JP4476675B2 - Chemically amplified positive photoresist composition - Google Patents
Chemically amplified positive photoresist composition Download PDFInfo
- Publication number
- JP4476675B2 JP4476675B2 JP2004115328A JP2004115328A JP4476675B2 JP 4476675 B2 JP4476675 B2 JP 4476675B2 JP 2004115328 A JP2004115328 A JP 2004115328A JP 2004115328 A JP2004115328 A JP 2004115328A JP 4476675 B2 JP4476675 B2 JP 4476675B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- component
- photoresist composition
- resin
- positive photoresist
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 54
- 229920002120 photoresistant polymer Polymers 0.000 title claims description 44
- 229920005989 resin Polymers 0.000 claims description 84
- 239000011347 resin Substances 0.000 claims description 84
- -1 aromatic hydroxy compound Chemical class 0.000 claims description 55
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 52
- 229920003986 novolac Polymers 0.000 claims description 52
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 34
- 239000000126 substance Substances 0.000 claims description 19
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 18
- 238000004090 dissolution Methods 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 150000001299 aldehydes Chemical class 0.000 claims description 16
- 230000002401 inhibitory effect Effects 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000006482 condensation reaction Methods 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 230000005855 radiation Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 18
- 230000000694 effects Effects 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 14
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 13
- 239000010408 film Substances 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 9
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 238000003860 storage Methods 0.000 description 8
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 8
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical class OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- IBGBGRVKPALMCQ-UHFFFAOYSA-N 3,4-dihydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1O IBGBGRVKPALMCQ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003759 ester based solvent Substances 0.000 description 5
- 238000005194 fractionation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000002513 implantation Methods 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 150000002576 ketones Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- COFKFSSWMQHKMD-UHFFFAOYSA-N n,n-didecyldecan-1-amine Chemical compound CCCCCCCCCCN(CCCCCCCCCC)CCCCCCCCCC COFKFSSWMQHKMD-UHFFFAOYSA-N 0.000 description 4
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 4
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 4
- 229920005591 polysilicon Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WUQYBSRMWWRFQH-UHFFFAOYSA-N 2-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=CC=C1O WUQYBSRMWWRFQH-UHFFFAOYSA-N 0.000 description 3
- PCYGLFXKCBFGPC-UHFFFAOYSA-N 3,4-Dihydroxy hydroxymethyl benzene Natural products OCC1=CC=C(O)C(O)=C1 PCYGLFXKCBFGPC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000007514 bases Chemical class 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000003405 preventing effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- OGRAOKJKVGDSFR-UHFFFAOYSA-N 2,3,5-trimethylphenol Chemical compound CC1=CC(C)=C(C)C(O)=C1 OGRAOKJKVGDSFR-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 2
- QTUVQQKHBMGYEH-UHFFFAOYSA-N 2-(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC=N1 QTUVQQKHBMGYEH-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- YCOXTKKNXUZSKD-UHFFFAOYSA-N 3,4-xylenol Chemical compound CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 2
- HMNKTRSOROOSPP-UHFFFAOYSA-N 3-Ethylphenol Chemical compound CCC1=CC=CC(O)=C1 HMNKTRSOROOSPP-UHFFFAOYSA-N 0.000 description 2
- ASHGTJPOSUFTGB-UHFFFAOYSA-N 3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1 ASHGTJPOSUFTGB-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 2
- FFWSICBKRCICMR-UHFFFAOYSA-N 5-methyl-2-hexanone Chemical compound CC(C)CCC(C)=O FFWSICBKRCICMR-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000004036 acetal group Chemical group 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 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
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ZCONCJFBSHTFFD-UHFFFAOYSA-N 2,3,5-triethylphenol Chemical compound CCC1=CC(O)=C(CC)C(CC)=C1 ZCONCJFBSHTFFD-UHFFFAOYSA-N 0.000 description 1
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 1
- BFQFFNWLTHFJOZ-UHFFFAOYSA-N 2-(1,3-benzodioxol-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=2C=C3OCOC3=CC=2)=N1 BFQFFNWLTHFJOZ-UHFFFAOYSA-N 0.000 description 1
- ORXBVLDMEZLJSC-UHFFFAOYSA-N 2-(4-butoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OCCCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ORXBVLDMEZLJSC-UHFFFAOYSA-N 0.000 description 1
- XBYTTXAEDHUVAH-UHFFFAOYSA-N 2-(4-butoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OCCCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XBYTTXAEDHUVAH-UHFFFAOYSA-N 0.000 description 1
- NLNVSTLNDJGLTL-UHFFFAOYSA-N 2-(4-ethoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 NLNVSTLNDJGLTL-UHFFFAOYSA-N 0.000 description 1
- YDBMRUAZKHZDPE-UHFFFAOYSA-N 2-(4-ethoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 YDBMRUAZKHZDPE-UHFFFAOYSA-N 0.000 description 1
- FVNIIPIYHHEXQA-UHFFFAOYSA-N 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C12=CC=CC=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 FVNIIPIYHHEXQA-UHFFFAOYSA-N 0.000 description 1
- QRHHZFRCJDAUNA-UHFFFAOYSA-N 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 QRHHZFRCJDAUNA-UHFFFAOYSA-N 0.000 description 1
- KHEUDQHXPYDZDC-UHFFFAOYSA-N 2-(4-propoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=CC(OCCC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 KHEUDQHXPYDZDC-UHFFFAOYSA-N 0.000 description 1
- IXQGCWUGDFDQMF-UHFFFAOYSA-N 2-Ethylphenol Chemical compound CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 1
- XTTBGXRWHFAGSV-UHFFFAOYSA-N 2-[2-(3,4-diethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OCC)C(OCC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XTTBGXRWHFAGSV-UHFFFAOYSA-N 0.000 description 1
- ZJRNXDIVAGHETA-UHFFFAOYSA-N 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZJRNXDIVAGHETA-UHFFFAOYSA-N 0.000 description 1
- YLNWVZWYQSFYQX-UHFFFAOYSA-N 2-[2-(3,5-diethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCOC1=CC(OCC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 YLNWVZWYQSFYQX-UHFFFAOYSA-N 0.000 description 1
- XCIXLYIKKUQVST-UHFFFAOYSA-N 2-[2-(3,5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound COC1=CC(OC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 XCIXLYIKKUQVST-UHFFFAOYSA-N 0.000 description 1
- NTDADACWCAILCY-UHFFFAOYSA-N 2-[2-(3-ethoxy-4-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OCC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 NTDADACWCAILCY-UHFFFAOYSA-N 0.000 description 1
- DBPSPKZXOUHFBO-UHFFFAOYSA-N 2-[2-(3-ethoxy-4-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OCC)C(OCCC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DBPSPKZXOUHFBO-UHFFFAOYSA-N 0.000 description 1
- OKNVJQFSYJFJJU-UHFFFAOYSA-N 2-[2-(3-ethoxy-5-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCOC1=CC(OC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 OKNVJQFSYJFJJU-UHFFFAOYSA-N 0.000 description 1
- MIOHLZKPMGYOFV-UHFFFAOYSA-N 2-[2-(3-ethoxy-5-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCCOC1=CC(OCC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 MIOHLZKPMGYOFV-UHFFFAOYSA-N 0.000 description 1
- LESOHSVCDCZUBU-UHFFFAOYSA-N 2-[2-(3-methoxy-4-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OCCC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 LESOHSVCDCZUBU-UHFFFAOYSA-N 0.000 description 1
- OGUBTLXKPIKDGN-UHFFFAOYSA-N 2-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound CCCOC1=CC(OC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 OGUBTLXKPIKDGN-UHFFFAOYSA-N 0.000 description 1
- ZNAIDOOXIMBHIB-UHFFFAOYSA-N 2-[2-(4-ethoxy-3-methoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OCC)=CC=C1C=CC1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 ZNAIDOOXIMBHIB-UHFFFAOYSA-N 0.000 description 1
- SULDZIWHCGZDPC-UHFFFAOYSA-N 2-[2-(4-ethoxy-3-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OCC)C(OCCC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 SULDZIWHCGZDPC-UHFFFAOYSA-N 0.000 description 1
- WNSIYKMOLQBDAA-UHFFFAOYSA-N 2-[2-(4-methoxy-3-propoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound C1=C(OC)C(OCCC)=CC(C=CC=2N=C(N=C(N=2)C(Cl)(Cl)Cl)C(Cl)(Cl)Cl)=C1 WNSIYKMOLQBDAA-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- UITUMGKYHZMNKN-UHFFFAOYSA-N 2-methyl-4-prop-1-en-2-ylphenol Chemical compound CC(=C)C1=CC=C(O)C(C)=C1 UITUMGKYHZMNKN-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 236TMPh Natural products CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 1
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- XSOIRBRXHZBZOO-UHFFFAOYSA-N 5-[4,6-bis(trichloromethyl)-1,3,5-triazin-2-yl]-8-methoxynaphthalene-2-carboxylic acid Chemical compound C12=CC=C(C(O)=O)C=C2C(OC)=CC=C1C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 XSOIRBRXHZBZOO-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- KVFDZFBHBWTVID-UHFFFAOYSA-N cyclohexanecarbaldehyde Chemical compound O=CC1CCCCC1 KVFDZFBHBWTVID-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- CSYSRRCOBYEGPI-UHFFFAOYSA-N diazo(sulfonyl)methane Chemical compound [N-]=[N+]=C=S(=O)=O CSYSRRCOBYEGPI-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 150000003903 lactic acid esters Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MXHTZQSKTCCMFG-UHFFFAOYSA-N n,n-dibenzyl-1-phenylmethanamine Chemical compound C=1C=CC=CC=1CN(CC=1C=CC=CC=1)CC1=CC=CC=C1 MXHTZQSKTCCMFG-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 229940079877 pyrogallol Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
Classifications
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- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
- G03F7/0236—Condensation products of carbonyl compounds and phenolic compounds, e.g. novolak resins
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
Landscapes
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Materials For Photolithography (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Description
本発明は、化学増幅型ポジ型ホトレジスト組成物に関するものである。 The present invention relates to a chemically amplified positive photoresist composition.
これまで、半導体素子、液晶表示素子（ＬＣＤ）、印刷版、バンプ形成、磁気ヘッド等を製造する分野においては、アルカリ可溶性樹脂とキノンジアジド基含有化合物（ＰＡＣ）を主成分とするｇ〜ｉ線ホトレジスト組成物や、酸解離性基含有化合物（樹脂）と光酸発生剤（ＰＡＧ）を主成分とするｉ線用、ＫｒＦ用、ＡｒＦ用又は電子線用化学増幅型ホトレジスト組成物などが一般に用いられてきた。 Until now, in the field of manufacturing semiconductor elements, liquid crystal display elements (LCD), printing plates, bump formation, magnetic heads, etc., g to i-line photoresists mainly composed of an alkali-soluble resin and a quinonediazide group-containing compound (PAC). Generally used are compositions, chemically amplified photoresist compositions for i-line, KrF, ArF or electron beam mainly composed of acid dissociable group-containing compound (resin) and photoacid generator (PAG). I came.
