CN106909024B - 一种感光性树脂组合物及其应用 - Google Patents
一种感光性树脂组合物及其应用 Download PDFInfo
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- CN106909024B CN106909024B CN201710190234.0A CN201710190234A CN106909024B CN 106909024 B CN106909024 B CN 106909024B CN 201710190234 A CN201710190234 A CN 201710190234A CN 106909024 B CN106909024 B CN 106909024B
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- alkyl
- meth
- acrylate
- photosensitive resin
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- 239000011342 resin composition Substances 0.000 title claims abstract description 20
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 40
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 31
- 239000011354 acetal resin Substances 0.000 claims abstract description 28
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- -1 Hydrogen Chemical class 0.000 claims description 42
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 125000003107 substituted aryl group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000008062 acetophenones Chemical class 0.000 claims 1
- 150000002460 imidazoles Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 150000003918 triazines Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 11
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 37
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 16
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 14
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 14
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 101710149812 Pyruvate carboxylase 1 Proteins 0.000 description 6
- 150000001241 acetals Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006359 acetalization reaction Methods 0.000 description 4
- 229920006243 acrylic copolymer Polymers 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- AGCPZMJBXSCWQY-UHFFFAOYSA-N 1,1,2,3,4-pentachlorobutane Chemical compound ClCC(Cl)C(Cl)C(Cl)Cl AGCPZMJBXSCWQY-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MINPZZUPSSVGJN-UHFFFAOYSA-N 1,1,1,4,4,4-hexachlorobutane Chemical compound ClC(Cl)(Cl)CCC(Cl)(Cl)Cl MINPZZUPSSVGJN-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- DYNFCHNNOHNJFG-UHFFFAOYSA-N 2-formylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=O DYNFCHNNOHNJFG-UHFFFAOYSA-N 0.000 description 2
