CN1871549A - Fluorinated photoresists prepared, deposited, developed and removed in carbon dioxide - Google Patents
Fluorinated photoresists prepared, deposited, developed and removed in carbon dioxide Download PDFInfo
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- CN1871549A CN1871549A CN 200480030777 CN200480030777A CN1871549A CN 1871549 A CN1871549 A CN 1871549A CN 200480030777 CN200480030777 CN 200480030777 CN 200480030777 A CN200480030777 A CN 200480030777A CN 1871549 A CN1871549 A CN 1871549A
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- photoresist
- olefinic
- unsaturated
- compound
- terpolymer
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- 229920002120 photoresistant polymer Polymers 0.000 title claims description 39
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims description 35
- 239000001569 carbon dioxide Substances 0.000 title claims description 17
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000002253 acid Substances 0.000 claims abstract description 35
- 229920001897 terpolymer Polymers 0.000 claims abstract description 32
- 239000000178 monomer Substances 0.000 claims abstract description 26
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 10
- 125000003367 polycyclic group Chemical group 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000003384 imaging method Methods 0.000 claims description 34
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 29
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 150000002148 esters Chemical class 0.000 claims description 16
- 239000002585 base Substances 0.000 claims description 15
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 230000005855 radiation Effects 0.000 claims description 8
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000011161 development Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- IZLFSDDOEKWVLD-UHFFFAOYSA-N 2-chloro-1,1,3,4,4,5,6,6,6-nonafluorohex-1-ene Chemical compound FC(C(F)(F)F)C(C(C(=C(F)F)Cl)F)(F)F IZLFSDDOEKWVLD-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001923 cyclic compounds Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- -1 polycyclic compound Chemical class 0.000 abstract description 14
- 238000000206 photolithography Methods 0.000 abstract description 7
- 125000004122 cyclic group Chemical group 0.000 abstract 2
- 239000000126 substance Substances 0.000 description 21
- 239000000463 material Substances 0.000 description 18
- 230000002378 acidificating effect Effects 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 125000000524 functional group Chemical group 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000002329 infrared spectrum Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 6
- 229920006362 Teflon® Polymers 0.000 description 6
- 230000000977 initiatory effect Effects 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 4
- 239000003833 bile salt Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 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 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- HSINOMROUCMIEA-FGVHQWLLSA-N (2s,4r)-4-[(3r,5s,6r,7r,8s,9s,10s,13r,14s,17r)-6-ethyl-3,7-dihydroxy-10,13-dimethyl-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-17-yl]-2-methylpentanoic acid Chemical compound C([C@@]12C)C[C@@H](O)C[C@H]1[C@@H](CC)[C@@H](O)[C@@H]1[C@@H]2CC[C@]2(C)[C@@H]([C@H](C)C[C@H](C)C(O)=O)CC[C@H]21 HSINOMROUCMIEA-FGVHQWLLSA-N 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 2
- QDOIZVITZUBGOQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n,n-bis(1,1,2,2,3,3,4,4,4-nonafluorobutyl)butan-1-amine;1,1,2,2,3,3,4,4,4-nonafluoro-n-(1,1,2,2,3,3,4,4,4-nonafluorobutyl)-n-(trifluoromethyl)butan-1-amine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F.FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QDOIZVITZUBGOQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 2
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 2
- 229930192627 Naphthoquinone Natural products 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000001118 alkylidene group Chemical group 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000003613 bile acid Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 2
- 230000004069 differentiation Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000671 immersion lithography Methods 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 1
- PITQFWWNUHMYIC-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylcyclohexyl)peroxycyclohexane Chemical compound C1CC(C(C)(C)C)CCC1OOC1CCC(C(C)(C)C)CC1 PITQFWWNUHMYIC-UHFFFAOYSA-N 0.000 description 1
- DAVVKEZTUOGEAK-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethyl 2-methylprop-2-enoate Chemical compound COCCOCCOC(=O)C(C)=C DAVVKEZTUOGEAK-UHFFFAOYSA-N 0.000 description 1
- IELQNQLDZIHBPK-UHFFFAOYSA-N 2-ethenoxy-1-ethoxy-1-methoxyethane Chemical compound CCOC(OC)COC=C IELQNQLDZIHBPK-UHFFFAOYSA-N 0.000 description 1
- CXDHJGCWMIOAQP-UHFFFAOYSA-N 2-pyridin-3-yl-1,4,5,6-tetrahydropyrimidine;hydrochloride Chemical compound Cl.C1CCNC(C=2C=NC=CC=2)=N1 CXDHJGCWMIOAQP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 208000005189 Embolism Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MARDFMMXBWIRTK-UHFFFAOYSA-N [F].[Ar] Chemical compound [F].[Ar] MARDFMMXBWIRTK-UHFFFAOYSA-N 0.000 description 1
- VFQHLZMKZVVGFQ-UHFFFAOYSA-N [F].[Kr] Chemical compound [F].[Kr] VFQHLZMKZVVGFQ-UHFFFAOYSA-N 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229920001871 amorphous plastic Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229940099352 cholate Drugs 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
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- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
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- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVZRBWKZFJCCIB-UHFFFAOYSA-N perfluorotributylamine Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)N(C(F)(F)C(F)(F)C(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RVZRBWKZFJCCIB-UHFFFAOYSA-N 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
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- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- 230000008961 swelling Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 239000002023 wood Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention provides a compound that is a terpolymer of: (a) at least one ethylenically unsaturated linear or branched compound that has at least one fluorine atom covalently coupled thereto; (b) at least one ethylenically unsaturated precursor of a cyclic or polycyclic compound that has at least one fluorine atom covalently coupled thereto forming a cyclic or polycyclic decrystallizing monomer in said terpolymer; and (c) at least one ethylenically unsaturated functional compound which as a monomer in said terpolymer changes solubility upon exposure to an acid or base. Methods of making and using such compounds in photolithography are also described.
