluorine (F), or further oxygen (O), as chief constituent components; and (c) the pellicle film has a thickness of from 0.1 to 10 microns (um).
These pellicle films are suited for the exposure method in the lithography using a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 manometers (nm), and exhibit excellent light resistance that was not obtained so far.
The pellicle film of the present invention contains impurities in decreased amounts, exhibits excellent transmission property for the ultraviolet rays and particularly for the vacuum ultraviolet rays, suppresses the reduction in the thickness caused by the photolysis, and exhibits excellent light resistance.
The method of the present invention removes
6 impurities that cause a drop in the ultraviolet ray transmission through a simple operation of passing the resin solution for forming the film through a filter that exhibits the adsorbing action based on the zeta potential or by effecting the precipitation using a soluble solvent.
According to the present invention, further, the pellicle little loses light resistance caused by the photolysis even when ultraviolet rays and, particularly, vacuum ultraviolet rays are used, enabling sharp and fine patterns to be formed by lithography for relatively long periods of time.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an ultraviolet spectral absorption curve representing the calculated results of the absorption wavelengths of the fluorine-contained resin of the chemical structure represented by the formula (1) relying on the molecular trajectory method, the calculated results corresponding to the molecular structures;
Fig. 2 is a graph plotting a relationship between the total dosage (J/cm2) and the amount of reduction (nm) in the thickness of the film by using a fluorine-contained resin (O) from which the impurities are not removed, a fluorine-contained resin (~) from which the impurities are removed by using a filter that exhibits the adsorbing action upon based on the zeta potential and a fluorine-contained resin (1) from which the impurities are moved by the treatment with a soluble solvent while projecting an ArF excimer laser of a wavelength of 193 nm; and Fig. 3 is a diagram illustrating a relationship between the potential energy for the colloidal particles (ordinate) and the distance among the colloidal particles (abscissa).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is based on a discovery that the removal of trace amount-metal components, high
According to the present invention, further, the pellicle little loses light resistance caused by the photolysis even when ultraviolet rays and, particularly, vacuum ultraviolet rays are used, enabling sharp and fine patterns to be formed by lithography for relatively long periods of time.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is an ultraviolet spectral absorption curve representing the calculated results of the absorption wavelengths of the fluorine-contained resin of the chemical structure represented by the formula (1) relying on the molecular trajectory method, the calculated results corresponding to the molecular structures;
Fig. 2 is a graph plotting a relationship between the total dosage (J/cm2) and the amount of reduction (nm) in the thickness of the film by using a fluorine-contained resin (O) from which the impurities are not removed, a fluorine-contained resin (~) from which the impurities are removed by using a filter that exhibits the adsorbing action upon based on the zeta potential and a fluorine-contained resin (1) from which the impurities are moved by the treatment with a soluble solvent while projecting an ArF excimer laser of a wavelength of 193 nm; and Fig. 3 is a diagram illustrating a relationship between the potential energy for the colloidal particles (ordinate) and the distance among the colloidal particles (abscissa).
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention is based on a discovery that the removal of trace amount-metal components, high
7 molecular components and incomplete molecular structure components from an organic polymer constituting the pellicle film is effective in decreasing the absorption of ultraviolet rays and, particularly, vacuum ultraviolet rays by the pellicle film and in decreasing the reduction in the thickness of the film caused by the photolysis.
The invention is further based on the discovery of the pellicle film having excellent light resistance that could not be obtained so far, owing to the treatment of the fluorine-contained resin constituting the pellicle film with a soluble solvent.
The present inventors have calculated the absorption wavelength corresponding to the molecular structure of the fluorine-contained resin (CYTOP) having the molecular structure represented by the following formula (1), -(CF2CFy)n-[-CF2-CF-CF-CFZ-]m- (1) O CFz relying on the molecular orbital method. As a result of calculation, there was obtained a vacuum ultraviolet ray spectral absorption curve shown in Fig. 1 from which it is obvious that no absorption occurs at a wavelength 193 nm of ArF beam.
With the practical fluorine-contained resin, however, the film 1 um thick absorbs light by about 0.5o as described above, and light resistance is deteriorated due to a reduction in the thickness of the film. This fact becomes readily obvious with reference to Examples and Comparative Examples appearing later.
The present inventors have conducted keen study concerning the cause that produces the difference, and
The invention is further based on the discovery of the pellicle film having excellent light resistance that could not be obtained so far, owing to the treatment of the fluorine-contained resin constituting the pellicle film with a soluble solvent.
The present inventors have calculated the absorption wavelength corresponding to the molecular structure of the fluorine-contained resin (CYTOP) having the molecular structure represented by the following formula (1), -(CF2CFy)n-[-CF2-CF-CF-CFZ-]m- (1) O CFz relying on the molecular orbital method. As a result of calculation, there was obtained a vacuum ultraviolet ray spectral absorption curve shown in Fig. 1 from which it is obvious that no absorption occurs at a wavelength 193 nm of ArF beam.
With the practical fluorine-contained resin, however, the film 1 um thick absorbs light by about 0.5o as described above, and light resistance is deteriorated due to a reduction in the thickness of the film. This fact becomes readily obvious with reference to Examples and Comparative Examples appearing later.
The present inventors have conducted keen study concerning the cause that produces the difference, and
8 have presumed that the cause is due to impurities (trace amount-metals and the like) contained in the polymers.
Therefore, the inventors have removed the impurities by using a filter that exhibits the adsorbing action based on the zeta potential or have removed the impurities by the treatment with a soluble solvent to make sure a remarkable improvement in the light resistance.
Reference should be made to Fig. 2 in which a relationship is plotted between the total dosage (J/cm~) and the reduction in the thickness of the film (nm) by using a fluorine-contained resin (O) from which the impurities are not removed, a fluorine-contained resin from which the impurities are removed by using a filter that exhibits the adsorbing action based on the zeta potential and a fluorine-contained resin (1) from which the impurities are moved by the treatment with a soluble solvent while projecting an ArF excimer laser beam of a wavelength of 193 nm.
It will be understood from these results that the removal of trace amount-metals and the like from the organic polymer is effective in suppressing the decrease in the light resistance caused by a reduction in the thickness of the film.
In the present invention, a drop in the light resistance due to the reduction in the thickness of the film is regarded to be a problem on account of the following reason. It has been known that the transmission factor of light of a particular wavelength generally varies depending upon the thickness of the film; i.e., the transmission factors for the thicknesses of the films describe a sine curve. Therefore, even when the thickness of the pellicle film is set to a predetermined value so as to exhibit a maximum transmission factor for light of a predetermined wavelength, the transmission factor decreases with a decrease in the thickness of the film
Therefore, the inventors have removed the impurities by using a filter that exhibits the adsorbing action based on the zeta potential or have removed the impurities by the treatment with a soluble solvent to make sure a remarkable improvement in the light resistance.
Reference should be made to Fig. 2 in which a relationship is plotted between the total dosage (J/cm~) and the reduction in the thickness of the film (nm) by using a fluorine-contained resin (O) from which the impurities are not removed, a fluorine-contained resin from which the impurities are removed by using a filter that exhibits the adsorbing action based on the zeta potential and a fluorine-contained resin (1) from which the impurities are moved by the treatment with a soluble solvent while projecting an ArF excimer laser beam of a wavelength of 193 nm.
It will be understood from these results that the removal of trace amount-metals and the like from the organic polymer is effective in suppressing the decrease in the light resistance caused by a reduction in the thickness of the film.
In the present invention, a drop in the light resistance due to the reduction in the thickness of the film is regarded to be a problem on account of the following reason. It has been known that the transmission factor of light of a particular wavelength generally varies depending upon the thickness of the film; i.e., the transmission factors for the thicknesses of the films describe a sine curve. Therefore, even when the thickness of the pellicle film is set to a predetermined value so as to exhibit a maximum transmission factor for light of a predetermined wavelength, the transmission factor decreases with a decrease in the thickness of the film
9 resulting in the degradation of the pellicle film. In this sense, it is obvious that suppressing the reduction in the thickness of the film as much as possible is important from the standpoint of extending the life (light resistance) of the pellicle film exposed to vacuum ultraviolet rays.
The organic polymer used for the pellicle film inevitably contains trace amount-metal components due to the step of preparing the resin. Examples of the trace amount-metals include alkali metal components such as sodium and the like, alkaline earth metal components such as calcium and the like, metal components of Group 8 of periodic table such as iron, cobalt, nickel and the like, and metal components of Group 4 of periodic table such as silicon and the like, that stem from the containers, equipment, starting materials for producing the resin and subsidiary materials. In general, the amounts of these metal components could become not smaller than 3 ppm.
In the impurity-free organic polymer used in the present invention, it is desired that the trace amount-metal components are not larger than 1 ppm, respectively, from the standpoint of light resistance.
When the trace amount-metal components exceed the above-mentioned range, the organic polymer constituting the pellicle film absorbs vacuum ultraviolet rays to a degree that is no longer negligible, and light resistance is considerably deteriorated compared with that of the organic polymer that lies within the above-mentioned range.
It is further considered that the presence of high molecular components in the organic polymer causes the pellicle film to lack homogeneity and, hence, spoils the light-transmitting property of the pellicle film. The high molecular components dissolve less in a solvent than the other resin components. It is therefore considered that the presence of high molecular components causes the pellicle film to lose homogeneity in its texture. Upon removing the high molecular components, the pellicle film exhibits improved homogeneity and improved light-s transmitting property.