- GNKZMNRKLCTJAY-UHFFFAOYSA-N 4'-Methylacetophenone Chemical compound CC(=O)C1=CC=C(C)C=C1 GNKZMNRKLCTJAY-UHFFFAOYSA-N 0.000 description 2
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 2
- MTRFEWTWIPAXLG-UHFFFAOYSA-N 9-phenylacridine Chemical compound C1=CC=CC=C1C1=C(C=CC=C2)C2=NC2=CC=CC=C12 MTRFEWTWIPAXLG-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 101150049492 DVR gene Proteins 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 101100084627 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) pcb-4 gene Proteins 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-M o-toluate Chemical compound CC1=CC=CC=C1C([O-])=O ZWLPBLYKEWSWPD-UHFFFAOYSA-M 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000003504 photosensitizing agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical compound ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- IBRIFDGHXDFGBY-UHFFFAOYSA-N (4-ethoxyphenyl)-phenylmethanone Chemical compound C1=CC(OCC)=CC=C1C(=O)C1=CC=CC=C1 IBRIFDGHXDFGBY-UHFFFAOYSA-N 0.000 description 1
- DFYJCXSOGSYMAJ-UHFFFAOYSA-N (4-tert-butylphenyl)-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C(=O)C1=CC=CC=C1 DFYJCXSOGSYMAJ-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- JWTGRKUQJXIWCV-UHFFFAOYSA-N 1,2,3-trihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(O)C(O)CO JWTGRKUQJXIWCV-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- MQESVSITPLILCO-UHFFFAOYSA-N 1-(4-butylphenyl)ethanone Chemical compound CCCCC1=CC=C(C(C)=O)C=C1 MQESVSITPLILCO-UHFFFAOYSA-N 0.000 description 1
- MLKIVXXYTZKNMI-UHFFFAOYSA-N 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one Chemical compound CCCCCCCCCCCCC1=CC=C(C(=O)C(C)(C)O)C=C1 MLKIVXXYTZKNMI-UHFFFAOYSA-N 0.000 description 1