Description
Related application
The present patent application requires the U.S. Provisional Patent Application 60/512 of submission on October 20th, 2003, the U.S. Provisional Patent Application 60/513 that on October 21st, 685 and 2003 submitted to, 049 rights and interests, the disclosure of these two patented claims are by reference and incorporated herein.
Invention field
But the present invention relates to be used in particular for the photo-corrosion-resisting agent composition of 157nm and 193nm photolithography and imaging low K dielectrics.
Background of invention
Teflon
_AF is tetrafluoroethene (TFE) and 2,2-two (trifluoromethyl)-4,5-two fluoro-1, the amorphous copolymer of 3-dioxole (PDD) (scheme 1).It combines the performance (as good light transmittance and the dissolubility in organic solvent) of amorphous plastics and the performance (low as thermal stability height, chemical stability excellence and surface energy) of (per) fluoropolymer.In addition, Teflon
_AF has some special performance: known to the SOLID ORGANIC polymkeric substance, it has minimum specific inductive capacity (Teflon
_The specific inductive capacity of AF 2400 is 1.90) and lowest refractive index (Teflon
_The refractive index of AF 2400 is 1.29) (Resnick, P.R.; Buck, W.H.ModernFluoropolymers; Scheirs, J., editor; John Wiley ﹠amp; Sons:Chichester, 1997, p 397).Low-refraction from the ultraviolet to the infrared wavelength and special penetrability make it be suitable for use as optical material.TFE and PDD synthetic existing explanation (scheme 1) (Michel, U. in supercritical carbon dioxide; Resnick, P.; Kipp, B.; Desimone, J.M.Macromolecules2003,36,7107-7113).The multipolymer that has prepared TFE and PDD, its glass transition temperature changes between 67 ℃ to 334 ℃ along with the variation of PDD amount in the chain.
Scheme 1
The main challenge that 157nm and 193nm photolithography develop be resist must be transmitted into jetting flat at least 40% to the resist layer bottom with photoresist circuit formation profile (French, R.H. after avoiding developing; Wheland, R.C.; Weiming, Q.; Lemon, M.F.; Zhang, E.; Gordon, J.; Petrov, V.A.; Cherstkov, V.F.; Delaygina, N.I.J.Fluorine Chem., 2003,122,63-80).Teflon_AF shows one of stock of the required transparency at these low wavelength.Yet this multipolymer lacks photoresist and shows the required chemical functionality of exposure back dissolubility difference.Referring to PCT application WO00/67072, EPO application 1246013 as United States Patent (USP) 6,593,058, Feiring and the Feldman of Feiring and Feldman.
Summary of the invention
First aspect of the present invention is a compound, and described compound is following terpolymer: (a) the unsaturated linear or hyperbranched compounds of at least a olefinic, and described compound has at least one fluorine atom covalently bound with it; (b) ring or the unsaturated precursor of at least a olefinic of polycyclic compund, described precursor have that at least one fluorine covalently bound with it is former to be given forming ring or encircle more and separate brilliant monomer in described terpolymer; Dissolubility after (c) the unsaturated functional compound of at least a olefinic, described functional compound change it and are being exposed in acid or the alkali as monomer in described terpolymer.
Second aspect of the present invention is the photoresist that comprises above-mentioned terpolymer and at least a photosensitive component.Described photoresist can be chosen wantonly and contain resistance solvent and any various other composition.
The 3rd aspect of the present invention is the method for preparing the photoresist image on substrate, described method comprises: (a) photo-corrosion-resisting agent composition is coated on the substrate, wherein said photo-corrosion-resisting agent composition comprises (i) above-mentioned terpolymer, (ii) photosensitive component and (iii) solvent (preferably carbon dioxide solvent); (b) dry described photo-corrosion-resisting agent composition to be removing described solvent in fact, thereby forms the photoresist layer at substrate; (c) with described photoresist floor imaging exposure to form district of imaging and imaging district not; (d) develop have the district of imaging and not the photoresist floor that has exposed in imaging district on substrate, to form relief image.
The 4th aspect of the present invention is the method for the above-mentioned terpolymer of preparation, and described method comprises the steps:
The bipolymer of unsaturated linear or hyperbranched compounds (having at least one fluorine atom covalently bound with it) of (i) at least a olefinic and the unsaturated ring of (ii) at least a olefinic or polycyclic compund (have at least one fluorine atom covalently bound with it and separate brilliant monomer to form in described terpolymer) (a) is provided; With
(b) make described bipolymer and the unsaturated functional compound of at least a olefinic (dissolubility after in described terpolymer, changing it and be exposed in acid or the alkali) the above-mentioned terpolymer of prepared in reaction in carbon dioxide solvent as monomer.
Accompanying drawing and following instructions by herein are elaborated to above and other objects of the present invention and aspect.
DESCRIPTION OF THE PREFERRED
" terpolymer " used herein is meant the multipolymer that three kinds of monomer copolymerizations make.
" ester vinyl ether " used herein comprises the fluorovinyl ether of formula CF2=CFOQZ, and wherein Q is an alkylidene, comprises fluoridizing and the perfluorinate alkylidene, contains 0-4 ether oxygens atom, and wherein C and O total atom number are 2 to 10 among the Q; Z for be selected from-COOR and-SO
2The group of F, wherein R is the C1-C4 alkyl.
" separating brilliant monomer " used herein is meant to be attached to and separates brilliant multipolymer in the multipolymer or give multipolymer unbodied monomer, preferably keep the Tg of multipolymer simultaneously more than room temperature.
The disclosure of all american documentation literatures of quoting herein by reference and incorporated herein.
A. terpolymer and preparation method thereof
Can be used for implementing linear or branching alefinically unsaturated compounds of the present invention and include but not limited to tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, vinylidene fluoride and fluorothene.