As will be described later by way of examples, the resin in a solution treated by using a filter that exhibits adsorbing action based on the zeta potential or the resin in a solution treated with a soluble solvent,
The organic polymer used for the pellicle film inevitably contains trace amount-metal components due to the step of preparing the resin. Examples of the trace amount-metals include alkali metal components such as sodium and the like, alkaline earth metal components such as calcium and the like, metal components of Group 8 of periodic table such as iron, cobalt, nickel and the like, and metal components of Group 4 of periodic table such as silicon and the like, that stem from the containers, equipment, starting materials for producing the resin and subsidiary materials. In general, the amounts of these metal components could become not smaller than 3 ppm.
In the impurity-free organic polymer used in the present invention, it is desired that the trace amount-metal components are not larger than 1 ppm, respectively, from the standpoint of light resistance.
When the trace amount-metal components exceed the above-mentioned range, the organic polymer constituting the pellicle film absorbs vacuum ultraviolet rays to a degree that is no longer negligible, and light resistance is considerably deteriorated compared with that of the organic polymer that lies within the above-mentioned range.
It is further considered that the presence of high molecular components in the organic polymer causes the pellicle film to lack homogeneity and, hence, spoils the light-transmitting property of the pellicle film. The high molecular components dissolve less in a solvent than the other resin components. It is therefore considered that the presence of high molecular components causes the pellicle film to lose homogeneity in its texture. Upon removing the high molecular components, the pellicle film exhibits improved homogeneity and improved light-s transmitting property.
As will be described later by way of examples, the resin in a solution treated by using a filter that exhibits adsorbing action based on the zeta potential or the resin in a solution treated with a soluble solvent,
10 has an inherent viscosity smaller than that of the resin that is not treated, from which it is confirmed that the high molecular components have been removed.
Among them, it can be judged that the high molecular components have been removed to a sufficient degree if the degree of drop of the inherent viscosity n is not less than 3~, usually, from 3~ to 60~ and, particularly, not less than 5~ and, particularly desirably, from 5% to 50~
with the solution of the starting resin as a reference.
In the pellicle film of the present invention, it is considered that the film comprises the fluorine-contained organic polymer. The incomplete molecular structure component in which double bonds are remained the fluorine contents are relatively small and so on among molecules constituting the fluorine-contained organic polymer might cause the photolysis upon exposure to light, and that the thickness of the pellicle film decreases due to the photolysis whereby the light resistance of the pellicle film decreases. Accordingly, in the present invention, the light resistance is improved by removing such incomplete molecular structure component from the fluorine-contained organic polymer.
According to the present invention, some impurities such as trace amount-metals, high molecular components and incomplete molecular structure components contained in the organic polymer, can be effectively removed by passing the
Among them, it can be judged that the high molecular components have been removed to a sufficient degree if the degree of drop of the inherent viscosity n is not less than 3~, usually, from 3~ to 60~ and, particularly, not less than 5~ and, particularly desirably, from 5% to 50~
with the solution of the starting resin as a reference.
In the pellicle film of the present invention, it is considered that the film comprises the fluorine-contained organic polymer. The incomplete molecular structure component in which double bonds are remained the fluorine contents are relatively small and so on among molecules constituting the fluorine-contained organic polymer might cause the photolysis upon exposure to light, and that the thickness of the pellicle film decreases due to the photolysis whereby the light resistance of the pellicle film decreases. Accordingly, in the present invention, the light resistance is improved by removing such incomplete molecular structure component from the fluorine-contained organic polymer.
According to the present invention, some impurities such as trace amount-metals, high molecular components and incomplete molecular structure components contained in the organic polymer, can be effectively removed by passing the
11 organic polymer through a filter that exhibits the adsorbing action based on the zeta potential or by treating the organic polymer with a soluble solvent prior to preparing the film.
The zeta (~) potential is also called interfacial electrokinetic potential, and is defined as a potential difference occurring in the interface between a solid (dispersing phase) and a liquid (dispersing medium) that are contacting to each other and are moving relative to each other. An electric double layer is generally formed in the interface between the solid and the liquid. In the electric double layer, a solid phase (or adsorbing layer) exists in a portion close to the solid to which are adhering ions of an electric charge opposite to that of the surf ace of the solid. When the solid and the liquid move relative to each other, it is considered that the potential difference that really dominates the motion is the potential difference between the surface of the solid phase and the interior of the solution (diffusing phase), since the solid phase moves together with the solid.
Concerning the electric charge of the dispersing phase, it has been said that when the dispersing medium and the dispersing phase have different dielectric constants, the one having a larger dielectric constant is positively charged and the one having a smaller dielectric constant is negatively charged.
In general, two forces, i.e., the zeta (~ ) potential and van der Waals are acting on the colloidal particles of the same kind (same electric charge) dispersing in the organic polymer solution, the former one acting as a repulsion and the latter one acting as an attraction.
Here, referring to Fig. 3, the potential energy for the colloidal particles is represented by the ordinate, the distance among the colloidal particles is represented by the abscissa, and it is presumed that the potential energy
The zeta (~) potential is also called interfacial electrokinetic potential, and is defined as a potential difference occurring in the interface between a solid (dispersing phase) and a liquid (dispersing medium) that are contacting to each other and are moving relative to each other. An electric double layer is generally formed in the interface between the solid and the liquid. In the electric double layer, a solid phase (or adsorbing layer) exists in a portion close to the solid to which are adhering ions of an electric charge opposite to that of the surf ace of the solid. When the solid and the liquid move relative to each other, it is considered that the potential difference that really dominates the motion is the potential difference between the surface of the solid phase and the interior of the solution (diffusing phase), since the solid phase moves together with the solid.
Concerning the electric charge of the dispersing phase, it has been said that when the dispersing medium and the dispersing phase have different dielectric constants, the one having a larger dielectric constant is positively charged and the one having a smaller dielectric constant is negatively charged.
In general, two forces, i.e., the zeta (~ ) potential and van der Waals are acting on the colloidal particles of the same kind (same electric charge) dispersing in the organic polymer solution, the former one acting as a repulsion and the latter one acting as an attraction.
Here, referring to Fig. 3, the potential energy for the colloidal particles is represented by the ordinate, the distance among the colloidal particles is represented by the abscissa, and it is presumed that the potential energy
12 higher than the origin O (zero) produces repulsion and the potential energy lower than the origin 0 (zero) produces an attraction. This state is considered to be as schematically illustrated in Fig. 3. That is, the colloidal particles that are brought close to each other from the sufficiently separated positions, are suppressed from approaching any more due to the barrier (B) created by the zeta potential. Therefore, the colloidal particles are not coagulated but remain stable.
On the other hand, when the organic polymer is passed through the filter that exhibits the adsorbing action based on zeta potential, the colloidal particles are effectively removed due to the adsorbing action of the colloidal particles having a charge opposite to zeta potential of the filter and the double trapping action based on the mechanical filtration.
In the case of the fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components, there is obtained the pellicle film of fluorine-contained resin having excellent light resistance that could not be obtained so far through the treatment of the fluorine-contained resin with the soluble solvent inclusive of the operation for removing at least any one of trace amount-metal components, high molecular components and components of incomplete molecular structures.
It is desired that the fluorine-contained resin treated with the soluble solvent is obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated.
It is desired that the amount of fluorine-contained resin component isolated and removed in the form of a solution is not larger than 60~ by weight and, desirably, from 3 to 60~ by weight and, particularly, from 5 to 50~ by weight
On the other hand, when the organic polymer is passed through the filter that exhibits the adsorbing action based on zeta potential, the colloidal particles are effectively removed due to the adsorbing action of the colloidal particles having a charge opposite to zeta potential of the filter and the double trapping action based on the mechanical filtration.
In the case of the fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components, there is obtained the pellicle film of fluorine-contained resin having excellent light resistance that could not be obtained so far through the treatment of the fluorine-contained resin with the soluble solvent inclusive of the operation for removing at least any one of trace amount-metal components, high molecular components and components of incomplete molecular structures.
It is desired that the fluorine-contained resin treated with the soluble solvent is obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated.
It is desired that the amount of fluorine-contained resin component isolated and removed in the form of a solution is not larger than 60~ by weight and, desirably, from 3 to 60~ by weight and, particularly, from 5 to 50~ by weight
13 of the whole amount.
Desirably, the thus obtained fluorine-contained resin contains the metal components in amounts of not larger than 1 ppm, respectively.
In this case, it is desired to use the fluorine-contained resin from which are removed at least any one of trace amount-metal components, high molecular components and components of incomplete molecular structures by the treatment with a soluble solvent.
The high molecular components can be removed, usually, by adding a bad solvent to the solution of the fluorine-contained resin to separate by precipitation the dissolved fluorine-contained resin in addition to using the filter that exhibits the adsorbing action based on the zeta potential. It is therefore desired to decrease the limiting viscosity (grams/deciliter) by more than 3~ and, usually, by about 5 to about 50% compared to the limiting viscosity (grams/deciliter) of the fluorine-contained resin of before being isolated.
According to the present invention, there is provided a pellicle simultaneously satisfying the following conditions (a) to (c):
(a) when the ArF excimer laser beam (~ - 193 nm) is irradiated under the following conditions, the total dosage before the thickness of the film is decreased by 5 nanometers (nm) is not smaller than 1420 joules/square centimeter (J/cm2), preferably, from 1420 to 28400 joules/square centimeter (J/cm2) and, particularly preferably, from 1420 to 14200 joules/square centimeter (J/cm2), ArF excimer laser beam irradiation conditions:
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate
Desirably, the thus obtained fluorine-contained resin contains the metal components in amounts of not larger than 1 ppm, respectively.