- VQYUAFDBUVMFKD-UHFFFAOYSA-N 1-(4-phenylsulfanylphenyl)octane-1,2-dione Chemical compound C1=CC(C(=O)C(=O)CCCCCC)=CC=C1SC1=CC=CC=C1 VQYUAFDBUVMFKD-UHFFFAOYSA-N 0.000 description 1
- IMDHDEPPVWETOI-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2,2-trichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)(Cl)Cl)C=C1 IMDHDEPPVWETOI-UHFFFAOYSA-N 0.000 description 1
- VMCRQYHCDSXNLW-UHFFFAOYSA-N 1-(4-tert-butylphenyl)-2,2-dichloroethanone Chemical compound CC(C)(C)C1=CC=C(C(=O)C(Cl)Cl)C=C1 VMCRQYHCDSXNLW-UHFFFAOYSA-N 0.000 description 1
- YACHFTBPTCCVPY-UHFFFAOYSA-N 1-[4-(2-hydroxyethoxy)phenyl]-2-methylpropan-1-one Chemical compound CC(C)C(=O)C1=CC=C(OCCO)C=C1 YACHFTBPTCCVPY-UHFFFAOYSA-N 0.000 description 1
- DJKZORJEYWYYHB-UHFFFAOYSA-N 1-[4-(dimethylamino)phenyl]-2-phenylethanone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)CC1=CC=CC=C1 DJKZORJEYWYYHB-UHFFFAOYSA-N 0.000 description 1
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 1
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- OAMHTTBNEJBIKA-UHFFFAOYSA-N 2,2,2-trichloro-1-phenylethanone Chemical compound ClC(Cl)(Cl)C(=O)C1=CC=CC=C1 OAMHTTBNEJBIKA-UHFFFAOYSA-N 0.000 description 1
- CERJZAHSUZVMCH-UHFFFAOYSA-N 2,2-dichloro-1-phenylethanone Chemical compound ClC(Cl)C(=O)C1=CC=CC=C1 CERJZAHSUZVMCH-UHFFFAOYSA-N 0.000 description 1
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
- DXUMYHZTYVPBEZ-UHFFFAOYSA-N 2,4,6-tris(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C(Cl)(Cl)Cl)=N1 DXUMYHZTYVPBEZ-UHFFFAOYSA-N 0.000 description 1
- QZZJTWAHFMBFSX-UHFFFAOYSA-N 2,4-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC=NC(C(Cl)(Cl)Cl)=N1 QZZJTWAHFMBFSX-UHFFFAOYSA-N 0.000 description 1
- NSWNXQGJAPQOID-UHFFFAOYSA-N 2-(2-chlorophenyl)-4,5-diphenyl-1h-imidazole Chemical class ClC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)N1 NSWNXQGJAPQOID-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
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- PNDRGJCVJPHPOZ-UHFFFAOYSA-N 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine Chemical compound ClC(Cl)(Cl)C1=NC(C(Cl)(Cl)Cl)=NC(C=CC=2OC=CC=2)=N1 PNDRGJCVJPHPOZ-UHFFFAOYSA-N 0.000 description 1