化学増幅型ホトレジスト組成物としては、下記特許文献１〜４に記載のもの等が知られている。
特許文献１には、ポリヒドロキシスチレンの水酸基の水素原子の一部を酸解離性溶解抑制基で保護してなる樹脂成分とＰＡＧを含有してなる組成物が記載されている。
特許文献２、３には、ノボラック樹脂など側鎖に水酸基を有するアルカリ可溶性樹脂と、特定の架橋剤と、酸発生剤を含有する化学増幅型ポジ型ホトレジスト組成物が記載されている。
特許文献４には、酸触媒の存在下で水酸基含有ポリマーとポリビニルエーテルとを反応させて得られた部分架橋ポリマーとＰＡＧを含有してなる組成物が記載されている。
Patent Document 1 describes a composition comprising a resin component obtained by protecting a part of hydrogen atoms of a hydroxyl group of polyhydroxystyrene with an acid dissociable, dissolution inhibiting group, and PAG.
Patent Documents 2 and 3 describe chemically amplified positive photoresist compositions containing an alkali-soluble resin having a hydroxyl group in a side chain such as a novolak resin, a specific crosslinking agent, and an acid generator.
Patent Document 4 describes a composition comprising a partially crosslinked polymer obtained by reacting a hydroxyl group-containing polymer with polyvinyl ether in the presence of an acid catalyst and PAG.
ところで、各分野における技術の進歩に伴って、用途によってはホトレジスト組成物に耐熱性が要求されるようになった。
例えば、１枚のガラス基板上に、ドライバ、ＤＡＣ（デジタル−アナログコンバーター）、画像プロセッサ、ビデオコントローラ、ＲＡＭなどの集積回路部分がディスプレイ部分と同時に形成される、いわゆる「システムＬＣＤ」と呼ばれる高機能ＬＣＤは次世代のＬＣＤとして期待されている（Semiconductor FPD World ２００１.９, pp.５０−６７）。
このようなシステムＬＣＤのＴＦＴ（薄膜トランジスタ）には、特に６００℃以下の低温プロセスで形成される低温ポリシリコンが、アモルファスシリコンに比べて電気抵抗が小さくて移動度が高いことから好適であるとされている。
低温ポリシリコンからなるＴＦＴを製造するには、ガラス基板上に低温プロセスでポリシリコン膜を形成した後、該低温ポリシリコン膜にＰやＢ等を打ち込む、いわゆる「インプランテーション工程」において、非常に高濃度の不純物を打ち込むことが必要とされている。このインプランテーション工程は、真空度の高い条件下で行われるが、不純物の打ち込みによる発熱作用により、基板上のレジストパターンが加熱されると、レジストパターンが形状変化を起こしたり、レジストパターン中のある成分がガス化して処理室内の真空度を下げるという問題がある。
ノボラック樹脂は安価で耐熱性に優れる樹脂成分として大変有用であるが、当該ノボラック樹脂の水酸基の水素原子の一部を酸解離性溶解抑制基で保護してなる樹脂成分は、著しく耐熱性に劣るため、化学増幅型ポジ型ホトレジスト組成物の樹脂成分としての利用は困難であった。
By the way, with the advancement of technology in each field, the photoresist composition is required to have heat resistance depending on the application.
For example, an integrated circuit portion such as a driver, a DAC (digital-to-analog converter), an image processor, a video controller, and a RAM is formed at the same time as a display portion on a single glass substrate. LCD is expected as the next generation LCD (Semiconductor FPD World 2001.9, pp. 50-67).
For such a TFT (thin film transistor) of the system LCD, low temperature polysilicon formed by a low temperature process of 600 ° C. or less is particularly suitable because it has a lower electrical resistance and higher mobility than amorphous silicon. ing.
In order to manufacture a TFT made of low-temperature polysilicon, a polysilicon film is formed on a glass substrate by a low-temperature process, and then P or B is implanted into the low-temperature polysilicon film. It is necessary to implant a high concentration of impurities. This implantation process is performed under a high degree of vacuum, but when the resist pattern on the substrate is heated due to the exothermic action due to the implantation of impurities, the resist pattern may change its shape or be in the resist pattern. There is a problem that the components are gasified to lower the degree of vacuum in the processing chamber.
The novolak resin is very useful as a resin component that is inexpensive and excellent in heat resistance, but the resin component obtained by protecting a part of the hydrogen atoms of the hydroxyl group of the novolak resin with an acid dissociable, dissolution inhibiting group is extremely inferior in heat resistance. For this reason, it has been difficult to use the chemically amplified positive photoresist composition as a resin component.
この問題を解決する手段として、樹脂成分の高分子量化や、嵩高い芳香族ヒドロキシ化合物を用いて合成したノボラック樹脂を用いるなどの方法が挙げられるが、当該方法はいずれも、樹脂成分のアルカリ溶解性が劣化する傾向にあることから、レジスト組成物の解像性の劣化につながるといった問題を有する。また、上記問題を解決する手段としては、インプランテーション工程前に「ポストベーク」と呼ばれる加熱処理工程を行うことが有効であるが、このポストベークは、インプランテーション時に加熱される温度に近い温度条件で、例えば１６０℃以上の高温で行われる。したがって、かかる加熱処理においてもレジストパターンの形状が変化しない等の耐熱性が必要である。 As means for solving this problem, there are methods such as increasing the molecular weight of the resin component and using a novolak resin synthesized using a bulky aromatic hydroxy compound. Therefore, there is a problem that the resolution of the resist composition is deteriorated. As a means for solving the above problem, it is effective to perform a heat treatment process called “post-bake” before the implantation process. This post-bake is performed under a temperature condition close to the temperature heated during the implantation. For example, it is performed at a high temperature of 160 ° C. or higher. Therefore, heat resistance is required such that the shape of the resist pattern does not change even in such heat treatment.
本発明は、上記事情に鑑みてなされたものであって、樹脂成分としてノボラック樹脂を用いながら、耐熱性に優れた化学増幅型ホトレジスト組成物を提供することを目的とする。 This invention is made | formed in view of the said situation, Comprising: It aims at providing the chemically amplified photoresist composition excellent in heat resistance, using a novolak resin as a resin component.
上記の目的を達成するために、本発明は以下の構成を採用した。
（Ａ）樹脂成分と、（Ｃ）放射線の照射により酸成分を発生する下記一般式（ＶＩＩＩ）で表される化合物と、有機溶剤とを含み、前記（Ｃ）成分から発生する酸成分の作用により、アルカリ水溶液に対する溶解性が増大する性質を有する化学増幅型ポジ型ホトレジスト組成物であって、
前記（Ａ）成分が、芳香族ヒドロキシ化合物と、少なくともホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒドを含むアルデヒド類とを縮合反応させて得られるノボラック樹脂（ａ１）の、全フェノール性水酸基の一部を酸解離性溶解抑制基で保護してなるアルカリ難溶性あるいは不溶性の樹脂成分を含むことを特徴とする化学増幅型ポジ型ホトレジスト組成物。
In order to achieve the above object, the present invention employs the following configuration.
(A) A resin component, (C) a compound represented by the following general formula (VIII) that generates an acid component upon irradiation with radiation, and an organic solvent, and the action of the acid component generated from the component (C) A chemically amplified positive photoresist composition having the property of increasing solubility in an alkaline aqueous solution,
The component (A) is a part of the total phenolic hydroxyl group of the novolak resin (a1) obtained by condensation reaction of an aromatic hydroxy compound and an aldehyde containing at least formaldehyde and a hydroxyl group-substituted aromatic aldehyde. A chemically amplified positive photoresist composition comprising an alkali hardly soluble or insoluble resin component protected with a dissociable dissolution inhibiting group.
前記（Ａ）成分が、前記ノボラック樹脂（ａ１）の、全フェノール性水酸基の一部を酸解離性溶解抑制基で保護してなるアルカリ難溶性あるいは不溶性の樹脂に、低分子量体を分別除去する処理を施して得られる樹脂成分を含むことが好ましい。
または、前記（Ａ）成分が、芳香族ヒドロキシ化合物と、少なくともホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒドを含むアルデヒド類とを縮合反応させて得られるノボラック樹脂であって、低分子量体を分別除去する処理が施された処理済ノボラック樹脂（ａ２）の、全フェノール性水酸基の一部を酸解離性溶解抑制基で保護してなるアルカリ難溶性あるいは不溶性の樹脂成分を含むことが好ましい。
The component (A) fractionates and removes a low molecular weight substance from an alkali hardly soluble or insoluble resin obtained by protecting a part of all phenolic hydroxyl groups of the novolak resin (a1) with an acid dissociable, dissolution inhibiting group. It is preferable that the resin component obtained by processing is included.
Alternatively, the component (A) is a novolak resin obtained by subjecting an aromatic hydroxy compound and an aldehyde containing at least formaldehyde and a hydroxyl group-substituted aromatic aldehyde to a condensation reaction, and the low molecular weight product is removed by separation. It is preferable that the treated novolak resin (a2) subjected to the above treatment contains an alkali hardly soluble or insoluble resin component obtained by protecting a part of all phenolic hydroxyl groups with an acid dissociable, dissolution inhibiting group.
本発明によれば、アルカリ可溶性樹脂として、縮合剤にヒドロキシル基置換芳香族アルデヒドを用いて合成されたノボラック樹脂（ａ１）を用いることにより、樹脂成分のアルカリ溶解性を損なうことなく、むしろ逆に向上させることができ、また耐熱性に優れた化学増幅型ポジ型ホトレジスト組成物を提供することができる。 According to the present invention, the novolac resin (a1) synthesized using a hydroxyl group-substituted aromatic aldehyde as the condensing agent is used as the alkali-soluble resin, so that the alkali solubility of the resin component is not adversely affected. It is possible to provide a chemically amplified positive photoresist composition that can be improved and has excellent heat resistance.
・（Ａ）成分
（Ａ）成分を構成するアルカリ難溶性あるいは不溶性の樹脂成分は、ノボラック樹脂（ａ１）と酸解離性溶解抑制基に対応する化合物との付加反応により合成することができる。
ノボラック樹脂（ａ１）は、芳香族ヒドロキシ化合物とアルデヒド類とを縮合反応させて得られる。
-Component (A) The alkali-insoluble or insoluble resin component constituting the component (A) can be synthesized by an addition reaction between the novolak resin (a1) and a compound corresponding to the acid dissociable, dissolution inhibiting group.
The novolak resin (a1) is obtained by subjecting an aromatic hydroxy compound and an aldehyde to a condensation reaction.