In this case, it is desired to use the fluorine-contained resin from which are removed at least any one of trace amount-metal components, high molecular components and components of incomplete molecular structures by the treatment with a soluble solvent.
The high molecular components can be removed, usually, by adding a bad solvent to the solution of the fluorine-contained resin to separate by precipitation the dissolved fluorine-contained resin in addition to using the filter that exhibits the adsorbing action based on the zeta potential. It is therefore desired to decrease the limiting viscosity (grams/deciliter) by more than 3~ and, usually, by about 5 to about 50% compared to the limiting viscosity (grams/deciliter) of the fluorine-contained resin of before being isolated.
According to the present invention, there is provided a pellicle simultaneously satisfying the following conditions (a) to (c):
(a) when the ArF excimer laser beam (~ - 193 nm) is irradiated under the following conditions, the total dosage before the thickness of the film is decreased by 5 nanometers (nm) is not smaller than 1420 joules/square centimeter (J/cm2), preferably, from 1420 to 28400 joules/square centimeter (J/cm2) and, particularly preferably, from 1420 to 14200 joules/square centimeter (J/cm2), ArF excimer laser beam irradiation conditions:
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate
14 of 20 L/min., (b) the pellicle film comprises a fluorine-contained resin comprising carbon (C) and fluorine (F), or further oxygen (O), as chief constituent components; and (c) the pellicle film has a thickness of from 0.1 to 10 microns (um).
By using the pellicle films obtained by the embodiments of the present invention, there is provided an exposure method which is used for the lithography using a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nanometers (nm).
[Pellicle film and method of its preparation]
Though there is no particular limitation, it is desired that the organic polymer for pellicle used in the present invention is a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components and, particularly, a fluorine-contained resin comprising carbon (C), fluorine (F) and oxygen (0) only as constituent components.
Among the above-mentioned fluorine-contained resins, it is desired to use a perfluoro amorphous fluorine-contained resin having a cyclic structure and, particularly, a cyclic ether structure on the main chain.
A suitable example of the perfluoro amorphous fluorine-contained resin is a perfluoro fluorine-contained resin containing, in the main chain, at least one of the recurring unit represented by the following formula (2), -CF2-CF-CF2-CF-CFZ- (2) (R)P (R)q R: perfluoroalkylene group, p: a number of 0 or 1, q: a number of 0, 1 or 2, a recurring unit represented by the following formula (3), -CFZ-CF-CFZ-CF-CFZ- (3) I I
O O
R: perfluoroalkylene group, a recurring unit of the following formula (4),
By using the pellicle films obtained by the embodiments of the present invention, there is provided an exposure method which is used for the lithography using a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nanometers (nm).
[Pellicle film and method of its preparation]
Though there is no particular limitation, it is desired that the organic polymer for pellicle used in the present invention is a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components and, particularly, a fluorine-contained resin comprising carbon (C), fluorine (F) and oxygen (0) only as constituent components.
Among the above-mentioned fluorine-contained resins, it is desired to use a perfluoro amorphous fluorine-contained resin having a cyclic structure and, particularly, a cyclic ether structure on the main chain.
A suitable example of the perfluoro amorphous fluorine-contained resin is a perfluoro fluorine-contained resin containing, in the main chain, at least one of the recurring unit represented by the following formula (2), -CF2-CF-CF2-CF-CFZ- (2) (R)P (R)q R: perfluoroalkylene group, p: a number of 0 or 1, q: a number of 0, 1 or 2, a recurring unit represented by the following formula (3), -CFZ-CF-CFZ-CF-CFZ- (3) I I
O O
R: perfluoroalkylene group, a recurring unit of the following formula (4),
15 - CF - CF -(4) R
R: perfluoroalkylene group, a recurring unit of the following formula (5), -CFZ-CF CF-CF2- (5) 2s I I
(R)p (R)q R: perfluoroalkylene group, p: a number of 0 or 1, q: a number of 0, 1 or 2, a recurring unit of the following formula (6),
R: perfluoroalkylene group, a recurring unit of the following formula (5), -CFZ-CF CF-CF2- (5) 2s I I
(R)p (R)q R: perfluoroalkylene group, p: a number of 0 or 1, q: a number of 0, 1 or 2, a recurring unit of the following formula (6),
16 -CFZ-CF CF-CFZ- (6) O O
R
R: perfluoroalkylene group, In the perfluoro fluorine-contained resin, the recurring units may all comprise the cyclic recurring units or the recurring units may partly comprise the cyclic recurring units and the remaining recurring units may comprise linear perfluoro monomer units.
The perfluoro amorphous fluorine-contained resin can be obtained by a method known per se, such as the cyclization polymerization of a perfluoroether monomer having double bonds at both terminals or the radical polymerization of a cyclic perfluoro monomer. In conducting the polymerization, another perfluoro monomer may be made present to obtain a copolymer.
As the perfluoroether monomer having double bonds at both terminals, there can be exemplified a perfluoroether represented by the following formula (7), CF2=CF-(CFz)n-0-(CF2)m-CF=CF2 __- (7) ( n = 1 to 5 , m = 1 to 5 , n + m = 1 to 6 ) such as perfluoroallylvinyl ether, perfluorodiallyl ether, perfluorobutenylvinyl ether, perfluorobutenylallylvinyl ether, perfluorodibutenyl ether, etc.
The perfluoroether monomer having double bonds at both terminals of another type will be a perfluoroalkylene glycol divinyl ether represented by the following formula CF2=CF-O-R-0-CF=CFZ --- (8)
R
R: perfluoroalkylene group, In the perfluoro fluorine-contained resin, the recurring units may all comprise the cyclic recurring units or the recurring units may partly comprise the cyclic recurring units and the remaining recurring units may comprise linear perfluoro monomer units.
The perfluoro amorphous fluorine-contained resin can be obtained by a method known per se, such as the cyclization polymerization of a perfluoroether monomer having double bonds at both terminals or the radical polymerization of a cyclic perfluoro monomer. In conducting the polymerization, another perfluoro monomer may be made present to obtain a copolymer.
As the perfluoroether monomer having double bonds at both terminals, there can be exemplified a perfluoroether represented by the following formula (7), CF2=CF-(CFz)n-0-(CF2)m-CF=CF2 __- (7) ( n = 1 to 5 , m = 1 to 5 , n + m = 1 to 6 ) such as perfluoroallylvinyl ether, perfluorodiallyl ether, perfluorobutenylvinyl ether, perfluorobutenylallylvinyl ether, perfluorodibutenyl ether, etc.
The perfluoroether monomer having double bonds at both terminals of another type will be a perfluoroalkylene glycol divinyl ether represented by the following formula CF2=CF-O-R-0-CF=CFZ --- (8)
17 R: perfluoroalkylene group, such as perfluoroethylene glycol divinyl ether, perfluorotetramethylene glycol divinyl ether, etc.
As the cyclic perfluoro monomer, there can be exemplified a monomer represented by the following formula (9).
CF = CF
O O (9) R
R: perfluoroalkylene group, and, particularly, perfluoro-2,2-dimethyl-1,3-dioxole.
As another monomer used for the copolymerization, there can be exemplified tetrafluoroethylene, hexafluoropropylene, perfluorovinylpropyl ether, perfluoroallylbutyl ether, perfluorodivinylethyl ether, perfluorovinylallyl ether, etc.
Though there is no particular limitation, concrete examples of the amorphous fluorine-contained resin include a cyclized copolymer of tetrafluoroethylene and perfluorovinylallyl ether such as CYTOP (trade name, manufactured by Asahi Glass Co.) represented by the above-mentioned formula (1), and a copolymer of tetrafluoroethylene and perfluoro-2,2-dimethyl-1,3-dioxole such as Teflon AF (trade name, manufactured by du Pont Co., U.S.A. and Mitsui-du Pont Fluorochemical Co.) represented by the following formula (10),
As the cyclic perfluoro monomer, there can be exemplified a monomer represented by the following formula (9).
CF = CF
O O (9) R
R: perfluoroalkylene group, and, particularly, perfluoro-2,2-dimethyl-1,3-dioxole.
As another monomer used for the copolymerization, there can be exemplified tetrafluoroethylene, hexafluoropropylene, perfluorovinylpropyl ether, perfluoroallylbutyl ether, perfluorodivinylethyl ether, perfluorovinylallyl ether, etc.
Though there is no particular limitation, concrete examples of the amorphous fluorine-contained resin include a cyclized copolymer of tetrafluoroethylene and perfluorovinylallyl ether such as CYTOP (trade name, manufactured by Asahi Glass Co.) represented by the above-mentioned formula (1), and a copolymer of tetrafluoroethylene and perfluoro-2,2-dimethyl-1,3-dioxole such as Teflon AF (trade name, manufactured by du Pont Co., U.S.A. and Mitsui-du Pont Fluorochemical Co.) represented by the following formula (10),
18 -(CF2CFz)n-[-CF-CF-]m-O O
C ---(10) To prepare the pellicle, the organic polymer is dissolved in a suitable solvent to prepare a solution thereof. In the case of the above-mentioned fluorine-contained resin, the solvent is an organic solvent of the fluorine type and, particularly, an organic solvent of the perfluoro type, such as perfluoro(2-butyltetrahydrofuran), perfluoro(2-propyltetrahydropyran), perfluorohydrofuran, perfluorooctane, etc.