- SEFYJVFBMNOLBK-UHFFFAOYSA-N 2-[2-[2-(oxiran-2-ylmethoxy)ethoxy]ethoxymethyl]oxirane Chemical compound C1OC1COCCOCCOCC1CO1 SEFYJVFBMNOLBK-UHFFFAOYSA-N 0.000 description 1
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 description 1
- VROBIBICHLALII-UHFFFAOYSA-N 2-benzyl-2-(dimethylamino)-1-(4-methylsulfanylphenyl)butan-1-one Chemical compound C=1C=C(SC)C=CC=1C(=O)C(CC)(N(C)C)CC1=CC=CC=C1 VROBIBICHLALII-UHFFFAOYSA-N 0.000 description 1
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- QPXVRLXJHPTCPW-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-(4-propan-2-ylphenyl)propan-1-one Chemical compound CC(C)C1=CC=C(C(=O)C(C)(C)O)C=C1 QPXVRLXJHPTCPW-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开了一种感光性树脂组合物及其应用,其组成为:a)碱溶性树脂是含有碳碳双键的聚乙烯醇缩醛树脂;b)乙烯基不饱和单体;c)光引发剂;d)溶剂。本发明的有益效果在于:其灵敏度、分辨力、平整度、粘结性和热稳定性优良,适宜形成半导体集成电路的绝缘平整化膜。
Description
技术领域
本发明涉及感光性树脂组合物领域,特别是涉及一种用于形成半导体集成电路的绝缘平整化膜的感光性树脂组合物及其应用。
背景技术
在生产半导体集成电路广泛的应用中,光刻技术一直被用来形成微型元件或者进行精细加工,随着对集成电路速度及集成密度的增加,对集成电路的设计要求越来越高,近年来用于光刻技术中的层间绝缘膜的形成技术作为新的应用正在引起人们的关注,尤其在FPD显示面板的高精度和微细技术的市场需求非常强烈,因为为了实现这样的高精度和微细技术,高度透明的绝缘膜是必要的材料,这样的透明绝缘层已经是FPD集成电路设计图案中必不可少的结构,很多专利对这项技术进行研究,层间绝缘膜的应用广义的讲包括层间绝缘膜、介电膜、平面化膜、隔离膜和保护膜等,功能虽有些不同,但是都具有共同的特点,经常能够通用,共同特点包括都是绝缘透明的,在集成电路制造过程中作为永久性膜不被剥离除去,作为器件的一部分,行使其保护、绝缘、平面化和隔离等功能。
随着绝缘平整化膜技术的发展,有机碱溶性感光型层间绝缘膜成为主流,由碱溶树脂和感光体系组成,如在CN100535747中发明的光敏树脂组合物包含一种碱溶树脂,醌二叠氮基光敏剂以及固化剂,碱溶树脂是丙烯酸树脂,固化剂是有环氧基团的物质,同时包含羧酸化合物;在CN100547485中发明的一种感光组合物,含有碱溶树脂,一种醌二叠氮部分的感光剂,环氧固化剂,碱溶树脂为丙烯酸树脂;在CN1828416中发明提供感光性树脂组合物,其不仅灵敏度、绝缘性、耐化学性等性能出色,还能够显著提高透过性和储存稳定性,适宜形成LCD制造工序中的层间绝缘膜,组成含有a)丙烯酸共聚物b)叠氮萘醌化合物c)溶剂,其中丙烯酸共聚物是1)不饱和羧酸、不饱和羧酸酐或他们的混合物,2)含有环氧基团的不饱和化合物3)烯类不饱和化合物共聚后除去未反应单体而得到;在CN1811597中发明提供感光性树脂组合物,其不仅灵敏度、绝缘性、平滑性、耐化学性等性能出色,还能够显著提高耐热性,使得在层间绝缘膜产生的渗气最小化,因而可确保后工序的可靠性,适宜形成LCD制造工序中的层间绝缘膜,组成含有a)丙烯酸共聚物b)叠氮萘醌化合物c)溶剂,其中丙烯酸共聚物是1)不饱和羧酸、不饱和羧酸酐或他们的混合物,2)含有环氧基团的不饱和化合物3)苯基马来酰亚胺类化合物;
以上碱显影感光型层间绝缘膜技术碱溶树脂采用丙烯酸树脂,感光体系采用PAC和环氧树脂及固化剂的体系,其热稳定性、灵敏度和分辨力等性能有待进一步提高。
发明内容
