JP3414708B2 - Method of forming patterned polysilazane film - Google Patents
Method of forming patterned polysilazane filmInfo
- Publication number
- JP3414708B2 JP3414708B2 JP2000262703A JP2000262703A JP3414708B2 JP 3414708 B2 JP3414708 B2 JP 3414708B2 JP 2000262703 A JP2000262703 A JP 2000262703A JP 2000262703 A JP2000262703 A JP 2000262703A JP 3414708 B2 JP3414708 B2 JP 3414708B2
- Authority
- JP
- Japan
- Prior art keywords
- polysilazane
- film
- photosensitive
- composition
- substrate
- 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 - Fee Related
Links
- 229920001709 polysilazane Polymers 0.000 title claims description 146
- 238000000034 method Methods 0.000 title claims description 35
- 239000000203 mixture Substances 0.000 claims description 73
- 239000000758 substrate Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 description 33
- 239000011248 coating agent Substances 0.000 description 32
- -1 naphthoquinonediazide sulfonates Chemical class 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- 239000007789 gas Substances 0.000 description 21
- 230000018109 developmental process Effects 0.000 description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000919 ceramic Substances 0.000 description 12
- 238000000354 decomposition reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 11
- 239000011229 interlayer Substances 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 238000005530 etching Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 229920002120 photoresistant polymer Polymers 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 230000001235 sensitizing effect Effects 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000005103 alkyl silyl group Chemical group 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 239000004973 liquid crystal related substance Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 238000000059 patterning Methods 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910020175 SiOH Inorganic materials 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- BNWKXMCELVEAPW-UHFFFAOYSA-N chembl3305990 Chemical compound O=C1C(=[N+]=[N-])C=CC2=C1C=CC=C2S(=O)(=O)O BNWKXMCELVEAPW-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000003776 cleavage reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- DLDWUFCUUXXYTB-UHFFFAOYSA-N (2-oxo-1,2-diphenylethyl) 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC(C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 DLDWUFCUUXXYTB-UHFFFAOYSA-N 0.000 description 1
- ZORJPNCZZRLEDF-UHFFFAOYSA-N (3-methoxy-3-methylbutoxy)carbonyloxy (3-methoxy-3-methylbutyl) carbonate Chemical compound COC(C)(C)CCOC(=O)OOC(=O)OCCC(C)(C)OC ZORJPNCZZRLEDF-UHFFFAOYSA-N 0.000 description 1
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- BLKRGXCGFRXRNQ-SNAWJCMRSA-N (z)-3-carbonoperoxoyl-4,4-dimethylpent-2-enoic acid Chemical compound OC(=O)/C=C(C(C)(C)C)\C(=O)OO BLKRGXCGFRXRNQ-SNAWJCMRSA-N 0.000 description 1
- FYRCDEARNUVZRG-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CC(C)CC(C)(C)C1 FYRCDEARNUVZRG-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- XSZYESUNPWGWFQ-UHFFFAOYSA-N 1-(2-hydroperoxypropan-2-yl)-4-methylcyclohexane Chemical compound CC1CCC(C(C)(C)OO)CC1 XSZYESUNPWGWFQ-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- CRJIYMRJTJWVLU-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yl 3-(5,5-dimethylhexyl)dioxirane-3-carboxylate Chemical compound CC(C)(C)CCCCC1(C(=O)OC(C)(C)CC(C)(C)C)OO1 CRJIYMRJTJWVLU-UHFFFAOYSA-N 0.000 description 1
- DPGYCJUCJYUHTM-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-yloxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)CC(C)(C)C DPGYCJUCJYUHTM-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- PJABOTZVAHGVAF-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-yl)-7,7-dimethyloctaneperoxoic acid Chemical compound CC(C)(C)CCCCC(C(=O)OO)C(C)(C)C1CCCCC1 PJABOTZVAHGVAF-UHFFFAOYSA-N 0.000 description 1
- CHKCPIUYSMYEEW-UHFFFAOYSA-N 2-(2-cyclohexylpropan-2-ylperoxy)-2-ethylhexanoic acid Chemical compound CCCCC(CC)(C(O)=O)OOC(C)(C)C1CCCCC1 CHKCPIUYSMYEEW-UHFFFAOYSA-N 0.000 description 1
- IEMBFTKNPXENSE-UHFFFAOYSA-N 2-(2-methylpentan-2-ylperoxy)propan-2-yl hydrogen carbonate Chemical compound CCCC(C)(C)OOC(C)(C)OC(O)=O IEMBFTKNPXENSE-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- VGZZAZYCLRYTNQ-UHFFFAOYSA-N 2-ethoxyethoxycarbonyloxy 2-ethoxyethyl carbonate Chemical compound CCOCCOC(=O)OOC(=O)OCCOCC VGZZAZYCLRYTNQ-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- MIRQGKQPLPBZQM-UHFFFAOYSA-N 2-hydroperoxy-2,4,4-trimethylpentane Chemical compound CC(C)(C)CC(C)(C)OO MIRQGKQPLPBZQM-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- BZGMEGUFFDTCNP-UHFFFAOYSA-N 2-hydroperoxy-2-methylpentane Chemical compound CCCC(C)(C)OO BZGMEGUFFDTCNP-UHFFFAOYSA-N 0.000 description 1
- RTEZVHMDMFEURJ-UHFFFAOYSA-N 2-methylpentan-2-yl 2,2-dimethylpropaneperoxoate Chemical compound CCCC(C)(C)OOC(=O)C(C)(C)C RTEZVHMDMFEURJ-UHFFFAOYSA-N 0.000 description 1
- WXDJDZIIPSOZAH-UHFFFAOYSA-N 2-methylpentan-2-yl benzenecarboperoxoate Chemical compound CCCC(C)(C)OOC(=O)C1=CC=CC=C1 WXDJDZIIPSOZAH-UHFFFAOYSA-N 0.000 description 1
- RPBWMJBZQXCSFW-UHFFFAOYSA-N 2-methylpropanoyl 2-methylpropaneperoxoate Chemical compound CC(C)C(=O)OOC(=O)C(C)C RPBWMJBZQXCSFW-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- KFGFVPMRLOQXNB-UHFFFAOYSA-N 3,5,5-trimethylhexanoyl 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOC(=O)CC(C)CC(C)(C)C KFGFVPMRLOQXNB-UHFFFAOYSA-N 0.000 description 1
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- NFWPZNNZUCPLAX-UHFFFAOYSA-N 4-methoxy-3-methylaniline Chemical compound COC1=CC=C(N)C=C1C NFWPZNNZUCPLAX-UHFFFAOYSA-N 0.000 description 1
- CDSULTPOCMWJCM-UHFFFAOYSA-N 4h-chromene-2,3-dione Chemical compound C1=CC=C2OC(=O)C(=O)CC2=C1 CDSULTPOCMWJCM-UHFFFAOYSA-N 0.000 description 1
- YPIFGDQKSSMYHQ-UHFFFAOYSA-M 7,7-dimethyloctanoate Chemical compound CC(C)(C)CCCCCC([O-])=O YPIFGDQKSSMYHQ-UHFFFAOYSA-M 0.000 description 1
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YYLLIJHXUHJATK-UHFFFAOYSA-N Cyclohexyl acetate Chemical compound CC(=O)OC1CCCCC1 YYLLIJHXUHJATK-UHFFFAOYSA-N 0.000 description 1
- 241000257465 Echinoidea Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JUIBLDFFVYKUAC-UHFFFAOYSA-N [5-(2-ethylhexanoylperoxy)-2,5-dimethylhexan-2-yl] 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C(CC)CCCC JUIBLDFFVYKUAC-UHFFFAOYSA-N 0.000 description 1
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 1
- WBWJXRJARNTNBL-UHFFFAOYSA-N [Fe].[Cr].[Co] Chemical compound [Fe].[Cr].[Co] WBWJXRJARNTNBL-UHFFFAOYSA-N 0.000 description 1
- BQCFCWXSRCETDO-UHFFFAOYSA-N [Fe].[Mn].[Cu] Chemical compound [Fe].[Mn].[Cu] BQCFCWXSRCETDO-UHFFFAOYSA-N 0.000 description 1
- GAMNLIVXXFFAQM-UHFFFAOYSA-N [bromo(dinitro)methyl]benzene Chemical compound [O-][N+](=O)C(Br)([N+]([O-])=O)C1=CC=CC=C1 GAMNLIVXXFFAQM-UHFFFAOYSA-N 0.000 description 1
- FUMLKAFCVQJVEZ-UHFFFAOYSA-N [bromo(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Br)C1=CC=CC=C1 FUMLKAFCVQJVEZ-UHFFFAOYSA-N 0.000 description 1
- PFDHBJNLFOINAY-UHFFFAOYSA-N [chloro(dinitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)([N+]([O-])=O)C1=CC=CC=C1 PFDHBJNLFOINAY-UHFFFAOYSA-N 0.000 description 1
- BVJSGOYEEDZAGW-UHFFFAOYSA-N [chloro(nitro)methyl]benzene Chemical compound [O-][N+](=O)C(Cl)C1=CC=CC=C1 BVJSGOYEEDZAGW-UHFFFAOYSA-N 0.000 description 1
- XQBQVMYWVQLMHW-UHFFFAOYSA-N [dinitro(phenyl)methyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC([N+]([O-])=O)([N+]([O-])=O)C1=CC=CC=C1 XQBQVMYWVQLMHW-UHFFFAOYSA-N 0.000 description 1
- NMYLMXLDMZZLGF-UHFFFAOYSA-N [dinitro(phenyl)methyl] acetate Chemical compound CC(=O)OC([N+]([O-])=O)([N+]([O-])=O)C1=CC=CC=C1 NMYLMXLDMZZLGF-UHFFFAOYSA-N 0.000 description 1
- ACERAGFRJFAUKC-UHFFFAOYSA-N [nitro(phenyl)methyl] 2,2,2-trichloroacetate Chemical compound ClC(Cl)(Cl)C(=O)OC([N+](=O)[O-])C1=CC=CC=C1 ACERAGFRJFAUKC-UHFFFAOYSA-N 0.000 description 1
- STOLYTNTPGXYRW-UHFFFAOYSA-N [nitro(phenyl)methyl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OC([N+]([O-])=O)C1=CC=CC=C1 STOLYTNTPGXYRW-UHFFFAOYSA-N 0.000 description 1
- QDHKQGOQBFPXLP-UHFFFAOYSA-N [nitro(phenyl)methyl] acetate Chemical compound CC(=O)OC([N+]([O-])=O)C1=CC=CC=C1 QDHKQGOQBFPXLP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- RJNQAWYDOFQOFG-UHFFFAOYSA-N benzoyl 3-methylbenzenecarboperoxoate Chemical compound CC1=CC=CC(C(=O)OOC(=O)C=2C=CC=CC=2)=C1 RJNQAWYDOFQOFG-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 229940114081 cinnamate Drugs 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- DDTBPAQBQHZRDW-UHFFFAOYSA-N cyclododecane Chemical compound C1CCCCCCCCCCC1 DDTBPAQBQHZRDW-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
- 238000007872 degassing Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 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
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000006502 nitrobenzyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- SRSFOMHQIATOFV-UHFFFAOYSA-N octanoyl octaneperoxoate Chemical compound CCCCCCCC(=O)OOC(=O)CCCCCCC SRSFOMHQIATOFV-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229930004008 p-menthane Natural products 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZVSLRJWQDNRUDU-UHFFFAOYSA-L palladium(2+);propanoate Chemical compound [Pd+2].CCC([O-])=O.CCC([O-])=O ZVSLRJWQDNRUDU-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- XTXFUQOLBKQKJU-UHFFFAOYSA-N tert-butylperoxy(trimethyl)silane Chemical compound CC(C)(C)OO[Si](C)(C)C XTXFUQOLBKQKJU-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OKYDCMQQLGECPI-UHFFFAOYSA-N thiopyrylium Chemical class C1=CC=[S+]C=C1 OKYDCMQQLGECPI-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N trans-p-menthane Natural products CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Materials For Photolithography (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、感光性ポリシラザ
ン組成物を用いてパターン化されたポリシラザン膜を形
成する方法、さらに詳細には、パターン形成時間が短縮
され、現像後のパターンに現像残渣が発生せず、且つ形
成されたパターンの基板への密着性が改善された、パタ
ーン化されたポリシラザン膜の形成方法に関する。FIELD OF THE INVENTION The present invention relates to a method for forming a patterned polysilazane film using a photosensitive polysilazane composition, and more specifically, shortening the pattern formation time and reducing the development residue in the pattern after development. The present invention relates to a method for forming a patterned polysilazane film that does not occur and has improved adhesion of the formed pattern to a substrate.