Generally, the concentration of the organic polymer in the solution is desirably from 1 to 20$ by weight and, particularly, from 2 to 10$ by weight from the standpoint of removing trace amount-metal components and trace amounts of colloidal components and preparing the film.
When the concentration becomes smaller than the above-mentioned range, the efficiency decreases for forming the film and for removing the impurities. When the concentration exceeds the above-mentioned range, on the other hand, the viscosity of the solution becomes so high that the operability decreases for forming the film and for removing the impurities.
According to the present invention, the organic polymer solution is filtered by using a filter that exhibits the adsorbing action based on the zeta potential or is treated with a soluble solvent to remove trace amount-metal components or trace amounts of colloidal components from the organic polymer solution.
As the filter, there can be exemplified any known
C ---(10) To prepare the pellicle, the organic polymer is dissolved in a suitable solvent to prepare a solution thereof. In the case of the above-mentioned fluorine-contained resin, the solvent is an organic solvent of the fluorine type and, particularly, an organic solvent of the perfluoro type, such as perfluoro(2-butyltetrahydrofuran), perfluoro(2-propyltetrahydropyran), perfluorohydrofuran, perfluorooctane, etc.
Generally, the concentration of the organic polymer in the solution is desirably from 1 to 20$ by weight and, particularly, from 2 to 10$ by weight from the standpoint of removing trace amount-metal components and trace amounts of colloidal components and preparing the film.
When the concentration becomes smaller than the above-mentioned range, the efficiency decreases for forming the film and for removing the impurities. When the concentration exceeds the above-mentioned range, on the other hand, the viscosity of the solution becomes so high that the operability decreases for forming the film and for removing the impurities.
According to the present invention, the organic polymer solution is filtered by using a filter that exhibits the adsorbing action based on the zeta potential or is treated with a soluble solvent to remove trace amount-metal components or trace amounts of colloidal components from the organic polymer solution.
As the filter, there can be exemplified any known
19 porous material for solid-liquid separation, such as woven fabric or nonwoven fabric of fibers, porous membrane or plate, layer filled with powdery particles, porous molded article, or a combination of two or more thereof provided at least part thereof exhibits the adsorbing action based on the zeta potential.
As the fiber for forming filter, there can be used a woven fabric or a nonwoven fabric comprising one or two or more kinds of natural fiber, regenerated fiber, synthetic fiber and inorganic fiber.
As the natural fiber, there can be exemplified cellulose fibers such as pulp fiber, cotton, rammy, etc.
and animal fibers such as wool, etc. As the regenerated fiber, there can be exemplified a regenerated cellulose fiber and acetate fiber produced by the viscose method or the cupro-ammonium method.
As the synthetic fiber, there can be exemplified an olefin resin comprising polyethylene or polypropylene, a polyvinyl alcohol fiber, polyvinyl chloride fiber, vinylidene chloride resin fiber, acrylic fiber, vinyl chloride-vinylidene chloride copolymer fiber, polyamide fiber such as nylon 6 or nylon 6-6, a thermoplastic polyester fiber such as polyethylene terephthalate, a fluorine-contained resin fiber such as polytetrafluoroethylene, as well as an aramid fiber and a liquid crystal polyester fiber.
As the inorganic fiber, there can be exemplified a glass fiber, a ceramic fiber, a carbon fiber, and a natural or synthetic mineral fiber. Though not limited thereto only, suitable examples of the mineral fiber include calcium silicate fiber, magnesium silicate fiber, basic magnesium silicate fiber such as sepiolite and asbestos.
The fiber for constituting the filter may be used in a single kind or in a combination of two or more kinds.
Besides, the form of the fiber may be a staple fiber or a filament fiber. Though there is no particular limitation, the thickness of the single fiber is usually not larger than 100 denier and, particularly, not larger than 50 5 denier.
As the porous film, there can be used the one produced by a means known per se, such as microphase separation method, drawing method or electric charge track etching method. According to the microphase separation 10 method, a homogeneous solution obtained by dissolving high molecules such as cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile, polysulfone, polyethersulfone, polyethylene, polypropylene, polyvinylidene fluoride or polyphenylene oxide in a 15 solvent, is thinly spread and is then immersed in a non-solvent which does not dissolve high molecules. Or, the solvent is vaporized from the high molecular solution that is spread to form a porous film. According to the drawing method, a film such as of polytetrafluoroethylene or
As the fiber for forming filter, there can be used a woven fabric or a nonwoven fabric comprising one or two or more kinds of natural fiber, regenerated fiber, synthetic fiber and inorganic fiber.
As the natural fiber, there can be exemplified cellulose fibers such as pulp fiber, cotton, rammy, etc.
and animal fibers such as wool, etc. As the regenerated fiber, there can be exemplified a regenerated cellulose fiber and acetate fiber produced by the viscose method or the cupro-ammonium method.
As the synthetic fiber, there can be exemplified an olefin resin comprising polyethylene or polypropylene, a polyvinyl alcohol fiber, polyvinyl chloride fiber, vinylidene chloride resin fiber, acrylic fiber, vinyl chloride-vinylidene chloride copolymer fiber, polyamide fiber such as nylon 6 or nylon 6-6, a thermoplastic polyester fiber such as polyethylene terephthalate, a fluorine-contained resin fiber such as polytetrafluoroethylene, as well as an aramid fiber and a liquid crystal polyester fiber.
As the inorganic fiber, there can be exemplified a glass fiber, a ceramic fiber, a carbon fiber, and a natural or synthetic mineral fiber. Though not limited thereto only, suitable examples of the mineral fiber include calcium silicate fiber, magnesium silicate fiber, basic magnesium silicate fiber such as sepiolite and asbestos.
The fiber for constituting the filter may be used in a single kind or in a combination of two or more kinds.
Besides, the form of the fiber may be a staple fiber or a filament fiber. Though there is no particular limitation, the thickness of the single fiber is usually not larger than 100 denier and, particularly, not larger than 50 5 denier.
As the porous film, there can be used the one produced by a means known per se, such as microphase separation method, drawing method or electric charge track etching method. According to the microphase separation 10 method, a homogeneous solution obtained by dissolving high molecules such as cellulose acetate, cellulose nitrate, polyvinyl chloride, polyacrylonitrile, polysulfone, polyethersulfone, polyethylene, polypropylene, polyvinylidene fluoride or polyphenylene oxide in a 15 solvent, is thinly spread and is then immersed in a non-solvent which does not dissolve high molecules. Or, the solvent is vaporized from the high molecular solution that is spread to form a porous film. According to the drawing method, a film such as of polytetrafluoroethylene or
20 polypropylene is drawn at a high temperature and is heat-treated to obtain a porous film. According to the electric charge track etching method, the high molecular film is irradiated with thermal neutrons and the damaged portions are selectively subjected to the chemical etching to obtain a porous film.
The porous film includes an inorganic film, for example, an alumina film and a zirconia film.
As the filler layer, there can be used diatomaceous earth, perlite, activated carbon or talc, which is adhesive, porous, and is not restricted by the filtering operation.
As the porous molded article, further, there can be used a ceramic sintered product such as biscuit sheet or Alundum, or a molded article obtained by integrally molding the fibrous filter members, porous films or filler
The porous film includes an inorganic film, for example, an alumina film and a zirconia film.
As the filler layer, there can be used diatomaceous earth, perlite, activated carbon or talc, which is adhesive, porous, and is not restricted by the filtering operation.
As the porous molded article, further, there can be used a ceramic sintered product such as biscuit sheet or Alundum, or a molded article obtained by integrally molding the fibrous filter members, porous films or filler
21 layers that are laminated in a plural number under the application of heat.
The zeta potential of the filtering material in the filter is usually determined by the filtering material.
As for the inorganic filtering material, the siliceous filtering material tends to possess zeta potential of the negative polarity whereas the aluminous filtering material and the filtering material of a metal silicate (inclusive of basic metal silicate) tend to possess zeta potential of the positive polarity.
The zeta potential of the organic high molecular filtering material is controlled by forming at least part of the organic high molecules using a copolymer resin having an anionic or cationic polar group, or by blending the organic high molecules with a copolymer resin having the polar group. As the anionic polar group, there can be exemplified any polar group such as carboxylic acid, sulfonic acid or phosphonic acid. As the cationic polar group, there can be exemplified any cationic group such as basic nitrogen-containing group like primary, secondary or tertiary amino group, quaternary ammonium group, amido group, imino group, imido group, hydrazino group, guanidino group or amidino group.
The copolymer resin having anionic or cationic polar group is obtained by incorporating a monomer having anionic or cationic polar group in a resin by the random copolymerization, block copolymerization or graft copolymerization.
Suitable examples of the monomer are as described below.
As the monomers of the carboxylic acid type, there can be exemplified ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, malefic acid, malefic anhydride, fumaric acid, and lower alkyl half esters of malefic acid or fumaric acid.
The zeta potential of the filtering material in the filter is usually determined by the filtering material.
As for the inorganic filtering material, the siliceous filtering material tends to possess zeta potential of the negative polarity whereas the aluminous filtering material and the filtering material of a metal silicate (inclusive of basic metal silicate) tend to possess zeta potential of the positive polarity.