ノボラック樹脂（ａ１）の合成に用いられる前記芳香族ヒドロキシ化合物としては、例えばフェノール；ｍ−クレゾール、ｐ−クレゾール、ｏ−クレゾール等のクレゾール類；２，３−キシレノール、２，５−キシレノール、３，５−キシレノール、３，４−キシレノール等のキシレノール類；ｍ−エチルフェノール、ｐ−エチルフェノール、ｏ−エチルフェノール、２，３，５−トリメチルフェノール、２，３，５−トリエチルフェノール、４−ｔｅｒｔ−ブチルフェノール、３−ｔｅｒｔ−ブチルフェノール、２−ｔｅｒｔ−ブチルフェノール、２−ｔｅｒｔ−ブチル−４−メチルフェノール、２−ｔｅｒｔ−ブチル−５−メチルフェノール等のアルキルフェノール類；ｐ−メトキシフェノール、ｍ−メトキシフェノール、ｐ−エトキシフェノール、ｍ−エトキシフェノール、ｐ−プロポキシフェノール、ｍ−プロポキシフェノール等のアルコキシフェノール類；ｏ−イソプロペニルフェノール、ｐ−イソプロペニルフェノール、２−メチル−４−イソプロペニルフェノール、２−エチル−４−イソプロペニルフェノール等のイソプロペニルフェノール類；フェニルフェノール等のアリールフェノール類；４，４’−ジヒドロキシビフェニル、ビスフェノールＡ、レゾルシノール、ヒドロキノン、ピロガロール等のポリヒドロキシフェノール類等を挙げることができる。これらは単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。中でも、ｍ−、ｐ−クレゾールが好ましい。 Examples of the aromatic hydroxy compound used in the synthesis of the novolak resin (a1) include phenols; cresols such as m-cresol, p-cresol, o-cresol; 2,3-xylenol, 2,5-xylenol, 3 Xylenols such as 1,5-xylenol, 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,3,5-triethylphenol, 4- alkylphenols such as tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol; p-methoxyphenol, m-methoxy Phenol, p-ethoxy Alkoxy phenols such as enol, m-ethoxyphenol, p-propoxyphenol, m-propoxyphenol; o-isopropenylphenol, p-isopropenylphenol, 2-methyl-4-isopropenylphenol, 2-ethyl-4- Examples include isopropenylphenols such as isopropenylphenol; arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4′-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone, and pyrogallol. These may be used alone or in combination of two or more. Of these, m- and p-cresol are preferable.
ノボラック樹脂（ａ１）の合成に用いられる前記アルデヒド類には、少なくともホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒドが含まれる。該ヒドロキシル基置換芳香族アルデヒドとしては、下記一般式（Ｉ）で表されるヒドロキシベンズアルデヒドが好ましく、特に式中のｎが１または２であるものが好ましい。具体的にはｏ−ヒドロキシベンズアルデヒド（サリチルアルデヒド）、ｐ−ヒドロキシベンズアルデヒド、３，４−ジヒドロキシベンズアルデヒド等が挙げられる。これらは単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。 The aldehydes used for the synthesis of the novolak resin (a1) include at least formaldehyde and a hydroxyl group-substituted aromatic aldehyde. As the hydroxyl group-substituted aromatic aldehyde, hydroxybenzaldehyde represented by the following general formula (I) is preferable, and those in which n is 1 or 2 are particularly preferable. Specific examples include o-hydroxybenzaldehyde (salicylaldehyde), p-hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde and the like. These may be used alone or in combination of two or more.
ノボラック樹脂（ａ１）の合成に用いられる前記アルデヒド類として、ヒドロキシル基置換芳香族アルデヒドの他にホルムアルデヒドを必須成分として使用することにより反応性の悪いヒドロキシル基置換芳香族アルデヒドを単独で使用するよりも高分子量化が可能になる。
また前記アルデヒド類として、前記ホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒド以外のアルデヒド類を併用してもよい。例えばパラホルムアルデヒド、トリオキサン、アセトアルデヒド、プロピオンアルデヒド、ブチルアルデヒド、トリメチルアセトアルデヒド、アクロレイン、クロトンアルデヒド、シクロヘキサンアルデヒド、フルフラール、フリルアクロレイン等が挙げられる。これらは２種以上を併用してもよい。
As the aldehydes used for the synthesis of the novolak resin (a1), in addition to the hydroxyl group-substituted aromatic aldehyde, formaldehyde is used as an essential component, so that the hydroxyl group-substituted aromatic aldehyde having poor reactivity is used alone. High molecular weight is possible.
Moreover, you may use together aldehydes other than the said formaldehyde and a hydroxyl group substituted aromatic aldehyde as said aldehydes. Examples include paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furyl acrolein and the like. Two or more of these may be used in combination.
前記芳香族ヒドロキシ化合物とアルデヒド類との縮合反応生成物は、酸性触媒の存在下、公知の方法で製造することができる。その際の酸性触媒としては、塩酸、硫酸、ギ酸、シュウ酸、パラトルエンスルホン酸等を使用することができる。
アルデヒド類の使用量は、芳香族ヒドロキシ化合物に対して５０〜１００モル％程度が好ましく、より好ましい範囲は６０〜８０モル％程度である。
ヒドロキシル基置換芳香族アルデヒドの使用量は、少なすぎると添加効果が十分に得られず、多すぎると高分子量化が困難になり効果が十分に得られなくなる傾向があり、また原料コストが高くなるので、全アルデヒド量に対して１０〜５０モル％程度が好ましく、より好ましい範囲は２０〜３５モル％程度である。
また、ホルムアルデヒドの使用量は、少なすぎると分子量が上がらず、多すぎると分子量増加によるアルカリ溶解速度の低下を伴う恐れがあるので、全アルデヒド量に対して５０〜９０モル％程度が好ましく、より好ましい範囲は６５〜８０モル％程度である。
使用するアルデヒド類のうち、ホルムアルデヒドとヒドロキシル基置換芳香族アルデヒドの合計が占める割合は、全アルデヒド量に対して８０モル％以上であることが好ましく、１００モル％であることがより好ましい。
The condensation reaction product of the aromatic hydroxy compound and the aldehyde can be produced by a known method in the presence of an acidic catalyst. In this case, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, paratoluenesulfonic acid, etc. can be used as the acidic catalyst.
The amount of aldehyde used is preferably about 50 to 100 mol%, more preferably about 60 to 80 mol%, based on the aromatic hydroxy compound.
If the amount of the hydroxyl group-substituted aromatic aldehyde is too small, the effect of addition cannot be sufficiently obtained, and if it is too large, it tends to be difficult to obtain a high molecular weight and the effect cannot be sufficiently obtained, and the raw material cost increases. Therefore, about 10-50 mol% is preferable with respect to the total amount of aldehyde, and a more preferable range is about 20-35 mol%.
Further, if the amount of formaldehyde used is too small, the molecular weight does not increase, and if it is too large, the alkali dissolution rate may decrease due to an increase in molecular weight, so about 50 to 90 mol% is preferable with respect to the total amount of aldehyde. A preferable range is about 65 to 80 mol%.
Of the aldehydes used, the proportion of the total of formaldehyde and the hydroxyl group-substituted aromatic aldehyde is preferably 80 mol% or more, more preferably 100 mol%, based on the total amount of aldehyde.
ノボラック樹脂（ａ１）の質量平均分子量（Ｍｗ）は、小さ過ぎると塗布性が悪くなる傾向があり、大き過ぎると解像性が劣化する傾向がある。ノボラック樹脂（ａ１）のＭｗの好ましい範囲は１０００〜１０００００であり、より好ましくは２０００〜５００００であり、さらに好ましくは３０００〜３００００である。 When the mass average molecular weight (Mw) of the novolak resin (a1) is too small, the coating property tends to be poor, and when it is too large, the resolution tends to deteriorate. The preferable range of Mw of the novolak resin (a1) is 1000 to 100,000, more preferably 2000 to 50000, and further preferably 3000 to 30000.
本実施形態において、ノボラック樹脂（ａ１）中の全フェノール性水酸基の少なくとも一部は、酸触媒反応により分解してアルカリ可溶性に変化する基、いわゆる酸解離性溶解抑制基で保護されており、これによってアルカリ難溶性あるいは不溶性となっている。
かかる酸解離性溶解抑制基としては、後述の（Ｃ）成分から発生する酸により解離するものであればよく、例えば、１−エトキシメチル基、１−エトキシエチル基、１−プロポキシメチル基、１−プロポキシエチル基、１−ｎ−ブトキシメチル基、１−ｉｓｏ−ブトキシメチル基、１−ｔｅｒｔ−ブトキシメチル基等のアルコキシアルキル基；ｔ−ブトキシカルボニル基、ｔ−ブトキシカルボニルメチル基、ｔ−ブトキシカルボニルエチル基等のアルコキシカルボニルアルキル基；テトラヒドロフラニル基；テトラヒドロピラニル基；直鎖状または分岐鎖状アセタール基；環状アセタール基；トリメチルシリル基、トリエチルシリル基、トリフェニルシリル基等のトリアルキルシリル基が挙げられる。
中でも下記化学式（II−１）で表されるエチルビニル基（エトキシエチル基）および下記化学式（II−２）で表されるｔ−ブトキシカルボニル基が、解像性に優れたホトレジスト組成物を得るうえで好ましく、特にエチルビニル基が好ましい。
In this embodiment, at least a part of all phenolic hydroxyl groups in the novolak resin (a1) is protected by a group that is decomposed by an acid-catalyzed reaction and changes to alkali solubility, a so-called acid dissociable, dissolution inhibiting group. It is hardly soluble or insoluble in alkali.
Such an acid dissociable, dissolution inhibiting group may be any group that can be dissociated by an acid generated from the later-described component (C), such as 1-ethoxymethyl group, 1-ethoxyethyl group, 1-propoxymethyl group, 1 -Alkoxyalkyl groups such as propoxyethyl group, 1-n-butoxymethyl group, 1-iso-butoxymethyl group, 1-tert-butoxymethyl group; t-butoxycarbonyl group, t-butoxycarbonylmethyl group, t-butoxy Alkoxycarbonylalkyl group such as carbonylethyl group; tetrahydrofuranyl group; tetrahydropyranyl group; linear or branched acetal group; cyclic acetal group; trialkylsilyl group such as trimethylsilyl group, triethylsilyl group and triphenylsilyl group Is mentioned.
In particular, an ethyl vinyl group (ethoxyethyl group) represented by the following chemical formula (II-1) and a t-butoxycarbonyl group represented by the following chemical formula (II-2) are used to obtain a photoresist composition having excellent resolution. The ethyl vinyl group is particularly preferable.
ノボラック樹脂（ａ１）中の全フェノール性水酸基のうち、酸解離性溶解抑制基によって保護されているフェノール性水酸基の割合（保護率）は１０〜５０モル％程度であることが好ましい。 It is preferable that the ratio (protection rate) of the phenolic hydroxyl group protected by the acid dissociable, dissolution inhibiting group among all the phenolic hydroxyl groups in the novolak resin (a1) is about 10 to 50 mol%.
・（Ｃ）成分
（Ｃ）成分としては、特に限定はなく、従来から化学増幅型のポジ型ホトレジスト組成物の材料として知られている光酸発生剤、例えばスルホニルジアゾメタン系酸発生剤、オニウム塩系酸発生剤、オキシムスルホネート系酸発生剤などを用いることができる。
Component (C) The component (C) is not particularly limited, and is a photoacid generator that has been conventionally known as a material for chemically amplified positive photoresist compositions, such as sulfonyldiazomethane acid generators, onium salts. An acid generator, an oxime sulfonate acid generator, or the like can be used.
（Ｃ）成分として、例えば以下のような化合物が、ｉ線露光に対する酸発生効率が高いことから、好ましく用いられる。
下記一般式（III）、（IV）で表されるもの。
As the component (C), for example, the following compounds are preferably used because of high acid generation efficiency for i-line exposure.