为了解决现有集成电路绝缘平整化膜的感光体系热稳定性、灵敏度和分辨力等性能不佳等问题,我们提出了一种感光性树脂组合物,其灵敏度、分辨力、平整度、粘结性和热稳定性优良,适宜形成半导体集成电路的绝缘平整化膜。
本发明是通过以下技术方案实现的:
为实现上述目的,本发明提供一种感光性树脂组合物,其组成为:a)碱溶性树脂是含有碳碳双键的聚乙烯醇缩醛树脂;b)乙烯基不饱和单体;c)光引发剂;d)溶剂。
聚乙烯醇缩醛树脂具有良好的柔软性,可以作为聚合物增塑剂使用,提升柔韧性和可加工性,同时其具有良好的粘附性、耐热性和成膜性,聚乙烯醇经过和不同的醛缩合得到不同的聚乙烯醇缩醛树脂。本发明的缩醛树脂含有以下结构单元IA)、IB)、IC)、ID)和IE)。
IA)结构单元:
其中R1是氢、烷基、取代烷基、芳香基和取代芳香基。
IA)重复单元缩醛化的醛类具体实例包括甲醛、乙醛、正丁醛、苯甲醛等。a的摩尔百分比为10-50%。
IB)结构单元:
其中R2为氢、烷基、取代烷基、羟基、芳香基和取代芳香基。b的摩尔百分比为10-30%。
IB)重复单元缩醛化的醛类实例包括2-羧基苯甲醛、3-羧基苯甲醛、4-羧基苯甲醛和3-羧基-4-羟基苯甲醛等。
IC)重复单元:
c的摩尔百分比为20-40%。
同时由于位阻的影响有部分羟基不会发生缩醛化反应,因此分子中含有IC)结构单元。
ID)结构单元:
d的摩尔百分比为1-3%。
在商品化的聚乙烯醇产品中有2%左右的醋酸乙烯酯的残留,因此分子中含有2%左右的ID)结构单元。
IE)结构单元:
其中R是H或甲基;R3是氢、羟基、烷基、取代烷基、芳香基和取代芳香基;A是含羟基烷基;e的摩尔百分比为10-40%。
IA)重复单元通过聚乙烯醇的羟基和醛进行缩醛化反应制得,催化剂采用强酸,如甲基磺酸、对甲苯磺酸、硫酸等在二甲基亚砜溶剂中反应,聚乙烯醇缩醛化以后从水溶性变成水不溶性,反应结束后在水中沉淀,便可得到固体的聚乙烯醇缩醛聚合物。
IB)重复单元按照IA)相同的方法得到,采用聚乙烯醇和含羧基的苯甲醛进行缩醛化反应。
IE)重复单元的得到采用IB)结构单元中的部分含羧基的聚乙烯醇缩醛聚合物,和含环氧基的(甲基)丙烯酸酯的环氧基发生如下反应得到含碳碳双键的的聚乙烯醇缩醛聚合物。
含有环氧基的的丙烯酸酯的实例如下:
R是H或甲基。
含碳碳双键的聚乙烯缩醛树脂的加入量为所有固体含量的20-80%。
乙烯基不饱和单体:作为单官能单体可举出(甲基)丙烯酰胺、羟甲基(甲基)丙烯酰胺、甲氧基甲基(甲基)丙烯酰胺、乙氧基甲基(甲基)丙烯酰胺、丙氧基甲基(甲基)丙烯酰胺、丁氧基甲基(甲基)丙烯酰胺、丙烯酸异冰片酯、N-苯基马来酰亚胺、马来酰亚胺、苯乙烯、N-羟甲基(甲基)丙烯酰胺、N-羟基甲基丙烯酰胺、(甲基)丙烯酸、富马酸、马来酸、马来酸酐、衣康酸、衣康酸酐、巴豆酸、2-丙烯酰胺基-2-甲基丙磺酸、叔丁基丙烯酰胺磺酸、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸-2-羟基丙酯、(甲基)丙烯酸-2-羟基丁酯、(甲基)-2-苯氧基-2羟基丙酯、邻苯二甲酸酐、2-(甲基)丙烯酰氧基-2-羟基丙酯、甘油单(甲基)丙烯酸酯、(甲基)丙烯酸四氢糠基酯、(甲基)丙烯酸二甲基氨基酯、(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸222-三氟乙酯、(甲基)丙烯酸2,2,3,3-四氟丙酯、邻苯二甲酸酐衍生物的(甲基)丙烯酸半酯等,这些单官能单体可单独使用或组合2种以上使用。
作为多官能单体可举出乙二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、聚丙二醇二(甲基)丙烯酸酯、丁二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,6己二醇二(甲基)丙烯酸酯、三羟甲基丙烷三丙烯酸酯、甘油二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、2,2-双(4-(甲基)丙烯酰氧基二乙氧基苯基)丙烷、2,2-双(4-(甲基)丙烯酰氧基聚乙氧基苯基)丙烷、(甲基)丙烯酸2-羟基-3-(甲基)丙烯酰氧基丙酯、乙二醇二缩水甘油基醚二(甲基)丙烯酸酯、二乙二醇二缩水甘油醚二(甲基)丙烯酸酯、邻苯二甲酸二缩水甘油基酯二(甲基)丙烯酸酯、甘油三丙烯酸酯、甘油多缩水甘油基醚多(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯、三甲基1,6-己二异氰酸酯与1,6己二异氰酸脂与(甲基)丙烯酸2-羟基乙酯的反应物、亚甲基双(甲基)丙烯酰胺、(甲基)丙烯酰胺亚甲基醚、多元醇与N-羟甲基(甲基)丙烯酰胺的缩合物等,这些多官能单体可以单独使用或组合2种以上使用。