The zeta potential of the organic high molecular filtering material is controlled by forming at least part of the organic high molecules using a copolymer resin having an anionic or cationic polar group, or by blending the organic high molecules with a copolymer resin having the polar group. As the anionic polar group, there can be exemplified any polar group such as carboxylic acid, sulfonic acid or phosphonic acid. As the cationic polar group, there can be exemplified any cationic group such as basic nitrogen-containing group like primary, secondary or tertiary amino group, quaternary ammonium group, amido group, imino group, imido group, hydrazino group, guanidino group or amidino group.
The copolymer resin having anionic or cationic polar group is obtained by incorporating a monomer having anionic or cationic polar group in a resin by the random copolymerization, block copolymerization or graft copolymerization.
Suitable examples of the monomer are as described below.
As the monomers of the carboxylic acid type, there can be exemplified ethylenically unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, malefic acid, malefic anhydride, fumaric acid, and lower alkyl half esters of malefic acid or fumaric acid.
22 As the monomers of the sulfonic acid type, there can be exemplified styrenesulfonic acid, and 2-acrylamide-2-methylpropanesulfonic acid.
As the monomers of the phosphonic acid type, there can be exemplified 2-acidphosphoxypropyl methacrylate, 2-acidphosphoxyethyl methacrylate and 3-chloro-2-acidphosphoxypropyl methacrylate.
As the basic nitrogen-containing (meth)acrylic monomer, there can be exemplified dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dibutylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, N,N-dimethylaminoethyl-N'-aminoethyl methacrylate, 3-acrylamide-3,3'-dimethylpropyl dimethylamine, and quaternary ammonium salt thereof.
As the cationic polar group-containing vinyl monomer, there can be exemplified diallyldimethylammonium chloride, vinyltrimethylammonium chloride, N-vinylcarbazole, 2-vinylimidazole, N-vinylpyrrole, N-vinylindole, N-vinylpyrrolidone, and quaternary vinylpyridinium.
Depending on the kind of impurities to be removed, the filter used in the present invention may exhibit the adsorbing action based on the negative zeta potential, may exhibit the adsorbing action based on the positive zeta potential, or may exhibit the adsorbing action based on the negative and positive zeta potentials.
The filter that exhibits the adsorbing action based on the zeta potential has been placed in the market in the trade name of Zeta Plus or Zeta Pore (both are registered trademarks) by Cuno Co., and is easily available.
It is desired that the impurities are removed by repetitively circulating the resin solution for forming pellicle film through the above-mentioned filter until the
As the monomers of the phosphonic acid type, there can be exemplified 2-acidphosphoxypropyl methacrylate, 2-acidphosphoxyethyl methacrylate and 3-chloro-2-acidphosphoxypropyl methacrylate.
As the basic nitrogen-containing (meth)acrylic monomer, there can be exemplified dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl methacrylate, diethylaminoethyl acrylate, dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate, dibutylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, N,N-dimethylaminoethyl-N'-aminoethyl methacrylate, 3-acrylamide-3,3'-dimethylpropyl dimethylamine, and quaternary ammonium salt thereof.
As the cationic polar group-containing vinyl monomer, there can be exemplified diallyldimethylammonium chloride, vinyltrimethylammonium chloride, N-vinylcarbazole, 2-vinylimidazole, N-vinylpyrrole, N-vinylindole, N-vinylpyrrolidone, and quaternary vinylpyridinium.
Depending on the kind of impurities to be removed, the filter used in the present invention may exhibit the adsorbing action based on the negative zeta potential, may exhibit the adsorbing action based on the positive zeta potential, or may exhibit the adsorbing action based on the negative and positive zeta potentials.
The filter that exhibits the adsorbing action based on the zeta potential has been placed in the market in the trade name of Zeta Plus or Zeta Pore (both are registered trademarks) by Cuno Co., and is easily available.
It is desired that the impurities are removed by repetitively circulating the resin solution for forming pellicle film through the above-mentioned filter until the
23 content of impurities is lowered down to a predetermined level. In general, the filtering pressure is from 0.1 to 2.45 kg/cm2 (gauge), but the temperature is not particularly limited and may generally be normal temperature. As required, however, the resin solution may be heated or cooled.
Prior to being passed through, or after having been passed through, the filter that exhibits the adsorbing action based on the zeta potential, further, the resin solution may be prefiltered or postfiltered using another filter. Or, the resin solution may be filtered through a plurality of stages using filters that exhibit the adsorbing action based on the zeta potential.
In the case of the fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components, in particular, there is obtained a pellicle film of the fluorine-contained resin having excellent light resistance, which could not be obtained so far, by the treatment with the soluble solvent of the fluorine-contained resin or by the above-mentioned operation for removing at least part of or, desirably, the majority portion of the trace amount-metal components and/or high molecular components and/or incomplete molecular structure components.
As the fluorine-contained resin treated with the soluble solvent, there can be used the fluorine-contained resin obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated. To remove the high molecular components, further, the dissolved fluorine-contained resin is usually isolated by precipitation by adding a bad solvent ~o the solution of the fluorine-contained resin or by changing the temperature of the solution in addition to using the filter that exhibits the
Prior to being passed through, or after having been passed through, the filter that exhibits the adsorbing action based on the zeta potential, further, the resin solution may be prefiltered or postfiltered using another filter. Or, the resin solution may be filtered through a plurality of stages using filters that exhibit the adsorbing action based on the zeta potential.
In the case of the fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components, in particular, there is obtained a pellicle film of the fluorine-contained resin having excellent light resistance, which could not be obtained so far, by the treatment with the soluble solvent of the fluorine-contained resin or by the above-mentioned operation for removing at least part of or, desirably, the majority portion of the trace amount-metal components and/or high molecular components and/or incomplete molecular structure components.
As the fluorine-contained resin treated with the soluble solvent, there can be used the fluorine-contained resin obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated. To remove the high molecular components, further, the dissolved fluorine-contained resin is usually isolated by precipitation by adding a bad solvent ~o the solution of the fluorine-contained resin or by changing the temperature of the solution in addition to using the filter that exhibits the
24 adsorbing effect based on the zeta potential.
The pellicle film is formed by using the organic polymer which is the fluorine-contained resin obtained by the treatment with a soluble solvent or by the operation for removing impurities relying upon the flow-spread film-forming method that is known per se, such as spin-coating method or knife-coating method. In general, the resin solution is permitted to flow and spread on the surface of a smooth substrate such as glass plate to form a thin film. The thickness of the thin film that is formed can be easily changed by changing the viscosity of the solution and the rotational speed of the substrate.
The thin film formed on the substrate is dried by such means as the hot air or the irradiation with infrared rays to remove the remaining solvent.
It is usually desired that the thickness of the pellicle is from 0.1 to 10 um so as to exhibit a high transmission factor for the wavelength of the vacuum ultraviolet rays, and is usually from 0.5 to 1 arm for the wavelength 193 nm of ArF beam.
The pellicle film of the present invention can be used in its form and can also be used by forming an inorganic or organic reflection-preventing film known per se on one surface or on both surfaces of the film.
[Pellicle and lithography]
The pellicle used for the exposure method of the present invention is obtained by lining one side of the pellicle frame with the pellicle film obtained by the above-mentioned method, and by applying an adhesive or by sticking a double-sided adhesive tape onto the other side of the pellicle frame, so that it can be attached on the mask.
Though there is no particular limitation, the pellicle frame is made of a metal such as aluminum, aluminum alloy or stainless steel, or synthetic resin or ceramics.
Further, the pellicle frame is lined with the pellicle film with a known adhesive such as silicon resin-type adhesive or fluorine resin-type adhesive.
5 The pellicle of this structure prevents the infiltration of foreign matter from the external side.
Even in case foreign matter adheres on the film, it is transferred in a blurred state through the exposure and no problem arouses.
10 In order to prevent the generation of dust within the pellicle, a layer of a known adhesive material may be formed on the inner surfaces of the pellicle frame and on the inner surfaces of to pellicle film. That is, with the adhesive layer being formed on the inside of the pellicle 15 frame and on the inside of the film, dust is prevented from being generated in the pellicle, and the floating dust is secured and is prevented from adhering onto the mask.
According to the exposure method of the present 20 invention, the pellicle equipped with the pellicle film prepared according to the above-mentioned method is mounted on a photomask or a reticle having a circuit pattern of a deposited film such as of chromium formed on the surface of a glass plate, and the circuit pattern is
The pellicle film is formed by using the organic polymer which is the fluorine-contained resin obtained by the treatment with a soluble solvent or by the operation for removing impurities relying upon the flow-spread film-forming method that is known per se, such as spin-coating method or knife-coating method. In general, the resin solution is permitted to flow and spread on the surface of a smooth substrate such as glass plate to form a thin film. The thickness of the thin film that is formed can be easily changed by changing the viscosity of the solution and the rotational speed of the substrate.
The thin film formed on the substrate is dried by such means as the hot air or the irradiation with infrared rays to remove the remaining solvent.
It is usually desired that the thickness of the pellicle is from 0.1 to 10 um so as to exhibit a high transmission factor for the wavelength of the vacuum ultraviolet rays, and is usually from 0.5 to 1 arm for the wavelength 193 nm of ArF beam.
The pellicle film of the present invention can be used in its form and can also be used by forming an inorganic or organic reflection-preventing film known per se on one surface or on both surfaces of the film.