Those represented by the following general formulas (III) and (IV).
（式中、ｍ’は０又は１；Ｘは１又は２；Ｒ１は、１又はそれ以上のＣ１−Ｃ１２アルキル基が置換していてもよいフェニル基、ヘテロアリール基等、又は、ｍ’が０の場合はさらにＣ２−Ｃ６アルコキシカルボニル基、フェノキシカルボニル基、ＣＮ等；Ｒ１’はＣ２−Ｃ１２アルキレン基等；Ｒ２はＲ１と同義等；Ｒ３はＣ１−Ｃ１８アルキル基等；Ｒ３’は、Ｘ＝１のときＲ３と同義等、Ｘ＝２のときＣ２−Ｃ１２アルキレン基、フェニレン基等；Ｒ４、Ｒ５は独立に水素原子、ハロゲン、Ｃ１−Ｃ６アルキル基等；ＡはＳ、Ｏ、ＮＲ６等；Ｒ６は水素原子、フェニル基等を示す。）で表される化合物（ＵＳＰ ６００４７２４）。具体的には、例えば下記式（Ｖ）で表されるチオレン含有オキシムスルホネートなどが挙げられる。 (Wherein m ′ is 0 or 1; X is 1 or 2; R 1 is a phenyl group, a heteroaryl group, or the like, optionally substituted by one or more C 1 -C 12 alkyl groups, or When m ′ is 0, C 2 -C 6 alkoxycarbonyl group, phenoxycarbonyl group, CN and the like; R 1 ′ is C 2 -C 12 alkylene group and the like; R 2 is synonymous with R 1 ; R 3 is C 1 -C 18 alkyl group or the like; R 3 'is, X = synonymous like and R 3 when 1, C 2 -C 12 alkylene group when X = 2, a phenylene group or the like; R 4, R 5 independently are hydrogen A compound represented by an atom, a halogen, a C 1 -C 6 alkyl group, etc .; A represents S, O, NR 6, etc .; R 6 represents a hydrogen atom, a phenyl group, etc. (USP 6004724). Specific examples include thiolene-containing oxime sulfonates represented by the following formula (V).
また、下記式（ＶI） In addition, the following formula (VI)
（式中、Ｒ６、Ｒ７は、それぞれ炭素数１〜３のアルキル基を示す。）で表されるビス（トリクロロメチル）トリアジン化合物、又は、該化合物（ＶI）と下記式（ＶII ） (Wherein R 6 and R 7 each represent an alkyl group having 1 to 3 carbon atoms) or a bis (trichloromethyl) triazine compound represented by the formula (VI) and the following formula (VII)
（式中、Ｚは、４−アルコキシフェニル基等を示す。）で表されるビス（トリクロロメチル）トリアジン化合物とを組み合わせたもの（特開平６−２８９６１４号公報、特開平７−１３４４１２号公報）。 (Wherein Z represents a 4-alkoxyphenyl group or the like) and a bis (trichloromethyl) triazine compound represented by the formula (JP-A-6-289614, JP-A-7-134212) .
トリアジン化合物（ＶI）としては、具体的には、例えば２−［２−（３，４−ジメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−メトキシ−４−エトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−メトキシ−４−プロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−エトキシ−４−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，４−ジエトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−エトキシ−４−プロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−プロポキシ−４−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−プロポキシ−４−エトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，４―ジプロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−，３，５−トリアジンなどを挙げることができる。これらのトリアジン化合物は単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。 Specific examples of the triazine compound (VI) include 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy-4-ethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy-4-propoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy-4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1, 3,5-triazine, 2- [2- (3,4-diethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy -4-propoxy Phenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy-4-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy-4-ethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dipropoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)-, 3,5-triazine and the like. These triazine compounds may be used alone or in combination of two or more.
一方、上記トリアジン化合物（ＶI）と所望に応じて組み合わせて用いられる上記トリアジン化合物（ＶII）としては、例えば２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−エトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−プロポキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−ブトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−メトキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−エトキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−プロポキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−ブトキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−メトキシ−６−カルボキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（４−メトキシ−６−ヒドロキシナフチル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（５−メチル−２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（５−エチル−２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（５−プロピル−２−フリル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，５−ジメトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−メトキシ−５−エトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−メトキシ−５−プロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−エトキシ−５−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，５−ジエトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−エトキシ−５−プロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−プロポキシ−５−メトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３−プロポキシ−５−エトキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−２−（３，５−ジプロポキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−（３，４−メチレンジオキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン、２−［２−（３，４−メチレンジオキシフェニル）エテニル］−４，６−ビス（トリクロロメチル）−１，３，５−トリアジンなどが挙げられる。これらのトリアジン化合物は１種用いてもよいし、２種以上を組み合わせて用いてもよい。 On the other hand, as the triazine compound (VII) used in combination with the triazine compound (VI) as desired, for example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3, 5-triazine, 2- (4-ethoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-propoxyphenyl) -4,6-bis (trichloromethyl)- 1,3,5-triazine, 2- (4-butoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-propoxynaphth ) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-butoxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxy-6-carboxynaphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy-6-hydroxynaphthyl) -4,6-bis (trichloromethyl) ) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-methyl) -2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (5-ethyl-2-furyl) ethenyl] -4,6-bis (trichloro Methyl) -1,3,5-triazine 2- [2- (5-propyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-methoxy-5-ethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3 , 5-triazine, 2- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-ethoxy -5-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-diethoxyphenyl) ethenyl] -4,6-bis ( Trichloromethyl) -1,3 , 5-triazine, 2- [2- (3-ethoxy-5-propoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy) -5-methoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3-propoxy-5-ethoxyphenyl) ethenyl] -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2-2 (3,5-dipropoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- ( 3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-methylenedioxyphenyl) ethenyl] -4,6- Screw (trick Romechiru) -1,3,5-triazine. These triazine compounds may be used alone or in combination of two or more.
また、下記式（VIII） Further, the following formula (VIII)
（式中、Ａｒは置換又は未置換のフェニル基、ナフチル基；ＲはＣ１〜Ｃ９のアルキル基；ｎは２又は３の整数を示す。）で表される化合物を挙げることができる。これらの化合物は単独で用いてもよいし、また２種以上を組み合わせて用いてもよい。以上例示した化合物の中でも、特に、上記式（Ｖ）で表される化合物および下記式（IX）で表される化合物は、ｉ線に対する酸発生効率に優れるため、好ましく用いられる。 (Wherein, Ar represents a substituted or unsubstituted phenyl group, a naphthyl group; R is an alkyl group of C 1 ~C 9; n is an integer of 2 or 3.) Can be mentioned compounds represented by. These compounds may be used alone or in combination of two or more. Among the compounds exemplified above, in particular, the compound represented by the above formula (V) and the compound represented by the following formula (IX) are preferably used because of excellent acid generation efficiency with respect to i-line.
本実施形態において、（Ｃ）成分は１種または２種以上混合して用いることができる。
（Ｃ）成分の配合量は、（Ａ）成分１００質量部に対して、１〜３０質量部、好ましくは１〜２０質量部とされる。
In this embodiment, (C) component can be used 1 type or in mixture of 2 or more types.
(C) The compounding quantity of a component shall be 1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-20 mass parts.
・（Ｄ）成分
本実施形態の化学増幅型ポジ型ホトレジスト組成物において、引置き安定性を高めるために、（Ｄ）成分として、塩基性化合物（好ましくはアミン類）を配合することが好ましい。
当該化合物としては、ホトレジスト組成物に対する相容性を有するものであれば良く、特に制限されるものではないが、例えば特開平９−６００１号公報に記載の化合物を挙げることができる。
-Component (D) In the chemically amplified positive photoresist composition of the present embodiment, it is preferable to blend a basic compound (preferably an amine) as the component (D) in order to enhance the stability of placement.
The compound is not particularly limited as long as it has compatibility with the photoresist composition, and examples thereof include compounds described in JP-A-9-6001.
特に、下記一般式（Ｘ）で表される比較的嵩高い特定の塩基性化合物（ｄ１）を配合することにより、経時的にレジスト組成物中に副生成される酸成分の量を抑制する効果もあり、レジスト組成物の長期保存安定性を向上させることができる。 In particular, by blending a relatively bulky specific basic compound (d1) represented by the following general formula (X), the effect of suppressing the amount of acid component by-produced in the resist composition over time In addition, the long-term storage stability of the resist composition can be improved.
一般式（Ｘ）においては、Ｘ、Ｙ、Ｚのうちのひとつ以上（好ましくは２以上、最も好ましくは３つ）が、下記（１）〜（４）
（１）炭素数４以上のアルキル基、
（２）炭素数３以上のシクロアルキル基、
（３）フェニル基、
（４）アラルアルキル基
から選ばれる基である。
また、当該Ｘ、Ｙ、Ｚのうち、前記（１）〜（４）ではないものは、
（１’）炭素数３以下のアルキル基、
（２’）水素原子、の中から選ばれる基または原子である。
Ｘ、Ｙ、Ｚは相互に同じでもよいし、異なっていてもよいが、Ｘ、Ｙ、Ｚのうち、２つ以上が前記（１）〜（４）から選ばれる基である場合には、これらに該当する基どうしは同じであることが、効果の安定性の点から、好ましい。
In the general formula (X), one or more (preferably 2 or more, most preferably 3) of X, Y and Z are the following (1) to (4):
(1) an alkyl group having 4 or more carbon atoms,
(2) a cycloalkyl group having 3 or more carbon atoms,
(3) phenyl group,
(4) A group selected from aralkyl groups.
Among the X, Y, and Z, those not (1) to (4)
(1 ′) an alkyl group having 3 or less carbon atoms,
(2 ′) a hydrogen atom, or a group or atom selected from.
X, Y and Z may be the same or different from each other, but when two or more of X, Y and Z are groups selected from the above (1) to (4), The groups corresponding to these are preferably the same from the viewpoint of the stability of the effect.
・・（１）炭素数４以上のアルキル基
前記（１）の場合、炭素数が４未満では、経時安定性を向上させることが難しい。炭素数はさらには５以上、特には８以上であることが好ましい。上限値は特に限定しないが、経時安定効果が認められ、また商業的に入手用であるの点から２０以下、特には１５以下とされる。なお、２０を超えると塩基性強度が弱くなり、保存安定性の効果が低下する。
アルキル基は直鎖状、分岐鎖状のいずれでもよい。
具体的には、例えばｎ−デシル基、ｎ−オクチル基、ｎ−ペンチル基等が好ましい。
(1) Alkyl group having 4 or more carbon atoms In the case of (1), if the carbon number is less than 4, it is difficult to improve the temporal stability. The number of carbon atoms is preferably 5 or more, particularly 8 or more. The upper limit value is not particularly limited, but is set to 20 or less, particularly 15 or less from the viewpoint that a time-stable effect is recognized and it is commercially available. In addition, when it exceeds 20, basic strength will become weak and the effect of storage stability will fall.
The alkyl group may be linear or branched.
Specifically, for example, n-decyl group, n-octyl group, n-pentyl group and the like are preferable.