光引发剂的具体例子包括苯乙酮类化合物、噻吨酮类化合物、咪唑类化合物、苯偶姻化合物和三嗪类化合物等,如1-羟基环己基苯酮、2-羟基-2甲基1-苯基丙烷-1-酮、1-(4-(2-羟基乙氧基)苯基)2-甲基丙烷-1酮、1-(4异丙基苯基)-2羟基2-甲基丙烷-1酮、1-(4-十二烷基苯基)-2羟基-2甲基丙烷-1酮、2,2-二甲氧基-1,2-二苯基乙烷-1酮、双(4-二甲氨基苯基)酮、2-甲基1-(4-(甲硫基)苯基)2-吗啉基丙烷-1酮、2-苄基-2二甲基氨基-1(4-(甲硫基)苯基)丁烷-1酮、1-(4(苯硫基)苯基)1,2辛烷二酮-2(O-苯甲酰肟)、O-乙酰基-1-(6-(2-甲基苯甲酰基)9乙基9H咔唑3-基)乙醛肟、2,4,6三甲基苯甲酰基二苯基氧化膦、4-苯甲酰基-4’甲基二甲基硫醚、4-二甲基氨基苯甲酸、4-二甲基氨基苯甲酸甲酯;4-二甲基氨基苯甲酸乙酯;4-二甲基氨基苯甲酸丁酯;4-二甲氨基-2乙基己酯苯甲酸、4-二甲氨基-2异戊基苯甲酸、苯偶酰-β甲氧基乙基缩醛、苯偶酰二甲基缩酮、1-苯基1,2丙烷二酮-2(乙氧基羰基肟)、邻苯甲酰基苯甲酸甲酯、2,4二乙基噻吨酮、2-氯噻吨酮、2,4-二甲基噻吨酮、1-氯4-丙氧基噻吨酮、2-异丙基噻吨酮、2-乙基蒽醌、八甲基蒽醌、1,2苯并蒽醌、2,3二苯基蒽醌、偶氮二异丁氰、过氧化异丙苯、2-巯基苯并咪唑、2-巯基苯并唑、2-巯基苯并噻唑、2-(邻氯苯基)4,5二苯基咪唑二聚体、2-(邻氯苯基)4,5二苯基唑二聚体、2-(邻氯苯基)4,5二甲氧基苯基咪唑二聚体、2-(邻氟苯基)4,5二甲氧基苯基咪唑二聚体;2-(邻(对)甲氧基苯基)4,5二甲氧基苯基咪唑二聚体、2-(对甲氧基苯基)4,5二甲氧基苯基咪唑二聚体、2,4,5三芳基咪唑二聚体、二苯甲酮、2-氯二苯甲酮、4,4’双(二乙基氨基)二苯甲酮,4,4’二氯二苯甲酮、3,3二甲基4-甲氧基二苯甲酮、苯偶姻、苯偶姻甲基醚、苯偶姻乙基醚、苯偶姻异丙基醚、苯偶姻正丁基醚、2,2-二乙氧基苯乙酮、对二甲基苯乙酮、对二甲氨基苯丙酮、二氯苯乙酮、三氯苯乙酮、对叔丁基苯乙酮、对叔丁基三氯苯乙酮、对叔丁基二氯苯乙酮、9-苯基吖啶、1,7双(9-吖啶基)庚烷、对甲氧基三嗪、2,4,6三(三氯甲基)均三嗪、2-甲基-4,6-双(三氯甲基)均三嗪、2-(2(呋喃—2基)乙烯基)4,6-双(三氯甲基)均三嗪、2-(4-二乙胺基-2甲基苯基)乙烯基)4,6-双(三氯甲基)均三嗪、2-(3,4-二甲基苯基)乙烯基4,6-双(三氯甲基)均三嗪等。
溶剂为烷醇类、乙二醇烷基醚乙酸酯类、乙二醇烷基醚丙酸酯类、乙二醇单烷基醚类、二乙二醇烷基醚类、丙二醇烷基醚类乙酸酯类、丙二醇烷基醚丙酸酯类、丙二醇单烷基醚类、二丙二醇烷基醚类、丁二醇单烷基醚类、二丁二醇烷基醚类等。
上述组分中还可以加入环氧树脂、环氧树脂固化剂、光产酸剂、抗氧剂、表面活性剂、硅烷偶联剂和酸类化合物等。
本发明同时提供一种半导体集成电路的绝缘平整化膜,其含有上述的感光树脂组合物的固化物。
本发明同时提供一种半导体集成电路的绝缘平整化膜的图案形成方法,其利用了上述的感光树脂组合物。
使用上述作为形成绝缘平整化膜的感光树脂组合物形成绝缘平整化膜在基材表面形成膜层的方法无特别限定,可以在膜形成用组合物为固体或高粘度凝胶的情况下,利用将规定量的膜形成组合物供给到基材上后对膜形成用组合物边加热边压制的方法成膜,在膜形成用组合物为液体的情况下可以利用涂布的方法如采用滚涂机、逆涂机、棒涂机、狭缝涂布机、旋转涂布机、帘幕式淋涂机等及其喷涂、浸涂涂布等方法形成膜层。
曝光的射线包括g线、h线、i线、远紫外及电子束等。
显影方法包括抗蚀剂常用的方法,如浸渍显影和喷淋显影等方法,显影液包括无机碱水溶液如氢氧化钠、氢氧化钾、碳酸钠、硅酸钠和氨水等;有机胺水溶液如乙胺、丙胺、二乙胺、三乙胺、四甲基氢氧化铵等。
与现有技术相比,本发明的有益效果在于:
1、灵敏度、分辨力、平整度、粘结性和热稳定性优良,适宜形成半导体集成电路的绝缘平整化膜。
具体实施方式
下面结合实施例,更具体地说明本发明的内容。应当理解,本发明的实施并不局限于下面的实施例,对本发明所做的任何形式上的变通或改变都落入本发明保护范围;且下述实施例中的方法,如无特别说明,均为本领域的常规方法。
实施例1:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.23g,对羧基苯甲醛7.03g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P1聚乙烯缩醛树脂14.25g,将上述P1聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式A环氧丙烯酸酯(R为甲基)3.63g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB1重量17.8g,酸值62mgKOH/g。