Can be used as implement ring of the present invention or many rings separate the ring of brilliant monomer precursor or polycyclic compund include but not limited to perfluor-(, 2-dimethyl-1, the 3-dioxole) (PDD) and perfluor-(2-methylene-4-methyl isophthalic acid, the 3-dioxolanes), and monomeric form but form the linear or hyperbranched compounds of cyclic compound when being attached in the multipolymer, as the CYTOP_ monomer (showing below) of Asahi Glass Company research and development, described CYTOP_ monomer forms the ring texture of following demonstration in multipolymer:
Repetitive in the monomer CYTOP polymkeric substance
Can be used to implement functional compound of the present invention and be generally the compound that wherein ethylenically unsaturated group and leaving group are connected by sour cleavable key (as ester or carboxylic acid ester bond).This compound comprises formula R
1-COO-R
2Or R
2-COO-R
1Compound, R wherein
1Be ethylenically unsaturated group, R
2Be aromatics or aliphatic leaving group.Preferred leaving group is ring-type, linear or branching C1 to C8 alkyl, can contain 1 or 2 heteroatomss, as O, S or N.The example of suitable functional compound includes but not limited to:
Other example that can be used to implement functional compound of the present invention comprises:
Other example that can be used to implement functional compound of the present invention comprises:
Wherein A=H, C (CH
3)
3Or Si (CH
3)
3
Other example of suitable functional compound is:
Other example that can be used to implement functional compound of the present invention includes but not limited to vinyl acetate, tert-butyl acrylate and 5-norborene-2-carboxylic acid tert-butyl ester.
In certain embodiments, the unsaturated functional compound of described at least a olefinic is the ester vinyl ether, preferred fluorinated ester vinyl ether, and the example includes but not limited to:
Wherein R is suitable aromatics or aliphatic protecting group, as low alkyl group (ethyl, the tert-butyl group), C
6H
5, the carboxylic acid group goes up any protecting group that shows in THP or compound as listed above or the monomer.
Terpolymer of the present invention can make by any suitable reactions polymerization in preferably carbon dioxide solvent such as liquid state or the supercritical carbon dioxide by at suitable solvent.As terpolymer A of the present invention can adopt radical initiator such as azo-compound or superoxide by bulk polymerization well known by persons skilled in the art, solution polymerization, suspension polymerization or emulsion polymerization technology, by other method preparation well known by persons skilled in the art (referring to the United States Patent (USP) 6 of for example Fiering etc., 593,058; The United States Patent (USP) 5,496,901 or 5,922,833 of DeSimone) or by their differentiation method preparation (according to the present invention, these differentiation methods will be apparent to those skilled in the art).Usually, the molar percentage of each comonomer can be 5% or 10% to 90% or 95% in the multipolymer.
In graft reaction of the present invention (the 3rd is monomer-grafted on " bipolymer " that existed), grafting can be undertaken by any appropriate technology of for example radiation, superoxide or other radical source, as United States Patent (USP) 5,736, described in 610.
In the embodiments of the invention, the ester vinyl ether (EVE) that contains the ester group that is exposed in the acid back cleavable reacts acquisition good yield (scheme 2,3) with TFE and PDD easily in supercritical carbon dioxide.The terpolymer that obtains (demonstrating special optics and thermal property) is as the matrix of the extremely low absorption official energy photo anti-corrosion agent material that contains PDD.
Scheme 2
Scheme 3
B. photo-corrosion-resisting agent composition
Photo-corrosion-resisting agent composition comprises above-mentioned polymkeric substance and other composition as described further below.
Photosensitive component (PAC).Composition of the present invention contains at least a photosensitive component (PAC), is generally the compound that acid or alkali are provided when being subjected to actinic radiation.If produce acid when being subjected to actinic radiation, this PAC is called photo-acid generator (PAG).If produce alkali when being subjected to actinic radiation, this PAC is called photic generated base alkaline agent (PBG).Suitable photo-acid generator of the present invention includes but not limited to: 1) sulfonium salt, 2) iodine _ salt and 3) Hydroxamates, include but not limited to described in the United States Patent (USP) 6,593,058 of Feiring etc. those.
The protecting group that removes by the PAC catalytic action.The fluorine-containing terpolymer of resist composition of the present invention can contain the component that one or more contain the protected acid group; described protected acid group can produce water wettability acidic group or base by the acid of light-sensitive compound (PAC) photodissociation generation or the catalytic action of alkali, and this water wettability acidic group or base make resist coating develop.Given protected acidic group select for acid is unstable based on it usually, thereby when the imaging exposure produces photic acid, acid meeting catalysis deprotection effect and the generation of the required water wettability acidic group of development under aqueous conditions.In addition, described fluorinated copolymer also can contain not shielded acid functional group.
Example with component (in being exposed to photic acid time generate carboxylic acid as hydrophilic radical) of protected acidic group includes but not limited to; A) can form or be rearranged into the cationic ester of uncle; B) lactone; C) acetal ester; D) β-cyclic ketones ester; E) α-cyclic ethers ester, and F) MEEMA (methoxyethoxyethyl methacrylate) and other are because anchimeric assistance and the ester of hydrolysis easily.A) some instantiations of class have the tert-butyl ester, 2-methyl-2-diamantane ester and isobornyl thiocyanoacetate.B) some instantiations of class have gamma-butyrolacton-3-base, gamma-butyrolacton-2-base, mavalonic lactone, 3-methyl-gamma-butyrolacton-3-base, 3-tetrahydrofuran base and 3-oxo cyclohexyl.C) some instantiations of class have 2-THP trtrahydropyranyl, 2-tetrahydrofuran base and 2,3-propylene carbonate-1-base.C) other example of class comprises the various esters that make by the vinyl ether addition, as ethoxyethyl group vinyl ether, methoxyethoxyethyl vinyl ether and acetate ethoxyethyl group vinyl ether.