・・（２）炭素数３以上のシクロアルキル基
当該シクロアルキル基において、特に炭素数４〜８のシクロアルキル基が商業的に入手可能であり、かつ経時安定性を向上させる効果に優れ好ましい。特に炭素数が６であるシクロヘキシル基が好ましい。
(2) A cycloalkyl group having 3 or more carbon atoms In the cycloalkyl group, a cycloalkyl group having 4 to 8 carbon atoms is commercially available, and is excellent in the effect of improving the stability over time. Particularly preferred is a cyclohexyl group having 6 carbon atoms.
・・（４）アラルアルキル基
アラルアルキル基は、一般式、−Ｒ’−Ｐ（Ｒ’はアルキレン基、Ｐは芳香族炭化水素基）で表されるものである。
Ｐとしてはフェニル基、ナフチル基等が挙げられるが、フェニル基が好ましい。
Ｒ’の炭素数は１以上であればよく、好ましくは１〜３である。
アラルアルキル基としては、例えばベンジル基、フェニルエチル基等が好ましい。
(4) Aralkyl group An aralkyl group is represented by the general formula, -R'-P (R 'is an alkylene group, and P is an aromatic hydrocarbon group).
Examples of P include a phenyl group and a naphthyl group, and a phenyl group is preferable.
The carbon number of R ′ may be 1 or more, preferably 1 to 3.
As the aralkyl group, for example, a benzyl group, a phenylethyl group and the like are preferable.
なお、Ｘ、Ｙ、Ｚのうち、前記（１）〜（４）ではないものは、前記（１’）、（２’）の中から選ばれる基または原子である。 Of X, Y, and Z, those other than (1) to (4) are groups or atoms selected from the above (1 ') and (2').
（１’）は、直鎖または分岐鎖のいずれでもよい。特にメチル基、エチル基が好ましい。
（ｄ１）成分としては、第３級アミンを構成するものが好ましく、Ｘ、Ｙ、Ｚのうち、前記（１）〜（４）でないものは、（１’）の中から選ばれることが好ましい。例えば、具体的には、トリ−ｎ−デシルアミン、メチル−ジ−ｎ−オクチルアミン、トリ−ｎ−ペンチルアミン、Ｎ，Ｎ−ジシクロヘキシルメチルアミン、トリベンジルアミン等が挙げられる。
中でも、トリ−ｎ−デシルアミン、メチル−ジ−ｎ−オクチルアミン、トリ−ｎ−ペンチルアミンから選ばれる１種以上が好ましく、特にトリ−ｎ−デシルアミンが好ましい。
(1 ′) may be either linear or branched. In particular, a methyl group and an ethyl group are preferable.
As the component (d1), those constituting a tertiary amine are preferable, and among X, Y, and Z, those other than (1) to (4) are preferably selected from (1 ′). . Specific examples include tri-n-decylamine, methyl-di-n-octylamine, tri-n-pentylamine, N, N-dicyclohexylmethylamine, tribenzylamine and the like.
Among these, at least one selected from tri-n-decylamine, methyl-di-n-octylamine, and tri-n-pentylamine is preferable, and tri-n-decylamine is particularly preferable.
本実施形態において、（Ｄ）成分は１種または２種以上の混合して用いることができる。
（Ｄ）成分は、樹脂固形分１００質量部に対して０．０１〜５．０質量部、特には０．１〜１．０質量部の範囲で配合することが、効果の点から好ましい。
In this embodiment, (D) component can be used 1 type or in mixture of 2 or more types.
(D) It is preferable from the point of an effect to mix | blend a component in 0.01-5.0 mass parts with respect to 100 mass parts of resin solid content, especially 0.1-1.0 mass part.
・有機溶剤
本実施形態のホトレジスト組成物における有機溶剤としては、化学増幅型のポジ型ホトレジスト組成物に用いられるものであれば、特に限定せずに用いることができる。
例えば、プロピレングリコールモノアルキルエーテルアセテート（例えばプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）等）、乳酸エステル（例えば乳酸エチル等）等のエステル系溶剤、アセトン、メチルエチルケトン、シクロヘキサノン、メチルイソアミルケトン、２−ヘプタノン等のケトン類；エチレングリコール、プロピレングリコール、ジエチレングリコール、あるいはこれらのモノメチルエーテル、モノエチルエーテル、モノプロピルエーテル、モノブチルエーテルまたはモノフェニルエーテル等の多価アルコール類およびその誘導体；ジオキサンのような環式エーテル類；等の非エステル系溶剤が挙げられる。なおエステル系溶剤は、有機カルボン酸とアルコールとの反応生成物であることから、遊離酸である有機カルボン酸を含有する。そのため、前記の（Ｄ）成分を配合しないホトレジスト組成物、または後述の保存安定剤を配合しないホトレジスト組成物においては、そのような遊離酸を含有しない非エステル系溶剤を選択することが好ましく、特にケトン類（ケトン系の溶剤）は好ましい。その中でも２−へプタノンは、塗膜性、（Ｃ）成分の溶解性の点からも好適である。
Organic Solvent The organic solvent in the photoresist composition of the present embodiment is not particularly limited as long as it is used for a chemically amplified positive photoresist composition.
For example, ester solvents such as propylene glycol monoalkyl ether acetate (for example, propylene glycol monomethyl ether acetate (PGMEA)), lactic acid ester (for example, ethyl lactate), acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, 2-heptanone, etc. Ketones; ethylene glycol, propylene glycol, diethylene glycol, or polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether and derivatives thereof; cyclic ethers such as dioxane; Non-ester solvents such as Since the ester solvent is a reaction product of an organic carboxylic acid and an alcohol, it contains an organic carboxylic acid that is a free acid. Therefore, in a photoresist composition not containing the component (D) or a photoresist composition not containing a storage stabilizer described later, it is preferable to select a non-ester solvent that does not contain such a free acid. Ketones (ketone solvents) are preferred. Among these, 2-heptanone is preferable from the viewpoint of coating properties and solubility of the component (C).
なお、エステル系溶剤も非エステル系溶剤も、ともに経時的に分解して酸を副生成する場合があるが、前記（Ｄ）成分の存在下、あるいは後述の保存安定剤の存在下においては、当該分解反応は抑制される。特にエステル系溶剤においてはその効果が顕著であり、当該（Ｄ）成分、保存安定剤の存在下においては、むしろエステル系溶剤が好ましく、特にＰＧＭＥＡは好適である。
なお、上記分解により副生成する酸成分としては、例えば２−ヘプタノンの場合、蟻酸、酢酸、プロピオン酸等を生じることが確認されている。
有機溶剤は１種または２種以上混合して用いることができる。
In addition, both ester solvents and non-ester solvents may decompose over time to generate an acid by-product, but in the presence of the component (D) or in the presence of a storage stabilizer described later, The decomposition reaction is suppressed. The effect is particularly remarkable in an ester solvent, and in the presence of the component (D) and the storage stabilizer, an ester solvent is preferable, and PGMEA is particularly preferable.
In addition, as an acid component byproduced by the said decomposition | disassembly, in the case of 2-heptanone, formic acid, acetic acid, propionic acid, etc. are confirmed to be produced.
The organic solvent can be used alone or in combination.
・その他の成分
本実施形態の化学増幅型ポジ型ホトレジスト組成物には、この他、必要に応じて以下の様な保存安定剤を配合すると好ましい。
当該保存安定剤としては、有機溶剤の分解反応を抑制する作用を有するものであれば特に限定されず、例えば、特開昭５８−１９４８３４号公報に記載されているような酸化防止剤を挙げることができる。酸化防止剤としてはフェノール系化合物とアミン系化合物が知られているが、特にフェノール系化合物が好ましく、中でも２，６−ジ（ｔｅｒｔ−ブチル）−ｐ−クレゾール及びその誘導体が、エステル系溶剤、ケトン系溶剤の劣化に対して有効であり、商業的に入手可能、かつ安価であって、さらに保存安定効果に優れる点で好ましい。特にプロピレングリコールモノアルキルエーテルアセテート、２−ヘプタノンに対する劣化防止効果に極めて優れる。
Other components In addition to the chemical amplification type positive photoresist composition of the present embodiment, the following storage stabilizer is preferably blended as necessary.
The storage stabilizer is not particularly limited as long as it has an action of suppressing the decomposition reaction of the organic solvent, and examples thereof include an antioxidant as described in JP-A No. 58-94834. Can do. As the antioxidant, phenolic compounds and amine compounds are known, and phenolic compounds are particularly preferable. Among them, 2,6-di (tert-butyl) -p-cresol and derivatives thereof are ester solvents, It is effective in terms of deterioration of the ketone solvent, is commercially available, is inexpensive, and is preferable in view of excellent storage stability. In particular, the effect of preventing deterioration of propylene glycol monoalkyl ether acetate and 2-heptanone is extremely excellent.
また、本実施形態のホトレジスト組成物には、本発明の目的を損なわない範囲で、必要に応じて相容性のある添加物、例えばレジスト膜の性能などを改良するための付加的樹脂、可塑剤、安定剤、界面活性剤、現像した像をより一層可視的にするための着色料、より増感効果を向上させるための増感剤やハレーション防止用染料、密着性向上剤などの慣用の添加物を含有させることができる。 In addition, the photoresist composition of the present embodiment includes a compatible additive, for example, an additional resin for improving the performance of the resist film, a plastic, and the like as long as the object of the present invention is not impaired. Conventional agents such as sensitizers, stabilizers, surfactants, colorants for making the developed image more visible, sensitizers and antihalation dyes for improving the sensitization effect, and adhesion improvers. Additives can be included.
・ポジ型ホトレジスト組成物の製造方法
本実施形態のポジ型ホトレジスト組成物は、（Ａ）成分、（Ｃ）成分、及び必要に応じてその他の成分を、有機溶剤に溶解させることによって製造することができる。
有機溶剤の使用量は、好ましくは（Ａ）、（Ｃ）成分及び必要に応じて用いられるその他の成分を溶解したときに、均一なポジ型ホトレジスト組成物が得られるように適宜調整される。好ましくは固形分濃度が１０〜５０質量％、さらに好ましくは２０〜３５質量％となる様に用いられる。なお、ポジ型ホトレジスト組成物の固形分は、（Ａ）、（Ｃ）成分及び必要に応じて用いられるその他の成分の合計に相当する。
-Method for producing positive photoresist composition The positive photoresist composition of the present embodiment is produced by dissolving the component (A), the component (C), and other components as required in an organic solvent. Can do.
The amount of the organic solvent used is suitably adjusted so that a uniform positive photoresist composition can be obtained when the components (A) and (C) and other components used as necessary are dissolved. The solid content is preferably 10 to 50% by mass, more preferably 20 to 35% by mass. The solid content of the positive photoresist composition corresponds to the sum of the components (A) and (C) and other components used as necessary.
・レジストパターンの形成方法
以下に、本実施形態のホトレジスト組成物を用いてレジストパターンを形成する方法の好適な一例を示す。
まず、（Ａ）成分および（Ｃ）成分、並びに必要に応じて添加される各種成分を溶剤に溶解し、これをスピンナー等で基板に塗布して塗膜を形成する。基板は、シリコン基板、ガラス基板など、用途に応じて適宜選択される。
-Formation method of a resist pattern Below, a suitable example of the method of forming a resist pattern using the photoresist composition of this embodiment is shown.