【０００２】[0002]
【従来の技術】半導体デバイスや液晶表示装置の製作な
どを始めとする種々の分野において、微細加工あるいは
パターニングのためにポジ型またはネガ型のフォトレジ
ストが用いられていることは周知である。従来、このよ
うなフォトレジストとして、ノボラック樹脂とキノンジ
アジド感光剤からなるポジ型感光性組成物、化学増幅型
のポジ型あるいはネガ型感光性組成物、ポリビニルシン
ナメート系感光性組成物、ビスアジド−ゴム系感光性組
成物、光重合系感光性組成物などのネガ型レジスト等種
々のものが用いられている。このようなフォトレジスト
には、使用目的に応じ種々の特性が要求される。例え
ば、半導体デバイスの加工においては、高感度、高解像
度、耐エッチング性などの特性が要求される。2. Description of the Related Art It is well known that a positive type or negative type photoresist is used for fine processing or patterning in various fields including the production of semiconductor devices and liquid crystal display devices. Conventionally, as such photoresists, positive photosensitive composition comprising a novolak resin and a quinonediazide photosensitizer, a chemically amplified positive-type or negative-working photosensitive composition, a polyvinyl cinnamate-based photosensitive compositions, bisazide - Rubber Various types of negative resists such as photosensitive photosensitive compositions and photopolymerizable photosensitive compositions have been used. Such photoresists are required to have various characteristics depending on the purpose of use. For example, in processing semiconductor devices, characteristics such as high sensitivity, high resolution, and etching resistance are required.
【０００３】一方、半導体デバイス、液晶表示装置、プ
リント回路基板などの製作においては、層間絶縁膜をは
じめ様々な要素がパターニング加工されている。このよ
うな要素は、例えば半導体デバイス等の製造工程（例え
ば、ＣＶＤによる配線蒸着工程）においては４００℃を
超える高温に曝される。従って、このような高温に曝さ
れる層間絶縁膜などの材料には、耐熱性の点から有機材
料では十分には対応できず、無機材料の使用が望まれて
いる。かかる無機材料としては、シリカ系セラミックス
膜が、耐熱性の他、耐磨耗性、耐蝕性、絶縁性、透明性
等にも優れているため、半導体デバイス、液晶表示装
置、プリント回路基板等において有用なパターン化被膜
として用いられている。On the other hand, in the fabrication of semiconductor devices, liquid crystal display devices, printed circuit boards, etc., various elements such as an interlayer insulating film are patterned. Such an element is exposed to a high temperature exceeding 400 ° C. in a manufacturing process (for example, a wiring deposition process by CVD) of a semiconductor device or the like. Therefore, with respect to materials such as the interlayer insulating film exposed to such a high temperature, the organic materials cannot sufficiently cope with heat resistance, and the use of inorganic materials is desired. As such an inorganic material, since the silica-based ceramic film is excellent in not only heat resistance but also abrasion resistance, corrosion resistance, insulation, transparency, etc., it is used in semiconductor devices, liquid crystal display devices, printed circuit boards, etc. Used as a useful patterned coating.
【０００４】このようなパターン化されたシリカ系セラ
ミックス膜は、パターン化されたフォトレジストをエッ
チィングマスクとして用い、セラミックス膜をエッチン
グすることにより形成されるのが一般的である。これに
対し、例えば、特開平５−８８３７３号公報には、基板
上にポリシラザンを含む塗布液を塗布して塗膜を形成
し、該塗膜に酸化雰囲気下で紫外線をパターン状に照射
して紫外線露光部分を硬化させた後、紫外線未露光部分
を除去し、その後パターン化されたポリシラザン膜をセ
ラミックス膜に転化することにより、セラミックス膜パ
ターンを形成する方法が記載されている。この方法は、
光照射部分が硬化して残留するのでネガ型のフォトレジ
ストであると見ることができる。Such a patterned silica-based ceramics film is generally formed by etching the ceramics film using a patterned photoresist as an etching mask. On the other hand, for example, in Japanese Unexamined Patent Publication No. 5-88373, a coating solution containing polysilazane is applied on a substrate to form a coating film, and the coating film is irradiated with ultraviolet rays in a pattern in an oxidizing atmosphere. A method of forming a ceramic film pattern by curing an ultraviolet-exposed portion, removing an unexposed portion of the ultraviolet light, and then converting the patterned polysilazane film into a ceramic film is described. This method
Since the light-irradiated portion is cured and remains, it can be regarded as a negative photoresist.
【０００５】[0005]
【発明が解決しようとする課題】ところで、半導体デバ
イス等の加工は微細化の一途をたどっており、このた
め、レジストのタイプとしては解像度の高いポジ型であ
って耐酸素プラズマ性など耐エッチィング性の高い材料
が望まれる。また、パターニングした被膜を層間絶縁膜
として残留させて使用する場合には、該被膜材料とし
て、上記の微細化に伴う要件の他、層間絶縁膜において
要求される高耐熱性、低誘電率、透明性等の諸特性に優
れた材料であることが望まれる。かかる要請に応えるべ
く、本発明者らは、特願平１１−２８３１０６号におい
て、ポリシラザンと光酸発生剤とを含むポジ型として機
能する感光性ポリシラザン組成物を用い、これを塗布し
て塗膜を形成する工程と、前記塗膜に光をパターン状に
照射する工程と、前記塗膜の照射された部分を溶解除去
する工程とを含んで成る、パターン化されたポリシラザ
ン膜の形成方法及び当該パターン化されたポリシラザン
膜を、周囲雰囲気において放置又は焼成することにより
シリカ系セラミックス被膜に転化させる工程を含んで成
る、パターン化された絶縁膜の形成方法を提案した。こ
の方法においては、感光性ポリシラザン組成物膜の露光
部分において生成した酸によりポリシラザンのＳｉ−Ｎ
結合が解裂し、Ｈ２Ｏ分子との反応によりシラノール
（Ｓｉ−ＯＨ）結合が形成され、ポリシラザンの分解が
起こる。この提案された方法においては、ポリシラザン
の分解を図るために、露光後の感光性ポリシラザン組成
物膜を水と接触させることが記載されている。 By the way, the processing of semiconductor devices and the like is steadily becoming finer. Therefore, the resist type is a positive type having a high resolution and is resistant to etching such as oxygen plasma resistance. A highly flexible material is desired. When the patterned film is used as an interlayer insulating film, the film material is required to have high heat resistance, low dielectric constant, and transparency, which are required for the interlayer insulating film, in addition to the requirements associated with the above miniaturization. It is desired that the material has excellent properties such as properties. In order to meet such a demand, the inventors of the present invention, in Japanese Patent Application No. 11-283106, use a photosensitive polysilazane composition which functions as a positive type and which contains a polysilazane and a photoacid generator, and apply this to form a coating film. And a step of irradiating the coating film with light in a pattern, and a step of dissolving and removing the irradiated portion of the coating film, and a method for forming a patterned polysilazane film, and We have proposed a method for forming a patterned insulating film, which comprises the step of converting a patterned polysilazane film into a silica-based ceramic film by leaving or firing it in an ambient atmosphere. In this method, the Si-N of polysilazane is generated by the acid generated in the exposed portion of the photosensitive polysilazane composition film.
The bond is cleaved, and a silanol (Si—OH) bond is formed by the reaction with the H 2 O molecule, and the polysilazane is decomposed. This proposed method describes that the photosensitive polysilazane composition film after exposure is brought into contact with water in order to decompose polysilazane.
【０００６】また、本発明者らは、特願平１２−１０８
０２３号において、ポリシラザンとして変性ポリシルセ
スキアザンを用いることにより、保存安定性が改善され
たポジ型として機能する感光性ポリシラザン組成物を提
供したが、露光後の感光性ポリシラザン組成物の分解を
行うための方法としては、上記特願平１１−２８３１０
６号と同じく感光性ポリシラザン組成物を水と接触させ
ることが記載されているのみである。しかし、露光した
感光性ポリシラザン組成物を水と接触させてポリシラザ
ンの分解を図る場合、ポリシラザンの分解が感光性ポリ
シラザン組成物の膜表面近傍でしか進まないためと考え
られるが、分解処理条件によってはその後のアルカリ水
溶液による現像時に露光部の除去が充分に行われず、現
像後にパターンに現像残渣が存在することがある。The inventors of the present invention have also filed Japanese Patent Application No. 12-108.
No. 023 provides a photosensitive polysilazane composition that functions as a positive type with improved storage stability by using a modified polysilsesquiazane as the polysilazane. However, the photosensitive polysilazane composition after exposure is decomposed. As a method for this, the above-mentioned Japanese Patent Application No. 11-28310 is used.
As in No. 6, it is only described that the photosensitive polysilazane composition is brought into contact with water. However, when the exposed photosensitive polysilazane composition is brought into contact with water to decompose the polysilazane, it is considered that the decomposition of the polysilazane proceeds only near the film surface of the photosensitive polysilazane composition, but depending on the decomposition treatment conditions. The exposed portion may not be sufficiently removed during the subsequent development with an aqueous alkaline solution, and a development residue may be present in the pattern after the development.
【０００７】本発明の目的は、感光性ポリシラザン組成
物を用いてパターン化されたポリシラザン膜を形成する
方法において、露光後の感光性ポリシラザン組成物の分
解工程におけるポリシラザンの分解に要する時間が短か
く、また現像後のパターンに現像残渣のない、パターン
化されたポリシラザン膜を形成する方法を提供すること
である。また、本発明の他の目的は、上記パターン化さ
れたポリシラザン膜の基板への密着性を改善する方法を
提供することである。An object of the present invention is to provide a method for forming a patterned polysilazane film using a photosensitive polysilazane composition, wherein the time required for the decomposition of polysilazane in the step of decomposing the photosensitive polysilazane composition after exposure is short. Another object of the present invention is to provide a method for forming a patterned polysilazane film having no development residue in the pattern after development. Another object of the present invention is to provide a method for improving the adhesion of the patterned polysilazane film to a substrate.
【０００８】[0008]
【課題を解決する手段】本発明者は、鋭意検討を行った
結果、ポリシラザンと光酸発生剤とを含む感光性ポリシ
ラザン組成物のようなポジ型として機能する感光性ポリ
シラザン組成物を用いてパターン化されたポリシラザン
膜を形成する際に、露光された感光性ポリシラザン組成
物膜を、水蒸気含有気体と接触させ、ポリシラザンの分
解を行う、即ち加湿処理することにより、短時間でポリ
シラザンの分解が行われ、且つ現像後のパターンに現像
残渣も発生しないこと、その際気体の水蒸気の含有量を
増す、或いは加湿処理時に感光性ポリシラザン組成物膜
を加熱された状態にすると分解時間の短縮化がさらに図
られること、また該膜が加熱されていると膜表面への結
露の条件も緩和されるため、加湿処理雰囲気の水蒸気分
圧をより高くすることが可能となり、これによりポリシ
ラザンの分解に要する時間をさらに短くすることができ
る上、現像時の加熱によりポリシラザン膜の基板への密
着性も向上することを見出して、本発明をなしたもので
ある。Means for Solving the Problems As a result of extensive studies, the present inventor has found that a pattern using a photosensitive polysilazane composition that functions as a positive type, such as a photosensitive polysilazane composition containing polysilazane and a photo-acid generator. In forming the polysilazane film, the exposed photosensitive polysilazane composition film is contacted with a water vapor-containing gas to decompose the polysilazane, that is, a humidification treatment is performed to decompose the polysilazane in a short time. Further, no development residue is generated in the pattern after development, in which case the content of water vapor in the gas is increased, or the photosensitive polysilazane composition film is heated during the humidification treatment, the decomposition time is further shortened. In addition, since the condition of dew condensation on the surface of the film is eased when the film is heated, the partial pressure of water vapor in the humidifying atmosphere is increased. In addition to the above, it is possible to further shorten the time required for the decomposition of polysilazane, and it was found that the adhesion of the polysilazane film to the substrate is improved by heating during development, and the present invention has been made. is there.