Example with component (generating alcohol as hydrophilic radical when being exposed to photic acid or alkali) of protected acidic group includes but not limited to tertbutyloxycarbonyl (t-BOC), tertbutyl ether and 3-cyclohexenyl group ether.
Among the present invention often (but not always), the component with protected group is the repetitive with protected acid group, and these repetitives have been attached in the basic copolymer resin of composition (as discussed above).Usually described protected acidic group exists in one or more comonomers, and described comonomer polymerization is to form given multipolymer of the present invention basis resin.Perhaps, multipolymer basis resin can be by forming with containing sour comonomer copolymerization among the present invention, and the acid functional group that contains acid copolymer that obtains subsequently can partly or entirely change into the derivant with protected acidic group by proper method.As instantiation, TFE/NB/t-BA multipolymer (multipolymer of tetrafluoroethene, norborene and tert-butyl acrylate) is for having the multipolymer basis resin of tert-butyl ester base as the protected acid group in the scope of the invention.
Resistance solvent and adjuvant.Various resistance solvents can be used for the present invention.It is desirable to, the resistance solvent (DI) of extreme ultraviolet resist (as the 193nm resist) should design/select and satisfy many-sided materials demand, comprises the adhesion behavior that hinders molten, anti-plasma etching and comprise the resist composition of specific DI adjuvant.Compound is dissolved in some resistance also can be as plastifier in the resist composition.
Various bile salt esters (being the cholate ester) can be used as the DI in the present composition especially.Known bile salt ester is effective resistance solvent of degree of depth ultraviolet resist, at first adopt (E.Reichmanis etc. by Reichmanis etc. in nineteen eighty-three, " The Effect of Substituents on thePhotosensitivity of 2-Nitrobenzyl Ester Deep UV Resists ", J.Electrochem.Soc.1983,130,1433-1437.).The DI that the bile salt ester is favored especially owing to several reasons becomes selects, comprise that they can obtain, their alicyclic carbon content height from natural source, particularly they the degree of depth of electromagnetic spectrum and vacuum ultraviolet (also being the far-ultraviolet region in essence) be transparent (as they are highly transparents at the 193nm place).In addition, the bile salt ester becomes that the DI that favors selects also owing to can replace and functionalization hydrophobicly arrives hydrophilic compatibility by what design make that it has a wide region according to hydroxyl.
Be suitable as those that the representational bile acid of adjuvant of the present invention and/or resistance solvent and bile acid derivative include but not limited to show in the United States Patent (USP) 6,593,058 of Feiring etc.
The invention is not restricted to use bile acid ester and related compound as resistance solvent.The resistance solvent of other type (as various adjacent nitrine naphthoquinones (DNQ) and diazonium cumarin (DC)) can be used for the present invention in some applications.Adjacent nitrine naphthoquinones and diazonium cumarin are applicable to the resist composition of imaging under upper wavelength UV light (as 365nm and possibility 248nm) usually.These resistance solvents are not preferred for the resist composition in the imaging of the UV of 193nm or lower wavelength light usually, this be since these compounds in this UV district strong absorption and usually transparent inadequately for the great majority application of low UV wavelength.
The component of negative photoresist embodiment.Certain embodiments of the present invention are negative photoresists.These negative photoresists comprise at least a binder polymer and at least a photosensitive component that photic acid is provided that contains acid-unstable group.The imaging exposure of resist provides photic acid, and described photic acid changes into polar functional group (for example ester functional group (low polarity) changes into acid functional group (high polarity)) with acid-unstable group.Develop in organic solvent or critical fluids (by the time low polarity in having) then, this produces negativity system, wherein keeps the exposure area and removes unexposed area.
Various different crosslinking chemicals can be used as photosensitive component essential or optional in the negativity composition of the present invention.(, choosing wantonly) but the polar group (being insoluble to organic solvent and critical fluids with medium/low polarity) that forms owing to exposure area is insoluble in the preferred embodiment of developer solution crosslinking chemical owing to crosslinking chemical in the crosslinked embodiment that is insoluble to developer solution is essential.Suitable crosslinking agent includes but not limited to various two-fold nitride, as 4,4 '-two nitrine diphenyl sulfide and 3,3 '-two nitrine diphenyl sulfones.Preferably, the negative resist composition that contains crosslinking chemical also contains and can react to generate the suitable functional group (as unsaturated carbon-carbon double bond (C.dbd.C bonds)) of cross-linked polymer with active substance (as nitrence), described active substance generates when being exposed to UV, described cross-linked polymer does not dissolve in developer solution, disperses or abundant swelling, thereby this gives composition negativity feature.
Other component.Composition of the present invention can contain optional other component.The example of other component that can add includes but not limited to resolution reinforcing agent, adhesion promotor, remaining reductive agent, coating aid, plastifier and Tg (glass transition temperature) modifier.
C. method step
Imaging exposure.Photo-corrosion-resisting agent composition of the present invention is responsive in those ultraviolet ranges of the ultraviolet range of electromagnetic wave spectrum, particularly wavelength≤365nm.The imaging exposure of resist composition of the present invention can carry out under many different ultraviolet wavelengths, and described wavelength includes but not limited to 365nm, 248nm, 193nm, 157nm and lower wavelength.Imaging exposure preferably carries out under the ultraviolet light of 248nm, 193nm, 157nm or lower wavelength; More preferably under the ultraviolet light of 193nm, 157nm or lower wavelength, carry out; Still more preferably under the ultraviolet light of 157mn or lower wavelength, carry out.Imaging exposure can carry out or carry out with the photomask non-digitalization with laser aid or similar device digitizing.Preferably use the laser aid digital imaging.The proper laser device that is used for composition digital imaging of the present invention includes but not limited in the argon-fluorine excimer laser of 193nmUV output, in the krypton-fluorine excimer laser of 248nm UV output with at fluorine (F2) laser instrument of 157nm output.Because the ultraviolet light of low wavelength is used for the corresponding high-resolution of imaging exposure (low resolving limit), uses low wavelength (as 193nm or 157nm or lower) to be preferable over usually and uses upper wavelength (as 248nm or higher).Specifically, owing to this reason is preferable over the imaging at 193nm in the 157nm imaging.