First, the components (A) and (C) and various components added as necessary are dissolved in a solvent, and this is applied to a substrate with a spinner or the like to form a coating film. The substrate is appropriately selected depending on the application, such as a silicon substrate or a glass substrate.
次いで、この塗膜が形成された基板を加熱処理（プリベーク）して残存溶媒を除去し、レジスト被膜を形成する。プリベーク方法としては、基板としてガラス基板を用いる場合には、ホットプレートと基板の間に隙間を持たせるプロキシミティベークを行うことが好ましい。本実施形態において、プリベーク時の加熱条件は、８０〜１５０℃、６０〜３００秒程度に好ましく設定される。
次いで、上記レジスト被膜に対し、マスクを介して選択的露光を行う。
ここで用いる光源としては、（Ｃ）成分の種類によって適宜選択することができ、例えばｉ線用のＰＡＧを用いるのであれば、光源としてｉ線（３６５ｎｍ）を用いることが好ましい。
Next, the substrate on which the coating film is formed is heat-treated (prebaked) to remove the remaining solvent, and a resist film is formed. As a pre-baking method, when a glass substrate is used as the substrate, it is preferable to perform proximity baking with a gap between the hot plate and the substrate. In the present embodiment, the heating conditions during pre-baking are preferably set to 80 to 150 ° C. and about 60 to 300 seconds.
Next, the resist film is selectively exposed through a mask.
The light source used here can be appropriately selected depending on the type of component (C). For example, if an i-line PAG is used, it is preferable to use i-line (365 nm) as the light source.
次いで、選択的露光後のレジスト被膜に対し、加熱処理（ポストエクスポージャーベーク：ＰＥＢ）を施す。ＰＥＢ方法としては、ホットプレートと基板の間に隙間を持たせるプロキシミティベーク、隙間を持たせないダイレクトベークが挙げられ、基板としてガラス基板を用いる場合には、基板の反りを生じさせることをなく、ＰＥＢによる拡散効果を得るために、プロキシミティベークを行った後、ダイレクトベークを行う方法が好ましい。本実施形態において、ＰＥＢ時の加熱条件は、８０〜１５０℃、６０〜３００秒程度に好ましく設定される。
上記ＰＥＢ後のレジスト被膜に対し、現像液、例えば１〜１０質量％テトラメチルアンモニウムヒドロキシド水溶液のようなアルカリ水溶液を用いた現像処理を施すと、露光部分が溶解除去されて、基板上にレジストパターンが同時に形成される。
次いで、レジストパターン表面に残った現像液を純水などのリンス液で洗い落とすことによりレジストパターンを形成できる。
Next, heat treatment (post-exposure baking: PEB) is applied to the resist film after selective exposure. Examples of PEB methods include proximity baking that provides a gap between the hot plate and the substrate, and direct baking that does not provide a gap. When a glass substrate is used as the substrate, the substrate is not warped. In order to obtain a diffusion effect by PEB, a method of performing direct baking after proximity baking is preferable. In this embodiment, the heating conditions during PEB are preferably set to 80 to 150 ° C. and about 60 to 300 seconds.
When the resist film after PEB is subjected to a development treatment using a developing solution, for example, an alkaline aqueous solution such as an aqueous solution of 1 to 10% by mass of tetramethylammonium hydroxide, the exposed portion is dissolved and removed, and a resist is formed on the substrate. A pattern is formed simultaneously.
Next, the resist pattern can be formed by washing away the developer remaining on the resist pattern surface with a rinse solution such as pure water.
本発明者等は、化学増幅型ポジ型ホトレジスト組成物の耐熱性に関して詳細に検討した結果、特にアルカリ可溶性樹脂のフェノール性水酸基に酸解離性溶解抑制基を反応させて付加させると、フェノール性水酸基の減少に伴って耐熱性が著しく低下することを見出した。これに対して、仮にアルカリ可溶性樹脂を高分子量化したり、嵩高い構成単位を導入するなどの方法で耐熱性を向上させようとすると、ホトレジスト組成物のアルカリ性現像液に対する溶解性の低下を引き起こして解像性の劣化につながるおそれがある。
一方、本実施形態によれば、特に（Ａ）成分を構成するアルカリ可溶性樹脂として、芳香族ヒドロキシ化合物と、ホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒドを含むアルデヒド類とを縮合反応して得られるノボラック樹脂（ａ１）を用いることにより、ポジ型ホトレジスト組成物の耐熱性を向上させることができる。これは、縮合剤にヒドロキシル基置換芳香族アルデヒドを含有させることにより、ノボラック樹脂（ａ１）におけるベンゼン環密度が増大し、その結果、立体障害が生じてノボラック樹脂（ａ１）自体の耐熱性が向上したことによると考えられる。
さらに、当該ヒドロキシル基置換芳香族アルデヒドを用いることにより、解像性も向上させることができる。これは、縮合剤にフェノール性水酸基を有する芳香族アルデヒド（ヒドロキシル基置換芳香族アルデヒド）を用いることにより、ノボラック樹脂（ａ１）中に存在するフェノール性水酸基が増大し、ノボラック樹脂（ａ１）自体のアルカリ溶解性が向上するためと考えられる。
また、本実施形態のポジ型ホトレジスト組成物は化学増幅型の機構を示すものであるので、未露光部分と露光部分との現像コントラストが強く、良好な解像性および感度を得ることができる。
さらに、ノボラック樹脂は安価で入手が容易であるので、低価格で耐熱性に優れたポジ型ホトレジスト組成物を提供することができる。
なお、ここでのポジ型ホトレジスト組成物としての耐熱性には、高温加熱処理時におけるレジストパターンの変形防止効果、レジストパターンの寸法変化の防止効果等が含まれる。
As a result of detailed studies on the heat resistance of the chemically amplified positive photoresist composition, the present inventors have found that when an acid dissociable, dissolution inhibiting group is added to the phenolic hydroxyl group of the alkali-soluble resin by reaction, the phenolic hydroxyl group is added. It has been found that the heat resistance is remarkably lowered with the decrease of. On the other hand, if it is attempted to improve the heat resistance by increasing the molecular weight of the alkali-soluble resin or introducing a bulky structural unit, the solubility of the photoresist composition in an alkaline developer is reduced. There is a possibility of degrading resolution.
On the other hand, according to this embodiment, a novolak resin obtained by condensation reaction of an aromatic hydroxy compound and an aldehyde containing formaldehyde and a hydroxyl group-substituted aromatic aldehyde, particularly as the alkali-soluble resin constituting the component (A) By using (a1), the heat resistance of the positive photoresist composition can be improved. This is because by adding a hydroxyl group-substituted aromatic aldehyde to the condensing agent, the density of the benzene ring in the novolak resin (a1) increases, resulting in steric hindrance and improved heat resistance of the novolak resin (a1) itself. This is probably due to the fact that
Furthermore, the resolution can also be improved by using the hydroxyl group-substituted aromatic aldehyde. This is because by using an aromatic aldehyde having a phenolic hydroxyl group (hydroxyl group-substituted aromatic aldehyde) as the condensing agent, the phenolic hydroxyl group present in the novolak resin (a1) increases, and the novolak resin (a1) itself It is thought that alkali solubility is improved.
Further, since the positive photoresist composition of the present embodiment exhibits a chemical amplification type mechanism, the development contrast between the unexposed part and the exposed part is strong, and good resolution and sensitivity can be obtained.
Furthermore, since novolak resins are inexpensive and easily available, it is possible to provide a positive photoresist composition that is inexpensive and excellent in heat resistance.
Here, the heat resistance of the positive photoresist composition includes a resist pattern deformation preventing effect and a resist pattern dimensional change preventing effect during high-temperature heat treatment.
［第２の実施形態］
本実施形態が第１の実施形態と異なる点は、（Ａ）成分を調製する際に、ノボラック樹脂（ａ１）と酸解離性溶解抑制基に対応する化合物とを反応させて得られた反応生成物（アルカリ難溶性あるいは不溶性の樹脂）に、低分子量体を分別除去する処理を施した樹脂成分を（Ａ）成分として用いる点である。
[Second Embodiment]
This embodiment is different from the first embodiment in that the reaction product obtained by reacting the novolak resin (a1) with the compound corresponding to the acid dissociable, dissolution inhibiting group when preparing the component (A). A resin component obtained by subjecting a product (a hardly alkali-soluble or insoluble resin) to a treatment for separating and removing a low molecular weight substance is used as the component (A).
本明細書における低分子量体には、例えば残留モノマー、モノマーが２分子結合したダイマー、３分子結合したトリマー等（モノマーおよび２〜３核体等）が含まれる。
低分子量体の分別処理方法としては、例えば、酸解離性溶解抑制基で保護されたノボラック樹脂を、イオン交換樹脂を用いて精製する方法を用いることができる。この方法によれば低分子量体とともに、酸成分やメタル成分を除去することも可能である。
または良溶媒に溶解したノボラック樹脂に貧溶媒を加えて分別沈殿させて沈殿物を取り出すことで低分子量体を除く方法を用いることもできる。
The low molecular weight body in the present specification includes, for example, residual monomers, dimers in which two monomers are bonded, trimers in which two molecules are bonded, and the like (monomers and 2-3 nuclei).
As a method for fractionating low molecular weight substances, for example, a method of purifying a novolak resin protected with an acid dissociable, dissolution inhibiting group using an ion exchange resin can be used. According to this method, it is possible to remove the acid component and the metal component together with the low molecular weight substance.
Alternatively, a method of removing a low molecular weight substance by adding a poor solvent to a novolak resin dissolved in a good solvent, fractional precipitation, and taking out the precipitate can be used.
かかる低分子量体の分別除去処理における収率は５０〜９５質量％の範囲が望ましい。５０質量％未満の場合は、後述の（Ｃ）成分から発生する酸成分の作用による、アルカリ水溶液に対する溶解性の増大が不十分となる。その結果、露光部と未露光部との間における溶解速度の差が小さくなり、解像性が低下してしまう。一方、９５質量％を超えた場合には、分別除去を行うことによる効果が十分に得られない。また、Ｍｗが５００以下の低分子量体の含有量は、ＧＰＣチャート上１５％以下、好ましくは１２％以下であることが好ましい。１５％以下とすることにより、レジストパターンの耐熱性向上効果が奏されるのと同時に、加熱処理時の昇華物の発生量を抑制する効果が奏される。 The yield in such a low molecular weight fraction removal treatment is desirably in the range of 50 to 95% by mass. When the amount is less than 50% by mass, the increase in solubility in an aqueous alkali solution due to the action of an acid component generated from the later-described component (C) is insufficient. As a result, the difference in dissolution rate between the exposed part and the unexposed part becomes small, and the resolution is lowered. On the other hand, when it exceeds 95 mass%, the effect by performing separation removal is not fully acquired. Further, the content of the low molecular weight substance having Mw of 500 or less is 15% or less, preferably 12% or less on the GPC chart. By setting it to 15% or less, the effect of improving the heat resistance of the resist pattern is exhibited, and at the same time, the effect of suppressing the amount of sublimate generated during the heat treatment is exhibited.