[Pellicle and lithography]
The pellicle used for the exposure method of the present invention is obtained by lining one side of the pellicle frame with the pellicle film obtained by the above-mentioned method, and by applying an adhesive or by sticking a double-sided adhesive tape onto the other side of the pellicle frame, so that it can be attached on the mask.
Though there is no particular limitation, the pellicle frame is made of a metal such as aluminum, aluminum alloy or stainless steel, or synthetic resin or ceramics.
Further, the pellicle frame is lined with the pellicle film with a known adhesive such as silicon resin-type adhesive or fluorine resin-type adhesive.
5 The pellicle of this structure prevents the infiltration of foreign matter from the external side.
Even in case foreign matter adheres on the film, it is transferred in a blurred state through the exposure and no problem arouses.
10 In order to prevent the generation of dust within the pellicle, a layer of a known adhesive material may be formed on the inner surfaces of the pellicle frame and on the inner surfaces of to pellicle film. That is, with the adhesive layer being formed on the inside of the pellicle 15 frame and on the inside of the film, dust is prevented from being generated in the pellicle, and the floating dust is secured and is prevented from adhering onto the mask.
According to the exposure method of the present 20 invention, the pellicle equipped with the pellicle film prepared according to the above-mentioned method is mounted on a photomask or a reticle having a circuit pattern of a deposited film such as of chromium formed on the surface of a glass plate, and the circuit pattern is
25 transferred by exposure onto the silicon wafer coated with the resist by using a source of light for exposure to ultraviolet rays having a wavelength over a range of from 140 to 200 nm.
According to the present invention, the pellicle little loses light resistance due to photolysis even when ultraviolet rays are used and, particularly, even when vacuum ultraviolet rays are used and, as a result, sharp and fine patterns can be stably formed by lithography for relatively extended periods of time.
EXAMPLE
According to the present invention, the pellicle little loses light resistance due to photolysis even when ultraviolet rays are used and, particularly, even when vacuum ultraviolet rays are used and, as a result, sharp and fine patterns can be stably formed by lithography for relatively extended periods of time.
EXAMPLE
26 The invention will be further described by way of Examples.
(Example 1) A fluorine-contained polymer resin CYTOP (of a grade of highly transmitting ultraviolet rays, manufactured by Asahi Glass Co.) was dissolved in a fluorine solvent F-top EF-L174 (produced by Tochem Products Co.) to prepare a solution containing 4~ by weight of the fluorine-contained polymer.
Next, the solution was circulated and filtered under the following conditions.
Filter material: Zeta Plus Filter (EC 050, produced by Cuno Co.) Flow rate: 4 ml/min Filtering time: 10 days The solution of the fluorine-contained polymer after filtered was dried at 120°C for 12 hours under reduced pressure to recover a dry fluorine-contained polymer.
About 1 g of the fluorine-contained polymer was burned, and the residue was analyzed by the ICP method to measure the amounts of metals contained in the fluorine-contained polymer. The results were as shown in Table 1.
The amounts of metal components in the fluorine-contained polymer were all smaller than a detectable limit of 1 ppm.
Further, the inherent viscosity [r~] of the fluorine-contained polymer refined by filtration was found by the limiting viscosity method (solvent: F-Top EF-L102 manufactured by Tochem Products Co.) to be 0.56 (dl/g).
(Comparative Example 1) A dry fluorine-contained polymer was recovered in quite the same manner as in Example 1 but without circulating the fluorine-contained polymer solution through the Zeta Plus Filter. The fluorine-contained polymer was analyzed for the presence of metal components
(Example 1) A fluorine-contained polymer resin CYTOP (of a grade of highly transmitting ultraviolet rays, manufactured by Asahi Glass Co.) was dissolved in a fluorine solvent F-top EF-L174 (produced by Tochem Products Co.) to prepare a solution containing 4~ by weight of the fluorine-contained polymer.
Next, the solution was circulated and filtered under the following conditions.
Filter material: Zeta Plus Filter (EC 050, produced by Cuno Co.) Flow rate: 4 ml/min Filtering time: 10 days The solution of the fluorine-contained polymer after filtered was dried at 120°C for 12 hours under reduced pressure to recover a dry fluorine-contained polymer.
About 1 g of the fluorine-contained polymer was burned, and the residue was analyzed by the ICP method to measure the amounts of metals contained in the fluorine-contained polymer. The results were as shown in Table 1.
The amounts of metal components in the fluorine-contained polymer were all smaller than a detectable limit of 1 ppm.
Further, the inherent viscosity [r~] of the fluorine-contained polymer refined by filtration was found by the limiting viscosity method (solvent: F-Top EF-L102 manufactured by Tochem Products Co.) to be 0.56 (dl/g).
(Comparative Example 1) A dry fluorine-contained polymer was recovered in quite the same manner as in Example 1 but without circulating the fluorine-contained polymer solution through the Zeta Plus Filter. The fluorine-contained polymer was analyzed for the presence of metal components
27 in the same manner as in Example 1.
The obtained results were as shown in Table 1.
Sodium and calcium that were not detected in Example 1 were detected. It was therefore confirmed that these metal components were removed by circulating the fluorine-contained polymer solution through the Zeta Plus Filter.
The inherent viscosity of the fluorine-contained polymer of Comparative Example 1 was measured in the same manner as in Example 1 to be 0.60, proving that the molecular weight was higher than that of the fluorine-contained polymer that was filtered through the Zeta Plus Filter. It was thus confirmed that the high molecular components of the fluorine-contained polymer were removed by the Zeta Plus Filter.
(Comparative Example 2) Among the fluorine-contained polymer solutions prepared in Example 1, use was made of the one that was not filtered through the Zeta Plus Filter to prepare a fluorine-contained polymer film (pellicle film) having a thickness of 0.8 ~m by the spin-coating method. The obtained film was irradiated with an ArF excimer laser beam (~ - 193 nm) under the following conditions.
Laser beam irradiation conditions:
Pulse energy density: 0.1 (mJ/cmz)/pulse Repeating frequency: 100 Hz Irradiation area: 10 mm x 10 mm Atmosphere: dry air flowing at a rate of 20 L/min_ A curve (A) in Fig. 2 represents a relationship between the total dosage of the ArF excimer laser beam and the amount of reduction in the thickness of the fluorine-contained polymer film caused by the irradiation with the laser beam.
If the reduction in the thickness of the film of 5 nm is presumed to be the service life of the pellicle film
The obtained results were as shown in Table 1.
Sodium and calcium that were not detected in Example 1 were detected. It was therefore confirmed that these metal components were removed by circulating the fluorine-contained polymer solution through the Zeta Plus Filter.
The inherent viscosity of the fluorine-contained polymer of Comparative Example 1 was measured in the same manner as in Example 1 to be 0.60, proving that the molecular weight was higher than that of the fluorine-contained polymer that was filtered through the Zeta Plus Filter. It was thus confirmed that the high molecular components of the fluorine-contained polymer were removed by the Zeta Plus Filter.
(Comparative Example 2) Among the fluorine-contained polymer solutions prepared in Example 1, use was made of the one that was not filtered through the Zeta Plus Filter to prepare a fluorine-contained polymer film (pellicle film) having a thickness of 0.8 ~m by the spin-coating method. The obtained film was irradiated with an ArF excimer laser beam (~ - 193 nm) under the following conditions.
Laser beam irradiation conditions:
Pulse energy density: 0.1 (mJ/cmz)/pulse Repeating frequency: 100 Hz Irradiation area: 10 mm x 10 mm Atmosphere: dry air flowing at a rate of 20 L/min_ A curve (A) in Fig. 2 represents a relationship between the total dosage of the ArF excimer laser beam and the amount of reduction in the thickness of the fluorine-contained polymer film caused by the irradiation with the laser beam.
If the reduction in the thickness of the film of 5 nm is presumed to be the service life of the pellicle film
28 which is the fluorine-contained polymer film in Fig. 1, then, it is learned that the pellicle film has a light resistance (life) of 960 J/cm2.
(Example 2) A fluorine-contained polymer film (pellicle film) was prepared in quite the same manner as in Comparative Example 2 but using the fluorine-contained polymer solution filtered through the Zeta Plus Filter among the fluorine-contained polymer solutions prepared in Example 1, and was irradiated with the ArF excimer laser beam to measure the amount of reduction in the thickness of the film.
The total dosage was 1420 J/cm2 before the amount of reduction in the thickness of the film reached 5 nm, from which it was learned that the light resistance was lengthened by about 1.5 times compared to that of Comparative Example 2.
(Example 3) A solution (the first solution) containing 4~ by weight of the fluorine-contained polymer was prepared in the same manner as Example 1 but using Perfload IL 263 (produced by Tokuyama Co.) as the fluorine solvent.
Next, impurities were removed with a soluble solvent in a manner as described below by using m-XHF (metaxylene hexafluoride) as a bad solvent.
0 The m-XHF was dropwisely added to the solution containing 4~ by weight of the fluorine-contained polymer at a volume ratio of 0.80 to 1 of the fluorine-contained polymer solution, and the supernatant solution was extracted (precipitated portion was removed in an amount of 24.1 by weight of the fluorine polymer in the first solution).