【０００９】すなわち、本発明は以下の構成からなるポ
リシラザン膜の形成方法である。
〔１〕感光性ポリシラザン組成物を基板に塗布し、露光
後現像することによりパターン化されたポリシラザン膜
を形成する方法において、露光された感光性ポリシラザ
ン組成物膜を、前記基板の温度に対する相対湿度が３５
％〜９０％の水蒸気含有気体と接触させた後現像を行う
ことを特徴とするパターン化されたポリシラザン膜の形
成方法。
〔２〕上記〔１〕のパターン化されたポリシラザン膜の
形成方法において、前記水蒸気含有気体との接触時に感
光性ポリシラザン組成物膜が加熱されていることを特徴
とするパターン化されたポリシラザン膜の形成方法。That is, the present invention is a method for forming a polysilazane film having the following constitution. [1] In a method of forming a patterned polysilazane film by applying a photosensitive polysilazane composition to a substrate and developing after exposure, the exposed photosensitive polysilazane composition film is treated with a relative humidity with respect to the temperature of the substrate. Is 35
A method for forming a patterned polysilazane film, which comprises performing development after contacting with a gas containing 90 to 90% of water vapor . [2] In the method for forming a patterned polysilazane film according to [1], the photosensitive polysilazane composition film is heated at the time of contact with the water vapor-containing gas . Of forming a coated polysilazane film.
【００１０】上記本発明の方法により形成されたパター
ン化されたポリシラザン膜は、そのまま例えばエッチン
グレジストあるいは表示素子などの素子中のパターン化
被膜として利用することができる。本発明の方法におい
て用いられる感光性ポリシラザン組成物はポジ型である
ので解像度は高く、また従来の有機材料系のレジストよ
りも耐酸素プラズマ性が高い。また、本発明の方法によ
り形成されたパターン化されたポリシラザン膜は、長時
間放置するか、または焼成することにより、シリカ系セ
ラミックスに転化され、この転化されたセラミックス膜
は高耐熱性、低誘電率、透明性等に優れた被膜であるの
で、層間絶縁膜などとして好適に用いることができる。The patterned polysilazane film formed by the method of the present invention can be used as it is as a patterned coating in an element such as an etching resist or a display element. Since the photosensitive polysilazane composition used in the method of the present invention is a positive type, it has a high resolution and a higher oxygen plasma resistance than conventional organic material-based resists. Further, the patterned polysilazane film formed by the method of the present invention is converted into silica-based ceramics by leaving it for a long time or by firing, and the converted ceramics film has high heat resistance and low dielectric constant. Since it is a film having excellent rate and transparency, it can be suitably used as an interlayer insulating film or the like.
【００１１】以下、本発明を更に詳細に説明する。本発
明のパターン化されたポリシラザン膜の形成方法は、こ
れに限定されるものではないが、（ａ）感光性ポリシラ
ザン組成物の基板に塗布して塗膜を形成する工程、
（ｂ）前記塗膜に光をパターン状に照射する露光工程、
（ｃ）パターン露光された基板を、必要であれば基板を
加熱した状態で、前記基板の温度に対する相対湿度が３
５％〜９０％の水蒸気を含む気体と接触させ、ポリシラ
ザンを分解させる加湿処理工程、（ｄ）前記塗膜の光照
射された部分を溶解除去する現像工程を含む。以下、本
発明のパターン化されたポリシラザン膜の形成方法を、
この例示した方法に沿って、具体的に説明する。The present invention will be described in more detail below. The method for forming a patterned polysilazane film of the present invention is not limited to this, but includes (a) a step of applying a photosensitive polysilazane composition onto a substrate to form a coating film,
(B) an exposure step of irradiating the coating film with light in a pattern,
(C) The relative humidity with respect to the temperature of the substrate is 3 with the substrate subjected to pattern exposure being heated if necessary.
A humidification treatment step of decomposing polysilazane by contacting with a gas containing 5% to 90% steam, and (d) a developing step of dissolving and removing the light-irradiated portion of the coating film are included. Hereinafter, the method for forming a patterned polysilazane film of the present invention,
A specific description will be given along the exemplified method.
【００１２】まず、本発明のパターン化されたポリシラ
ザン膜を形成する方法においては、感光性組成物とし
て、ポリシラザンと光酸発生剤を含む感光性ポリシラザ
ン組成物のようなポジ型として機能する感光性ポリシラ
ザン組成物が用いられる。このポリシラザンと光酸発生
剤を含む感光性ポリシラザン組成物において用いられる
ポリシラザンとしては、例えば、次のようなものを挙げ
ることができる。First, in the method for forming a patterned polysilazane film of the present invention, the photosensitive composition functions as a positive photosensitive resin such as a photosensitive polysilazane composition containing polysilazane and a photo-acid generator. A polysilazane composition is used. Examples of the polysilazane used in the photosensitive polysilazane composition containing the polysilazane and the photoacid generator include the following.
【００１３】（イ）一般式（Ｉ）(A) General formula (I)
【化１】
（式中、Ｒ１、Ｒ２及びＲ３は、各々独立に、水素原
子、アルキル基、アルケニル基、シクロアルキル基、ア
リール基、これらの基以外でケイ素又は窒素に直結する
部分が炭素である基、アルキルシリル基、アルキルアミ
ノ基又はアルコキシ基を表す。）で表される骨格を含む
数平均分子量１００〜５０，０００のポリシラザン又は
その変性物。[Chemical 1] (In the formula, R 1 , R 2 and R 3 are each independently a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and a portion other than these groups, which is directly bonded to silicon or nitrogen, is carbon. Group, an alkylsilyl group, an alkylamino group or an alkoxy group), and a polysilazane having a number average molecular weight of 100 to 50,000 or a modified product thereof.
【００１４】（ロ）一般式（II）：
−（ＳｉＲ４（ＮＲ５）１．５）ｎ− （II）
（式中、Ｒ４及びＲ５は、各々独立に、水素原子、アル
キル基、アルケニル基、シクロアルキル基、アリール
基、これらの基以外でケイ素又は窒素に直結する部分が
炭素である基、アルキルシリル基、アルキルアミノ基又
はアルコキシ基を表し、ｎは任意の整数である。）で表
される骨格を含む数平均分子量１００〜１００，０００
のポリシルセスキアザン及びその変性物。[0014] (b) the general formula (II): - (SiR 4 (NR 5) 1.5) n - (II) ( wherein, R 4 and R 5 are each independently a hydrogen atom, an alkyl group, An alkenyl group, a cycloalkyl group, an aryl group, a group in which the part directly bonded to silicon or nitrogen other than these groups is carbon, an alkylsilyl group, an alkylamino group or an alkoxy group, and n is an arbitrary integer.) Number average molecular weight including the skeleton represented by 100 to 100,000
Polysilsesquiazane and its modified products.
【００１５】（ハ）主たる繰り返し単位として−（ＲＳ
ｉＮ３）−、−（ＲＳｉＮ２Ｏ）−、−（ＲＳｉＮ
Ｏ２）−及び−（ＲＳｉＯ３）−〔式中、Ｒはアルキル
基、アルケニル基、シクロアルキル基、アリール基、ア
ルキルアミノ基又はアルキルシリル基である〕を含む数
平均分子量３００〜１００，０００のポリオルガノシロ
キサザン。(C) As the main repeating unit,-(RS
iN 3) -, - (RSiN 2 O) -, - (RSiN
O 2 )-and-(RSiO 3 )-[in the formula, R is an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group] including a number average molecular weight of 300 to 100,000. Polyorganosiloxazane.
【００１６】（ニ）一般式（III）：
−〔ＳｉＲ６（ＮＲ７）１．５〕− （III）
を基本構成単位とし、さらに一般式：
−〔ＳｉＲ６ ２ＮＲ７〕−及び／又は−〔ＳｉＲ
６ ３（ＮＲ７）０．５〕−
で表される他の構成単位を前記基本構成単位に対して
０．１モル％〜１００モル％含有する数平均分子量１０
０〜１００，０００の変性ポリシルセスキアザン。（式
中、Ｒ６は、各々独立に、炭素数１〜３のアルキル基又
は置換もしくは無置換フェニル基を表し、Ｒ７は、各々
独立に、水素、炭素数１〜３のアルキル基又は置換もし
くは無置換フェニル基を表す。）[0016] (d) In formula (III): - [SiR 6 (NR 7) 1.5] - (III) is a basic unit, further general formula: - [SiR 6 2 NR 7] - and / or -[SiR
6 3 (NR 7 ) 0.5 ]-containing 0.1 mol% to 100 mol% of the other structural unit represented by the formula (1) to a number average molecular weight of 10
0 to 100,000 modified polysilsesquiazanes. (In the formula, each R 6 independently represents an alkyl group having 1 to 3 carbon atoms or a substituted or unsubstituted phenyl group, and each R 7 independently represents hydrogen, an alkyl group having 1 to 3 carbon atoms or a substituted group. Or represents an unsubstituted phenyl group.)
【００１７】本発明で用いられる感光性ポリシラザン組
成物において、ポリシラザンは、ポリシラザン単独は勿
論のこと、ポリシラザンと他のポリマーとの共重合体や
ポリシラザンと他の化合物との混合物も利用できる。用
いられるポリシラザンには、鎖状、環状又は架橋構造を
有するもの、あるいは分子内にこれら複数の構造を同時
に有するものがあり、これら単独でもあるいは混合物で
も利用できる。これらポリシラザンについては、得られ
る膜の硬度や緻密性の点からはペルヒドロポリシラザン
が好ましく、可撓性の点からはオルガノポリシラザンが
好ましい。これらポリシラザンの選択は、当業者であれ
ば用途に合わせて適宜行うことができる。In the photosensitive polysilazane composition used in the present invention, not only polysilazane alone but also a copolymer of polysilazane and another polymer or a mixture of polysilazane and another compound can be used. The polysilazanes to be used include those having a chain structure, a cyclic structure or a crosslinked structure, or those having a plurality of these structures simultaneously in the molecule, and these can be used alone or in a mixture. Of these polysilazanes, perhydropolysilazanes are preferable from the viewpoint of hardness and denseness of the obtained film, and organopolysilazanes are preferable from the viewpoint of flexibility. Those skilled in the art can appropriately select these polysilazanes according to the application.
【００１８】上記で述べたポリシラザンは、公知である
か公知の方法にしたがって製造することができる。具体
的には、ポリシラザンの製造については、例えば、特公
昭６３−１６３２５号公報、特開昭６１−８９２３０号
公報、同６２−１５６１３５号公報、D.Seyferthら，Co
mmunication of Am. Cer. Soc., C-13, January（198
3）、Po1ym. Prepr., Am. Chem. Soc., Div. Po1ym. Ch
em., 25, 10（1984）などに記載されている。また、分
子内に架橋構造を有するポリシラザンについては、特開
昭４９−６９７１７号公報、D.SeyferthらCommunicatio
n of Am. Cer. Soc., C-132, July（1984）で報告され
ている様なものであってもよいし、さらに構造中に金属
原子を含むポリメタロシラザンであってもよい。The polysilazanes mentioned above are known or can be produced according to known methods. Specifically, regarding the production of polysilazane, for example, JP-B-63-16325, JP-A-61-89230, JP-A-62-156135, D. Seyferth et al., Co.
mmunication of Am. Cer. Soc., C-13, January (198
3), Po1ym. Prepr., Am. Chem. Soc., Div. Po1ym. Ch
em., 25 , 10 (1984). Further, regarding polysilazanes having a cross-linked structure in the molecule, JP-A-49-69717 and D. Seyferth et al. Communicatio
n of Am. Cer. Soc., C-132, July (1984), or a polymetallosilazane containing a metal atom in the structure may be used.
【００１９】その他、特開昭６２−１９５０２４号公報
に報告されているような繰り返し単位が〔（ＳｉＨ２）
ｎ（ＮＨ）ｍ〕及び〔（ＳｉＨ２）ｒＯ〕（これら式
中、ｎ、ｍ、ｒはそれぞれ１、２又は３である）で表さ
れるポリシロキサザン、特開平２−８４４３７号公報に
報告されているようなポリシラザンにボロン化合物を反
応させて製造する耐熱性に優れたポリボロシラザン、特
開昭６３−８１１２２号、同６３−１９１８３２号、特
開平２−７７４２７号公報に報告されているようなポリ
シラザンとメタルアルコキシドとを反応させて製造する
ポリメタロシラザン、特開平１−１３８１０８号、同１
−１３８１０７号、同１−２０３４２９号、同１−２０
３４３０号、同４−６３８３３号、同３−３２０１６７
号公報に報告されているような分子量を増加させたり
（上記公報の前４者）、耐加水分解性を向上させた（後
２者）無機シラザン高重合体や改質ポリシラザン、特開
平２−１７５７２６号、同５−８６２００号、同５−３
３１２９３号、同３−３１３２６号公報に報告されてい
るようなポリシラザンに有機成分を導入した厚膜化に有
利な共重合ポリシラザン、特開平５−２３８８２７号、
同６−１２２８５２号、同６−２９９１８８号、同６−
３０６３２９号、同６−２４０２０８号、同７−１９６
９８６号公報に報告されているようなポリシラザンにセ
ラミックス化を促進するための触媒化合物を付加又は添
加したプラスチックやアルミニウムなどの金属への施工
が可能で、より低温でセラミックス化する低温セラミッ
クス化ポリシラザンなども同様に使用できる。In addition, the repeating unit as reported in JP-A-62-195024 is [(SiH 2 )
n (NH) m] and [(SiH 2 ) rO] (wherein n, m, and r are 1, 2 or 3 respectively), and polysiloxazane described in JP-A-2-84437. Polyborosilazanes having excellent heat resistance, which are produced by reacting a polysilazane with a boron compound as reported, are reported in JP-A-63-81122, JP-A-63-191832, and JP-A-2-77427. As described above, polymetallosilazanes produced by reacting polysilazanes with metal alkoxides, JP-A-1-138108 and 1
138107, 1-203429, 1-20
No. 3430, No. 4-63833, No. 3-320167.