本実施形態によれば、第１の実施形態と同様に良好な解像性および感度を得ることができるとともに、ポジ型ホトレジスト組成物の耐熱性をさらに向上させることができる。また低分子量体が分別除去されているので、加熱時に発生する昇華物を低減させることができる。 According to this embodiment, good resolution and sensitivity can be obtained as in the first embodiment, and the heat resistance of the positive photoresist composition can be further improved. Moreover, since the low molecular weight substance is separated and removed, sublimates generated during heating can be reduced.
［第３の実施形態］
本実施形態が第１の実施形態と異なる点は、（Ａ）成分を調製する際に、前記ノボラック樹脂（ａ１）に代えて、該ノボラック樹脂（ａ１）に低分子量体を分別除去する処理を施して得られる処理済ノボラック樹脂（ａ２）を用いる点である。そして該処理済ノボラック樹脂（ａ２）と酸解離性溶解抑制基に対応する化合物とを反応させて得られるアルカリ難溶性あるいは不溶性の樹脂を（Ａ）成分として用いる。
[Third Embodiment]
This embodiment is different from the first embodiment in that, when preparing the component (A), instead of the novolak resin (a1), a process of separating and removing low molecular weight substances in the novolak resin (a1). It is a point using the processed novolak resin (a2) obtained by giving. Then, an alkali poorly soluble or insoluble resin obtained by reacting the treated novolak resin (a2) with a compound corresponding to the acid dissociable, dissolution inhibiting group is used as the component (A).
本実施形態における低分子量体の分別処理方法としては、例えば、ノボラック樹脂（ａ１）を、イオン交換樹脂を用いて精製する方法を用いることができる。この方法によれば低分子量体とともに、酸成分やメタル成分を除去することも可能である。
またはノボラック樹脂（ａ１）を良溶媒、例えばメタノール、エタノール等のアルコール、アセトン、メチルエチルケトン等のケトンや、エチレングリコールモノエチルエーテルアセテート、テトラヒドロフラン等に溶解し、次いで水中に注ぎ沈殿させる等の方法によっても低分子量体を分別除去することができる。
または、ノボラック樹脂（ａ１）の合成反応の途中で例えば水蒸気蒸留を行うことによっても２核体等の低核体含有量を減少させることができる（特開２０００−１３１８５号公報参照）。
As a method for fractionating low molecular weight substances in the present embodiment, for example, a method of purifying the novolac resin (a1) using an ion exchange resin can be used. According to this method, it is possible to remove the acid component and the metal component together with the low molecular weight substance.
Alternatively, the novolac resin (a1) may be dissolved in a good solvent, for example, an alcohol such as methanol or ethanol, a ketone such as acetone or methyl ethyl ketone, ethylene glycol monoethyl ether acetate, tetrahydrofuran or the like, and then poured into water and precipitated. Low molecular weight substances can be separated and removed.
Alternatively, the content of low nuclei such as dinuclear can also be reduced by performing, for example, steam distillation in the middle of the synthesis reaction of the novolak resin (a1) (see JP 2000-13185 A).
かかる低分子量体の分別除去処理における収率は、第２の実施形態と同じ理由で、５０〜９５質量％の範囲が望ましい。また、Ｍｗが５００以下の低分子量体の含有量は、ＧＰＣチャート上１５％以下、好ましくは１２％以下であることが好ましい。１５％以下とすることにより、レジストパターンの耐熱性向上効果が奏されるのと同時に、加熱処理時の昇華物の発生量を抑制する効果が奏される。 For the same reason as in the second embodiment, the yield in such low molecular weight fraction removal treatment is desirably in the range of 50 to 95% by mass. Further, the content of the low molecular weight substance having Mw of 500 or less is 15% or less, preferably 12% or less on the GPC chart. By setting it to 15% or less, the effect of improving the heat resistance of the resist pattern is exhibited, and at the same time, the effect of suppressing the amount of sublimate generated during the heat treatment is exhibited.
本実施形態によれば、第１の実施形態と同様に良好な解像性および感度を得ることができるとともに、ポジ型ホトレジスト組成物の耐熱性をさらに向上させることができる。また低分子量体が分別除去されているので、加熱時に発生する昇華物を低減させることができる。
特に第３の実施形態の方が第２の実施形態に比べて分別溶剤に対する各分子量での溶解性の差が大きいため高収率でより効率的に低分子量体を除去することができる。
According to this embodiment, good resolution and sensitivity can be obtained as in the first embodiment, and the heat resistance of the positive photoresist composition can be further improved. Moreover, since the low molecular weight substance is separated and removed, sublimates generated during heating can be reduced.
In particular, since the third embodiment has a greater difference in solubility at each molecular weight in the fractionation solvent than the second embodiment, the low molecular weight body can be more efficiently removed in a high yield.
以下、実施例を示して本発明をさらに詳細に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited to a following example.
［ポジ型ホトレジスト組成物の評価方法］
下記の実施例または比較例のポジ型ホトレジスト組成物について下記の諸物性（１）〜（３）の評価方法を以下に示す。
（１）感度評価：ポジ型ホトレジスト組成物をスピンナーを用いてシリコン基板上に塗布したのち、これをホットプレート上で１４０℃、９０秒間乾燥（プリベーク）して、膜厚１．４８μｍのレジスト被膜を形成した。
次いで、この膜にラインアンドスペースが１：１の１．５μｍレジストパターン対応のマスク（レチクル）を介して、ミラープロジェクション・アライナーＭＰＡ−６００ＦＡ（キャノン社製；ｇｈi線露光装置）を用いて、１．５μｍＬ＆Ｓを忠実に再現することのできる露光量（Ｅｏｐ露光量）にて選択的露光を行った。
次いで、１４０℃、９０秒間の加熱条件で、ＰＥＢを施した。
次いで、２３℃、２．３８質量％ＴＭＡＨ水溶液（テトラメチルアンモニウムヒドロキシド水溶液；製品名「ＮＭＤ−３」東京応化工業株式会社製）用いて９０秒間の現像処理を行った後、純水で３０秒間リンスし、スピン乾燥した。
感度評価の指標として、１．５μｍＬ＆Ｓのレジストパターンを忠実に再現できる露光量（Ｅｏｐ、単位：ｍＪ／ｃｍ２）を用いた。
[Evaluation Method of Positive Photoresist Composition]
The following evaluation methods for the physical properties (1) to (3) of the positive photoresist compositions of the following examples or comparative examples are shown below.
(1) Sensitivity evaluation: A positive photoresist composition is applied onto a silicon substrate using a spinner, and then dried (prebaked) at 140 ° C. for 90 seconds on a hot plate to form a resist film having a thickness of 1.48 μm. Formed.
Next, a mirror projection aligner MPA-600FA (manufactured by Canon Inc .; ghi line exposure apparatus) is used for the film through a mask (reticle) corresponding to a 1.5 μm resist pattern with a line and space of 1: 1. Selective exposure was performed with an exposure amount (Eop exposure amount) that can faithfully reproduce 5 μmL & S.
Next, PEB was applied under heating conditions of 140 ° C. for 90 seconds.
Next, after developing for 90 seconds using 23 ° C., 2.38 mass% TMAH aqueous solution (tetramethylammonium hydroxide aqueous solution; product name “NMD-3” manufactured by Tokyo Ohka Kogyo Co., Ltd.), 30 Rinse for 2 seconds and spin dry.
As an index for sensitivity evaluation, an exposure amount (Eop, unit: mJ / cm 2 ) capable of faithfully reproducing a 1.5 μmL & S resist pattern was used.
（２）解像性評価：上記Ｅｏｐ露光量における限界解像度を求めた。
（３）耐熱性評価：上記Ｅｏｐ露光量において、１．５μｍＬ＆Ｓが描かれた基板を、１６０℃に設定されたホットプレート上に１分間静置した後、断面形状を観察した。その結果、１．５μｍＬ＆Ｓの寸法変化率が±１０％以内であったものを○、±１０％を超えたものを×として表した。
(2) Evaluation of resolution: The limiting resolution at the above Eop exposure amount was determined.
(3) Evaluation of heat resistance: In the above Eop exposure amount, a substrate on which 1.5 μmL & S was drawn was allowed to stand on a hot plate set at 160 ° C. for 1 minute, and then the cross-sectional shape was observed. As a result, the dimensional change rate of 1.5 μmL & S was within ± 10%, and the one exceeding ± 10% was represented as x.
［（Ａ）成分の調製例］
（調製例１；分別除去なし）
ノボラック樹脂（ａ１）を合成し、その全フェノール性水酸基の一部をエチルビニル基で保護して樹脂成分（Ａ１）を調製した。低分子量体の分別除去処理は行わなかった。
すなわちノボラック樹脂（ｍ−クレゾール／ｐ−クレゾール＝６／４（モル比）、ホルマリン／サリチルアルデヒド＝３／１（モル比）、Ｍｗ＝５５００）（ａ１）の２０質量％溶液［溶媒＝１，４−ジオキサン］２５０ｇにｐ−トルエンスルホン酸・１水和物０．０１ｇ、およびエチルビニルエーテル９ｇを添加し、２２℃で２時間反応を行った。次いで、反応液に０．０１ｇのトリエチルアミンを添加し、これを純水１０００ｍｌ中に注ぎ、反応物を沈殿させた。濾別した後、得られた沈殿物をメタノール２５０ｇに溶解し、その溶液をイオン交換樹脂に通した。その後、ＰＧＭＥＡに溶剤置換し、フェノール性水酸基の３０％がエトキシエチル基で保護されたノボラック樹脂（Ａ１）溶液１２５ｇを得た。
[Preparation example of component (A)]
(Preparation Example 1; no separation removal)
A novolac resin (a1) was synthesized, and a resin component (A1) was prepared by protecting a part of the total phenolic hydroxyl groups with an ethyl vinyl group. The low molecular weight product was not separated and removed.
That is, a 20% by mass solution of novolak resin (m-cresol / p-cresol = 6/4 (molar ratio), formalin / salicylaldehyde = 3/1 (molar ratio), Mw = 5500) (a1) [solvent = 1, 4-Dioxane] 0.01 g of p-toluenesulfonic acid monohydrate and 9 g of ethyl vinyl ether were added to 250 g and reacted at 22 ° C. for 2 hours. Next, 0.01 g of triethylamine was added to the reaction solution, which was poured into 1000 ml of pure water to precipitate the reaction product. After separation by filtration, the resulting precipitate was dissolved in 250 g of methanol, and the solution was passed through an ion exchange resin. Thereafter, the solvent was replaced with PGMEA to obtain 125 g of a novolak resin (A1) solution in which 30% of the phenolic hydroxyl groups were protected with ethoxyethyl groups.