02 The supernatant solution obtained in 1~ above was dropwisely added to the m-XHF at a ratio of 0.73 to 1 of the m-XHF, and the precipitated portion was extracted
(Example 2) A fluorine-contained polymer film (pellicle film) was prepared in quite the same manner as in Comparative Example 2 but using the fluorine-contained polymer solution filtered through the Zeta Plus Filter among the fluorine-contained polymer solutions prepared in Example 1, and was irradiated with the ArF excimer laser beam to measure the amount of reduction in the thickness of the film.
The total dosage was 1420 J/cm2 before the amount of reduction in the thickness of the film reached 5 nm, from which it was learned that the light resistance was lengthened by about 1.5 times compared to that of Comparative Example 2.
(Example 3) A solution (the first solution) containing 4~ by weight of the fluorine-contained polymer was prepared in the same manner as Example 1 but using Perfload IL 263 (produced by Tokuyama Co.) as the fluorine solvent.
Next, impurities were removed with a soluble solvent in a manner as described below by using m-XHF (metaxylene hexafluoride) as a bad solvent.
0 The m-XHF was dropwisely added to the solution containing 4~ by weight of the fluorine-contained polymer at a volume ratio of 0.80 to 1 of the fluorine-contained polymer solution, and the supernatant solution was extracted (precipitated portion was removed in an amount of 24.1 by weight of the fluorine polymer in the first solution).
02 The supernatant solution obtained in 1~ above was dropwisely added to the m-XHF at a ratio of 0.73 to 1 of the m-XHF, and the precipitated portion was extracted
29 and the unprecipitated portion was removed. The unprecipitated portion contained the fluorine polymer in amount of 3.8~ by weight with respect to the fluorine polymer in the first solution.
The precipitated portion obtained in ~2 was dried in quite the same manner as in Example 1 to recover the dried fluorine-contained polymer. The fluorine-contained polymer was analyzed for the presence of metal components in the same manner as in Example 1.
The obtained results were as shown in Table 1.
Though the sodium and calcium were detected in Comparative Example 1, the amounts of Na and Ca were smaller than the detectable limit in Example 3. From the results, it was confirmed that the metal components had been removed by the treatment with the soluble solvent.
The inherent viscosity of the fluorine-contained polymer of Example 3 was measured in the same manner as in Example 1 to be 0.44, proving that the molecular weight was smaller than that of the fluorine-contained polymer of Comparative Example 1, from which it was confirmed that the high molecular components of the fluorine-contained polymer were removed by the treatment with the soluble solvent.
(Example 4) The precipitated portion obtained in ~ of Example 3 was dissolved in a fluorine solvent Perfload IL-263 to prepare a solution containing 4% by weight of the fluorine-contained polymer.
A fluorine-contained polymer film (pellicle film) was prepared in quite the same manner as in Comparative Example 2 but using the above solution, and was irradiated with the ArF excimer laser beam to measure the amount of reduction in the thickness of the film. The results were as shown in Fig. 2(c).
The total dosage was 2080 J/cm2 before the amount of reduction in the thickness of the film reached 5 nm, from which it was learned that the light resistance was lengthened by more than 2 times compared to that of Comparative Example 2.
Table 1 (unit in ppm) Element Example 1 Comparative Example 10 Example 1 Ag <1 <1 <1 A1 <1 <1 <1 As <1 <1 <1 15 Ba <1 <1 <1 Ca <1 2.9 <1 Cd <1 <1 <1 Ce <1 <1 <1 Co <1 <1 <1 20 Cr <1 <1 <1 Cu <1 <1 <1 Fe <1 <1 <1 Ga <1 <1 <1 Ge <1 <1 <1 25 Hf <1 <1 <1 La <1 <1 <1 Li <1 <1 <1 Mg <1 <1 <1 Mn <1 <1 <1
The precipitated portion obtained in ~2 was dried in quite the same manner as in Example 1 to recover the dried fluorine-contained polymer. The fluorine-contained polymer was analyzed for the presence of metal components in the same manner as in Example 1.
The obtained results were as shown in Table 1.
Though the sodium and calcium were detected in Comparative Example 1, the amounts of Na and Ca were smaller than the detectable limit in Example 3. From the results, it was confirmed that the metal components had been removed by the treatment with the soluble solvent.
The inherent viscosity of the fluorine-contained polymer of Example 3 was measured in the same manner as in Example 1 to be 0.44, proving that the molecular weight was smaller than that of the fluorine-contained polymer of Comparative Example 1, from which it was confirmed that the high molecular components of the fluorine-contained polymer were removed by the treatment with the soluble solvent.
(Example 4) The precipitated portion obtained in ~ of Example 3 was dissolved in a fluorine solvent Perfload IL-263 to prepare a solution containing 4% by weight of the fluorine-contained polymer.
A fluorine-contained polymer film (pellicle film) was prepared in quite the same manner as in Comparative Example 2 but using the above solution, and was irradiated with the ArF excimer laser beam to measure the amount of reduction in the thickness of the film. The results were as shown in Fig. 2(c).
The total dosage was 2080 J/cm2 before the amount of reduction in the thickness of the film reached 5 nm, from which it was learned that the light resistance was lengthened by more than 2 times compared to that of Comparative Example 2.
Table 1 (unit in ppm) Element Example 1 Comparative Example 10 Example 1 Ag <1 <1 <1 A1 <1 <1 <1 As <1 <1 <1 15 Ba <1 <1 <1 Ca <1 2.9 <1 Cd <1 <1 <1 Ce <1 <1 <1 Co <1 <1 <1 20 Cr <1 <1 <1 Cu <1 <1 <1 Fe <1 <1 <1 Ga <1 <1 <1 Ge <1 <1 <1 25 Hf <1 <1 <1 La <1 <1 <1 Li <1 <1 <1 Mg <1 <1 <1 Mn <1 <1 <1
30 Mo <1 <1 <1 Na <1 4.8 <1 Ni <1 <1 <1 P <1 <1 <1 Pb <1 <1 <1 Pd <1 <1 <1
31 Table 1(continued) (unit in ppm) Element Example 1 Comparative Example 3 Example 1 Sb <1 <1 <1 Se <1 <1 <1 Si <1 <1 <1 Sn <1 <1 <1 Sr <1 <1 <1 Ti <1 <1 <1 V <1 <1 <1 Zn <1 <1 <1 Zr <1 <1 <1
Claims (21)
1. A pellicle film simultaneously satisfying the following conditions (a) to (c):
(a) when an ArF excimer laser beam (.lambda. = 193 nm) is irradiated under the following conditions, the total dosage before the thickness of the film is decreased by 5 nanometers (nm) is not smaller than 1420 joules/square centimeter (J/cm2), ArF excimer laser beam irradiation conditions:
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate of 20 L/min., (b) the pellicle film comprises a fluorine-contained resin comprising carbon (C) and fluorine (F) or further oxygen (O) as chief constituent components; and (c) the pellicle film has a thickness of from 0.1 to 10 µm.
(a) when an ArF excimer laser beam (.lambda. = 193 nm) is irradiated under the following conditions, the total dosage before the thickness of the film is decreased by 5 nanometers (nm) is not smaller than 1420 joules/square centimeter (J/cm2), ArF excimer laser beam irradiation conditions:
pulse energy density: 0.1 (mJ/cm2)/pulse repeating frequency: 100 Hz irradiated area: 10 mm x 10 mm atmosphere: dry air flowing at a rate of 20 L/min., (b) the pellicle film comprises a fluorine-contained resin comprising carbon (C) and fluorine (F) or further oxygen (O) as chief constituent components; and (c) the pellicle film has a thickness of from 0.1 to 10 µm.
2. A pellicle film obtained by using, as a material of pellicle film, an impurity-free organic polymer obtained by treating an organic polymer to remove trace amount-metal components and/or high molecular components contained in the organic polymer.
3. A pellicle film obtained by using, as a material of pellicle film, an impurity-free organic polymer obtained by treating an organic polymer to remove at least a portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer.
4. A method of preparing a pellicle film of claim 3 by conducting the operation for obtaining an impurity-free organic polymer by removing the trace amount-metal components and/or high molecular components contained in the organic polymer, by using a filter that exhibits the adsorbing action based on the zeta potential.
5. A method of preparing a pellicle film of claim 3 by conducting the operation for obtaining an impurity-free organic polymer by removing at least a portion of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the organic polymer, by using a filter that exhibits the adsorbing action based on the zeta potential.
6. A pellicle film obtained by a method of preparing a pellicle film of claim 4.
7. A pellicle film obtained by a method of preparing a pellicle film of claim 5.
8. A pellicle film in which the contents of trace amount-metal components in the impurity-free organic polymer are not larger than 1 ppm, respectively.
9. A pellicle film of claim 2 or 3, wherein the organic polymer is a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components.
10. A pellicle film of claim 2 or 3, wherein the organic polymer is a fluorine-contained resin comprising carbon (C), fluorine (F) and oxygen (O) only as chief constituent components.
11. An exposure method by using a pellicle film of claim 8 in the lithography that uses a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nm.
12. An exposure method by using a pellicle film of claim 1 or 2 in the lithography that uses a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nm.
13. A pellicle film using a fluorine-contained resin comprising carbon (C) and fluorine (F) as chief constituent components, the fluorine resin being treated with a soluble solvent.
14. A pellicle film using, as a fluorine-contained resin treated with a soluble solvent, the fluorine-contained resin obtained by isolating part of the dissolved fluorine-contained resin from the solution of a soluble solvent of the fluorine-contained resin in the form of a solution and/or being precipitated.