Inorganic silazane high polymers and modified polysilazanes having increased molecular weights (former 4 of the above publications) and improved hydrolysis resistance (former 2) as reported in JP-A-2- No. 175726, No. 5-86200, No. 5-3
Copolymerized polysilazanes which are advantageous for thickening by introducing an organic component into polysilazane as reported in Japanese Patent Nos. 31293 and 3-31326, JP-A-5-238827,
6-122852, 6-299188, 6-
306329, 6-240208, 7-196.
As disclosed in Japanese Patent No. 986, it is possible to apply to a metal such as plastic or aluminum in which a catalyst compound for promoting ceramic formation is added or added to polysilazane, and low temperature ceramized polysilazane that ceramizes at a lower temperature. Can be used as well.
【００２０】本発明において好適に用いることができる
ポリシラザンは、主として上記一般式（II）で表される
骨格を含む数平均分子量１００〜１００，０００、好ま
しくは３００〜１０，０００のポリシルセスキアザンお
よびその誘導体である。より好適なポリシルセスキアザ
ンは、式（II）中、Ｒ４がメチル基であり且つＲ５が水
素であるポリメチルシラザン又は、式（II）中、Ｒ４が
フェニル基であり且つＲ５が水素であるポリフェニルシ
ラザンである。このようなポリシラザンは、通常のポリ
シラザンを合成する際のアンモノリシスにおいて、出発
原料にＲ４ＳｉＣｌ３を使用することにより容易に得ら
れる。ポリシラザンを合成する際のアンモノリシスにつ
いては、例えば特公昭６３−１６３２５号公報を参照さ
れたい。Polysilazanes which can be preferably used in the present invention include polysilsesquiazanes having a number average molecular weight of 100 to 100,000, preferably 300 to 10,000, which mainly contains a skeleton represented by the general formula (II). And its derivatives. More preferable polysilsesquiazane is polymethylsilazane in which R 4 is a methyl group and R 5 is hydrogen in the formula (II), or R 4 is a phenyl group and R 5 in the formula (II). Is polyphenylsilazane in which is hydrogen. Such polysilazane can be easily obtained by using R 4 SiCl 3 as a starting material in ammonolysis when synthesizing ordinary polysilazane. For ammonolysis in synthesizing polysilazane, see, for example, Japanese Patent Publication No. 63-16325.
【００２１】また、上記（ハ）で述べたポリオルガノシ
ロキサザンも本発明において好適に用いることができる
ポリシラザンである。このポリオルガノシロキサザン
は、一般式ＲｎＳｉＸ４−ｎ〔式中、Ｒはアルキル基、
アルケニル基、シクロアルキル基、アリール基、アルキ
ルアミノ基又はアルキルシリル基であり、Ｘはハロゲン
原子であり、そしてｎは１又は２である〕で示される有
機ハロシランを、アンモニア及び水と反応させることに
より製造することができる。このようなポリオルガノシ
ロキサザンは、高温で処理した場合でも低い誘電率を示
す焼成膜を得ることができるので、特に層間絶縁膜の前
駆体として有用である。また、ポリオルガノシロキサザ
ンの場合、主鎖に含まれる酸素含有量を変化させること
により焼成膜の比誘電率を制御でき、所望の比誘電率を
容易に得ることができるという利点もある。このような
ポリオルガノシロキサザン及びその製造方法の詳細につ
いては、特願平１０−５２８６３３号明細書（ＷＯ９８
／０２９４７５）を参照されたい。The polyorganosiloxazane described in (c) above is also a polysilazane that can be preferably used in the present invention. The polyorganosiloxane Southern has the general formula R n SiX 4-n [wherein, R is an alkyl group,
An alkenyl group, a cycloalkyl group, an aryl group, an alkylamino group or an alkylsilyl group, X is a halogen atom, and n is 1 or 2] with ammonia and water. Can be manufactured by. Such a polyorganosiloxazane is particularly useful as a precursor of an interlayer insulating film, because a baked film having a low dielectric constant can be obtained even when treated at a high temperature. Further, in the case of polyorganosiloxazane, there is also an advantage that the relative dielectric constant of the fired film can be controlled by changing the oxygen content contained in the main chain, and a desired relative dielectric constant can be easily obtained. For details of such a polyorganosiloxazane and a method for producing the same, Japanese Patent Application No. 10-528633 (WO98).
/ 029475).
【００２２】また、本発明においては、上記（ニ）に記
載された変性ポリシルセスキアザンもポリシラザンとし
て好ましく用いることができる。この変性ポリシルセス
キアザンは、通常のポリシラザンを合成する際のアンモ
ノリシスにおいて、出発原料としてＲ６ＳｉＣｌ３、Ｒ
６ ２ＳｉＣｌ２及び／又はＲ６ ３ＳｉＣｌを、後二者を
上記他の構成単位の含有比率に対応するモル比率で使用
することにより容易に得ることができる。In the present invention, the modified polysilsesquiazane described in (d) above can also be preferably used as the polysilazane. This modified polysilsesquiazane is used as a starting material for R 6 SiCl 3 and R 6 in ammonolysis when synthesizing ordinary polysilazane.
6 2 SiCl 2 and / or R 6 3 SiCl can be easily obtained by using the latter two in a molar ratio corresponding to the content ratio of the above-mentioned other structural units.
【００２３】本発明において好ましく用いられる感光性
ポリシラザン組成物には、光酸発生剤が含まれる。この
光酸発生剤の例としては、具体的には過酸化物、ナフト
キノンジアジドスルホン酸エステル、ニトロベンジルエ
ステルなどが挙げられる。また、ベンゾイントシレート
も有用である。これらの光酸発生剤は、必要に応じて組
み合わせて使用することもできる。以下、過酸化物、ナ
フトキノンジアジドスルホン酸エステル、ニトロベンジ
ルエステルの具体例を示すが、これは単なる例示であっ
て、本発明のパターン化された感光性ポリシラザン組成
物に用いることができる光酸発生剤が、これら具体的に
記載されたものに限定されるものではない。The photosensitive polysilazane composition preferably used in the present invention contains a photoacid generator. Specific examples of the photoacid generator include peroxides, naphthoquinonediazide sulfonates, nitrobenzyl esters and the like. Benzoin tosylate is also useful. These photo-acid generators can be used in combination as required. Hereinafter, specific examples of the peroxide, naphthoquinone diazide sulfonic acid ester, and nitrobenzyl ester are shown, but these are merely examples, and the photo-acid generating that can be used in the patterned photosensitive polysilazane composition of the present invention is shown. The agent is not limited to those specifically described.
【００２４】過酸化物系の光酸発生剤：３，３’，４，
４’−テトラ（ｔ−ブチルペルオキシジカルボニル）ベ
ンゾフェノン、ｔ−ブチルペルオキシベンゾエート、メ
チルエチルケトンペルオキシド、シクロヘキサノンペル
オキシド、メチルシクロヘキサノンペルオキシド、メチ
ルアセトアセテートペルオキシド、アセチルアセトンペ
ルオキシド、１，１−ビス（ｔ−ヘキシルペルオキシ）
３，３，５−トリメチルシクロヘキサン、１，１−ビス
（ｔ−ヘキシルペルオキシ）シクロヘキサン、１，１−
ビス（ｔ−ブチルペルオキシ）３，３，５−トリメチル
シクロヘキサン、ジ−ｔ−ブチルペルオキシ−２−メチ
ルシクロヘキサン、１，１−ビス（ｔ−ブチルペルオキ
シ）シクロヘキサン、１，１−ビス（ｔ−ブチルペルオ
キシ）シクロドデカン、２，２−ビス（ｔ−ブチルペル
オキシ）ブタン、ｎ−ブチル ４，４−ビス（ｔ−ブチ
ルペルオキシ）バレレート、２，２−ビス（４，４−ジ
−ｔ−ブチルペルオキシシクロヘキシル）プロパン、Ｐ
−メンタンヒドロペルオキシド、ジイソプロピルベンゼ
ンヒドロペルオキシド、１，１，３，３−テトラメチル
ブチルヒドロペルオキシド、クメンヒドロペルオキシ
ド、ｔ−ヘキシルヒドロペルオキシド、ｔ−ブチルヒド
ロペルオキシド、α，α’−ビス（ｔ−ブチルペルオキ
シ）ジイソプロピルベンゼン、ジクミルペルオキシド、
２，５−ジメチル−２，５−ビス（ｔ−ブチルペルオキ
シ）ヘキサン、ｔ−ブチルクミルペルオキシド、ジ−ｔ
−ブチルペルオキシド、２，５−ジメチル−２，５−ビ
ス（ｔ−ブチルペルオキシ）ヘキシン−３、イソブチリ
ルペルオキシド、３，５，５−トリメチルヘキサノイル
ペルオキシド、オクタノイルペルオキシド、ラウロイル
ペルオキシド、ステアロイルペルオキシド、コハク酸ペ
ルオキシド、ｍ−トルオイルベンゾイルペルオキシド、
ベンゾイルペルオキシド、ジ−ｎ−プロピルペルオキシ
ジカーボネート、ジイソプロピルペルオキシジカーボネ
ート、ビス（４−ｔ−ブチルシクロヘキシル）ペルオキ
シジカーボネート、ジ−２−エトキシエチルペルオキシ
ジカーボネート、ジ−２−エチルヘキシルペルオキシジ
カーボネート、ジ−３−メトキシブチルペルオキシジカ
ーボネート、ジ（３−メチル−３−メトキシブチル）ペ
ルオキシジカーボネート、α，α’−ビス（ネオデカノ
イルペルオキシ）ジイソブロピルベンゼン、クミルペル
オキシネオデカノエート、１，１，３，３−テトラメチ
ルブチルペルオキシネオデカノエート、１−シクロヘキ
シル−１−メチルエチルペルオキシネオデカノエート、
ｔ−ヘキシルペルオキシネオデカノエート、ｔ−ブチル
ペルオキシネオデカノエート、ｔ−ヘキシルペルオキシ
ピバレート、ｔ−ブチルペルオキシピバレート、１，
１，３，３−テトラメチルブチルペルオキシ−２−エチ
ルヘキサノエート、２，５−ジメチル−２，５−ビス
（２−エチルヘキサノイルペルオキシ）ヘキサン、１−
シクロヘキシル−１−メチルエチルペルオキシ−２−エ
チルヘキサノエート、ｔ−ヘキシルペルオキシ ２−エ
チルヘキサノエート、ｔ−ブチルペルオキシ ２−エチ
ルヘキサノエート、ｔ−ブチルペルオキシイソブチレー
ト、ｔ−ヘキシルペルオキシイソプロピルモノカーボネ
ート、ｔ−ブチルペルオキシマレイン酸、ｔ−ブチルペ
ルオキシ ３，５，５−トリメチルヘキサノエート、ｔ
−ブチルペルオキシラウレート、２，５−ジメチル−
２，５−（ｍ−トルオイルペルオキシ）ヘキサン、ｔ−
ブチルペルオキシイソプロピルモノカーボネート、ｔ−
ブチルペルオキシ ２−エチルヘキシルモノカーボネー
ト、ｔ−ヘキシルペルオキシベンゾエート、２，５−ジ
メチル−２，５−ビス（ベンゾイルペルオキシ）ヘキサ
ン、ｔ−ブチルペルオキシアセテート、ｔ−ブチルペル
オキシ−ｍ−トルオイルベンゾエート、ビス（ｔ−ブチ
ルペルオキシ）イソフタレート、ｔ−ブチルペルオキシ
アリルモノカーボネート、ｔ−ブチルトリメチルシリル
ペルオキシド、１，３−ジ（ｔ−ブチルペルオキジカル
ボニル）ベンゼン、等。Peroxide type photo-acid generator: 3, 3 ', 4,
4'-tetra (t-butylperoxydicarbonyl) benzophenone, t-butylperoxybenzoate, methylethylketone peroxide, cyclohexanone peroxide, methylcyclohexanone peroxide, methylacetoacetate peroxide, acetylacetone peroxide, 1,1-bis (t-hexylperoxy)
3,3,5-Trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-
Bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, di-t-butylperoxy-2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butyl) Peroxy) cyclododecane, 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (4,4-di-t-butylperoxy) Cyclohexyl) propane, P
-Menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide, α, α'-bis (t-butyl) Peroxy) diisopropylbenzene, dicumyl peroxide,
2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t
-Butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide , Succinic acid peroxide, m-toluoyl benzoyl peroxide,
Benzoyl peroxide, di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di- -3-Methoxybutylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, α, α'-bis (neodecanoylperoxy) diisobropyrbenzene, cumylperoxy neodecanoate, 1 , 1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl-1-methylethylperoxyneodecanoate,
t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate, t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,
1,3,3-Tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-
Cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy 2-ethylhexanoate, t-butylperoxy 2-ethylhexanoate, t-butylperoxyisobutyrate, t-hexylperoxyisopropyl Monocarbonate, t-butylperoxymaleic acid, t-butylperoxy 3,5,5-trimethylhexanoate, t
-Butyl peroxylaurate, 2,5-dimethyl-
2,5- (m-toluoylperoxy) hexane, t-
Butyl peroxyisopropyl monocarbonate, t-
Butyl peroxy 2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butyl peroxyacetate, t-butyl peroxy-m-toluoyl benzoate, bis ( t-Butylperoxy) isophthalate, t-butylperoxyallylmonocarbonate, t-butyltrimethylsilylperoxide, 1,3-di (t-butylperoxydicarbonyl) benzene, etc.