（調製例２；保護後に分別除去）
調製例１において得られたノボラック樹脂（Ａ１）溶液を３０質量％のＰＧＭＥＡ溶液に調製し、その溶液にｎ−ヘプタン２７０ｇを添加し、生成した沈殿物を取り出し、当該沈殿物をＰＧＭＥＡに溶解し、次いで濃縮を行いｎ−ヘプタンを除去し、ノボラック樹脂（Ａ２）溶液を得た。分別処理における収率は７６質量％、Ｍｗ＝７２００であった。
(Preparation Example 2; separation removal after protection)
The novolak resin (A1) solution obtained in Preparation Example 1 is prepared in a 30% by mass PGMEA solution, 270 g of n-heptane is added to the solution, the generated precipitate is taken out, and the precipitate is dissolved in PGMEA. Then, concentration was performed to remove n-heptane, and a novolak resin (A2) solution was obtained. The yield in the fractionation treatment was 76% by mass and Mw = 7200.
（調製例３；保護前に分別除去）
ノボラック樹脂の低分子量体を分別処理して処理済ノボラック樹脂（ａ２）を調製した後、該処理済ノボラック樹脂（ａ２）の全フェノール性水酸基の一部をエチルビニル基で保護して樹脂成分（Ａ３）を調製した。
すなわちノボラック樹脂（ｍ−クレゾール／ｐ−クレゾール＝６／４（モル比）、ホルマリン／サリチルアルデヒド＝３／１（モル比）、Ｍｗ＝５５００）（ａ１）をメタノールに溶解し、３０質量％のメタノール溶液１５０ｇを調整し、これに純水１１５ｇを添加し沈殿物を得た。得られた沈殿物を１，４−ジオキサンに溶解させ、濃縮を行い水分を除去し、ノボラック樹脂（ａ２）溶液を得た。分別処理における収率は８０質量％であった。
分別処理して得られた処理済ノボラック樹脂（ａ２）の２０質量％溶液［溶媒＝１，４−ジオキサン］１８０ｇにｐ−トルエンスルホン酸・１水和物０．０１ｇ、およびエチルビニルエーテル６．５ｇを添加し、２２℃で２時間反応を行った。次いで、反応液に０．０１ｇのトリエチルアミンを添加し、これを純水１０００ｍｌ中に注ぎ、反応物を沈殿させた。濾別した沈殿物をメタノール２５０ｇに溶解し、その溶液をイオン交換樹脂に通した。その後、ＰＧＭＥＡに溶剤置換し、ノボラック樹脂（ａ２）の全フェノール性水酸基の３０％がエチルビニル基で保護された樹脂成分（Ａ３）を得た。
(Preparation Example 3; separation removal before protection)
After the fractional treatment of the low molecular weight novolak resin to prepare a treated novolak resin (a2), a part of the total phenolic hydroxyl groups of the treated novolak resin (a2) is protected with an ethyl vinyl group to obtain a resin component (A3 ) Was prepared.
That is, a novolak resin (m-cresol / p-cresol = 6/4 (molar ratio), formalin / salicylaldehyde = 3/1 (molar ratio), Mw = 5500) (a1) was dissolved in methanol, and 30% by mass 150 g of methanol solution was prepared, and 115 g of pure water was added thereto to obtain a precipitate. The obtained precipitate was dissolved in 1,4-dioxane, concentrated to remove moisture, and a novolak resin (a2) solution was obtained. The yield in the fractionation treatment was 80% by mass.
180 g of a 20% by mass solution [solvent = 1,4-dioxane] of a treated novolak resin (a2) obtained by fractionation treatment, 0.01 g of p-toluenesulfonic acid monohydrate, and 6.5 g of ethyl vinyl ether Was added and reacted at 22 ° C. for 2 hours. Next, 0.01 g of triethylamine was added to the reaction solution, which was poured into 1000 ml of pure water to precipitate the reaction product. The precipitate separated by filtration was dissolved in 250 g of methanol, and the solution was passed through an ion exchange resin. Thereafter, the solvent was replaced with PGMEA to obtain a resin component (A3) in which 30% of all phenolic hydroxyl groups of the novolak resin (a2) were protected with ethyl vinyl groups.
（調製例４〜６）
調製例１〜３において、縮合剤（ホルマリン／サリチルアルデヒド＝３／１（モル比））をホルマリンとｐ−ヒドロキシベンズアルデヒドの混合物（ホルマリン／ｐ−ヒドロキシベンズアルデヒド＝３／１（モル比））に変更した他は同様にして、それぞれ樹脂成分（Ａ４）〜（Ａ６）を調製した。
(Preparation Examples 4 to 6)
In Preparation Examples 1 to 3, the condensing agent (formalin / salicylaldehyde = 3/1 (molar ratio)) was changed to a mixture of formalin and p-hydroxybenzaldehyde (formalin / p-hydroxybenzaldehyde = 3/1 (molar ratio)). In the same manner, resin components (A4) to (A6) were prepared.
（調製例７〜９）
調製例１〜３において、縮合剤（ホルマリン／サリチルアルデヒド＝３／１（モル比））をホルマリンと３，４−ジヒドロキシベンズアルデヒドの混合物（ホルマリン／３，４−ジヒドロキシベンズアルデヒド＝３／１（モル比））に変更した他は同様にして、それぞれ樹脂成分（Ａ７）〜（Ａ９）を調製した。
(Preparation Examples 7 to 9)
In Preparation Examples 1 to 3, the condensing agent (formalin / salicylaldehyde = 3/1 (molar ratio)) is a mixture of formalin and 3,4-dihydroxybenzaldehyde (formalin / 3,4-dihydroxybenzaldehyde = 3/1 (molar ratio). Resin components (A7) to (A9) were prepared in the same manner except that they were changed to)).
（比較例調製例１）
調製例１において、縮合剤（ホルマリン／サリチルアルデヒド＝３／１（モル比））をホルマリンのみに変更した他は同様にして、樹脂成分（Ａ１０）を調製した。
(Comparative Example Preparation Example 1)
A resin component (A10) was prepared in the same manner as in Preparation Example 1 except that the condensing agent (formalin / salicylaldehyde = 3/1 (molar ratio)) was changed to only formalin.
（実施例１〜９および比較例１）
上記調製例１〜９、および比較調製例１でそれぞれ得た（Ａ１）〜（Ａ１０）成分１００質量部に対して、（Ｃ）成分[上記式（ＩＸ）の化合物]：３質量部、および（Ｄ）成分[トリ−ｎ−デシルアミン]：０．２質量部をＰＧＭＥＡに溶解し、さらに界面活性剤としてＸＲ−１０４（大日本インキ社製）を５００ｐｐｍ配合し、３５質量％濃度の溶液に調整した後、これを孔径０．２μｍのメンブランフィルターを用いてろ過し、ホトレジスト組成物を調製した。
このホトレジスト組成物について前記（１）〜（３）の物性を評価した。その結果を下記表１に示す。
(Examples 1 to 9 and Comparative Example 1)
(C) component [compound of formula (IX)]: 3 parts by mass with respect to 100 parts by mass of components (A1) to (A10) obtained in Preparation Examples 1 to 9 and Comparative Preparation Example 1, respectively; (D) Component [tri-n-decylamine]: 0.2 part by mass is dissolved in PGMEA, and further 500 ppm of XR-104 (Dainippon Ink Co., Ltd.) is blended as a surfactant into a 35% by mass solution. After the adjustment, this was filtered using a membrane filter having a pore size of 0.2 μm to prepare a photoresist composition.
The physical properties of (1) to (3) were evaluated for this photoresist composition. The results are shown in Table 1 below.
表１の結果より、実施例１〜９は縮合剤にフェノール性水酸基を有する芳香族アルデヒドを用いてノボラック樹脂を合成したものであり、縮合剤がホルマリンのみであった比較例１に比べて解像性および耐熱性が向上した。また、実施例の中でも、特に、（Ａ）成分の調製工程で低分子量体の分別処理を行なった実施例２，３，５，６，８，９は耐熱性がより優れていた。
From the results shown in Table 1, Examples 1 to 9 were prepared by synthesizing a novolak resin using an aromatic aldehyde having a phenolic hydroxyl group as a condensing agent, and compared with Comparative Example 1 where the condensing agent was only formalin. Imageability and heat resistance were improved. Of the examples, in particular, Examples 2, 3, 5, 6, 8, and 9 in which the low molecular weight fractionation treatment was performed in the preparation step of the component (A) were more excellent in heat resistance.
Claims (3)
前記（Ａ）成分が、芳香族ヒドロキシ化合物と、少なくともホルムアルデヒドおよびヒドロキシル基置換芳香族アルデヒドを含むアルデヒド類とを縮合反応させて得られるノボラック樹脂（ａ１）の、全フェノール性水酸基の一部を酸解離性溶解抑制基で保護してなるアルカリ難溶性あるいは不溶性の樹脂成分を含むことを特徴とする化学増幅型ポジ型ホトレジスト組成物。
The component (A) is a part of the total phenolic hydroxyl group of the novolak resin (a1) obtained by condensation reaction of an aromatic hydroxy compound and an aldehyde containing at least formaldehyde and a hydroxyl group-substituted aromatic aldehyde. A chemically amplified positive photoresist composition comprising an alkali hardly soluble or insoluble resin component protected with a dissociable dissolution inhibiting group.
The component (A) is a novolak resin obtained by a condensation reaction of an aromatic hydroxy compound and an aldehyde containing at least formaldehyde and a hydroxyl group-substituted aromatic aldehyde, and is subjected to a treatment for separating and removing low molecular weight substances. The treated novolak resin (a2) comprises a hardly alkali-soluble or insoluble resin component obtained by protecting a part of all phenolic hydroxyl groups with an acid dissociable, dissolution inhibiting group. Chemically amplified positive photoresist composition.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| JP2004115328A JP4476675B2 (en) | 2004-04-09 | 2004-04-09 | Chemically amplified positive photoresist composition |
| TW094110322A TWI296741B (en) | 2004-04-09 | 2005-03-31 | Chemically amplified positive photoresist composition |
| KR1020050028473A KR20060045521A (en) | 2004-04-09 | 2005-04-06 | Chemically amplified positive photoresist composition |
| CN2005100648392A CN1680875B (en) | 2004-04-09 | 2005-04-06 | Chemically amplified posative opto-corrosionproof agent composition |
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| JP2004115328A JP4476675B2 (en) | 2004-04-09 | 2004-04-09 | Chemically amplified positive photoresist composition |
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| JP4476675B2 true JP4476675B2 (en) | 2010-06-09 |
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| JP (1) | JP4476675B2 (en) |
| KR (1) | KR20060045521A (en) |
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| EP0716344A1 (en) * | 1994-12-05 | 1996-06-12 | Konica Corporation | Light-sensitive composition and light-sensitive lithographic printing plate using the same |
| JP3796982B2 (en) * | 1998-06-02 | 2006-07-12 | 住友化学株式会社 | Positive resist composition |
| JP2002072477A (en) * | 2000-06-12 | 2002-03-12 | Jsr Corp | Radiation sensitive resin composition |
| KR100783603B1 (en) * | 2002-01-05 | 2007-12-07 | 삼성전자주식회사 | Photoresist Composition And Method of Forming Pattern Using The Same |
| TW200306324A (en) * | 2002-04-22 | 2003-11-16 | Tokyo Ind Co Ltd | Novolak resin solution, positive photoresist composition, and method of producing same |
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| TW200537250A (en) | 2005-11-16 |
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