15. A method of preparing a pellicle film of claim 13 or 14, wherein the fluorine-contained resin contains metal components in amounts of not larger than 1 ppm, respectively.
16. A pellicle film using a fluorine-contained resin treated with a soluble solvent to remove at least part of at least any one of trace amount-metal components, high molecular components and incomplete molecular structure components contained in the fluorine-contained resin.
17. An exposure method by using a pellicle film of claim 13 or 14 in the lithography that uses a source of light for exposure to ultraviolet rays having wavelengths over a range of from 140 to 200 nm.
18. A pellicle to be mounted on a mask used in photolithography for preventing adhesion of foreign matters onto a circuit pattern of the mask, the pellicle comprising:
a pellicle frame made of a metal, synthetic resin or ceramics, and a pellicle film lined on one side of the pellicle frame by an adhesive, wherein:
the pellicle film is made of a fluorine polymer composed only of carbon (C), fluorine (F) and optionally oxygen (0), the fluorine polymer having been made impurity-free to such an extent that at least one of the following conditions (1) and (2) are satisfied:
(1) no more than 1 ppm of metal components are contained in the fluorine polymer, and (2) high molecular components have been removed so that the fluorine polymer has an inherent viscosity 3 to 60%
lower than that of the fluorine polymer before removal of the high molecular components.
a pellicle frame made of a metal, synthetic resin or ceramics, and a pellicle film lined on one side of the pellicle frame by an adhesive, wherein:
the pellicle film is made of a fluorine polymer composed only of carbon (C), fluorine (F) and optionally oxygen (0), the fluorine polymer having been made impurity-free to such an extent that at least one of the following conditions (1) and (2) are satisfied:
(1) no more than 1 ppm of metal components are contained in the fluorine polymer, and (2) high molecular components have been removed so that the fluorine polymer has an inherent viscosity 3 to 60%
lower than that of the fluorine polymer before removal of the high molecular components.
19. A method for producing a pellicle film to be used for preventing adhesion of foreign matters onto a circuit pattern of a mask used in photolithography, which process comprises:
(A) providing a starting fluorine polymer composed only of carbon (C), fluorine (F) and optionally oxygen (O) containing metal components in a trace amount that is more than 1 ppm and high molecular components;
[B] dissolving the starting fluorine polymer in a suitable organic solvent to prepare a solution containing 1 to 20% by weight of the starting fluorine polymer;
[C] (a) filtering the solution through a filter which exhibits an absorbing action based on a zeta potential or (b) precipitating out a part of the fluorine polymer from the solution by changing a temperature or by adding a bad solvent in which the fluorine polymer is insoluble, thereby purifying the fluorine polymer to such an extent that at least one of the following conditions (1) and (2) are satisfied:
(1) no more than 1 ppm of metal components are contained in the fluorine polymer, and (2) high molecular components have been removed so that the fluorine polymer has an inherent viscosity 3 to 60%
lower than that of the fluorine polymer before removal of the high molecular components; and [D] forming a thin film having a thickness of 0.1 to 10 µm from the solution of the purified fluorine polymer.
(A) providing a starting fluorine polymer composed only of carbon (C), fluorine (F) and optionally oxygen (O) containing metal components in a trace amount that is more than 1 ppm and high molecular components;
[B] dissolving the starting fluorine polymer in a suitable organic solvent to prepare a solution containing 1 to 20% by weight of the starting fluorine polymer;
[C] (a) filtering the solution through a filter which exhibits an absorbing action based on a zeta potential or (b) precipitating out a part of the fluorine polymer from the solution by changing a temperature or by adding a bad solvent in which the fluorine polymer is insoluble, thereby purifying the fluorine polymer to such an extent that at least one of the following conditions (1) and (2) are satisfied:
(1) no more than 1 ppm of metal components are contained in the fluorine polymer, and (2) high molecular components have been removed so that the fluorine polymer has an inherent viscosity 3 to 60%
lower than that of the fluorine polymer before removal of the high molecular components; and [D] forming a thin film having a thickness of 0.1 to 10 µm from the solution of the purified fluorine polymer.
20. The method according to claim 19, wherein in step [B], variant (a) is chosen.
21. The method of claim 19, wherein variant (b) of step [C] is conducted by:
precipitating a part of the starting fluorine polymer from the solution by adding the bad solvent;
removing the precipitated part of the fluorine polymer, to obtain a supernatant solution;
adding the supernatant solution to the bad solvent to precipitate a further part of the starting fluorine polymer;
removing the precipitated further part of the starting fluorine polymer; and dissolving the precipitated further part in a suitable organic solvent to prepare a solution thereof.
precipitating a part of the starting fluorine polymer from the solution by adding the bad solvent;
removing the precipitated part of the fluorine polymer, to obtain a supernatant solution;
adding the supernatant solution to the bad solvent to precipitate a further part of the starting fluorine polymer;
removing the precipitated further part of the starting fluorine polymer; and dissolving the precipitated further part in a suitable organic solvent to prepare a solution thereof.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP26842898 | 1998-09-22 | ||
JP268428/98 | 1998-09-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
CA2282924A1 true CA2282924A1 (en) | 2000-03-22 |
Family
ID=17458362
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002282924A Abandoned CA2282924A1 (en) | 1998-09-22 | 1999-09-21 | Pellicle, method of preparing the same and exposure method |
Country Status (6)
Country | Link |
---|---|
US (1) | US6620555B1 (en) |
EP (1) | EP0989457A3 (en) |
KR (1) | KR20000023289A (en) |
CA (1) | CA2282924A1 (en) |
SG (1) | SG87830A1 (en) |
TW (1) | TW420770B (en) |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001037043A1 (en) * | 1999-11-17 | 2001-05-25 | E.I. Du Pont De Nemours And Company | Ultraviolet and vacuum ultraviolet transparent polymer compositions and their uses |
KR100677782B1 (en) * | 2000-01-17 | 2007-02-05 | 제이에스알 가부시끼가이샤 | Process for Preparing the Material for Insulation Film |
US6593035B1 (en) | 2001-01-26 | 2003-07-15 | Advanced Micro Devices, Inc. | Pellicle for use in small wavelength lithography and a method for making such a pellicle using polymer films |
US6544693B2 (en) | 2001-01-26 | 2003-04-08 | Advanced Micro Devices, Inc. | Pellicle for use in small wavelength lithography and a method for making such a pellicle |
TW200422793A (en) * | 2002-11-15 | 2004-11-01 | Mitsui Chemicals Inc | Pellicle with small gas production amount |
EP1983370A4 (en) * | 2006-02-01 | 2010-08-18 | Mitsui Chemicals Inc | Pellicle for high numerical aperture exposure device |
JP2007267272A (en) * | 2006-03-29 | 2007-10-11 | Matsushita Electric Ind Co Ltd | Condenser microphone |
KR101164460B1 (en) * | 2006-04-07 | 2012-07-18 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Pellicle for lithography |
TW201113645A (en) * | 2009-09-01 | 2011-04-16 | Asahi Glass Co Ltd | Coating material composition for liquid immersion exposure apparatus, laminate, method for forming laminate, and liquid immersion exposure apparatus |
WO2012004950A1 (en) * | 2010-07-08 | 2012-01-12 | 三井化学株式会社 | Pellicle film |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4970099A (en) * | 1989-05-19 | 1990-11-13 | E. I. Du Pont De Nemours And Company | Perfluoropolymer coated pellicles |
US5061024C1 (en) * | 1989-09-06 | 2002-02-26 | Dupont Photomasks Inc | Amorphous fluoropolymer pellicle films |
ATE122477T1 (en) | 1989-09-06 | 1995-05-15 | Du Pont | NON-REFLECTIVE FILM COVERING. |
JP2524436B2 (en) * | 1990-09-18 | 1996-08-14 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Surface treatment method |
JP3088783B2 (en) * | 1991-06-20 | 2000-09-18 | 旭化成工業株式会社 | Highly transparent pellicle |
JP3186844B2 (en) * | 1992-06-22 | 2001-07-11 | 旭化成株式会社 | Pellicle and manufacturing method thereof |
JPH0885728A (en) * | 1994-07-20 | 1996-04-02 | Mitsui Petrochem Ind Ltd | Production of thin fluororesin film |
JPH08220734A (en) * | 1995-02-10 | 1996-08-30 | Asahi Glass Co Ltd | Thin film for pellicle |
JP3433658B2 (en) * | 1997-11-21 | 2003-08-04 | 三井化学株式会社 | Method of preventing pellicle film deterioration in lithography |
-
1999
- 1999-09-15 TW TW088115887A patent/TW420770B/en not_active IP Right Cessation
- 1999-09-18 KR KR1019990040269A patent/KR20000023289A/en not_active Application Discontinuation
- 1999-09-21 CA CA002282924A patent/CA2282924A1/en not_active Abandoned
- 1999-09-21 SG SG9904402A patent/SG87830A1/en unknown
- 1999-09-22 EP EP99118048A patent/EP0989457A3/en not_active Withdrawn
- 1999-09-22 US US09/404,241 patent/US6620555B1/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
TW420770B (en) | 2001-02-01 |
US6620555B1 (en) | 2003-09-16 |
EP0989457A3 (en) | 2000-05-03 |
EP0989457A2 (en) | 2000-03-29 |
SG87830A1 (en) | 2002-04-16 |
KR20000023289A (en) | 2000-04-25 |
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Legal Events
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EEER | Examination request | ||
FZDE | Discontinued |