【００２５】ナフトキノンジアジドスルホン酸エステ
ル：１，２−ナフトキノン−（２）−ジアジド−５−ス
ルホン酸クロライド、１，２−ナフトキノン−（２）−
ジアジド−４−スルホン酸クロライド、２，３，４−ト
リヒドロキシベンゾフェノンと６−ジアゾ−５，６−ジ
ヒドロ−５−オキソ−ナフタレン−１−スルホン酸との
（モノ〜トリ）エステル、２，３，４，４’−トリヒド
ロキシベンゾフェノンと６−ジアゾ−５，６−ジヒドロ
−５−オキソ−ナフタレン−１−スルホン酸との（モノ
〜トリ）エステル、等。Naphthoquinone diazide sulfonic acid ester: 1,2-naphthoquinone- (2) -diazide-5-sulfonic acid chloride, 1,2-naphthoquinone- (2)-
Diazido-4-sulfonic acid chloride, (mono-tri) ester of 2,3,4-trihydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid, 2,3 , 4,4'-Trihydroxybenzophenone and 6-diazo-5,6-dihydro-5-oxo-naphthalene-1-sulfonic acid (mono-tri) ester, and the like.
【００２６】ニトロベンジルエステル：ニトロベンジル
トシレート、ジニトロベンジルトシレート、ニトロベン
ジルクロライド、ジニトロベンジルクロライド、ニトロ
ベンジルブロミド、ジニトロベンジルブロミド、ニトロ
ベンジルアセテート、ジニトロベンジルアセテート、ニ
トロベンジルトリクロロアセテート、ニトロベンジルト
リフルオロアセテート、等。Nitrobenzyl ester: Nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl chloride, dinitrobenzyl chloride, nitrobenzyl bromide, dinitrobenzyl bromide, nitrobenzyl acetate, dinitrobenzyl acetate, nitrobenzyl trichloroacetate, nitrobenzyl trifluoro Acetate, etc.
【００２７】これら光酸発生剤の感光性ポリシラザン組
成物中での含有量は、光酸発生剤の種類及び感光性組成
物の用途に応じ適宜の量とされるが、一般にはポリシラ
ザン重量に対して０．０５〜５０重量％、好ましくは
０．１〜２０重量％、より好ましくは１〜２０重量％で
ある。The content of these photoacid generators in the photosensitive polysilazane composition is an appropriate amount depending on the type of the photoacid generator and the use of the photosensitive composition, but it is generally based on the weight of polysilazane. 0.05 to 50% by weight, preferably 0.1 to 20% by weight, more preferably 1 to 20% by weight.
【００２８】本発明で使用されるポリシラザンと光酸発
生剤を含む感光性ポリシラザン組成物には、必要に応じ
増感色素が含有されてもよい。光酸発生剤及び増感色素
の組み合わせによっては、露光の際高圧水銀灯（３６０
〜４３０ｎｍ）などのより安価な光源により露光を行う
ことが可能となる。増感色素としては、クマリン、ケト
クマリン及びそれらの誘導体、ピリリウム塩及びチオピ
リリウム塩や、シアニン染料、カルボシアニン染料など
の染料が挙げられる。これら増感色素は、ポリシラザン
重量に対して一般に０．０５〜５０重量％、好ましくは
１〜２０重量％で用いられる。The photosensitive polysilazane composition containing the polysilazane and the photo-acid generator used in the present invention may optionally contain a sensitizing dye. Depending on the combination of the photoacid generator and the sensitizing dye, a high pressure mercury lamp (360
It becomes possible to perform exposure with a cheaper light source such as ˜430 nm). Examples of the sensitizing dye include coumarin, ketocoumarin and their derivatives, pyrylium salts and thiopyrylium salts, and dyes such as cyanine dyes and carbocyanine dyes. These sensitizing dyes are generally used in an amount of 0.05 to 50% by weight, preferably 1 to 20% by weight, based on the weight of polysilazane.
【００２９】また、増感色素を用いた場合には、得られ
た被膜が着色することがある。当該組成物をエッチング
レジストなどのレジストとして使用する場合には、所望
のパターニング加工の終了後に当該レジストは除去され
るのでレジストの着色が問題となることはほとんどな
い。しかしながら、パターン化された被膜を焼成し、パ
ターニング後に該被膜を除去することなく使用する場
合、例えば焼成後の被膜を表示素子の層間絶縁膜などと
して用いる場合には、焼成後の被膜が可視光に対して透
明であることが必要な場合もある。このような場合で
も、通常、被膜焼成時に、感光性ポリシラザン組成物中
に含まれる光酸発生剤により増感色素が分解され、被膜
は透明化されるためあまり問題となることはないが、使
用目的によっては更に透明無着色の被膜が必要とされる
場合もある。このような場合には、感光性ポリシラザン
組成物中に、被膜焼成時に増感色素を分解することがで
きるが、光反応には関与しない酸化触媒を別途添加して
もよい。このような酸化触媒の例としては、プロピオン
酸パラジウム、酢酸パラジウム、アセチルアセトナート
白金、エチルアセトナート白金、パラジウム微粒子、白
金微粒子などの金属の有機化合物や微粒子等を挙げるこ
とができる。酸化触媒を添加する場合、酸化触媒の量
は、ポリシラザン重量に対して一般に０．０５〜１０重
量％、好ましくは０．１〜５重量％である。このような
酸化触媒を添加することにより、不要な色素を分解し脱
色することができる他、ポリシラザンのセラミックス化
を促進することもできる。When a sensitizing dye is used, the resulting coating may be colored. When the composition is used as a resist such as an etching resist, since the resist is removed after the desired patterning process is completed, coloring of the resist hardly poses a problem. However, when a patterned film is baked and used without removing the film after patterning, for example, when the film after baking is used as an interlayer insulating film of a display element, etc., the film after baking has visible light. It may be necessary to be transparent to. Even in such a case, usually, at the time of baking the film, the sensitizing dye is decomposed by the photo-acid generator contained in the photosensitive polysilazane composition, and the film becomes transparent, so there is not much problem, but it is used. Depending on the purpose, a transparent uncolored coating may be required. In such a case, the sensitizing dye can be decomposed at the time of baking the film, but an oxidation catalyst not involved in the photoreaction may be added to the photosensitive polysilazane composition. Examples of such an oxidation catalyst include metal organic compounds and fine particles such as palladium propionate, palladium acetate, acetylacetonato platinum, ethyl acetonato platinum, palladium fine particles, and platinum fine particles. If an oxidation catalyst is added, the amount of oxidation catalyst is generally 0.05 to 10% by weight, preferably 0.1 to 5% by weight, based on the weight of polysilazane. By adding such an oxidation catalyst, unnecessary dyes can be decomposed and decolorized, and also polysilazane can be made into ceramics.
【００３０】また、感光性ポリシラザン組成物には、顔
料を添加することにより、耐熱性、絶縁性、硬度に優
れ、パターン精度の良好なカラーフィルターやブラック
マトリックスを得ることができる。ポリシラザン組成物
に添加することができる顔料の例として、グラファイ
ト、カーボンブラック、チタンブラック、酸化鉄、銅ク
ロム系プラック、銅鉄マンガン系ブラック、コバルト鉄
クロム系ブラック等が挙げられる。顔料添加量は、一般
にポリシラザン重量に対して０．０５〜１０００重量
％、好ましくは１０〜５００重量％である。By adding a pigment to the photosensitive polysilazane composition, it is possible to obtain a color filter or a black matrix having excellent heat resistance, insulating property and hardness and good pattern accuracy. Examples of pigments that can be added to the polysilazane composition include graphite, carbon black, titanium black, iron oxide, copper chromium-based plaque, copper iron manganese-based black, and cobalt iron chromium-based black. The amount of pigment added is generally 0.05 to 1000% by weight, preferably 10 to 500% by weight, based on the weight of polysilazane.
【００３１】感光性ポリシラザン組成物において溶剤を
使用する場合には、ベンゼン、トルエン、キシレン、エ
チルベンゼン、ジエチルベンゼン、トリメチルベンゼ
ン、トリエチルベンゼン等の芳香族化合物；シクロヘキ
サン；シクロヘキセン；デカヒドロナフタレン；ジペン
テン；ｎ−ペンタン、ｉ−ペンタン、ｎ−ヘキサン、ｉ
−ヘキサン、ｎ−ヘプタン、ｉ−ヘプタン、ｎ−オクタ
ン、ｉ−オクタン、ｎ−ノナン、ｉ−ノナン、ｎ−デカ
ン、ｉ−デカン等の飽和炭化水素化合物；エチルシクロ
ヘキサン；メチルシクロヘキサン；ｐ−メンタン；ジプ
ロピルエーテル、ジブチルエーテル等のエーテル類；メ
チルイソブチルケトン（ＭＩＢＫ）等のケトン類；酢酸
ブチル、酢酸シクロヘキシル、ステアリン酸ブチル、乳
酸エチル等のエステル類；エチレングリコールモノメチ
ルエーテル、エチレングリコールモノエチルエーテル等
のエチレングリコールモノアルキルエーテル類；エチレ
ングリコールモノメチルエーテルアセテート、エチレン
グリコールモノエチルエーテルアセテート等のエチレン
グリコールモノアルキルエーテルアセテート類；プロピ
レングリコールモノメチルエーテル、プロピレングリコ
ールモノエチルエーテル等のプロピレングリコールモノ
アルキルエーテル類；プロピレングリコールモノメチル
エーテルアセテート、プロピレングリコールモノエチル
エーテルアセテート等の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類等を使用することが好まし
い。これらの溶剤を使用する場合、ポリシラザンの溶解
度や溶剤の蒸発速度を調節するために、２種類以上の溶
剤を混合してもよい。溶剤の使用量は、組成物中、ポリ
シラザン濃度が０．１〜５０重量％、より好ましくは
０．１〜４０重量％となる量で用いられる。When a solvent is used in the photosensitive polysilazane composition, aromatic compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene and triethylbenzene; cyclohexane; cyclohexene; decahydronaphthalene; dipentene; n- Pentane, i-pentane, n-hexane, i
Saturated hydrocarbon compounds such as -hexane, n-heptane, i-heptane, n-octane, i-octane, n-nonane, i-nonane, n-decane, and i-decane; ethylcyclohexane; methylcyclohexane; p-menthane Ethers such as dipropyl ether and dibutyl ether; ketones such as methyl isobutyl ketone (MIBK); esters such as butyl acetate, cyclohexyl acetate, butyl stearate and ethyl lactate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ethylene glycol monoalkyl ether acetates such as; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; Propylene glycol Methyl ether, propylene glycol monoalkyl ethers such as propylene glycol monoethyl ether; propylene glycol monomethyl ether acetate, it is preferred to use a propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate. When these solvents are used, two or more kinds of solvents may be mixed in order to adjust the solubility of polysilazane and the evaporation rate of the solvent. The amount of the solvent used is such that the polysilazane concentration in the composition is 0.1 to 50% by weight, more preferably 0.1 to 40% by weight.