配方:
实施例2:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.84g,对羧基苯甲醛5.75g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P2聚乙烯缩醛树脂14.7g,将上述P2聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式A环氧丙烯酸酯(R为甲基)2.42g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB2重量17.1g,酸值60mgKOH/g。
配方:除了含碳碳双键的聚乙烯醇缩醛PCB2替代PCB1,其余和实施例1相同。
实施例3:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,37%甲醛溶液2.07g,对羧基苯甲醛5.75g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P3聚乙烯缩醛树脂13.2g,将上述P3聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式A环氧丙烯酸酯(R为甲基)2.42g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB3重量15.6g,酸值62mgKOH/g。
配方:除了含碳碳双键的聚乙烯醇缩醛PCB3替代PCB1,其余和实施例1相同。
实施例4:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.23g,对羧基苯甲醛7.03g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P4聚乙烯缩醛树脂15.2g,将上述P4聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式B环氧丙烯酸酯(R为甲基)5.78g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB4重量20.1g,酸值60mgKOH/g。
配方:除了含碳碳双键的聚乙烯醇缩醛PCB4替代PCB1,其余和实施例1相同。
实施例5:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.53g,对羧基苯甲醛6.39g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P5聚乙烯缩醛树脂15.3g,将上述P5聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式B环氧丙烯酸酯(R为甲基)4.82g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB5重量20.6g,酸值56mgKOH/g。
配方:除了含环氧基的聚乙烯醇缩醛PCB5替代PCB1,其余和实施例1相同。
实施例6:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.23g,对羧基苯甲醛7.03g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P6聚乙烯缩醛树脂15.2g,将上述P6聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式C环氧丙烯酸酯(R为甲基)6.09g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB6重量21.1g,酸值63mgKOH/g。
配方:除了含环氧基的聚乙烯醇缩醛PCB6替代PCB1,其余和实施例1相同。
实施例7:
称取PVA-103(日本可乐丽)7.5g加入到250ml三口烧瓶中,搅拌下加入二甲基亚砜100g,升温至80℃溶解,降温至60℃,加入1g对甲苯磺酸,正丁醛1.84g,邻羧基苯甲醛7.03g,70℃下反应5小时,加入20gDMSO稀释,分散在2升水中,得白色粉末,过滤水洗后,在60℃下热风干燥,得到P7聚乙烯缩醛树脂15.2g,将上述P7聚乙烯醇缩醛树脂、乙二醇单甲醚100g加入到250ml三口烧瓶中溶解,加入0.15g四丁基氯化铵,0.07g对苯二酚,式A环氧丙烯酸酯(R为甲基)3.63g,110℃下反应4小时,然后冷却至40℃,分散在2升水中,得到含碳碳双键的聚乙烯醇缩醛树脂PCB7重量18.6g,酸值54mgKOH/g。
配方:除了含环氧基的聚乙烯醇缩醛PCB7替代PCB1,其余和实施例1相同。
对比例1:
采用丙烯酸树脂Rd替代PCB1,其余和实施例1相同。
对比例2:
碱溶树脂P7替代PCB1,其余和实施例1相同。
性能检测方法:
将上述实施例1-7和比较例1-2感光性树脂组合物溶解后,用0.2微米的Millipore过滤器过滤,然后采用旋涂法将感光树脂组合物样品涂覆到玻璃基板上,接着于100℃在加热板上烘焙90S,获得一个具有3μm厚的抗蚀膜。通过ABM公司生产的正面对准光刻机,用全光线最佳曝光量透过一个测试掩膜图案曝光,并在23℃采用0.4%的氢氧化四甲基铵水溶液进行显影,持续60S,用纯水清洗1分钟,以形成具有掩膜图案的膜。
(1)灵敏度
以上的最佳曝光量确定为灵敏度。
(2)分辨率
采用扫描电子显微镜(SEM)对上述所述图案进行观察,在5μm线条和间隔宽度的最佳曝光量处形成的最小线条和间隔图案宽度,用来作为分辨率。
(3)耐热性评价
测定形成的掩膜图案的上下和左右的宽度,此时将烘焙前为基准,然后在烘箱中230℃烘烤60分钟,考察面积变化率为1-20%时设为Ο,面积变化率为20-40%时设为△,面积变化率为大于40%时设为×。
(4)显影后平整度
使用椭圆计来测定通过以上方法形成的膜在显影后的平整度,此时基于整个基板平整度大于95%时以Ο表示,平整度为90-95%以Δ表示,平整度小于90%以×表示。
(5)粘结性
将上述实施例1-7和比较例1-2感光性组分溶解后,接着用0.2微米的Millipore过滤器过滤,然后采用旋涂法将感光树脂组合物样品涂覆到玻璃基板上,接着于100℃在加热板上烘焙90S,获得一个具有3μm厚的膜。通过ABM公司生产的正面对准光刻机,用全光线用最佳曝光量全面曝光,并在23℃采用0.4%的氢氧化四甲基铵水溶液进行显影,持续60S,用纯水清洗1分钟,以形成全膜,采用GB/T9286-1998《色漆和清漆漆膜的划格试验》用划格测试膜层的粘结性。
| 灵敏度mJ/cm<sup>2</sup> | 平整度 | 分辨率μm | 耐热性 | 粘结性 | |
| 实施例1 | 285 | Ο | 3 | Ο | 0-1级 |
| 实施例2 | 280 | Ο | 3 | Ο | 0-1级 |
| 实施例3 | 275 | Ο | 3 | Ο | 0-1级 |
| 实施例4 | 280 | Ο | 3 | Ο | 0-1级 |
| 实施例5 | 285 | Ο | 3 | Ο | 0-1级 |
| 实施例6 | 280 | Ο | 3 | Ο | 0-1级 |
| 实施例7 | 280 | Ο | 3 | Ο | 0-1级 |
| 比较例1 | 300 | Δ | 4 | Δ | 0-1级 |
| 比较例2 | 320 | Ο | 4 | Ο | 0-1级 |
从以上结果看出,本发明的感光性树脂组合物形成的膜的灵敏度、分辨力、平整性、耐热性和粘结性良好,验证了本发明。
Claims (3)
1.一种感光性树脂组合物,其特征在于,所述感光性树脂组合物由以下质量百分比的原料和溶剂组成:
碱溶性树脂:20-80%;
乙烯基不饱和单体:10-60%;
光引发剂:2-12%;
所述碱溶性树脂为含碳碳双键的聚乙烯醇缩醛树脂,含有以下IA)、IB)、IC)、ID)和IE)重复单元;
IA)重复单元:
其中R1是氢、烷基、取代烷基、芳香基和取代芳香基,IA)的摩尔百分比为10-50%;
IB)重复单元:
其中R2是氢、烷基、取代烷基、芳香基和取代芳香基,IB)的摩尔百分比为10-30%;
IC)重复单元:
其中IC)的摩尔百分比为20-40%;
ID)重复单元:
其中ID)的摩尔百分比为1-3%;
IE)重复单元:
其中R是H或甲基;R3是氢、羟基、烷基、取代烷基、芳香基和取代芳香基;A是含羟基烷基;IE)的摩尔百分比为10-40%;
所述乙烯基不饱和单体为乙烯基单官能度和多官能度单体的一种或两种以上的组合;
所述光引发剂包括苯乙酮类化合物、噻吨酮类化合物、咪唑类化合物、苯偶姻化合物和三嗪类化合物的一种或两种以上的组合;
所述溶剂为烷醇类,乙二醇烷基醚乙酸酯类,乙二醇烷基醚丙酸酯类,乙二醇单烷基醚类,二乙二醇烷基醚类,丙二醇烷基醚类乙酸酯类,丙二醇烷基醚丙酸酯类,丙二醇单烷基醚类,二丙二醇烷基醚类,丁二醇单烷基醚类,二丁二醇烷基醚类中的至少一种。
2.一种半导体集成电路的绝缘平整化膜,其特征在于,所述绝缘平整化膜中含有如权利要求1所述的感光性树脂组合物。
3.一种半导体集成电路的绝缘平整化膜的图案形成方法,其特征在于,所述图案形成方法中使用了如权利要求1所述的感光性树脂组合物。
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