Develop.Terpolymer in the resist composition of the present invention must contain the required enough functional groups of developing behind the imaging exposure under ultraviolet light.Preferably, functional group is acid or protected acid, develops thereby may adopt alkaline developer (as sodium hydroxide solution, potassium hydroxide solution or Ammonia) to carry out water law.
But the photoresist of handling when water law is coated with or is applied on the substrate; under ultraviolet light during imaging exposure; the development of described photo-corrosion-resisting agent composition can require adhesive material should contain enough acidic groups (as the carboxylic acid group) and/or protected acidic group, described protected acidic group when exposure for to the small part deprotection to give the processing characteristics of photoresist (or other light imaging coating composition) in aqueous base developers.Under positive photoresist layer situation, adopt aqueous alkaline liquid as the full aqueous solution that contains the 0.262N tetramethyl ammonium hydroxide (usually develop down be less than or equal 120 seconds at 25 ℃) or 1% weight sodium carbonate (30 ℃ develop usually down be less than 2 or equal 2 minutes) in the developing process, the part that is exposed to UV radiation of photoresist layer will be removed, but the unexposed portion of photoresist layer is unaffected in fact.Under the made of as negative-photoresistlayer layer situation, adopt in critical fluids or the organic solvent developing process, the part that is not exposed to UV radiation of photoresist layer will be removed, but the exposed portion of photoresist layer is unaffected in fact.
Critical fluids used herein be heated near or surpass its critical temperature and be compressed near or surpass one or more materials of its emergent pressure.Critical fluids among the present invention is for being higher than under the described fluid critical temperature 15 ℃ temperature and being higher than 5 atmospheric pressure under the described fluid emergent pressure at least at least.Carbon dioxide can be used as critical fluids of the present invention.Various organic solvents also can be used as developer of the present invention.These include but not limited to halogenated solvent and non-halogenated solvent.Preferred halogenated solvent, more preferably fluorated solvent.
By following indefiniteness embodiment the present invention is described in more detail.
Experiment
A. raw material and method
Reagent.TFE derives from DuPont, at CO
2In 50% weight potpourri, directly use.(the 230-400 order Sigma) filters purifying to PDD (DuPont) by silica gel.EVE derives from DuPont, passes through distillation purifying before use.Teflon
_AF 1601 (fluoridize and do not fluoridize) derives from DuPont.The pure CO of SFC
2Derive from Air Products.Two (perfluor-2-N-propoxyl group propionyl) superoxide is according to known method (Zhao, C.; Zhou, R.; Pan, H.; Jin, X.; Qu, Y.; Wu, C.; Jiang, X., J.Org.Chem.1980,47,2009-2013) 1,1,2-three chloro-1,2,2-HFC-143a (Freon
_113) preparation is kept on the dry ice in.Concentration is determined by iodimetric titration, is generally 11% weight.
Tetrafluoroethene, PDD and EVE are at CO
2In copolymerization.Polyreaction is carried out in the 25mL reaction under high pressure observation ward that stirring rod, thermopair, rupture disk and sapphire window (make available endoscopic observation reaction mixture) are housed.By before injection adding EVE and the PDD, CO is adopted in the hyperbaric chamber under argon shield
2Purging is to get rid of oxygen and to be cooled to about 5 ℃ with ice bath.Remove ice bath behind the closed chamber, under agitation use manual pump (HIP, Model 62-6-10) to introduce TFE/CO
2Potpourri (50% weight).TFE for the definite amount of weighing is forced into 103bar (1500psig) with pump.TFE/CO
2The density of the volume calculation of potpourri under 103bar (1500psig).Also being forced into 103bar (1500psig) again introduces calculated volume by the valve between repeated open pump and the reaction observation ward.In this method, the temperature of autoclave keeps below 10 ℃.Add thermal response observation ward subsequently to desired reaction temperature (being generally 15 ℃-35 ℃), initiator solution (two (perfluor-2-N-propoxyl group propionyl) superoxide) is transferred to by injection be connected to CO
2The tubule of pipeline.Adopt automatic syringe pump (ISCO, Model 260D) to use additional C O then
2Observation ward pressurizes and introduces initiating agent simultaneously to reaction.After the reaction, slowly discharge CO
2, use CO
2The residual multipolymer of extraction in the hyperbaric chamber three times to 138bar (2000) psig to remove unreacted monomer and initiating agent remnants.
Characterize.Glass transition temperature is measured under nitrogen by Seiko Instruments DSC 220system.The rate of heat addition of dsc measurement is 10K/ minute.The NMR spectrum at room temperature uses phenyl-hexafluoride solution (10% weight) to measure.
19The F-NMR spectrum is observed on the 400MHz spectrometer, uses benzotrifluoride as interior mark.The resonance of phenyl-hexafluoride presaturation.Have embolus and fill deuterium for the effective internal lock of doing of the 5mm NMR of benzene.
19The parameter of F-NMR nuclear is as follows: 90 ° of pulses are 8.40 μ s, and sweep length is 200ppm, and the transient state number is 512, relaxation delay 10s.IR spectrum carries out (Bruker IFS 66v/S) with the thin polymer film on the NaCl plate.Film adopts Fluorinert
_The FC-75 solution-cast obtains.Absorbance measurement adopts VUV-VASE to carry out by Will Conley at International SEMATECH.The film of measuring absorbance adopts on Fluorinert_FC-40 solution-cast to the two inch disk and obtains.
B. result and discussion
Reaction conditions is to the influence of polymer performance.The multipolymer of TFE, PDD and EVE is at CO
2In synthetic and with NMR spectrum, IR spectrum, differential scanning calorimetry (DSC) and VUV-VASE sign (table 1).The glassy friable material that obtains demonstrates the dissolubility similar to Teflon_AF in phenyl-hexafluoride, Fluorinert_FC-75 and Fluorinert_FC-40.The free-standing film of material adopts the FC-75 of 5% weight and FC-40 solution-cast to make.