【００３２】さらに、感光性ポリシラザン組成物には、
必要に応じシリカ等の酸化物系無機物、炭化珪素、窒化
珪素などの非酸化物系無機物、金属粉などの充填材、レ
ベリング剤、消泡剤、帯電防止剤、紫外線吸収剤、ＰＨ
調整剤、分散剤・表面改質剤、可塑剤、乾燥促進剤、流
れ止め剤を加えてもよい。Further, the photosensitive polysilazane composition contains
If necessary, oxide-based inorganic materials such as silica, non-oxide-based inorganic materials such as silicon carbide and silicon nitride, fillers such as metal powder, leveling agents, defoaming agents, antistatic agents, ultraviolet absorbers, PH
A regulator, a dispersant / surface modifier, a plasticizer, a drying accelerator, and a flow preventive may be added.
【００３３】感光性ポリシラザン組成物は、ロールコー
ト、浸漬コート、バーコート、スピンコート、スプレー
コートなど従来知られた塗布法或いは印刷などにより、
シリコン基板、ガラス基板等の任意の基板上に塗布さ
れ、塗膜が形成される。塗膜は、必要に応じ、該塗膜を
乾燥させ且つその後の脱ガス量を減少させるため、４０
〜２００℃、好ましくは６０〜１２０℃の温度で、ホッ
トプレートによる場合には１０〜１８０秒間、好ましく
は３０〜９０秒間、クリーンオーブンによる場合には１
〜３０分間、好ましくは５〜１５分間、プリベーク（加
熱処理）される。塗膜は必要であれば繰り返して塗布す
ることにより所望の膜厚とすることもできる。所望の膜
厚は、例えば、フォトレジストの場合には０．０５〜２
μｍ、層間絶縁膜の場合には０．５〜４μｍ、カラーフ
ィルターやブラックマトリックスの場合には０．３〜３
μｍ、等が目安となる。The photosensitive polysilazane composition is prepared by a conventionally known coating method such as roll coating, dip coating, bar coating, spin coating or spray coating or printing.
A coating film is formed by coating on any substrate such as a silicon substrate or a glass substrate. The coating may be dried at 40% to reduce the amount of degassing and subsequent drying of the coating as needed.
To 200 ° C, preferably 60 to 120 ° C, for 10 to 180 seconds, preferably 30 to 90 seconds when using a hot plate, and 1 when using a clean oven.
It is prebaked (heat treatment) for about 30 minutes, preferably for 5 to 15 minutes. If necessary, the coating film can be repeatedly applied to obtain a desired film thickness. The desired film thickness is, for example, 0.05 to 2 in the case of photoresist.
μm, 0.5 to 4 μm for interlayer insulating film, 0.3 to 3 for color filter or black matrix
The standard is μm.
【００３４】感光性ポリシラザン組成物の塗膜は、次い
で露光される。この露光工程においては、高圧水銀灯、
低圧水銀灯、メタルハライドランプ、キセノンランプ、
エキシマレーザー、Ｘ線、電子線等を露光光源として用
い、必要に応じフォトマスクを用いてパターン状の光照
射がなされる。露光の際の照射光のエネルギー量は、光
源や塗膜の膜厚にもよるが、通常０．０５ｍＪ／ｃｍ２
以上、望ましくは０．１ｍＪ／ｃｍ２、以上である。上
限は特にないが、あまりに照射量を多く設定すると処理
時間の関係から実用的でなく、通常１０００ｍＪ／ｃｍ
２以下である。露光は、一般に周囲雰囲気（大気中）あ
るいは窒素雰囲気とすればよいが、ポリシラザンの分解
を促進するために酸素含有量を富化した雰囲気を採用し
てもよい。The coating of the photosensitive polysilazane composition is then exposed. In this exposure process, a high pressure mercury lamp,
Low-pressure mercury lamp, metal halide lamp, xenon lamp,
Excimer laser, X-ray, electron beam or the like is used as an exposure light source, and if necessary, a photomask is used to perform patterned light irradiation. The amount of energy of the irradiation light at the time of exposure is usually 0.05 mJ / cm 2 though it depends on the light source and the film thickness of the coating film.
As described above, it is preferably 0.1 mJ / cm 2 or more. There is no particular upper limit, but if the irradiation amount is set too high, it is not practical due to the processing time, and it is usually 1000 mJ / cm 2.
It is 2 or less. The exposure may be generally performed in an ambient atmosphere (in the air) or a nitrogen atmosphere, but an atmosphere enriched in oxygen content may be used to accelerate the decomposition of polysilazane.
【００３５】光酸発生剤を含む感光性ポリシラザン組成
物の露光により、組成物内に酸が発生し、これによりポ
リシラザンのＳｉ−Ｎ結合が解裂する。次いで、露光さ
れた感光性ポリシラザン組成物は、加湿処理にかけられ
る。この加湿処理により膜中に水分供給が継続的に行わ
れると、一旦Ｓｉ−Ｎ結合の解裂に寄与した酸が繰返し
解裂触媒として働き、ＳｉＯＨ化が促進されこととな
る。Exposure of the photosensitive polysilazane composition containing a photoacid generator generates an acid in the composition, which causes the Si—N bond of the polysilazane to be cleaved. The exposed photosensitive polysilazane composition is then subjected to a humidification treatment. When moisture is continuously supplied to the film by this humidification treatment, the acid that once contributed to the cleavage of the Si—N bond repeatedly acts as a cleavage catalyst to promote the formation of SiOH.
【００３６】したがって、感光性ポリシラザン組成物と
接触される気体の湿度は高ければ高いほどポリシラザン
の分解は速くなるが、気体の湿度があまりに高くなりす
ぎると、感光性ポリシラザン組成物により形成された膜
表面に気体からの水蒸気が結露する恐れがある。一旦結
露が起こると結露した水は水素結合によって見かけ上大
きな分子としてしか動けないためと考えられるが、感光
性ポリシラザン組成物により形成された膜の表面近傍で
しかポリシラザンの分解作用が進まない場合もある。ま
た、これにより、結露した水が付着した部分の分解速度
が低くなるためと推測されるが、その後のアルカリ水溶
液による現像時に露光域に除去できない領域、即ち現像
残渣が発生する場合もある。これを防ぐため、塗布膜表
面に結露が生じない範囲で気体の湿度条件が調整される
必要がある。この気体の湿度は、基板の温度に対する相
対湿度という尺度で表現した場合、３５％ＲＨ以上が好
ましく、より好ましくは４０％ＲＨ以上、更に好ましく
は５０％ＲＨ以上である。相対湿度の上限は特にない
が、あまり高くなると上記したように結露が発生する恐
れがあり、この観点から９０％ＲＨ以下の相対湿度を有
する気体を利用するのが実用的である。 Therefore, the higher the humidity of the gas contacted with the photosensitive polysilazane composition, the faster the decomposition of the polysilazane, but if the humidity of the gas is too high, the film formed by the photosensitive polysilazane composition Water vapor from gas may condense on the surface. It is considered that once the condensation occurs, the condensed water can move only as an apparently large molecule due to a hydrogen bond, but in some cases, the decomposition action of polysilazane proceeds only in the vicinity of the surface of the film formed by the photosensitive polysilazane composition. is there. It is also presumed that this reduces the decomposition rate of the portion to which the condensed water adheres, but in the subsequent development with an alkaline aqueous solution, an unremovable area, that is, a development residue may occur. In order to prevent this, it is necessary to adjust the humidity conditions of the gas within the range where condensation does not occur on the surface of the coating film. The humidity of the gas is preferably 35% RH or higher, more preferably 40% RH or higher, and even more preferably 50% RH or higher when expressed in terms of the relative humidity with respect to the temperature of the substrate. There is no particular upper limit to the relative humidity, but if it is too high, dew condensation may occur as described above. From this viewpoint, it is practical to use a gas having a relative humidity of 90% RH or less.
【００３７】このポリシラザンの加湿工程においては、
水蒸気を含む気体が基板に触れるようにしてやればよ
い。露光された感光性ポリシラザン組成物の膜と水蒸気
を含む気体との接触のためには、通常加湿処理装置内に
露光された感光性ポリシラザン組成物の膜を有する基板
を置き、水蒸気を含む気体をこの処理装置内に連続的に
導入するようにしてやればよい。また、この時必要であ
れば導入する気体の湿度を更に加湿して、被膜に接触す
る気体の湿度を高くするようにしてもよい。処理装置の
内容量が大きく、被膜の分解に要する水分が十分に装置
内に存在する場合には、処理装置に水蒸気を含む気体を
連続的に供給しなくてもよいし、処理装置内に水蒸気の
みを補充するようにしてもよい。このとき、基板を、例
えば加熱プレートに乗せ、加湿処理中加熱を行うように
することが好ましい。過剰な水蒸気が基板に触れないよ
う所定時間上記の状態を保持した後、基板は取り出さ
れ、室温に戻される。基板の加熱温度は、温度が高いけ
れば高いほど塗膜表面への結露が起こり難くなる。この
ため、気体に含有される絶対水蒸気量をより高く設定す
ることができるので、基板の加熱温度は高い温度である
方が好ましい。加熱温度は室温以上、望ましくは３０℃
以上とされるが、１００℃以上の温度においては、加圧
型の加熱・加湿器でないと水蒸気分圧を上げることがで
きないので注意が必要である。またあまり高い温度であ
ると、加湿により生成したＳｉＯＨがＳｉＯＳｉ化し、
アルカリ水溶液に不溶となる恐れがある。したがって実
用的な上限温度は１００℃程度である。なお、上記にお
いては基板を処理装置内におく場合について述べたが、
加湿処理は処理装置を用いず大気中で行ってもよい。ま
た、基板の加熱は、上記加熱プレートによる加熱の他、
加湿処理に用いる気体を予め加温しておき、これを加湿
処理装置に導入するなど任意の方法で行えばよい。In the step of humidifying the polysilazane,
The gas containing water vapor may be brought into contact with the substrate. For contact between the exposed film of the photosensitive polysilazane composition and the gas containing water vapor, the substrate having the film of the exposed photosensitive polysilazane composition is usually placed in a humidification treatment apparatus, and the gas containing water vapor is added. It suffices to introduce them continuously into this processing apparatus. At this time, if necessary, the humidity of the introduced gas may be further humidified to increase the humidity of the gas contacting the coating. If the internal volume of the processing equipment is large and the water required for decomposition of the coating is sufficient in the equipment, it is not necessary to continuously supply a gas containing water vapor to the processing equipment. You may make it replenish only. At this time, it is preferable that the substrate is placed on, for example, a heating plate and heating is performed during the humidification process. After holding the above state for a predetermined time so that excess water vapor does not touch the substrate, the substrate is taken out and returned to room temperature. The higher the heating temperature of the substrate, the more difficult the dew condensation occurs on the surface of the coating film. Therefore, since the absolute amount of water vapor contained in the gas can be set higher, the heating temperature of the substrate is preferably higher. Heating temperature is room temperature or higher, preferably 30 ° C
As described above, it should be noted that at a temperature of 100 ° C. or higher, the partial pressure of water vapor cannot be increased unless it is a pressure type heating / humidifying device. If the temperature is too high, the SiOH generated by humidification becomes SiOSi,
May be insoluble in alkaline aqueous solution. Therefore, the practical upper limit temperature is about 100 ° C. In the above, the case where the substrate is placed in the processing apparatus has been described.
The humidification treatment may be performed in the air without using a treatment device. In addition to the heating by the heating plate, the heating of the substrate
The gas used for the humidification treatment may be heated in advance and introduced into a humidification treatment device by any method.
【００３８】ポリシラザンの分解促進工程後、感光性ポ
リシラザン組成物膜は、パドル現像、ディップ現像、シ
ャワー現像など公知の現像方法を用い、アルカリ現像液
により現像される。これにより、感光性ポリシラザン組
成物膜の露光部分が除去され、未露光部分が基板上に残
留してパターンが形成される。未露光部のポリシラザン
膜はアルカリ現像液にはほとんど膨潤しないので、照射
光のパターンと分解除去されるポリシラザンのパターン
はほぼ完全に一致し、良好なパターン精度が得られる。After the step of accelerating the decomposition of polysilazane, the photosensitive polysilazane composition film is developed with an alkali developing solution using a known developing method such as paddle development, dip development or shower development. As a result, the exposed portion of the photosensitive polysilazane composition film is removed, and the unexposed portion remains on the substrate to form a pattern. Since the unexposed portion of the polysilazane film hardly swells in the alkaline developing solution, the pattern of the irradiation light and the pattern of the polysilazane to be decomposed and removed almost completely coincide with each other, and good pattern accuracy can be obtained.
【００３９】アルカリ現像液としては、例えば、テトラ
メチルアンモニウムヒドロキシド（ＴＭｌＡＨ）、コリ
ン、珪酸ナトリウム・水酸化ナトリウム、水酸化カリウ
ム等の水溶液が挙げられる。ポリシラザン膜が、半導体
デバイスのエッチィングパターンとして用いられる場
合、或いはシリカ系セラミックスに転化された後層間絶
縁膜として用いられる場合には、現像液中に金属イオン
を含まないアルカリの水溶液を用いることが望ましい。
現像に要する時間は、膜厚や溶剤にもよるが、一般に
０．１〜５分、好ましくは０．５〜３分である。また、
現像処理温度は、一般に２０〜５０℃、好ましくは２０
〜３０℃である。Examples of the alkaline developer include aqueous solutions of tetramethylammonium hydroxide (TM1AH), choline, sodium silicate / sodium hydroxide, potassium hydroxide and the like. When the polysilazane film is used as an etching pattern of a semiconductor device, or when it is used as an interlayer insulating film after being converted into silica-based ceramics, an alkaline aqueous solution containing no metal ion in the developer should be used. desirable.
The time required for development depends on the film thickness and the solvent, but is generally 0.1 to 5 minutes, preferably 0.5 to 3 minutes. Also,
The development processing temperature is generally 20 to 50 ° C., preferably 20.
~ 30 ° C.
【００４０】現像後のパターン化されたポリシラザン膜
は、純水でリンスされ、乾燥され、そのままエッチング
マスクとして用いられるか、または純水リンス後長時間
（例えば、１日以上）放置する又は焼成することにより
シリカ系セラミックス被膜に転化され、層間絶縁膜等と
して使用される。焼成温度は、用いるポリシラザンの種
類や基板、電子部品等の耐熱性にもよるが、一般に５０
〜１０００℃、好ましくは１００〜１０００℃、より好
ましくは１５０℃〜４５０℃で、５分以上、好ましくは
１０分以上とする。焼成雰囲気は、一般に周囲雰囲気
（大気中）とすればよいが、ポリシラザンの酸化を促進
するために酸素含有量及び／又は水蒸気分圧を富化した
雰囲気を採用してもよい。このようにして得られたシリ
カ系セラミックス被膜は、誘電率５以下、場合によって
は誘電率３．３以下、抵抗率１０１ ３Ω・ｃｍ以上を示
すことができる。The patterned polysilazane film after development is rinsed with pure water, dried and used as an etching mask as it is, or after rinsing with pure water, it is left for a long time (for example, 1 day or more) or baked. As a result, it is converted into a silica-based ceramic coating and used as an interlayer insulating film or the like. The firing temperature generally depends on the type of polysilazane used and the heat resistance of the substrate, electronic component, etc.
To 1000 ° C., preferably 100 to 1000 ° C., more preferably 150 ° C. to 450 ° C., for 5 minutes or longer, preferably 10 minutes or longer. The firing atmosphere may be generally an ambient atmosphere (in the air), but an atmosphere enriched in oxygen content and / or water vapor partial pressure may be adopted to promote the oxidation of polysilazane. Thus silica ceramic film obtained has a dielectric constant of 5 or less, in some cases may exhibit a dielectric constant 3.3 or less, resistivity 10 1 3 Ω · cm or more.
【００４１】[0041]
【実施例】以下、実施例により本発明をさらに具体的に
説明するが、本発明の態様がこれら実施例記載のものに
限定されるものではない。
実施例１
−［ＳｉＣＨ３（ＮＨ）１．５］−を基本構成とし、−
［Ｓｉ（ＣＨ３）３（ＮＨ）０．５］−を５モル％含有
する変性ポリシルセスキアザンに対し、光酸発生剤とし
て、式（ＩＶ）：The present invention will be described in more detail with reference to the following examples, but the embodiments of the present invention are not limited to those described in these examples. EXAMPLE 1 - [SiCH 3 (NH) 1.5] - was used as a basic structure, -
For modified polysilsesquiazane containing 5 mol% of [Si (CH 3 ) 3 (NH) 0.5 ]-, a compound represented by formula (IV):
【００４２】 [0042]
【化２】 [Chemical 2]
【００４３】で示されるトリアジン誘導体を１重量％添
加し、この混合物を全固形分濃度が１０重量％濃度とな
るように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）で希釈して、感光性ポリシラザン
組成物を調製した。この感光性ポリシラザン組成物をシ
リコン基板上にスピンコート（１０００ｒｐｍ）し、９
０℃、９０秒のプリベークを行い、０．４μｍ厚の塗膜
を形成した。この感光性ポリシラザン組成物の塗膜を有
する基板を、露光装置として、ＫｒＦエキシマレーザ露
光装置を用い、種々の線幅を有する１：１ライン・アン
ド・スペースパターンを有するマスクを通して、１０ｍ
Ｊ／ｃｍ２から１０００ｍＪ／ｃｍ２まで１５ｍＪ／ｃ
ｍ２ステップで照射量を変えて露光した。次いで、２５
℃、６０％ＲＨにて５分間の加湿処理を行い、基板を
２．３８重量％ＴＭＡＨ水溶液で１分間現像し、その後
基板を純水によりリンスして、得られたパターンをＳＥ
Ｍ観察し、露光部の膜が完全に除去できた露光量を感度
として定義して観察し、表１の結果を得た。The triazine derivative represented by 1% by weight was added, and the mixture was diluted with propylene glycol monomethyl ether acetate (PGMEA) so that the total solid content concentration became 10% by weight to obtain a photosensitive polysilazane composition. Prepared. This photosensitive polysilazane composition was spin-coated (1000 rpm) on a silicon substrate,
Prebaking was performed at 0 ° C. for 90 seconds to form a coating film having a thickness of 0.4 μm. A substrate having a coating film of this photosensitive polysilazane composition was used as an exposure device using a KrF excimer laser exposure device, and was passed through a mask having a 1: 1 line-and-space pattern having various line widths for 10 m.
15 mJ / c from J / cm 2 to 1000 mJ / cm 2
Exposure was performed by changing the irradiation amount in m 2 steps. Then 25
Humidification treatment is performed at 60 ° C. and 60% RH for 5 minutes, the substrate is developed with a 2.38 wt% TMAH aqueous solution for 1 minute, and then the substrate is rinsed with pure water to obtain an SE pattern.
M was observed, and the exposure amount at which the film in the exposed portion was completely removed was defined as sensitivity and observed, and the results in Table 1 were obtained.
【００４４】比較例１
加湿処理条件を表１記載の条件とすること以外は実施例
１と同様に行い、表１の結果を得た。Comparative Example 1 The results of Table 1 were obtained in the same manner as in Example 1 except that the humidification treatment conditions were those shown in Table 1.
【００４５】[0045]
【表１】 [Table 1]
【００４６】上記表１の結果から、処理時の雰囲気の湿
度を上昇させることにより、感光性ポリシラザン組成物
の感度が向上し、これにより、処理時間を短縮すること
ができることが分かる。From the results shown in Table 1 above, it can be seen that the sensitivity of the photosensitive polysilazane composition is improved by increasing the humidity of the atmosphere during the treatment, and thereby the treatment time can be shortened.
【００４７】実施例２〜４
−［ＳｉＣＨ３（ＮＨ）１．５］−を基本構成とし、−
［Ｓｉ（ＣＨ３）２（ＮＨ）］−を１０モル％含有する
変性ポリシルセスキアザンに対し、光酸発生剤として、
式（Ｖ）：Examples 2 to 4-[SiCH 3 (NH) 1.5 ] -as a basic constitution,
As a photo-acid generator, a modified polysilsesquiazane containing 10 mol% of [Si (CH 3 ) 2 (NH)]-
Formula (V):
【００４８】[0048]
【化３】 [Chemical 3]
【００４９】で示されるスルホキシム誘導体を５重量
％、増感色素として、式（ＶＩ）：5% by weight of the sulfoxime derivative represented by the formula (VI):
【００５０】 [0050]
【化４】 [Chemical 4]
【００５１】で示されるクマリン誘導体を１０重量％そ
れぞれ添加し、全固形分濃度が１０重量％濃度となるよ
うに酢酸ブチルで希釈して、感光性ポリシラザン組成物
を調製した。この感光性組成物をシリコン基板上にスピ
ンコート（１０００ｒｐｍ）し、スピン乾燥を行い、
０．４μｍ厚の塗膜を形成した。次いでｉ線露光装置に
て種々の線幅を有する１：１ライン・アンド・スペース
パターンを有するマスクを通して、０．１ｍＪ／ｃｍ２
から１ｍＪ／ｃｍ２までは０．１ｍＪ／ｃｍ２ステップ
の照射量、１ｍＪ／ｃｍ２から１０ｍＪ／ｃｍ２までは
１ｍＪ／ｃｍ２ステップの照射量、１０ｍＪ／ｃｍ２か
ら１００ｍＪ／ｃｍ２までは１０ｍＪ／ｃｍ ２ステップ
の照射量、１００ｍＪ／ｃｍ２から１０００ｍＪ／ｃｍ
２までは１００ｍＪ／ｃｍ２ステップの照射量によりそ
れぞれ露光した。次いで、露光された基板を加湿処理装
置内の加熱プレート上に乗せ、表２に記載の加湿処理条
件で処理し、実施例１と同様にして現像処理、リンス処
理を行い、表２に記載の感度を得た。10% by weight of the coumarin derivative represented by
Add each to bring the total solids concentration to 10% by weight.
Photosensitive polysilazane composition diluted with sea urchin butyl acetate
Was prepared. This photosensitive composition is spun on a silicon substrate.
Spin coating (1000 rpm), spin dry,
A coating film having a thickness of 0.4 μm was formed. Then to the i-line exposure device
1: 1 line and space with various line widths
0.1 mJ / cm through a patterned maskTwo
To 1 mJ / cmTwoUp to 0.1 mJ / cmTwoStep
Irradiation dose of 1mJ / cmTwoTo 10 mJ / cmTwoUntil
1 mJ / cmTwoStep dose, 10 mJ / cmTwoOr
100 mJ / cmTwoUp to 10 mJ / cm TwoStep
Dose of 100mJ / cmTwoTo 1000 mJ / cm
TwoUp to 100 mJ / cmTwoDepending on the irradiation amount of the step
Each was exposed. Then, the exposed substrate is treated with a humidification treatment device.
Place it on the heating plate in the storage room,
Processing in the same manner as in Example 1 and developing and rinsing.
Then, the sensitivity shown in Table 2 was obtained.
【００５２】比較例２
加湿処理条件を表２記載の条件とすること以外は実施例
２と同様に行い、表２の結果を得た。Comparative Example 2 The results of Table 2 were obtained in the same manner as in Example 2 except that the humidification treatment conditions were those shown in Table 2.
【００５３】[0053]
【表２】 [Table 2]
【００５４】表１及び表２から明らかなように、処理を
行う際に基板を加熱することにより、処理時間の短縮化
が図れるとともに、同じ湿度で処理を行っても加熱条件
下で加湿処理を行えば感度の向上が見られ、したがって
これによる処理時間の短縮化も可能となることが分か
る。As is clear from Tables 1 and 2, by heating the substrate during the treatment, the treatment time can be shortened, and even if the treatment is performed at the same humidity, the humidification treatment can be performed under the heating condition. It can be seen that the sensitivity is improved if it is carried out, and thus the processing time can be shortened.