Table 1
| Numbering | (℃) | The EVE/PDD/T FE of charging (% mole) | Initiating agent (% mole) | Pressure (psi) | c a(％) | Relaxation time (hour) | EVE/PDD/ TFE forms (% mole) | Productive rate (%) | Tg b (℃) |
| l | 15 | 7/73/20 | 1 | 3500 | 22 | 4 | - | 56 | 160 |
| 2 | 35 | 25/55/20 | 0.2 | 3500 | 19 | 4 | 18/54/28 | 30 | 109 |
| 3 | 15 | 25/55/20 | 0.2 | 3500 | 21 | 0.5 | - | 5 | - |
| 4 | 15 | 25/55/20 | 1 | 1500 | 18 | 4 | - | 16 | - |
| 5 | 5 | 7/73/20 | 1 | 3500 | 19 | 0.5 | - | 42 | 143 |
| 6 | 5 | 10/71/19 | 0.2 | 1500 | 19 | 4 | 7/61/32 | 38 | 133 |
| 7 | 5 | 26/54/20 | 1 | 1500 | 20 | 0.5 | - | 19 | - |
| 8 | 15 | 8/72/20 | 0.2 | 1500 | 17 | 0.5 | - | 28 | - |
| 9 | 35 | 18/63/19 | 0.2 | 3500 | 20 | 20 | 12/59/29 | 30 | - |
aMonomer concentration (weight/volume)
bMeasure in the heating process in the second time: 25-400 ℃, heating for the first time: 25-300 ℃, the rate of heat addition: 10 ℃/minute
According to reaction conditions, the polyreaction productive rate is 5% to 56%.Adopt the Plackett-Burman statistical model to carry out a series of eight experiments with observation monomer feed ratio, initiator concentration, temperature, pressure and the influence in reaction time.As expected, productive rate is along with EVE number percent in the charging reduces, temperature raises, initiator concentration improves, pressure improves and the reaction time prolongs and improves.
Adopt
19The quantitative information that F-NMR spectrum provides terpolymer to form.Being attached to EVE number percent in the polymer chain (determining by the NMR spectrum integral) improves along with the raising of EVE amount in the monomer feed.Determine the NMR peak according to the previous work that EVE monosomic analysis and DeSimone and colleague thereof carry out.
IR spectrum passes through 1800cm
-1Carbonyl stretching, extension (this does not exist in TFE and PDD multipolymer spectrum) appears in the place proves that EVE is attached in the polymer chain.The contrast of the different terpolymer IR spectrum of EVE combination degree demonstrates when EVE introduces in the chain, other peak relatively, and the intensity of carbonyl peak improves (table 2).
Table 2
| Numbering | EVE (% mole) | L1 | L2 | L2/L1 |
| 5 | - | 48.7 | 73.0 | 1.50 |
| 6 | 7 | 42.3 | 71.7 | 1.70 |
| 9 | 12 | 43.7 | 82.0 | 1.87 |
| 2 | 18 | 42.2 | 82.3 | 1.95 |
The glass transition temperature that observes by DSC is along with the raising of EVE content reduces.This thinks that TFE content roughly remains unchanged and the EVE monomer that rotates freely has replaced PDD more.Yet when in conjunction with 18% mole of EVE, the glass transition temperature of the material that obtains is 109 ℃.This shows that the thermal behavior of PDD/TFE base terpolymer should be suitable for photolithography and use.
The absorbance at the 157.6nm place that VUV-VASE measures is compared with the absorbance at the 157.6nm place of Teflon_AF, when in conjunction with 7% mole of EVE, and reduction at first, and when other EVE is attached in the polymer chain, increase (table 3) subsequently.The absorbance that increases can increase with the carbonyl of following EVE to be explained.Equally, when TFE roughly remained unchanged, the EVE that amount increases in the chain had replaced the low-down PDD monomer of absorbance.Compare with the absorbance of Teflon_AF, it may be because the difference of PDD molar percentage that the initial a small amount of of absorbance reduces.Even when the EVE content of measuring is the highest (18% mole), material still is very low the absorption, suitably is lower than 1 required μ m of photolithography
-1Threshold value.
Table 3
| Numbering | EVE (% mole) | 157.6nm(μm -1) | 193nm(μm -1) |
| 5 | - | 0.13 | 0.01 |
| 9 | 12 | 0.25 | 0.01 |
| 2 | 18 | 0.57 | 0.02 |
| Teflon _AF1601 | - | 0.15 | 0.004 |
| TFE and PDD multipolymer a | - | 0.15 | 0.02 |
aAt CO
2In synthetic 76/24PDD/TFE (% mole)
Synthesizing of other Teflon_AF sill.Above-mentioned system has extended to and has comprised the unsaturated functional compound of other olefinic (as acrylic acid tertiary butyl ester or methacrylic acid tertiary butyl ester), and this provides an alternative embodiment of the invention.Tert-butyl group back in being exposed to acid (originating from light-sensitive compound) disconnects, and this provides dissolubility to change, because the more or less developer solution (promptly being respectively positivity or negative tone) that is dissolved in of polymkeric substance that obtains.Prepare a series of TFE of containing polymkeric substance, also synthesized a series of non-TFE sill (as follows) in addition.These systems extend to and comprise norborene (NB) (it is used for improving dissolubility and the raising corrosion stability of resist at the conventional solvent that is used for photolithography).
As mentioned above, when the unsaturated functional compound of olefinic (as t-BuAc) is exposed in the acid (originating from light-sensitive compound), can disconnect and think that the high resolving power imaging provides dissolubility to change (referring to as follows).
(from left to right) as can be seen, the tert-butyl group disconnect, and therefore eliminate isobutylene and regenerate acid.This method should be the high resolving power imaging essential contrast is provided.This individual system also obtains chemistry amplifies, thereby per molecule light-sensitive compound (PAC) can disconnect many groups.
A. raw material and method
Reagent.TFE derives from DuPont, at CO
2In 50% weight potpourri and directly the use.(the 230-400 order Sigma) filters purifying to PDD (DuPont) by silica gel.
Tert-butyl acrylate/metering system tert-butyl acrylate derives from Aldrich and passes through through neutral activated alumina purifying.Norborene (NB) derives from Aldrich and directly uses.The pure CO of SFC
2Derive from Air Products.Two (4-tert-butylcyclohexyl) peroxide two carbonic esters (Perkadox_16) derive from polymer chemicals and directly use.
Copolymerization.Polyreaction is carried out in the 25mL reaction under high pressure observation ward that stirring rod, thermopair, rupture disk and sapphire window (make available endoscopic observation reaction mixture) are housed.Initiating agent adds (when comprising NB, also with its adding) in the container at first.Under argon shield,, container was purged 30 minutes, be cooled to 5 ℃ with ice bath subsequently with argon gas by before injection adding t-BuAc and the PDD.Remove ice bath behind the closed chamber, under agitation use manual pump (HIP, Model 62-6-10) to introduce TFE/CO
2Potpourri (50% weight) (when using).TFE for the definite amount of weighing is forced into 103bar (1500psig) with pump.TFE/CO
2The volume of potpourri is by the density calculation under the 103bar (1500psig).Also be forced into 103bar (1500psig) again by the valve between repeated open pump and the reaction observation ward, introduce calculated volume.In this method, the temperature of autoclave keeps below 10 ℃.Reacting observation ward then adopts automatic syringe pump (ISCO, Model 260D) to use CO
2Pressurization.Be heated to desired reaction temperature (50 ℃) with afterreaction observation ward, the pressure under this temperature of reaction is 3000psig.Reaction slowly discharges CO after finishing
2, use CO
2Residual multipolymer three times (138bar/2000psig) in the extraction hyperbaric chamber is to remove unreacted monomer.
Characterize.Glass transition temperature is measured under nitrogen by Seiko Instruments DSC 220system.The rate of heat addition of dsc measurement is 10K/ minute.IR spectrum carries out (Bruker IFS 66v/S) with the thin polymer film on the NaCl plate.On Seiko RTG 220, carry out thermogravimetric analysis (TGA) to determine the decomposition temperature and the thermal cracking temperature of unsaturated functional compound (tBuAc).Adopt Waters 2690 GPC determining molecular weights, adopt THF as solvent, retention time is measured with RI-detector p-poly-phenyl ethene reference material.
B. result and discussion
Reaction conditions is to the influence of polymer performance.As follows at CO
2In a series of Teflon_-AF of preparation contain the TFE variant.Polymkeric substance directly separates from reactor with high yield.The polymkeric substance that obtains has a series of different glass transition temperatures, and several have a high Tg (〉=120 ℃) that is enough to as photoresist.Polymkeric substance demonstrates the dissolubility (as dissolving in phenyl-hexafluoride) that can compare with Teflon_-AF.
| TFE (% mole) | PDD (% mole) | TBuAc (% mole) | Productive rate (%) | Initiating agent (% mole) | Tg |
| 20 | 73 | 7 | 54.7 | 1 | 86 |
| 20 | 62 | 18 | 42.7 | 1 | 96 |
| 20 | 55 | 25 | 20.8 | 1 | 120 |
| 20 | 55 | 25 | 53.5 | 0.5 | 132 |
| 20 | 55 | 25 | 15.3 | 0.26 | 139 |
| 10 | 65 | 25 | 42.8 | 0.5 | 141 |
| 30 | 45 | 25 | 35.7 | 0.5 | 48 |
Reaction conditions: 50 ℃, 15 hours, at CO
2In, 3000psig, employing Perkadox_16 be as initiating agent.
These polymkeric substance conducts are used for the photoresist of 193nm, 157nm and immersion lithography method and but the low-K dielectric of imaging is assessed.These materials have the CO of being used in addition
2The potentiality of the increase of base deposition and development, this can be avoided using a large amount of toxic solvents and prevent that image from destroying.Use this commercially available chemistry to amplify the applicability that the unsaturated functional compound of olefinic (as t-BuAc) will enlarge this Teflon_-AF based platform.
In addition, do not add TFE and prepare similar polymkeric substance (referring to as follows).First kind of multipolymer (NB/PDD/t-BuAc) is dissolved in the conventional solvent that is used for photolithography.This provides a kind of improved approach for this method, promptly gives the performance that above-mentioned TFE sill can deposit and develop with conventional solvent.This will make us these new materials can be applied in many new lithographic process, thereby influence several critical lithography techniques of future generation.
The PDD/t-BuAc multipolymer separates with 64% productive rate, and Tg is 142 ℃.The Tg of multipolymer (productive rate is 22%) that contains NB is near 150 ℃.In addition, this multipolymer is dissolved in the propylene glycol monomethyl ether acetate (PGMEA), and it is the industrial standard thing that is used for resist rotary coating deposition.Also measured the molecular weight (Mw=2884 gram/mole, Mn=2167 gram/mole) of this polymkeric substance, this is sufficiently high for the high Tg material of preparation, and is enough low for the dissolution that raising is provided in the developing process.This material has been spun onto on a series of different size silicon chips (2-6 inch).In addition, in the presence of PAC (photo-acid generator 336), the tert-butyl group can rupture under ultraviolet light, confirms by IR spectrum.The carboxylic acid functionalized polymkeric substance that obtains is dissolved in the standard base (SB) developer solution (tetramethyl ammonium hydroxide (TMAH)), and shielded polymkeric substance is insoluble.This provides essential contrast for high-resolution picture.The absorbance of these materials adopts VUV-VASE to measure by Will Conley at International SEMATECH.These materials are about to imaging.
In a word, for the first time under the low temperature at CO
2In synthesized the TFE/PDD/EFE terpolymer.Prepared the terpolymers with different compositions, they have glass transition temperature in a big way: 109 ℃ to 160 ℃.Adopt Plackett-Burman model investigation monomer feed, initiator concentration, temperature, pressure and the influence in reaction time.NMR and IR spectrum have confirmed that EVE is attached in the polymer chain.These materials are presented at the low-down absorbance of 157.6nm and 193nm.Confirmed ester group, shown the functional group that EVE and EVE analog can be used as provides the dissolubility contrast with acid fracture EVE.In addition, the polymkeric substance of the synthetic unsaturated functional compound of other olefinic of a series of employing (as t-BuAc).These materials by provide have influence several key lithography techniques of future generation (193nm, 157nm and immersion lithography method) but the material and the imaging dielectric of the more wide region of necessary performance have been expanded this method.
More than describe the present invention, should not be construed as the present invention is limited.The present invention determines by the coordinator of following claim and the claim that comprised.
Claims (20)
1. photoresist, described photoresist comprises:
(a) a kind of compound, described compound are following terpolymers:
(i) the unsaturated linear or hyperbranched compounds of at least a olefinic, described compound has at least one fluorine atom covalently bound with it;
The (ii) ring or the unsaturated precursor of at least a olefinic of polycyclic compund, described precursor has at least one fluorine atom covalently bound with it to form ring or encircle more and separate brilliant monomer in described terpolymer; With
Dissolubility after the unsaturated functional compound of (iii) at least a olefinic, described functional compound change it and are being exposed in acid or the alkali as monomer in described terpolymer; With
(b) light-sensitive compound.
2. the photoresist of claim 1, the unsaturated linear or hyperbranched compounds of wherein said at least a olefinic is selected from tetrafluoroethene, chlorotrifluoroethylene, trifluoro-ethylene, vinylidene fluoride and fluorothene.
3. the photoresist of claim 1, the unsaturated precursor of at least a olefinic of wherein said ring or polycyclic compund is a formula
Cyclic compound.
4. the photoresist of claim 1, the formula of the unsaturated precursor of at least a olefinic of wherein said ring or polycyclic compund is CF
2=CFCF
2CF
2OCF=CF
2
5. the photoresist of claim 1, the unsaturated precursor of at least a olefinic of wherein said ring or polycyclic compund is selected from:
Wherein A=H, C (CH
3)
3Or Si (CH
3)
3,
Vinyl acetate, tert-butyl acrylate and 5-norborene-2-carboxylic acid tert-butyl ester.
6. the photoresist of claim 1, the unsaturated functional compound of wherein said at least a olefinic has at least one fluorine atom covalently bound with it.
7. the photoresist of claim 1, the unsaturated functional compound of wherein said at least a olefinic is the ester vinyl ether.
8. the photoresist of claim 1, the unsaturated functional compound of wherein said at least a olefinic is the fluorinated esters vinyl ether.
9. the photoresist of claim 1, the unsaturated functional compound of wherein said at least a olefinic is for being selected from
The fluorinated esters vinyl ether.
10. the photoresist of claim 1, wherein said at least a photosensitive component is a photo-acid generator.
11. the photoresist of claim 1, wherein said at least a photosensitive component is photic generated base alkaline agent.
12. a method for preparing the photoresist image on substrate, described method comprises:
(a) photo-corrosion-resisting agent composition is coated on the substrate, wherein said photo-corrosion-resisting agent composition comprises the terpolymer of (i) claim 1, (ii) photosensitive component and (iii) solvent;
(b) dry described photo-corrosion-resisting agent composition to be removing described solvent in fact, thereby forms the photoresist layer on substrate;
(c) with described photoresist floor imaging exposure to form district of imaging and imaging district not; With
(d) develop have the district of imaging and not the photoresist floor that has exposed in imaging district on substrate, to form relief image.
13. the method for claim 12, wherein said solvent comprises carbon dioxide.
14. the method for claim 12, wherein said imaging exposure adopt UV radiation to carry out.
15. the method for claim 12, the UV radiation that wherein said imaging exposure employing wavelength is 157nm or 193nm is carried out.
16. the method for claim 12, wherein said development step adopt the supercritical solution that comprises carbon dioxide to carry out.
17. a method for preparing the terpolymer of claim 1, described method comprises the steps:
(a) the unsaturated linear or hyperbranched compounds of (i) at least a olefinic with at least one fluorine atom covalently bound with it is provided and (ii) at least aly has at least one fluorine atom covalently bound and separate the unsaturated ring of olefinic of brilliant monomer or the bipolymer of polycyclic compund in described terpolymer, to form with it; With
(b) make the terpolymer of described bipolymer and the unsaturated functional compound of at least a olefinic prepared in reaction claim 1 in carbon dioxide solvent, the dissolubility after described functional compound changes it and is exposed to acid or alkali as monomer in described terpolymer.
18. the method for claim 17, wherein said carbon dioxide are liquid carbon dioxide.
19. the method for claim 17, wherein said carbon dioxide are supercritical carbon dioxide.
20. the method for claim 17, wherein said bipolymer prepares in carbon dioxide solvent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US51268503P | 2003-10-20 | 2003-10-20 | |
| US60/512,685 | 2003-10-20 | ||
| US60/513,049 | 2003-10-21 | ||
| US10/968,390 | 2004-10-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1871549A true CN1871549A (en) | 2006-11-29 |
Family
ID=37444493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480030777 Pending CN1871549A (en) | 2003-10-20 | 2004-10-20 | Fluorinated photoresists prepared, deposited, developed and removed in carbon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1871549A (en) |
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2004
- 2004-10-20 CN CN 200480030777 patent/CN1871549A/en active Pending
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