【００５５】実施例５〜７
−［ＳｉＣＨ３（ＮＨ）１．５］−を基本構成とし、−
［Ｓｉ（Ｐｈ）２（ＮＨ）］−を１０モル％含有する変
性ポリシルセスキアザン（Ｐｈ：フェニル基）に対し光
酸発生剤として、式（ＶＩＩ）：Examples 5 to 7-[SiCH 3 (NH) 1.5 ] -as a basic constitution,
A modified polysilsesquiazane (Ph: phenyl group) containing 10 mol% of [Si (Ph) 2 (NH)]-is used as a photoacid generator in the formula (VII):
【００５６】[0056]
【化５】 [Chemical 5]
【００５７】で示される過酸化物を１重量％添加し、こ
の混合物を全固形分濃度が３０重量％濃度となるように
ＰＧＭＥＡで希釈して、感光性ポリシラザン組成物を調
製した。この感光性ポリシラザン組成物をシリコン基板
上に３０００ｒｐｍでスピンコートし、６０℃、６０秒
のプリベークを行い、０．８μｍ厚の塗膜を形成した。
この感光性ポリシラザン組成物の塗膜を有する基板を、
露光装置として電子線露光装置を用い、種々の線幅を有
する１：１ライン・アンド・スペースパターンを有する
マスクを通して、８０μＣ／ｃｍ２の露光量でパターン
焼付けを行った。次いで、表３に記載の加湿処理条件で
基板の処理を行った後、２．３８重量％ＴＭＡＨ水溶液
で１分間現像し、その後基板を純水リンスして、得られ
たパターンをＳＥＭにて観察し、パターンの倒壊の様子
を確認した。倒壊しない最小パターン線幅を表３に示
す。A photosensitive polysilazane composition was prepared by adding 1% by weight of a peroxide represented by the formula (3) and diluting this mixture with PGMEA so that the total solid content concentration was 30% by weight. This photosensitive polysilazane composition was spin-coated on a silicon substrate at 3000 rpm and prebaked at 60 ° C. for 60 seconds to form a 0.8 μm-thick coating film.
A substrate having a coating film of this photosensitive polysilazane composition,
Using an electron beam exposure apparatus as an exposure apparatus, pattern printing was performed at an exposure dose of 80 μC / cm 2 through a mask having a 1: 1 line and space pattern having various line widths. Then, after treating the substrate under the humidifying treatment conditions shown in Table 3, the substrate was developed with a 2.38 wt% TMAH aqueous solution for 1 minute, and then the substrate was rinsed with pure water, and the obtained pattern was observed by SEM. Then, it was confirmed that the pattern collapsed. Table 3 shows the minimum pattern line width that does not cause collapse.
【００５８】[0058]
【表３】 [Table 3]
【００５９】表３から明らかなように、加熱、加湿条件
下での現像処理により、パターンの倒壊が起こりにくく
なる、すなわちパターンの基板への密着性が改善される
ことが分かる。As is clear from Table 3, the patterning is less likely to be collapsed, that is, the adhesion of the pattern to the substrate is improved by the development treatment under the conditions of heating and humidification.
【００６０】[0060]
【発明の効果】以上詳述したように、本発明によれば、
感光性ポリシラザン組成物の露光後のポリシラザン分解
促進処理を水蒸気含有気体を用いて行うことにより、短
時間で加湿処理を行うことができる。また、その際気体
の湿度を高くすることにより感度の改善が図られるとと
もに、処理時間の短縮を図ることもできる。さらに、そ
の際基板を加熱した状態で加湿処理を行えば更に高湿度
条件での処理が可能となり、更なる感度の改善、処理速
度のアップ、基板と感光性ポリシラザン組成物との密着
性の改善も可能となるという効果を得ることができる。
また、本発明により得られたパターン化されたポリシラ
ザン膜は、そのままでエッチィングレジストなどのレジ
ストあるいは表示素子などを構成する被膜として利用す
ることができるとともに、シリカ系セラミックス被膜に
転化させることにより、半導体デバイスあるいは液晶表
示装置などの層間絶縁膜等として使用することができ
る。As described in detail above, according to the present invention,
By performing the polysilazane decomposition accelerating treatment after the exposure of the photosensitive polysilazane composition by using the steam-containing gas, the humidifying treatment can be performed in a short time. Further, at that time, by increasing the humidity of the gas, the sensitivity can be improved and the processing time can be shortened. Further, at that time, if the substrate is subjected to a humidification treatment in a heated state, the treatment can be performed in a higher humidity condition, further improving the sensitivity, increasing the processing speed, and improving the adhesion between the substrate and the photosensitive polysilazane composition. It is also possible to obtain the effect that it becomes possible.
Further, the patterned polysilazane film obtained by the present invention can be used as it is as a coating constituting a resist such as an etching resist or a display element, and by converting it into a silica-based ceramic coating, It can be used as an interlayer insulating film for semiconductor devices or liquid crystal display devices.
フロントページの続き (56)参考文献 特開2000−181069（ＪＰ，Ａ) 特開 平10−319597（ＪＰ，Ａ) 特開 昭52−58374（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) G03F 7/38 G03F 7/075 H01L 21/027 Continuation of the front page (56) Reference JP 2000-181069 (JP, A) JP 10-319597 (JP, A) JP 52-58374 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) G03F 7/38 G03F 7/075 H01L 21/027
Claims (2)
し、露光後現像することによりパターン化されたポリシ
ラザン膜を形成する方法において、露光された感光性ポ
リシラザン組成物膜を、前記基板の温度に対する相対湿
度が３５％〜９０％の水蒸気含有気体と接触させた後現
像を行うことを特徴とするパターン化されたポリシラザ
ン膜の形成方法。1. A method of forming a patterned polysilazane film by applying a photosensitive polysilazane composition to a substrate and developing after exposure to light. In the method, the exposed photosensitive polysilazane composition film is exposed to the temperature of the substrate. Relative humidity
A method for forming a patterned polysilazane film, which comprises performing development after contacting with a vapor-containing gas having a degree of 35% to 90% .
ラザン膜の形成方法において、前記水蒸気含有気体との
接触時に感光性ポリシラザン組成物膜が加熱されている
ことを特徴とするパターン化されたポリシラザン膜の形
成方法。2. The method for forming a patterned polysilazane film according to claim 1, wherein the vapor-containing gas is used.
A method for forming a patterned polysilazane film, wherein the photosensitive polysilazane composition film is heated at the time of contact .
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000262703A JP3414708B2 (en) | 2000-08-31 | 2000-08-31 | Method of forming patterned polysilazane film |
| EP01958459A EP1239332B1 (en) | 2000-08-31 | 2001-08-24 | Photosensitive polysilazane composition, method of forming pattern therefrom, and method of burning coating film thereof |
| DE60126736T DE60126736T2 (en) | 2000-08-31 | 2001-08-24 | RADIATION SENSITIVE POLYSILAZAN COMPOSITION, PATTERN PRODUCED THEREOF, AND A METHOD OF SURFACING A CORRESPONDING COATING FILM |
| KR1020027005509A KR100793620B1 (en) | 2000-08-31 | 2001-08-24 | Formation of Photosensitive Polysilazane Composition and Patterned Interlayer Insulator |
| CNB018025781A CN100395662C (en) | 2000-08-31 | 2001-08-24 | Photosensitive polysilazane composition, method of forming pattern using same, and method of sintering its coating film |
| PCT/JP2001/007251 WO2002019037A1 (en) | 2000-08-31 | 2001-08-24 | Photosensitive polysilazane composition, method of forming pattern therefrom, and method of burning coating film thereof |
| US10/110,656 US6902875B2 (en) | 2000-08-31 | 2001-08-24 | Photosensitive polysilazane composition, method of forming pattern therefrom, and method of burning coating film thereof |
| AT01958459T ATE354818T1 (en) | 2000-08-31 | 2001-08-24 | RADIATION SENSITIVE POLYSILAZANE COMPOSITION, PATTERNS PRODUCED THEREFROM AND A METHOD FOR ASHING A CORRESPONDING COATING FILM |
| KR1020077014474A KR100804444B1 (en) | 2000-08-31 | 2001-08-24 | Forming method of patterned polysilazane film and firing method of photosensitive polysilazane coating film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000262703A JP3414708B2 (en) | 2000-08-31 | 2000-08-31 | Method of forming patterned polysilazane film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002072502A JP2002072502A (en) | 2002-03-12 |
| JP3414708B2 true JP3414708B2 (en) | 2003-06-09 |
Family
ID=18750343
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000262703A Expired - Fee Related JP3414708B2 (en) | 2000-08-31 | 2000-08-31 | Method of forming patterned polysilazane film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3414708B2 (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4836363B2 (en) * | 2000-08-11 | 2011-12-14 | 和之 杉田 | Method for forming resist pattern |
| JP3758669B2 (en) | 2003-10-07 | 2006-03-22 | 日立化成工業株式会社 | Radiation curable composition, storage method thereof, cured film forming method, pattern forming method, pattern using method, electronic component and optical waveguide |
| KR100869882B1 (en) | 2003-10-07 | 2008-11-24 | 히다치 가세고교 가부시끼가이샤 | Radiation curable composition, forming method of cured film and patterning method |
| JP2008525626A (en) * | 2004-12-29 | 2008-07-17 | スリーエム イノベイティブ プロパティズ カンパニー | Multiphoton polymerizable preceramic polymer composition |
| JP4240018B2 (en) | 2005-02-04 | 2009-03-18 | セイコーエプソン株式会社 | Film pattern forming method, device and manufacturing method thereof, electro-optical device, and electronic apparatus |
| JP2007059633A (en) * | 2005-08-24 | 2007-03-08 | Tokyo Electron Ltd | Substrate heating apparatus and substrate heating method |
| JP5105220B2 (en) * | 2006-05-23 | 2012-12-26 | 有限会社コンタミネーション・コントロール・サービス | Silica membrane, bioactive material having the silica membrane, and method for forming the same |
| JP4222390B2 (en) | 2006-07-25 | 2009-02-12 | セイコーエプソン株式会社 | PATTERN FORMATION METHOD AND LIQUID CRYSTAL DISPLAY DEVICE MANUFACTURING METHOD |
| JP4718584B2 (en) * | 2008-07-01 | 2011-07-06 | ヤスハラケミカル株式会社 | Treatment liquid for dissolving polysilazane and method for manufacturing semiconductor device using the same |
-
2000
- 2000-08-31 JP JP2000262703A patent/JP3414708B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2002072502A (en) | 2002-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100212933B1 (en) | Positive resist composition | |
| US7625687B2 (en) | Silsesquioxane resin | |
| KR100804444B1 (en) | Forming method of patterned polysilazane film and firing method of photosensitive polysilazane coating film | |
| CN113015940A (en) | Silanol-containing organic-inorganic hybrid coatings for high resolution patterning | |
| EP1164435B1 (en) | Photosensitive polysilazane composition and method of forming patterned polysilazane film | |
| KR101920649B1 (en) | Polymer-containing developer | |
| JP3414708B2 (en) | Method of forming patterned polysilazane film | |
| JPH0436755A (en) | Resist composition | |
| US20040081912A1 (en) | Photosensitive polysilazane composition and method of forming patterned polysilazane film | |
| JP2002311591A (en) | Photosensitive composition used for forming interlayer dielectric | |
| TWI842839B (en) | Functional polyhydrogensilsesquioxane resin composition, method of producing thereof and the use thereof | |
| JP3421009B2 (en) | Photosensitive composition for interlayer insulating film and method for forming patterned interlayer insulating film | |
| JP2004077874A (en) | Forming method of photosensitive composition for interlayer insulating film and patternizing interlayer insulating film | |
| JP3414710B2 (en) | Method for firing photosensitive polysilazane coating film | |
| JP2003302761A (en) | Positive photosensitive resin composition and semiconductor device | |
| JP2008034604A (en) | Method of manufacturing patterned film, positive photosensitive composition, and semiconductor element | |
| JP2006085029A (en) | Pattern formation method using photosensitive polysilazane film | |
| JP2001288270A (en) | Modified polysilsesquiazane, photosensitive composition, and method of forming patterned modified polysilsesquiazane film | |
| TW200401951A (en) | Photosensitive composition for interlayer insulating film and forming method of patterned interlayer insulating film | |
| JP4655633B2 (en) | Radiation curable composition, storage method thereof, cured film forming method, pattern forming method, pattern using method, electronic component and optical waveguide | |
| JP2573996B2 (en) | Pattern forming material | |
| TWI252383B (en) | Photosensitive polysilazane composition, pattern-forming method using it, and calcination method of its coating film | |
| JPH1192666A (en) | Photopolymerizable polysilazane composition and method for forming patterned ceramic film | |
| JPH08334900A (en) | Chemical amplification positive type resist material | |
| JP2006195175A (en) | Radiation-curing composition, method for storing the same, method for forming cured film, pattern forming method, pattern using method, electronic component, and optical waveguide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090404 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090404 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100404 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110404 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120404 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313115 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120404 Year of fee payment: 9 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130404 Year of fee payment: 10 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130404 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140404 Year of fee payment: 11 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313117 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R371 | Transfer withdrawn |
Free format text: JAPANESE INTERMEDIATE CODE: R371 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |