JPH0122308B2 - - Google Patents
Info
- Publication number
- JPH0122308B2 JPH0122308B2 JP59032610A JP3261084A JPH0122308B2 JP H0122308 B2 JPH0122308 B2 JP H0122308B2 JP 59032610 A JP59032610 A JP 59032610A JP 3261084 A JP3261084 A JP 3261084A JP H0122308 B2 JPH0122308 B2 JP H0122308B2
- Authority
- JP
- Japan
- Prior art keywords
- mol
- dianhydride
- temperature
- diamine
- formula
- 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
Links
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 49
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 41
- 150000004985 diamines Chemical class 0.000 claims description 35
- 239000004065 semiconductor Substances 0.000 claims description 31
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 25
- 229920005575 poly(amic acid) Polymers 0.000 claims description 24
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 21
- 229920006015 heat resistant resin Polymers 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 9
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 7
- -1 Tetracarboxylic acid dianhydride Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000002798 polar solvent Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000000151 deposition Methods 0.000 claims 1
- 229920005989 resin Polymers 0.000 description 33
- 239000011347 resin Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 29
- 239000000047 product Substances 0.000 description 23
- 229920001721 polyimide Polymers 0.000 description 20
- 230000000977 initiatory effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000009719 polyimide resin Substances 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 235000012431 wafers Nutrition 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000006159 dianhydride group Chemical group 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000004642 Polyimide Substances 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 230000007257 malfunction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- OLQWMCSSZKNOLQ-ZXZARUISSA-N (3s)-3-[(3r)-2,5-dioxooxolan-3-yl]oxolane-2,5-dione Chemical compound O=C1OC(=O)C[C@H]1[C@@H]1C(=O)OC(=O)C1 OLQWMCSSZKNOLQ-ZXZARUISSA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KBLZUSCEBGBILB-UHFFFAOYSA-N 2,2-dimethylthiolane 1,1-dioxide Chemical compound CC1(C)CCCS1(=O)=O KBLZUSCEBGBILB-UHFFFAOYSA-N 0.000 description 1
- YXOKJIRTNWHPFS-UHFFFAOYSA-N 2,5-dimethylhexane-1,6-diamine Chemical compound NCC(C)CCC(C)CN YXOKJIRTNWHPFS-UHFFFAOYSA-N 0.000 description 1
- SDWGBHZZXPDKDZ-UHFFFAOYSA-N 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=C(Cl)C(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O SDWGBHZZXPDKDZ-UHFFFAOYSA-N 0.000 description 1
- JZWGLBCZWLGCDT-UHFFFAOYSA-N 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic acid Chemical compound ClC1=CC(C(O)=O)=C2C(C(=O)O)=CC(Cl)=C(C(O)=O)C2=C1C(O)=O JZWGLBCZWLGCDT-UHFFFAOYSA-N 0.000 description 1
- WPAJQCZZXQFHBB-UHFFFAOYSA-N 2-[2-(2,5-dicarboxyphenyl)propan-2-yl]terephthalic acid Chemical compound C=1C(C(O)=O)=CC=C(C(O)=O)C=1C(C)(C)C1=CC(C(O)=O)=CC=C1C(O)=O WPAJQCZZXQFHBB-UHFFFAOYSA-N 0.000 description 1
- DZLUPKIRNOCKJB-UHFFFAOYSA-N 2-methoxy-n,n-dimethylacetamide Chemical compound COCC(=O)N(C)C DZLUPKIRNOCKJB-UHFFFAOYSA-N 0.000 description 1
- JRBJSXQPQWSCCF-UHFFFAOYSA-N 3,3'-Dimethoxybenzidine Chemical compound C1=C(N)C(OC)=CC(C=2C=C(OC)C(N)=CC=2)=C1 JRBJSXQPQWSCCF-UHFFFAOYSA-N 0.000 description 1
- NUIURNJTPRWVAP-UHFFFAOYSA-N 3,3'-Dimethylbenzidine Chemical group C1=C(N)C(C)=CC(C=2C=C(C)C(N)=CC=2)=C1 NUIURNJTPRWVAP-UHFFFAOYSA-N 0.000 description 1
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- UCFMKTNJZCYBBJ-UHFFFAOYSA-N 3-[1-(2,3-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=CC(C(O)=O)=C(C(O)=O)C=1C(C)C1=CC=CC(C(O)=O)=C1C(O)=O UCFMKTNJZCYBBJ-UHFFFAOYSA-N 0.000 description 1
- POTQBGGWSWSMCX-UHFFFAOYSA-N 3-[2-(3-aminopropoxy)ethoxy]propan-1-amine Chemical compound NCCCOCCOCCCN POTQBGGWSWSMCX-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- YEEIWUUBRYZFEH-UHFFFAOYSA-N 3-methoxyhexane-1,6-diamine Chemical compound NCCC(OC)CCCN YEEIWUUBRYZFEH-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- ICNFHJVPAJKPHW-UHFFFAOYSA-N 4,4'-Thiodianiline Chemical compound C1=CC(N)=CC=C1SC1=CC=C(N)C=C1 ICNFHJVPAJKPHW-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QGRZMPCVIHBQOE-UHFFFAOYSA-N 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1C(C(O)=O)CC(C)=C2C(C(O)=O)C(C(O)=O)CC(C)=C21 QGRZMPCVIHBQOE-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- TYNNEOUATWMCIY-UHFFFAOYSA-N 4-(4-aminophenyl)phosphonoylaniline Chemical compound C1=CC(N)=CC=C1P(=O)C1=CC=C(N)C=C1 TYNNEOUATWMCIY-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 1
- IJJNNSUCZDJDLP-UHFFFAOYSA-N 4-[1-(3,4-dicarboxyphenyl)ethyl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 IJJNNSUCZDJDLP-UHFFFAOYSA-N 0.000 description 1
- LBNFPUAJWZYIOQ-UHFFFAOYSA-N 4-n-(4-aminophenyl)-4-n-methylbenzene-1,4-diamine Chemical compound C=1C=C(N)C=CC=1N(C)C1=CC=C(N)C=C1 LBNFPUAJWZYIOQ-UHFFFAOYSA-N 0.000 description 1
- IIEKUGPEYLGWQQ-UHFFFAOYSA-N 5-[4-(4-amino-2-methylpentyl)phenyl]-4-methylpentan-2-amine Chemical compound CC(N)CC(C)CC1=CC=C(CC(C)CC(C)N)C=C1 IIEKUGPEYLGWQQ-UHFFFAOYSA-N 0.000 description 1
- DUZDWKQSIJVSMY-UHFFFAOYSA-N 5-[4-(6-amino-2-methylhexan-2-yl)phenyl]-5-methylhexan-1-amine Chemical compound NCCCCC(C)(C)C1=CC=C(C(C)(C)CCCCN)C=C1 DUZDWKQSIJVSMY-UHFFFAOYSA-N 0.000 description 1
- MBRGOFWKNLPACT-UHFFFAOYSA-N 5-methylnonane-1,9-diamine Chemical compound NCCCCC(C)CCCCN MBRGOFWKNLPACT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000004380 ashing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- GCAIEATUVJFSMC-UHFFFAOYSA-N benzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1C(O)=O GCAIEATUVJFSMC-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- CBLAIDIBZHTGLV-UHFFFAOYSA-N dodecane-2,11-diamine Chemical compound CC(N)CCCCCCCCC(C)N CBLAIDIBZHTGLV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- GBASTSRAHRGUAB-UHFFFAOYSA-N ethylenetetracarboxylic dianhydride Chemical compound O=C1OC(=O)C2=C1C(=O)OC2=O GBASTSRAHRGUAB-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000015654 memory Effects 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- KADGVXXDDWDKBX-UHFFFAOYSA-N naphthalene-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C21 KADGVXXDDWDKBX-UHFFFAOYSA-N 0.000 description 1
- OBKARQMATMRWQZ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 OBKARQMATMRWQZ-UHFFFAOYSA-N 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- VQXBKCWOCJSIRT-UHFFFAOYSA-N octadecane-1,12-diamine Chemical compound CCCCCCC(N)CCCCCCCCCCCN VQXBKCWOCJSIRT-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- JGGWKXMPICYBKC-UHFFFAOYSA-N phenanthrene-1,8,9,10-tetracarboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=C(C(O)=O)C(C(O)=O)=C3C(C(=O)O)=CC=CC3=C21 JGGWKXMPICYBKC-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- RTHVZRHBNXZKKB-UHFFFAOYSA-N pyrazine-2,3,5,6-tetracarboxylic acid Chemical compound OC(=O)C1=NC(C(O)=O)=C(C(O)=O)N=C1C(O)=O RTHVZRHBNXZKKB-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- YKWDNEXDHDSTCU-UHFFFAOYSA-N pyrrolidine-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C1NC(C(O)=O)C(C(O)=O)C1C(O)=O YKWDNEXDHDSTCU-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- LUEGQDUCMILDOJ-UHFFFAOYSA-N thiophene-2,3,4,5-tetracarboxylic acid Chemical compound OC(=O)C=1SC(C(O)=O)=C(C(O)=O)C=1C(O)=O LUEGQDUCMILDOJ-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Description
本発明はテトラカルボン酸ジ無水物とジアミン
とを原料とする耐熱性樹脂を使用した半導体装置
の製造方法に関するものである。
その目的とするところは、閉環処理により、イ
ミド化した硬化樹脂が著しく高い熱分解開始温度
を有している耐熱性樹脂を半導体素子表面に塗布
して、素子表面を高温、高湿、高バイアスから保
護し、更にはα線等の放射線等からも保護し高信
頼性の半導体装置を提供することにある。
従来、少くとも２個の炭素原子を含有するジア
ミンを、少くとも２個の炭素原子を含む４価の基
を含有し、しかもそのジ無水物基のカルボニル基
の精々２個が該４価の基の炭素原子のいずれか１
個の結合されているテトラカルボン酸ジ無水物と
反応せしめて、それによりポリアミツク酸生成物
を生成せしめ、ついでこのものを50℃より高い温
度に加熱して該ポリアミツク酸生成物をポリイミ
ドに変化せしめることによりポリイミド類を製造
することは良く知られたことである。また製造さ
れたポリイミド類は、ジアミン及びテトラカルボ
ン酸ジ無水物なる基からなる反覆単位を有するこ
とを特徴とし、更にまた、該ジアミン基が少くと
も２個の炭素原子を含む２価の基を含有し、且該
テトラカルボン酸ジ無水物基は少くとも２個の炭
素原子を含む２価の基を含有し、その際ジ無水物
基のカルボニル基の精々２個は４価の基の炭素原
子のいずれか１個に結合していることを特徴とし
ていることも公知である。更には又、テトラカル
ボン酸ジ無水物としてピロメリツト酸ジ無水物、
ベンゾフエノンテトラカルボン酸ジ無水物、２，
３，６，７―ナフタレンテトラカルボン酸ジ無水
物、３，3′，４，4′―ジフエニルテトラカルボン
酸ジ無水物、１，２，５，６―ナフタレンテトラ
カルボン酸ジ無水物、２，2′，３，3′―ジフエニ
ルテトラカルボン酸ジ無水物、２，２―ビス
（３，４―ジカルボキシジフエニル）プロパンジ
無水物、３，４，９，10―ペリレンテトラカルボ
ン酸ジ無水物、ビス（３，４―ジカルボキシジフ
エニル）エーテルジ無水物、エチレンテトラカル
ボン酸ジ無水物、ナフタレン―１，２，４，５―
テトラカルボン酸ジ無水物、ナフタレン―１，
４，５，８―テトラカルボン酸ジ無水物、デカヒ
ドロナフタレン―１，４，５，８―テトラカルボ
ン酸ジ無水物、４，８―ジメチル―１，２，３，
５，６，７―ヘキサヒドロナフタレン―１，２，
５，６―テトラカルボン酸ジ無水物、２，６―ジ
クロロナフタレン―１，４，５，８―テトラカル
ボン酸ジ無水物、２，７―ジクロロナフタレン―
１，４，５，８―テトラカルボン酸ジ無水物、
２，３，４，７―テトラクロロナフタレン―１，
４，５，８―テトラカルボン酸ジ無水物、フエナ
ンスレン―１，８，９，10―テトラカルボン酸ジ
無水物、シクロペンタン―１，２，３，４―テト
ラカルボン酸ジ無水物、ピロリジン―２，３，
４，５―テトラカルボン酸ジ無水物、ピラジン―
２，３，５，６―テトラカルボン酸ジ無水物、
２，２―ビス（２，５―ジカルボキシフエニル）
プロパンジ無水物、１，１―ビス（２，３―ジカ
ルボキシフエニル）エタンジ無水物、１，１―ビ
ス（３，４―ジカルボキシフエニル）エタンジ無
水物、ビス（２，３―ジカルボキシフエニル）メ
タンジ無水物、ビス（３，４―ジカルボキシフエ
ニル）メタンジ無水物、ビス（３，４―ジカルボ
キシフエニル）スルホンジ無水物、ベンゼン―
１，２，３，４―テトラカルボン酸ジ無水物、
１，２，３，４―ブタンテトラカルボン酸ジ無水
物、チオフエン―２，３，４，５―テトラカルボ
ン酸ジ無水物などを使用し、またジアミンとして
ｍ―フエニレンジアミン、ｐ―フエニレンジアミ
ン、４，4′―ジアミノジフエニルプロパン、４，
4′―ジアミノジフエニルメタン、ベンジジン、
４，4′―ジアミノジフエニルスルフイド、４，
4′―ジアミノジフエニルスルホン、３，3′―ジア
ミノジフエニルスルホン、４，4′ジアミノジフエ
ニルエーテル、２，６―ジアミノピリジン、ビス
（４―アミノフエニル）ホスフインオキシド、ビ
ス（４―アミノフエニル）―Ｎ―メチルアミン、
１，５―ジアミノナフタリン、３，3′―ジメチル
―４，4′―ジアミノビフエニル、３，3′―ジメト
キシベンジジン、２，４―ビス（β―アミノ―ｔ
―ブチル）トルエン、ビス（ｐ―β―アミノ―ｔ
―ブチルフエニル）エーテル、ｐ―ビス（２―メ
チル―４―アミノペンチル）ベンゼン、ｐ―ビス
（１，１―ジメチル―５―アミノペンチル）ベン
ゼン、ｍ―キシリレンジアミン、ｐ―キシリレン
ジアミン、ビス（ｐ―アミノシクロヘキシル）メ
タン、エチレンジアミン、プロピレンジアミン、
ヘキサメチレンジアミン、ヘプタメチレンジアミ
ン、オクタメチレンジアミン、ノナメチレンジア
ミン、デカメチレンジアミン、３―メチルヘプタ
メチレンジアミン、４，４―ジメチルヘプタメチ
レンジアミン、２，11―ジアミノドデカン、１，
２―ビス（３―アミノプロポキシ）エタン、２，
２―ジメチルプロピレンジアミン、３―メトキシ
ヘキサメチレンジアミン、２，５―ジメチルヘキ
サメチレンジアミン、５―メチルノナメチレンジ
アミン、１，４―ジアミノシクロヘキサン、１，
12―ジアミノオクタデカン、２，５―ジアミノ―
１，３，４―オキサジアゾール、などを使用する
ことも既に行なわれている。
これらのポリイミド樹脂を半導体素子表面にコ
ートし、パツシベーシヨン特性の向上や耐α線防
止に効果のある事は知られている。
半導体表面コート用としてポリイミド樹脂の様
な高耐熱性樹脂が必要な主な理由は以下の通りで
ある。
(イ) 半導体素子は外部からの温度に対し非常に敏
感であり、高温にさらされると品質が著しく低
下する。そのため素子表面を耐熱性の優れたポ
リイミド樹脂で覆い耐熱保護が行なわれてい
る。即ちパツシベーシヨン特性向上のために必
須と言われている。
(ロ) 又半導体素子を超LSI（64KビツトRAM以
上）として用いた場合チツプを封止するモール
ド材料又はセラミツクのふたに含まれている天
然物から発生するα線により超LSIに誤動作が
生じ易くなるため、表面をポリイミド樹脂でコ
ートし保護する方法がとられている。この場合
も特にセラミツクのフタで封止（ハーメチツク
封止）する際は480〜500℃の高温に耐えるポリ
イミド樹脂が必要となる。
(ハ) 更には半導体素子表面にメモリーや回路を形
成しICを製造する工程でよりコンパクト化す
るために、表面の多層配線化が行なわれるよう
になつてきた。この時の絶縁膜にポリイミド樹
脂が用いられるが、この場合も電極のアルミニ
ウム蒸着後のアニール温度（450〜500℃）に耐
える必要がある。
この様に半導体素子表面の保護、品質保持のた
めに耐熱性に富むポリイミド樹脂が重要な材料と
して用いられている。
しかし現在の性能では決して満足しておらず、
耐熱性が不充分なために素子の品質が充分に保た
れず、一部信頼性が低下しているのが現状であ
る。
なぜなら現在のポリイミド樹脂は熱分解開始温
度が約450℃であり、前述した(イ)、(ロ)、(ハ)の必要
耐熱性よりも低い。そのため皮膜の特性劣化や分
解ガスの発生のため半導体デイバイスとしての信
頼性が本来の性能よりも低下させて使用されてい
る。
この様な現状をふまえ本発明者等は、ポリイミ
ド樹脂の優れた諸特性を保持したまゝ、熱分解開
始温度を480℃以上に向上せしめる事を目的に鋭
意研究の結果、
一般式
（R1はベンゼン環、縮合ベンゼン環）
で表わされるテトラカルボン酸ジ無水物(A)99〜80
モル％および
一般式
（X1は―CO―，―Ｏ―，―SO2―，―Ｓ―，
―CH2―，
The present invention relates to a method for manufacturing a semiconductor device using a heat-resistant resin made from tetracarboxylic dianhydride and diamine. The purpose of this is to coat the surface of a semiconductor element with a heat-resistant resin whose imidized cured resin has a significantly high thermal decomposition initiation temperature through ring-closing treatment, and to protect the element surface from high temperatures, high humidity, and high bias conditions. It is an object of the present invention to provide a highly reliable semiconductor device that is protected from radiation such as alpha rays and is further protected from radiation such as alpha rays. Conventionally, diamines containing at least two carbon atoms have been used to prepare diamines containing a tetravalent group containing at least two carbon atoms, and in which at most two of the carbonyl groups of the dianhydride group are Any one of the carbon atoms in the group
reacting with the attached tetracarboxylic dianhydride, thereby forming a polyamic acid product, which is then heated to a temperature above 50°C to convert the polyamic acid product to a polyimide. It is well known that polyimides can be prepared by The produced polyimides are characterized in that they have repeating units consisting of diamine and tetracarboxylic dianhydride groups, and furthermore, the diamine group has a divalent group containing at least two carbon atoms. and the tetracarboxylic dianhydride group contains a divalent group containing at least 2 carbon atoms, in which case at most two of the carbonyl groups of the dianhydride group are carbon atoms of the tetravalent group. It is also known that it is characterized by being bonded to any one of the atoms. Furthermore, as the tetracarboxylic dianhydride, pyromellitic dianhydride,
Benzophenonetetracarboxylic dianhydride, 2,
3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2 , 2',3,3'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxydiphenyl)propane dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride Anhydride, bis(3,4-dicarboxydiphenyl)ether dianhydride, ethylenetetracarboxylic dianhydride, naphthalene-1,2,4,5-
Tetracarboxylic dianhydride, naphthalene-1,
4,5,8-tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,
5,6,7-hexahydronaphthalene-1,2,
5,6-tetracarboxylic dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-
1,4,5,8-tetracarboxylic dianhydride,
2,3,4,7-tetrachloronaphthalene-1,
4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic dianhydride, pyrrolidine- 2, 3,
4,5-tetracarboxylic dianhydride, pyrazine-
2,3,5,6-tetracarboxylic dianhydride,
2,2-bis(2,5-dicarboxyphenyl)
Propane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, bis(2,3-dicarboxyphenyl) phenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-
1,2,3,4-tetracarboxylic dianhydride,
1,2,3,4-butanetetracarboxylic dianhydride, thiophene-2,3,4,5-tetracarboxylic dianhydride, etc. are used, and m-phenylene diamine, p-phenylene are used as diamines. Diamine, 4,4'-diaminodiphenylpropane, 4,
4′-diaminodiphenylmethane, benzidine,
4,4'-diaminodiphenyl sulfide, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4' diaminodiphenyl ether, 2,6-diaminopyridine, bis(4-aminophenyl)phosphine oxide, bis(4-aminophenyl) -N-methylamine,
1,5-diaminonaphthalene, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxybenzidine, 2,4-bis(β-amino-t
-butyl) toluene, bis(p-β-amino-t
-butylphenyl) ether, p-bis(2-methyl-4-aminopentyl)benzene, p-bis(1,1-dimethyl-5-aminopentyl)benzene, m-xylylenediamine, p-xylylenediamine, bis (p-aminocyclohexyl)methane, ethylenediamine, propylenediamine,
Hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, 3-methylheptamethylene diamine, 4,4-dimethylheptamethylene diamine, 2,11-diaminododecane, 1,
2-bis(3-aminopropoxy)ethane, 2,
2-dimethylpropylenediamine, 3-methoxyhexamethylenediamine, 2,5-dimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,4-diaminocyclohexane, 1,
12-diaminooctadecane, 2,5-diamino-
The use of 1,3,4-oxadiazole, etc. has also already been carried out. It is known that coating the surface of a semiconductor element with these polyimide resins is effective in improving passivation characteristics and preventing alpha rays. The main reasons why highly heat-resistant resins such as polyimide resins are necessary for semiconductor surface coating are as follows. (a) Semiconductor elements are extremely sensitive to external temperatures, and their quality deteriorates significantly when exposed to high temperatures. For this reason, the element surface is covered with polyimide resin, which has excellent heat resistance, for heat-resistant protection. That is, it is said to be essential for improving the passivation characteristics. (b) Also, when a semiconductor element is used as a super LSI (64K bit RAM or more), the super LSI is likely to malfunction due to α rays generated from natural substances contained in the molding material or ceramic lid used to seal the chip. Therefore, a method is used to protect the surface by coating it with polyimide resin. In this case as well, especially when sealing with a ceramic lid (hermetic sealing), a polyimide resin that can withstand high temperatures of 480 to 500°C is required. (c) Furthermore, in order to form memories and circuits on the surface of semiconductor elements and make them more compact in the process of manufacturing ICs, multilayer wiring on the surface has begun to be performed. Polyimide resin is used for the insulating film at this time, but in this case as well, it is necessary to withstand the annealing temperature (450 to 500°C) after aluminum evaporation of the electrodes. As described above, polyimide resin, which is highly heat resistant, is used as an important material to protect the surface of semiconductor elements and maintain quality. However, we are not satisfied with the current performance,
Currently, due to insufficient heat resistance, the quality of the element cannot be maintained sufficiently, and reliability has partially deteriorated. This is because the thermal decomposition initiation temperature of current polyimide resins is approximately 450°C, which is lower than the required heat resistance of (a), (b), and (c) described above. Therefore, due to deterioration of film characteristics and generation of decomposed gas, semiconductor devices are used with reliability lower than their original performance. In view of this current situation, the inventors of the present invention have conducted intensive research with the aim of increasing the thermal decomposition initiation temperature to 480°C or higher while maintaining the excellent properties of polyimide resin, and have developed the general formula. (R 1 is benzene ring, fused benzene ring) Tetracarboxylic dianhydride (A)99-80
Mol% and general formula (X 1 is -CO-, -O-, -SO 2 -, -S-,
―CH 2 ―,
【式】，
で表わされるテトラカルボン酸ジ無水物(B)１〜20
モル％とからなるテトラカルボン酸ジ無水物と一
般式 H2N―R2―NH2
（R2はベンゼン環、縮合ベンゼン環）
で表わされるジアミン(C)99〜60モル％および一般
式[Formula], Tetracarboxylic dianhydride (B) 1-20
Tetracarboxylic dianhydride consisting of mol % and diamine (C) 99 to 60 mol % represented by the general formula H 2 N—R 2 —NH 2 (R 2 is a benzene ring, fused benzene ring) and the general formula
【式】（X2は―
CO―，―Ｏ―，―SO2―，―Ｓ―，―CH2―，
[Formula] (X 2 is - CO-, -O-, -SO 2 -, -S-, -CH 2 -,
【式】）
で表わされるジアミン(D)１〜40モル％とからなる
ジアミンとを、無水の条件下に、不活性ガス雰囲
気中、有機極性溶媒中で、０〜100℃で反応させ
て、ポリアミツク酸生成物の固有粘度を0.5〜2.5
にする事により熱分解開始温度480〜580℃の高耐
熱ポリイミド樹脂が得られるという驚くべき事実
を見い出しこの樹脂を使用して本発明を完成する
に到つたものである。即ち本発明の特徴は、熱分
解開始温度に及ぼす諸要因につき詳細に検討の結
果、樹脂構造と共に樹脂重合度が著しく大きな影
響を及ぼしているという新たな知見を得てなされ
たものである。これまでにも耐熱性向上の為の努
力は種々行なわれてきた。即ちその第一の方法
は、樹脂に含まれる結合の安定性、言いかえれば
結合のエネルギーを出来るだけ大きくする事であ
る。単結合のみからなる脂肪族鎖樹脂の耐熱性は
著しく悪い。これは単結合の結合エネルギーが例
えばＣ―Ｃ（80kcal／mol）、Ｃ―Ｎ（62kcal／
mol）と小さい為である。一方、二重結合、三重
結合の結合エネルギーは例えばＣ＝Ｃ（142kcal／
mol）、Ｃ≡Ｃ（186kcal／mol）、Ｃ＝Ｎ
（121kcal／mol）、Ｃ≡Ｎ（191kcal／mol）とは
るかに大きい。従つて耐熱性を高める為には樹脂
の主鎖中に多重結合や芳香族環などを導入するこ
とである。芳香族環や複素環などは共鳴により安
定化を受けている為、より一層耐熱性の向上には
有利であると考えられる。第二の方法は、樹脂の
主鎖中に対称性のよい芳香族環を導入し融点やガ
ラス転移点を高くすることである。一般に融点
（以下Tmという）と融解のエンタルピー（以下
ΔHmという）及び融解のエントロピー（以下
ΔSmという）との間にはTm＝ΔHm／ΔSmの関係があ
る。ここでΔHmは分子間力に、ΔSmは主として
分子の屈曲性や対称性に関係した量である。Tm
はΔHmよりもΔSmにより大きく左右されること
が多く、樹脂の主鎖にパラ結合芳香環が多いほど
ΔSmが小さくなりTmが高くなることがわかつて
いる。即ち耐熱性を向上させるには対称性のよい
芳香族環を導入する事が必要となる。
この様に耐熱性向上の為の理論付けはほゞ完成
し耐熱性樹脂の分子構造もこれにのつとつて設計
されてきた。ところがここで云う耐熱性は、いわ
ゆる熱分解温度であり、分解が激しくおこる温度
についての研究が主であつた。本発明において問
題にしているのは熱分解温度ではなく、熱分解開
始温度であり、分解がはじまる温度である。これ
については今まであまり研究されてきた例はな
い。本発明者等は熱分解温度と熱分解開始温度に
ついて詳細に検討した結果、熱分解温度が高いも
のが必ずしも熱分解温度が高いとは限らないとい
う知見を得た。勿論耐熱性向上の為には理論に基
く分子設計が基本であり分子構造の効果が最も大
きい事は明らかであるがその上で、熱分解開始温
度に及ぼす要因として樹脂重合度が著しく大きい
ことを発見した。即ち樹脂重合度が小さいほど熱
分解開始温度が高いという驚くべき知見である。
一般に樹脂重合度が大きいほど熱分解温度は高く
なり理論的にもこれは明らかである。ところが熱
分解開始温度は逆に低くなるという事実はこれま
で知られていなかつた。
ここに云う熱分解開始温度とは、示差熱天秤分
析法で加熱により減量がはじまる温度を指してい
る。熱分解開始温度が低くなる理由は明確ではな
いが、分子構造的に結合エネルギーが弱い側鎖官
能基あるいは主鎖でも単結合部分が切れるという
本来の熱分解の他に、ポリアミツク酸を加熱等の
方法により閉環処理する際に生成する水などの揮
発性成分あるいは未反応原料や残留溶剤が、重合
度が大きな樹脂では、一般に溶融粘度が高い為に
揮散できずに硬化樹脂中にとじ込められてしまう
為ではないかと考えられる。樹脂重合度は、主と
して、原料であるテトラカルボン酸ジ無水物とジ
アミンの仕込モル比によつて決定され、モル比が
１に近ずくほど高くなるがモル比が一定でも、反
応の諸条件例えば原料純度、含水量、反応温度、
反応時間、反応停止剤量、反応溶媒系などによつ
てもかえる事が可能である。
本発明の方法は
一般式
（R1はベンゼン環、縮合ベンゼン環）
で表わされるテトラカルボン酸ジ無水物(A)99〜80
モル％および
一般式
（X1は―CO―，―Ｏ―，―SO2―，―Ｓ―，
―CH2―，A diamine consisting of 1 to 40 mol% of diamine (D) represented by [Formula]) is reacted at 0 to 100°C under anhydrous conditions in an inert gas atmosphere in an organic polar solvent, Intrinsic viscosity of polyamic acid products from 0.5 to 2.5
The inventors discovered the surprising fact that a highly heat-resistant polyimide resin with a thermal decomposition initiation temperature of 480 to 580 DEG C. can be obtained by using this method, and completed the present invention using this resin. That is, the present invention is characterized by the fact that, as a result of a detailed study of the various factors that affect the thermal decomposition initiation temperature, new findings have been obtained that, together with the resin structure, the resin polymerization degree has a significantly large effect. Various efforts have been made to improve heat resistance. That is, the first method is to increase the stability of the bonds contained in the resin, or in other words, the energy of the bonds as much as possible. The heat resistance of aliphatic chain resins consisting only of single bonds is extremely poor. This means that the bond energy of a single bond is, for example, C-C (80kcal/mol), C-N (62kcal/mol),
This is because it is small (mol). On the other hand, the bond energy of double bonds and triple bonds is, for example, C=C (142kcal/
mol), C≡C (186kcal/mol), C=N
(121kcal/mol) and C≡N (191kcal/mol), which are much larger. Therefore, in order to improve heat resistance, it is necessary to introduce multiple bonds, aromatic rings, etc. into the main chain of the resin. Since aromatic rings and heterocycles are stabilized by resonance, they are considered to be advantageous in further improving heat resistance. The second method is to increase the melting point and glass transition point by introducing an aromatic ring with good symmetry into the main chain of the resin. Generally, there is a relationship of Tm=ΔHm/ΔSm between the melting point (hereinafter referred to as Tm), the enthalpy of melting (hereinafter referred to as ΔHm), and the entropy of melting (hereinafter referred to as ΔSm). Here, ΔHm is a quantity related to intermolecular force, and ΔSm is a quantity mainly related to the flexibility and symmetry of molecules. Tm
is often influenced more by ΔSm than ΔHm, and it is known that the more para-bonded aromatic rings there are in the main chain of the resin, the smaller ΔSm and the higher Tm. That is, in order to improve heat resistance, it is necessary to introduce an aromatic ring with good symmetry. In this way, the theory for improving heat resistance has been almost completed, and the molecular structure of heat-resistant resins has been designed based on this theory. However, the heat resistance referred to here refers to the so-called thermal decomposition temperature, and research has mainly focused on the temperature at which decomposition occurs violently. In the present invention, the problem is not the thermal decomposition temperature, but the thermal decomposition initiation temperature, which is the temperature at which decomposition begins. Until now, there has not been much research on this subject. As a result of a detailed study of the thermal decomposition temperature and the thermal decomposition start temperature, the present inventors have found that a material with a high thermal decomposition temperature does not necessarily have a high thermal decomposition temperature. Of course, in order to improve heat resistance, molecular design based on theory is fundamental, and it is clear that the molecular structure has the greatest effect, but on top of that, it is important to note that the degree of resin polymerization is extremely large as a factor that affects the thermal decomposition initiation temperature. discovered. That is, this is a surprising finding that the lower the resin polymerization degree, the higher the thermal decomposition initiation temperature.
Generally, the higher the resin polymerization degree, the higher the thermal decomposition temperature, and this is theoretically clear. However, it was not known until now that the temperature at which thermal decomposition begins decreases. The thermal decomposition start temperature referred to herein refers to the temperature at which weight loss starts due to heating as determined by differential thermal balance analysis. The reason why the thermal decomposition onset temperature is lower is not clear, but in addition to the original thermal decomposition in which single bonds are broken even in the side chain functional groups or the main chain, which have weak binding energy due to the molecular structure, polyamic acid can be heated, etc. In resins with a high degree of polymerization, volatile components such as water, unreacted raw materials, and residual solvents generated during the ring-closing process are generally trapped in the cured resin without being able to volatilize due to the high melt viscosity. It is thought that this is to store it away. The degree of resin polymerization is mainly determined by the molar ratio of the raw materials, tetracarboxylic dianhydride and diamine, and increases as the molar ratio approaches 1, but even if the molar ratio is constant, the reaction conditions such as Raw material purity, water content, reaction temperature,
It is also possible to change the reaction time, amount of reaction terminator, reaction solvent system, etc. The method of the present invention uses the general formula (R 1 is benzene ring, fused benzene ring) Tetracarboxylic dianhydride (A)99-80
Mol% and general formula (X 1 is -CO-, -O-, -SO 2 -, -S-,
―CH 2 ―,
【式】，
で表わされるテトラカルボン酸ジ無水物(B)１〜20
モル％とからなるテトラカルボン酸ジ無水物と一
般式 H2N―R2―NH2
（R2はベンゼン環、縮合ベンゼン環）
で表わされるジアミン(C)99〜60モル％および一般
式[Formula], Tetracarboxylic dianhydride (B) 1-20
Tetracarboxylic dianhydride consisting of mol % and diamine (C) 99 to 60 mol % represented by the general formula H 2 N—R 2 —NH 2 (R 2 is a benzene ring, fused benzene ring) and the general formula
【式】
（X2は―CO―，―Ｏ―，―SO2―，―Ｓ―，
―CH2―，[Formula] (X 2 is -CO-, -O-, -SO 2 -, -S-,
―CH 2 ―,
【式】，
で表わされるジアミン(D)１〜40モル％とからなる
ジアミンとを、無水の条件下に、不活性ガス雰囲
気中、有機極性溶媒中で、０〜100℃で反応させ
た、ポリアミツク酸生成物の固有粘度が0.5〜2.5
で、イミド化後の硬化物の熱分解開始温度が480
〜580℃の耐熱性樹脂を半導体素子表面に塗布し、
加熱硬化して半導体素子表面に被着することを特
徴とする半導体装置の製造方法である。
本発明におけるテトラカルボン酸ジ無水物(A)
は、熱分解開始温度を高める効果を有するもので
ある。一般式A diamine consisting of 1 to 40 mol% of diamine (D) represented by [Formula], was reacted at 0 to 100°C under anhydrous conditions in an inert gas atmosphere in an organic polar solvent, The intrinsic viscosity of polyamic acid products is 0.5~2.5
The thermal decomposition onset temperature of the cured product after imidization is 480
~580℃ heat-resistant resin is applied to the surface of the semiconductor element,
This is a method for manufacturing a semiconductor device, characterized in that it is heat-cured and adhered to the surface of a semiconductor element. Tetracarboxylic dianhydride (A) in the present invention
has the effect of increasing the thermal decomposition start temperature. general formula
【式】で表わされ
る化合物の内R1がベンゼン環、縮合ベンゼン環
であるものが効果が大きく、特にこの中でもピロ
メリツト酸ジ無水物が優れている。樹脂中に占め
るテトラカルボン酸ジ無水物成分中のテトラカル
ボン酸ジ無水物(A)の割合が高いほど熱分解開始温
度は高くなるが、樹脂としては剛直になつてく
る。
本発明におけるテトラカルボン酸ジ無水物(B)
は、樹脂の剛直性を改善する効果を有するもので
ある。
一般式
で表わされる化合物は芳香環をつなぐX1をはさ
んだ主鎖単結合により可撓性に優れたものであ
る。
X1としては―CO―，―Ｏ―，―SO2―，―Ｓ
―，―CH2―，Among the compounds represented by the formula, those in which R 1 is a benzene ring or a fused benzene ring are highly effective, and among these, pyromellitic dianhydride is particularly excellent. The higher the proportion of tetracarboxylic dianhydride (A) in the tetracarboxylic dianhydride component in the resin, the higher the thermal decomposition initiation temperature, but the resin becomes more rigid. Tetracarboxylic dianhydride (B) in the present invention
has the effect of improving the rigidity of the resin. general formula The compound represented by has excellent flexibility due to the main chain single bond sandwiching X 1 that connects the aromatic rings. For X 1 , -CO-, -O-, -SO 2 -, -S
―、―CH 2 ―、
【式】などが効果
があるが、特にこの中でもベンゾフエノンテトラ
カルボン酸ジ無水物が優れている。樹脂中に占め
るテトラカルボン酸ジ無水物成分中のテトラカル
ボン酸ジ無水物(B)の割合が高いほど剛直性は改善
されるが、目的とする熱分解開始温度が低下する
為テトラカルボン酸ジ無水物(A)が80モル％以上に
対し、テトラカルボン酸ジ無水物(B)は20モル％以
下でなければならない。
本発明におけるジアミン(C)は熱分解開始温度を
高める効果を有するものである。
一般式 H2N―R2―NH2で表わされる化合物
の内R2がベンゼン環、縮合ベンゼン環であるも
のが効果が大きく、特にこの中でもパラフエニレ
ンジアミンが優れている。樹脂中に占めるジアミ
ン成分中のジアミン(C)の割合が高いほど熱分解開
始温度は高くなるが、樹脂としては剛直になつて
くる。
本発明におけるジアミン(D)は樹脂の剛直性を改
善する効果を有するものである。
一般式Formulas such as [Formula] are effective, and among these, benzophenonetetracarboxylic dianhydride is particularly excellent. The higher the proportion of tetracarboxylic dianhydride (B) in the tetracarboxylic dianhydride component in the resin, the better the rigidity will be, but since the desired thermal decomposition initiation temperature will be lowered, The content of the anhydride (A) must be 80 mol% or more, while the tetracarboxylic dianhydride (B) must be 20 mol% or less. The diamine (C) in the present invention has the effect of increasing the thermal decomposition initiation temperature. Of the compounds represented by the general formula H 2 N—R 2 —NH 2 , those in which R 2 is a benzene ring or a condensed benzene ring are highly effective, and among these, paraphenylenediamine is particularly excellent. The higher the proportion of diamine (C) in the diamine component in the resin, the higher the temperature at which thermal decomposition begins, but the resin becomes more rigid. The diamine (D) in the present invention has the effect of improving the rigidity of the resin. general formula
【式】で表
わされる化合物は芳香環をつなぐX2をはさんだ
主鎖単結合により可撓性に優れたものである。
X2としては―CO―，―Ｏ―，―SO2，―Ｓ―，
―CH2―，The compound represented by the formula has excellent flexibility due to the single bond in the main chain sandwiching X 2 that connects the aromatic rings. As for X 2 , -CO-, -O-, -SO 2 , -S-,
―CH 2 ―,
【式】などが効果があ
るが、特にこの中でも４，4′―ジアミノジフエニ
ルエーテルが優れている。樹脂中に占めるジアミ
ン成分中のジアミン(D)の割合が高いほど剛直性は
改善されるが目的とする熱分解開始温度が低下す
る為、ジアミン(C)が60モル％以上に対しジアミン
(D)は40モル％以下でなければならない。
本発明における反応系の溶媒はその官能基がテ
トラカルボン酸ジ無水物又はジアミン類と反応し
ないダイポールモーメントを有する有機極性溶媒
である。系に対し不活性であり、かつ生成物に対
して溶媒であること以外に、この有機極性溶媒は
反応成分の少なくとも一方、好ましくは両者に対
して溶媒でなければならない。この種の溶媒とし
て代表的なものは、Ｎ，N′―ジメチルホルムア
ミド、Ｎ，Ｎ―ジメチルアセトアミド、Ｎ，Ｎ―
ジエチルホルムアミド、Ｎ，Ｎ―ジエチルアセト
アミド、Ｎ，Ｎ―ジメチルメトキシアセトアミ
ド、ジメチルスルホキシド、ヘキサメチルフオス
ホアミド、Ｎ―メチル―２―ピロリドン、ピリジ
ン、ジメチルスルホン、テトラメチレンスルホ
ン、ジメチルテトラメチレンスルホンなどがあり
これらの溶媒は単独であるいは組合せて使用され
る。この他にも溶媒として組合せて用いられるも
のとしてベンゼン、ベンゾニトリル、ジオキサ
ン、ブチロラクトン、キシレン、トルエン、シク
ロヘキサンなどの非溶媒が、原料の分散媒、反応
調節剤、あるいは生成物からの溶媒の揮散調節
剤、皮膜平滑剤などとして使用される。
本発明は一般に無水の条件下で行う事が好まし
い。これはテトラカルボン酸ジ無水物が水により
開環し不活性化し反応を停止させる恐れがある為
である。この為仕込原料中の水分も溶媒中の水分
も除去する必要がある。しかし一方反応の進行を
調節し、樹脂重合度をコントロールする為にあえ
て水を添加する事も行なわれる。また本発明は不
活性ガス雰囲気中で行なわれる事が好ましい。こ
れはジアミン類の酸化を防止する為である。不活
性ガスとしては一般に乾燥窒素ガスが使用され
る。
本発明における耐熱性樹脂の反応の方法は、次
の様な種々の方法で行なわれる。
ジアミン類とテトラカルボン酸ジ無水物を予
め混合し、その混合物を少量づつ有機溶媒中に
撹拌しながら添加する。この方法は、ポリイミ
ド樹脂の様な発熱反応においては比較的有利で
ある。
これとは逆に、ジアミン類とテトラカルボン
酸ジ無水物の混合物に、撹拌しながら、溶剤を
添加する方法もある。
一般によく行なわれる方法はジアミン類だけ
を溶剤にとかしておき、これに反応速度をコン
トロールできる割合でテトラカルボン酸ジ無水
物を加える方法である。
またジアミン類とテトラカルボン酸ジ無水物
を別々に溶剤にとかしておき、ゆつくりと反応
器中で二つの溶液を加える事もできる。
更には予めジアミン類過剰のポリアミツク酸
生成物とテトラカルボン酸ジ無水物過剰のポリ
アミツク酸生成物を作つておき、これを反応器
中で更に反応させる事もできる。
反応の温度は０〜100℃が好ましい。０℃以下
だと反応の速度がおそく、100℃以上であると生
成したポリアミツク酸が徐々に閉環反応を開始す
る為である。通常、反応は20℃前後で行なわれ、
発熱反応である為冷却が必要である。ポリアミツ
ク酸の重合度は計画的にコントロールできる。テ
トラカルボン酸ジ無水物とジアミンとが等モルに
近いほど重合度は大きくなる。いずれか一方の原
料が５％以上多くなると重合度は著しく低下す
る。通常一方の原料を１〜３％多く用いる事が、
作業性・加工性の上でよく行なわれる。重合度を
コントロールする為に、フタル酸無水物やアニリ
ンで末端封鎖したり、水を添加して酸無水物基の
一方を開環し不活性化する事もできる。
本発明におけるポリアミツク酸生成物の固有粘
度は0.5〜2.5が好ましい。0.5より低いと熱分解開
始温度の向上には良いが、熱分解温度は低目とな
り、皮膜形成性も低下する。2.5より高いと皮膜
形成性の優れたものとなるが、熱分解開始温度が
低下する。
本発明の方法により製造されたポリアミツク酸
生成物は、使用するにあたつて各種のシランカツ
プリング剤、ボランカツプリング剤、チタネート
系カツプリング剤、アルミニウム系カツプリング
剤その他キレート系の接着性・密着性向上剤や各
種溶剤、フローエージエントを加えてもよく、又
これらに加えて通常の酸硬化剤、アミン硬化剤、
ポリアミド硬化剤及びイミダゾール、３級アミン
等の硬化促進剤の少量を加えてもよく、又ポリサ
ルフアイド、ポリエステル、低分子エポキシ等の
可撓性賦与剤及び粘度調整剤、タルク、クレー、
マイカ、長石粉末、石英粉末、酸化マグネシウム
等の充填剤、カーボンブラツク、フエロシアニン
ブルー等の着色剤、テトラブロモフエニルメタ
ン、トリブチルフオスフエート等の難燃剤、三酸
化アンチモン、メタホー酸バリウム等の難燃助剤
の少量を加えてもよく、これらを添加する事によ
り多くの用途が開かれる。この耐熱性樹脂を用い
て半導体素子の表面に被着させた半導体装置の製
造方法は樹脂組成物を溶剤で溶かし均一に混合
し、濃度５〜55％にし、半導体基板もしくは絶縁
体基板上の配線導体層表面に流延し、厚さ0.1〜
500μの範囲で均一な厚みに塗布し、次に乾燥機
中で50〜500℃の温度で、必要により２段階もし
くはそれ以上のステツプで５分〜30時間乾燥して
樹脂皮膜を形成せしめる。樹脂を流延させる装置
としては、ホイーラー、スピンナー、ロールコー
ター、ドクターブレード、ギーサ、フローコータ
ー等を用いる。乾燥には電熱、赤外線、蒸気、高
周波或いはそれらの併用等を用いる。
半導体素子上で皮膜を形成したポリイミド樹脂
は使用方法によつては部分的にエツチングを行な
う場合がある。主な理由はボンデイングパツト部
の開口又は多層配線の層間の導通のためである。
代表的なエツチング法は乾式法の場合はプラズマ
で灰化し、湿式法の場合はヒドラジン系やテトラ
メチルアンモニウムハイドロオキサイド等の強ア
ルカリをエツチング液として用いる。
尚本発明の方法において、樹脂塗膜と基板との
密着性を更に向上させるためには、基板上に表面
処理剤を下塗りするとより一層効果が生じる。特
に通常密着性に乏しいシリコーン基材や金メツキ
を有する回路板に顕著な効果がある。
表面処理剤として通常のシランカツプリング
剤、ボランカツプリング剤を用いると効果がある
が、特に本発明に用いる樹脂から得られる塗膜に
はシランカツプリング剤の方が効果が大きい。シ
ランカツプリング剤としてはビニルシラン系、ア
ミノシラン系、エポキシシラン系等があるが、中
でもアミノシラン系が本発明に用いる樹脂から成
る塗膜とシリコーン基板の間に介在すると非常に
相剰効果を生じ、顕著に接着性が向上する。アミ
ノシラン系カツプリング剤としては、ｎ―β―
（アミノエチル）γ―アミノプロピルメトキシシ
ラン、ｎ―β（アミノエチル）γ―アミノプロピ
ルメチルジメトキシシラン、ｎ―フエニルγ―ア
ミノプロピルトリメトキシシラン、γ―アミノプ
ロピルトリメトキシシラン等である。
本発明が用いられる主な用途としては、各種半
導体素子の表面を保護するコート用塗膜として、
又その上に多層配線を行う耐熱耐湿絶縁膜として
用いられる。例えば半導体、トランジスター、リ
ニアーIC、ハイブリツドIC、発光ダイオード、
LSI、超LSI等の電子回路用配線構造体である。
その他の用途として半導体素子表面のα線等の放
射線の防止用として用いられる。更には半導体素
子以外の用途として液晶の配向膜や太陽電池の内
部材料としても有用である。
以下実施例で本発明を説明する。
実施例 １
温度計、撹拌機、及び乾燥窒素ガス吹込口を備
えた４ツ口フラスコに精製した無水のパラフエニ
レンジアミン0.9モル及び４，4′―ジアミノジフ
エニルエーテル0.1モルを仕込み、これに無水の
Ｎ，N′―ジメチルアセトアミド95％と無水のジ
アセトンアルコール５％の混合溶剤を、全仕込み
原料中の固形分割合が15％になるだけの量を加え
て溶解させた。次いで精製した無水のピロメリツ
ト酸ジ無水物0.9モル及び無水のベンゾフエノン
テトラカルボン酸ジ無水物0.1モルを、撹拌下に
少量ずつ添加し、その間15℃の冷水を循環させて
急激な発熱反応を外部より冷却した。添加後フラ
スコ内部温度を20℃に設定し、乾燥窒素ガスを流
入させながら、10時間撹拌を続けて反応を進め
た。反応終了後、一部を大量の水中へ投入させて
ポリアミツク酸を沈殿させ、ろ過後１mmＨｇで16
時間減圧乾燥した。生成物0.5ｇをＮ―メチル―
２―ピロリドン100mlに溶解し、ウベローゼ型毛
細管粘度計で温度30℃にて固有粘度を測定した結
果1.5であつた。反応生成物の残りをＮ―メチル
―２―ピロリドンで10％濃度になる様に希釈し
て、ワイヤーボンデイングされたIC素子上にド
ロツピング法により滴下した。これを乾燥器中で
150℃、250℃、350℃で各１時間ずつ加熱して、
厚み10μのポリイミド皮膜を作成した。この素子
をセラミツクのフタで気密封止（ハーメチツク封
止）した。封止時の温度は500℃である。IC上の
皮膜の性能を第１表に示す。
熱分解開始温度は563℃と非常に高いものであ
つた。又分解ガス発生量（480℃、１時間加熱）
は2ppmとほぼゼロに近いものである。
そのためハートチツク封止品の内部ガスを調べ
た所、ガス量はほとんどなく充分な気密封止が保
たれている事がわかつた。このICの高温、高湿
バイアス試験（85℃、85％RH、10V印加）では
2000hrでも不良は全く発生しなかつた。
比較例 １
実施例１の耐熱性樹脂の代りに市販のポリイミ
ド樹脂pyre―ML（デユポン社製）を使用し、実
施例１と同様な方法でハーメチツク封止品を作成
した。この皮膜の性能を第１表に示す。
熱分解開始温度は450℃であり、そのためハー
メチツク封止時の温度（500℃）で分解ガスが発
生し、封止品の内部に多量のガスがたまつてい
た。このICの信頼性試験（85℃、85％RH、10V
印加）では200hrsでICのアルミニウム電極が腐食
し実用性がなかつた。
比較例 ２
実施例１で反応を１時間で中止し、反応終了後
大量の水中へ投入して、反応生成物を沈殿させろ
過減圧乾燥した。得られたポリアミツク酸の固有
粘度は0.3であつた。実施例１と同様な方法で、
ハーメチツク封止品を作成した所、皮膜にクラツ
クが発生し非常にもろかつた。
比較例 ３
実施例１で反応温度を10℃に保ちながら、25時
間撹拌を行ない反応を進めた。得られたポリアミ
ツク酸の固有粘度は3.5であつた。実施例１と同
様な方法でハーメチツク封止品を作成した。第１
表に示したようにこの皮膜の熱分解開始温度は
460℃であるため、封止時に分解ガスが発生し、
ICの信頼性試験（85℃、85％RH，10V加電）で
は300hrsでIC上のアルミニウム電極のシヨートが
発生した。
実施例 ２
実施例１と同じ装置でジアミンとしてパラフエ
ニレンジアミン0.7モル及び４，4′―ジアミノジ
フエニルエーテル0.3モルをＮ―メチル―２―ピ
ロリドンに溶解させ、これにピロメリツト酸ジ無
水物0.9モル及びベンゾフエノンテトラカルボン
酸ジ無水物0.1モルをＮ―メチル―２―ピロリド
ンに溶解させた溶液を撹拌下に乾燥窒素を流入さ
せながら１時間かけて滴下した。溶液中の固形分
濃度が10％になるようにＮ，N′―ジメチルアセ
トアミドを添加し、溶液温度を20℃に保持しなが
ら16時間反応を進めた。得られたポリアミツク酸
の固有粘度は2.0であつた。この生成物をトルエ
ンで５％濃度になるように希釈し、スピンナーを
用いて、アルミニウム電極をつけたシリコントラ
ンジスター表面に厚み2μに塗布した。乾燥器中
で100℃、１時間更に250℃で30分熱処理した後、
ヒドラジン系エツチング液でアルミニウム電極の
上の皮膜をエツチングし開口する。エツチング後
400℃で30分熱処理しその上にアルミニウムを蒸
着して２層構造を持つトランジスターを作成し
た。更に電極をアニール（500℃、30分）して、
トランジスターの電流変化を調べた所＋0.1％と
ほとんど変化しなかつた。同様な方法で比較例１
のpyreML（デユポン社製）を使用するとアニー
ル後の電流変化は−55％と低減した。
比較例 ４
実施例２で酸無水物としてピロメリツト酸ジ無
水物1.0モルを使用する他は同様にして反応させ、
固有粘度1.5のポリアミツク酸を得た。これを実
施例２と同様な方法で、シリコントランジスター
上に塗布したが、エツチング後400℃、30分で熱
処理すると皮膜にクラツクが発生した。
比較例 ５
実施例２で酸無水物としてピロメリツト酸ジ無
水物0.7モル及びベンゾフエノンテトラカルボン
酸ジ無水物を使用する他は同様にして反応させ、
固有粘度1.5のポリアミツク酸を得た。これを実
施例２と同様な方法で、２層構造を持つトランジ
スターを作成した。皮膜の特性を第１表に示す。
熱分解開始温度は452℃であるため、トランジス
ターのアルミニウム電極をアニール（500℃、30
分）した所、電流変化は−65％と低下してしまつ
た。
実施例 ３
実施例１と同じ装置にピロメリツト酸ジ無水物
0.8モル及びベンゾフエノンテトラカルボン酸ジ
無水物0.2モルをジメチルホルムアミドに溶解さ
せ、乾燥窒素を流入させ撹拌させながら、パラフ
エニレンジアミン0.7モル及び４，4′―ジアミノ
ジフエニルエーテル0.3モルを添加した。溶液中
の固形分濃度が15％になるようにＮ，N′―ジメ
チルアセトアミドを添加し、更に20℃で20時間反
応を続けた。得られたポリアミツク酸の固有粘度
は1.0であつた。
この生成物を超LSI（64Kビツト）の半導体素子
回路が形成されたシリコンウエハー上にスピンナ
ーで回転塗布し、乾燥器中で100℃、200℃で各１
時間加熱し、ウエハー全面にポリイミド皮膜を厚
み60μ形成させた。次いでネガレジストを塗布し
乾燥後露光、現像し、ヒドラジン系エツチング液
でボンデイングパツト部上の皮膜をエツチング除
去した。ネガレジスト除去後400℃で１時間熱処
理しシリコンウエハーをスクライブしてそれぞれ
５mm角のチツプに切断した。この半導体素子をセ
ラミツクス基板にマウントし金線ワイヤでボンデ
イングした後、セラミツクのフタでガラスシール
した。シール温度は500℃である。素子上の皮膜
の特性を第１表に示す。熱分解開始温度は540℃
と非常に高く、又分解ガス発生量（480℃、１時
間加熱）は5ppmと少なかつた。そのためハーメ
チツク封止内の気密性が良く、高温、高湿の信頼
性試験（85℃、85％RH、10V印加）で2000hrs以
上不良が発生しなかつた。又α線による誤動作も
全くなかつた。同様な方法で比較例１に用いた
pyreML（デユポン社製）を使用すると、封止素
子は高温、高湿バイアス試験で300hrsで回路の断
線不良が生じた。
比較例 ６
実施例３でジアミンとしてパラフエニレンジア
ミン１モルを使用する以外は全く同様にして固有
粘度1.5のポリアミツク酸を得た。これを実施例
３と同様な方法でシリコンウエハー上に塗布した
が、皮膜のエツチング後にクラツクが発生しはが
れてしまつた。
比較例 ７
実施例３でジアミンとしてパラフエニレンジア
ミン0.5モル及び４，4′―ジアミノジフエニルエ
ーテル0.5モルを使用して、固有粘度1.5のポリア
ミツク酸を得た。この生成物を使用して実施例３
と同様な方法で超LSIのセラミツク封止品を作成
した。この皮膜の特性を第１表に示す。熱分解開
始温度は462℃であり、封止素子は高温、高湿バ
イアス試験で400hrsでアルミ回路の腐食によるシ
ヨートが発生した。
実施例 ４
実施例１で酸無水物として２，３，６，７―ナ
フタレンテトラカルボン酸ジ無水物0.9モル及び
ベンゾフエノンテトラカルボン酸ジ無水物0.1モ
ルを使用する他は同様に反応させ、固有粘度1.5
のポリアミツク酸を得た。これを実施例１と同様
にICの表面保護膜とし用いセラミツク封止した
所、信頼性試験、高温、高湿、バイアス試験で
2000hrs以上不良が発生しなかつた。
実施例 ５
実施例２でジアミンとしてｍ―フエニレンジア
ミン0.9モル及び４，4′―ジアミノジフエニルエ
ーテル0.2モルを使用する他は同様に反応させ、
固有粘度1.3のポリアミツク酸を得た。実施例２
と同様な方法で、トランジスターの２層構造を作
成し500℃、30分のアニールを行つたが、電流変
化は−0.2％と少なかつた。
実施例 ６
実施例３でジアミンとしてジアミノナフタレン
0.8モル及び４，4′―ジアミノジフエニルエーテ
ル0.2モルを使用する他は同様に反応させ、固有
粘度1.7のポリアミツク酸を得た。実施例３と同
様に超LSIの保護膜として使用しセラミツク封止
したが、高温、高湿、バイアス試験で2000hrs以
上不良が全く発生せず、α線によるソフトエラー
も全くなかつた。Formulas such as [Formula] are effective, and among these, 4,4'-diaminodiphenyl ether is particularly excellent. The higher the proportion of diamine (D) in the diamine component in the resin, the better the rigidity will be, but the target thermal decomposition initiation temperature will be lower.
(D) must be 40 mol% or less. The solvent of the reaction system in the present invention is an organic polar solvent whose functional group has a dipole moment that does not react with the tetracarboxylic dianhydride or diamines. In addition to being inert to the system and solvent to the product, the organic polar solvent must be solvent to at least one, preferably both, of the reaction components. Typical solvents of this type are N,N'-dimethylformamide, N,N-dimethylacetamide, N,N-
Diethylformamide, N,N-diethylacetamide, N,N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphamide, N-methyl-2-pyrrolidone, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetramethylenesulfone, etc. Yes, these solvents may be used alone or in combination. In addition, non-solvents such as benzene, benzonitrile, dioxane, butyrolactone, xylene, toluene, and cyclohexane are used in combination as solvents, and can be used as dispersion media for raw materials, reaction regulators, or to control the volatilization of solvents from products. It is used as a coating agent, film smoothing agent, etc. It is generally preferred that the present invention be carried out under anhydrous conditions. This is because the tetracarboxylic dianhydride is ring-opened by water, becomes inactive, and there is a risk of stopping the reaction. For this reason, it is necessary to remove both the moisture in the raw materials and the moisture in the solvent. However, in order to adjust the progress of the reaction and control the degree of resin polymerization, water is sometimes intentionally added. Further, the present invention is preferably carried out in an inert gas atmosphere. This is to prevent oxidation of diamines. Dry nitrogen gas is generally used as the inert gas. The reaction of the heat-resistant resin in the present invention can be carried out in the following various ways. Diamines and tetracarboxylic dianhydride are mixed in advance, and the mixture is added little by little to an organic solvent with stirring. This method is relatively advantageous in exothermic reactions such as those for polyimide resins. Conversely, there is also a method of adding a solvent to a mixture of diamines and tetracarboxylic dianhydride while stirring. A commonly used method is to dissolve only diamines in a solvent and add tetracarboxylic dianhydride to this in a proportion that allows the reaction rate to be controlled. It is also possible to dissolve diamines and tetracarboxylic dianhydride separately in a solvent and slowly add the two solutions in a reactor. Furthermore, it is also possible to prepare in advance a polyamic acid product containing an excess of diamines and a polyamic acid product containing an excess of tetracarboxylic dianhydride, and then further react them in a reactor. The reaction temperature is preferably 0 to 100°C. This is because if the temperature is below 0°C, the reaction rate is slow, and if it is above 100°C, the produced polyamic acid gradually starts the ring-closing reaction. Usually, the reaction is carried out at around 20℃,
Cooling is required as it is an exothermic reaction. The degree of polymerization of polyamic acid can be controlled in a planned manner. The closer the moles of tetracarboxylic dianhydride and diamine are to equimolar, the higher the degree of polymerization becomes. When the amount of either raw material increases by 5% or more, the degree of polymerization decreases significantly. Usually, using 1 to 3% more of one raw material is
This is often done for workability and processability. In order to control the degree of polymerization, it is also possible to end-block with phthalic anhydride or aniline, or add water to ring-open one of the acid anhydride groups to inactivate it. The polyamic acid product according to the invention preferably has an intrinsic viscosity of 0.5 to 2.5. If it is lower than 0.5, it is good for improving the thermal decomposition start temperature, but the thermal decomposition temperature becomes low and the film forming property also decreases. If it is higher than 2.5, the film forming property will be excellent, but the temperature at which thermal decomposition starts will be lowered. When used, the polyamic acid product produced by the method of the present invention has the adhesion and adhesion properties of various silane coupling agents, borane coupling agents, titanate coupling agents, aluminum coupling agents, and other chelate coupling agents. Improvers, various solvents, and flow agents may be added, and in addition to these, ordinary acid curing agents, amine curing agents,
Small amounts of polyamide curing agents and curing accelerators such as imidazole and tertiary amines may be added, as well as flexibility agents and viscosity modifiers such as polysulfides, polyesters, low molecular weight epoxies, talc, clay, etc.
Fillers such as mica, feldspar powder, quartz powder, magnesium oxide, coloring agents such as carbon black and ferrocyanine blue, flame retardants such as tetrabromophenylmethane and tributyl phosphate, antimony trioxide, barium metaphoate, etc. Small amounts of flame retardant aids may also be added, and their addition opens up many applications. The method for manufacturing semiconductor devices using this heat-resistant resin is to dissolve the resin composition in a solvent, mix it uniformly, make a concentration of 5 to 55%, and then wire the resin composition on the semiconductor substrate or insulator substrate. Cast on the surface of the conductor layer, thickness 0.1~
The resin film is coated to a uniform thickness of 500 μm, and then dried in a dryer at a temperature of 50 to 500° C. in two or more steps, if necessary, for 5 minutes to 30 hours to form a resin film. As a device for casting the resin, a wheeler, a spinner, a roll coater, a doctor blade, a gisa, a flow coater, etc. are used. For drying, electric heat, infrared rays, steam, high frequency, a combination thereof, etc. are used. A polyimide resin film formed on a semiconductor element may be partially etched depending on the method of use. The main reason is the opening in the bonding pad or the conduction between layers of multilayer wiring.
Typical etching methods include ashing with plasma in the case of a dry method, and use of a strong alkali such as hydrazine or tetramethylammonium hydroxide as an etching solution in the case of a wet method. In the method of the present invention, in order to further improve the adhesion between the resin coating film and the substrate, it is more effective to undercoat the substrate with a surface treatment agent. It is particularly effective for silicone substrates and circuit boards with gold plating, which usually have poor adhesion. It is effective to use ordinary silane coupling agents and borane coupling agents as surface treatment agents, but silane coupling agents are particularly effective for coating films obtained from the resin used in the present invention. Silane coupling agents include vinyl silane, amino silane, and epoxy silane, but when amino silane is interposed between the coating film made of the resin used in the present invention and the silicone substrate, it causes a significant additive effect, which is noticeable. Improves adhesion. As an aminosilane coupling agent, n-β-
(aminoethyl)γ-aminopropylmethoxysilane, n-β(aminoethyl)γ-aminopropylmethyldimethoxysilane, n-phenylγ-aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and the like. The main uses of the present invention are as a coating film to protect the surfaces of various semiconductor devices,
It is also used as a heat-resistant and moisture-resistant insulating film on which multilayer wiring is formed. For example, semiconductors, transistors, linear ICs, hybrid ICs, light emitting diodes,
This is a wiring structure for electronic circuits such as LSI and VLSI.
Other uses include preventing radiation such as alpha rays on the surface of semiconductor devices. Furthermore, it is useful as an alignment film for liquid crystals and as an internal material for solar cells in applications other than semiconductor devices. The present invention will be explained below with reference to Examples. Example 1 0.9 mole of purified anhydrous paraphenylene diamine and 0.1 mole of 4,4'-diaminodiphenyl ether were charged into a four-necked flask equipped with a thermometer, a stirrer, and a dry nitrogen gas inlet, and the A mixed solvent of 95% anhydrous N,N'-dimethylacetamide and 5% anhydrous diacetone alcohol was added in an amount sufficient to make the solid content of the total raw materials 15%. Next, 0.9 mol of purified anhydrous pyromellitic dianhydride and 0.1 mol of anhydrous benzophenonetetracarboxylic dianhydride were added little by little with stirring, while cold water at 15°C was circulated to cause a rapid exothermic reaction. Cooled from the outside. After the addition, the internal temperature of the flask was set at 20°C, and while dry nitrogen gas was introduced, stirring was continued for 10 hours to advance the reaction. After the reaction, a portion was poured into a large amount of water to precipitate polyamic acid, and after filtration, it was heated at 1 mmHg at 16
Dry under reduced pressure for an hour. 0.5g of the product was converted into N-methyl-
It was dissolved in 100 ml of 2-pyrrolidone, and the intrinsic viscosity was measured at 30°C using an Uberose capillary viscometer and found to be 1.5. The remainder of the reaction product was diluted with N-methyl-2-pyrrolidone to a concentration of 10% and dropped onto the wire-bonded IC element by a dropping method. Put this in the dryer
Heat at 150℃, 250℃, and 350℃ for 1 hour each.
A polyimide film with a thickness of 10μ was created. This element was hermetically sealed with a ceramic lid. The temperature during sealing is 500°C. The performance of the film on the IC is shown in Table 1. The thermal decomposition onset temperature was extremely high at 563°C. Also, amount of cracked gas generated (heated at 480℃ for 1 hour)
is 2ppm, which is almost zero. Therefore, when we investigated the internal gas of the Hartchick-sealed product, we found that there was very little gas and that a sufficient airtight seal was maintained. In the high temperature, high humidity bias test (85℃, 85%RH, 10V applied) of this IC,
No defects occurred even after 2000 hours. Comparative Example 1 A hermetically sealed product was produced in the same manner as in Example 1, using commercially available polyimide resin Pyre-ML (manufactured by DuPont) in place of the heat-resistant resin in Example 1. The performance of this film is shown in Table 1. The temperature at which thermal decomposition begins is 450°C, so decomposition gas was generated at the hermetically sealed temperature (500°C), and a large amount of gas accumulated inside the sealed product. Reliability test of this IC (85℃, 85%RH, 10V
(applied voltage), the aluminum electrodes of the IC corroded after 200 hours, making it impractical. Comparative Example 2 In Example 1, the reaction was stopped after 1 hour, and after the reaction was completed, it was poured into a large amount of water to precipitate the reaction product, which was then filtered and dried under reduced pressure. The intrinsic viscosity of the obtained polyamic acid was 0.3. In the same manner as in Example 1,
When a hermetically sealed product was created, cracks occurred in the film and it was extremely brittle. Comparative Example 3 As in Example 1, the reaction was continued by stirring for 25 hours while maintaining the reaction temperature at 10°C. The intrinsic viscosity of the obtained polyamic acid was 3.5. A hermetically sealed product was produced in the same manner as in Example 1. 1st
As shown in the table, the starting temperature of thermal decomposition of this film is
Since the temperature is 460℃, decomposition gas is generated during sealing.
In an IC reliability test (85°C, 85% RH, 10V applied), shorting of the aluminum electrode on the IC occurred in 300 hours. Example 2 Using the same equipment as in Example 1, 0.7 mol of paraphenylene diamine and 0.3 mol of 4,4'-diaminodiphenyl ether as diamines were dissolved in N-methyl-2-pyrrolidone, and 0.9 mol of pyromellitic dianhydride was dissolved therein. A solution prepared by dissolving 0.1 mole of benzophenonetetracarboxylic dianhydride in N-methyl-2-pyrrolidone was added dropwise over 1 hour while stirring and flowing dry nitrogen. N,N'-dimethylacetamide was added so that the solid concentration in the solution was 10%, and the reaction was allowed to proceed for 16 hours while maintaining the solution temperature at 20°C. The intrinsic viscosity of the obtained polyamic acid was 2.0. This product was diluted with toluene to a concentration of 5%, and applied using a spinner to a thickness of 2 μm on the surface of a silicon transistor equipped with an aluminum electrode. After heat treatment at 100℃ for 1 hour in a dryer and 30 minutes at 250℃,
Etch the film on the aluminum electrode with a hydrazine-based etching solution to open it. After etching
After heat treatment at 400℃ for 30 minutes, aluminum was deposited on top of the heat treatment to create a transistor with a two-layer structure. Furthermore, the electrode was annealed (500℃, 30 minutes),
When I investigated the change in the transistor current, I found that there was almost no change at +0.1%. Comparative example 1 in the same way
When using pyreML (manufactured by DuPont), the current change after annealing was reduced to -55%. Comparative Example 4 The reaction was carried out in the same manner as in Example 2 except that 1.0 mol of pyromellitic dianhydride was used as the acid anhydride.
Polyamic acid with an intrinsic viscosity of 1.5 was obtained. This was coated on a silicon transistor in the same manner as in Example 2, but cracks occurred in the film when heat treated at 400°C for 30 minutes after etching. Comparative Example 5 The reaction was carried out in the same manner as in Example 2 except that 0.7 mol of pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride were used as the acid anhydrides.
Polyamic acid with an intrinsic viscosity of 1.5 was obtained. A transistor having a two-layer structure was produced using the same method as in Example 2. The properties of the film are shown in Table 1.
Since the starting temperature of thermal decomposition is 452°C, the aluminum electrode of the transistor is annealed (500°C, 30°C).
minutes), the current change decreased to -65%. Example 3 Pyromellitic dianhydride was added to the same apparatus as in Example 1.
Dissolve 0.8 mol and 0.2 mol of benzophenone tetracarboxylic dianhydride in dimethylformamide, and add 0.7 mol of paraphenylene diamine and 0.3 mol of 4,4'-diaminodiphenyl ether while stirring with flowing dry nitrogen. did. N,N'-dimethylacetamide was added so that the solid concentration in the solution was 15%, and the reaction was further continued at 20°C for 20 hours. The intrinsic viscosity of the obtained polyamic acid was 1.0. This product was spin-coated using a spinner onto a silicon wafer on which a VLSI (64K bit) semiconductor element circuit was formed, and then heated in a dryer at 100°C and 200°C for one coat each.
The wafer was heated for a period of time to form a polyimide film with a thickness of 60 μm over the entire surface of the wafer. Next, a negative resist was applied, dried, exposed and developed, and the film on the bonding pad was etched away using a hydrazine etching solution. After removing the negative resist, the silicon wafers were heat-treated at 400° C. for 1 hour and cut into 5 mm square chips by scribing the silicon wafers. This semiconductor element was mounted on a ceramic substrate, bonded with gold wire, and then sealed with a glass lid using a ceramic lid. The sealing temperature is 500℃. Table 1 shows the properties of the film on the device. Thermal decomposition starting temperature is 540℃
The amount of cracked gas generated (heated at 480°C for 1 hour) was as low as 5 ppm. Therefore, the airtightness within the hermetic seal is good, and no defects occurred for more than 2000 hours in a high temperature, high humidity reliability test (85°C, 85% RH, 10V applied). Furthermore, there were no malfunctions caused by alpha rays. Used in Comparative Example 1 in the same manner.
When using pyreML (manufactured by Dupont), the sealing element failed in a high temperature, high humidity bias test after 300 hours. Comparative Example 6 A polyamic acid having an intrinsic viscosity of 1.5 was obtained in exactly the same manner as in Example 3 except that 1 mol of paraphenylene diamine was used as the diamine. This was coated on a silicon wafer in the same manner as in Example 3, but cracks occurred after the film was etched and it peeled off. Comparative Example 7 Using 0.5 mol of paraphenylene diamine and 0.5 mol of 4,4'-diaminodiphenyl ether as the diamine in Example 3, polyamic acid having an intrinsic viscosity of 1.5 was obtained. Example 3 using this product
A ceramic-encapsulated VLSI product was created using the same method as described above. The properties of this film are shown in Table 1. The thermal decomposition onset temperature was 462°C, and the sealing element experienced shoots due to corrosion of the aluminum circuit after 400 hours in a high-temperature, high-humidity bias test. Example 4 A reaction was carried out in the same manner as in Example 1 except that 0.9 mol of 2,3,6,7-naphthalenetetracarboxylic dianhydride and 0.1 mol of benzophenonetetracarboxylic dianhydride were used as acid anhydrides. Intrinsic viscosity 1.5
of polyamic acid was obtained. This was used as a surface protection film for an IC in the same manner as in Example 1, and sealed in ceramic.
No defects occurred for more than 2000hrs. Example 5 A reaction was carried out in the same manner as in Example 2 except that 0.9 mol of m-phenylenediamine and 0.2 mol of 4,4'-diaminodiphenyl ether were used as the diamine.
Polyamic acid with an intrinsic viscosity of 1.3 was obtained. Example 2
Using the same method as above, we created a two-layer transistor structure and annealed it at 500°C for 30 minutes, but the current change was as small as -0.2%. Example 6 Diaminonaphthalene as diamine in Example 3
Polyamic acid having an intrinsic viscosity of 1.7 was obtained by carrying out the same reaction except that 0.8 mol and 0.2 mol of 4,4'-diaminodiphenyl ether were used. As in Example 3, it was used as a protective film for a VLSI and sealed in ceramic, but no defects occurred for more than 2000 hours in high temperature, high humidity, and bias tests, and there were no soft errors caused by alpha rays.
【表】【table】
【表】
実施例及び比較例の皮膜の性能を第１表にまと
めて示した。これから明らかなように本発明で使
用する耐熱性ポリイミド樹脂は熱分解開始温度が
480℃以上と高く、皮膜形成性等も良好である。
又480℃、１時間と高温で処理した場合の分解ガ
ス発生量も10ppm以下と少なく、耐電圧の劣化も
少ないという従来にない特長を有している。
本発明に使用する樹脂の固有粘度は0.5〜2.5の
範囲内で必要で0.5以下であると硬化物がもろく
なり皮膜形成時にクラツクが発生する（比較例
２）。又固有粘度が2.5以上になると、硬化物の熱
分解開始温度が低下してしまう（比較例３）。
本発明に使用する樹脂の酸無水物成分の内ベン
ゾフエノンテトラカルボン酸ジ無水物は１〜20モ
ル％が必要であり、１モル％以下にすると硬化皮
膜がもろくなり実用性がない（比較例４）。又20
モル％以上使用すると熱分解開始温度が低下し
480℃以上のものは得られない（比較例５）。
本発明に使用する樹脂のジアミン成分の内４，
4′―ジアミノジフエニルエーテルは１〜40モル％
の範囲が必要である。１モル％以下にすると硬化
皮膜はもろくなり（比較例６）、40モル％以上使
用すると熱分解開始温度が480℃以下になつてし
まう（比較例７）。
以上述べた如く、本発明で使用する耐熱性樹脂
皮膜は従来のポリイミド樹脂の優れた特性を維持
したまま、更に熱分解開始温度を480℃以上に向
上させた事を特徴とするものであり、これを半導
体素子表面の保護膜として使用した場合、セラミ
ツク封止時やアルミニウム電極のアニール時の高
温処理による皮膜の特性劣化や分解発生ガスがほ
とんどないため、素子の信頼性は従来より大巾に
向上させる事ができる。[Table] Table 1 summarizes the performance of the films of Examples and Comparative Examples. As is clear from this, the heat-resistant polyimide resin used in the present invention has a thermal decomposition initiation temperature.
It has a high temperature of 480℃ or higher, and has good film-forming properties.
Furthermore, when treated at high temperatures of 480°C for 1 hour, the amount of decomposed gas generated is as low as 10 ppm or less, and the withstand voltage deteriorates little, which is an unprecedented feature. The intrinsic viscosity of the resin used in the present invention must be within the range of 0.5 to 2.5; if it is less than 0.5, the cured product becomes brittle and cracks occur during film formation (Comparative Example 2). Moreover, when the intrinsic viscosity is 2.5 or more, the thermal decomposition initiation temperature of the cured product decreases (Comparative Example 3). Among the acid anhydride components of the resin used in the present invention, benzophenonetetracarboxylic dianhydride must be present in an amount of 1 to 20 mol%; if it is less than 1 mol%, the cured film becomes brittle and is not practical (comparison). Example 4). 20 again
If more than mol% is used, the temperature at which thermal decomposition starts will decrease.
A temperature higher than 480°C cannot be obtained (Comparative Example 5). Of the diamine components of the resin used in the present invention, 4
4′-diaminodiphenyl ether is 1 to 40 mol%
A range of is required. When the amount is less than 1 mol %, the cured film becomes brittle (Comparative Example 6), and when it is used more than 40 mol %, the thermal decomposition initiation temperature becomes 480° C. or less (Comparative Example 7). As mentioned above, the heat-resistant resin film used in the present invention is characterized by an improved thermal decomposition initiation temperature of 480°C or higher while maintaining the excellent properties of conventional polyimide resins. When this film is used as a protective film on the surface of a semiconductor element, there is almost no deterioration of film properties or decomposition gases caused by high-temperature treatment during ceramic sealing or annealing aluminum electrodes, making the element much more reliable than before. It can be improved.
Claims (1)
モル％および 一般式 （X1は―CO―，―Ｏ―，―SO2―，―Ｓ―，
―CH2―，【式】【式】） で表わされるテトラカルボン酸ジ無水物(B)１〜20
モル％とからなるテトラカルボン酸ジ無水物と 一般式 H2N―R2―NH2 （R2 はベンゼン環、縮合ベンゼン環） で表わされるジアミン(C)99〜60モル％および 一般式 （X2は―CO―，―Ｏ―，―SO2―，―Ｓ―，
―CH2―，【式】【式】） で表わされるジアミン(D)１〜40モル％とからなる
ジアミンとを、無水の条件下に、不活性ガス雰囲
気中、有機極性溶媒中で、０〜100℃で反応させ
たポリアミツク酸生成物の固有粘度が0.5〜2.5で
イミド化後の硬化物の熱分解開始温度が480〜580
℃の耐熱性樹脂を半導体素子表面に塗布し、加熱
硬化して半導体素子表面に被着することを特徴と
する半導体装置の製造方法。 ２ (A)がピロメリツト酸ジ無水物であり(B)がベン
ゾフエノンテトラカルボン酸ジ無水物である特許
請求の範囲第１項記載の耐熱性樹脂を半導体素子
表面に塗布し、加熱硬化して半導体素子表面に被
着することを特徴とする半導体装置の製造方法。 ３ (C)がパラフエニレンジアミンであり(D)が４，
4′―ジアミノジフエニルエーテルである特許請求
の範囲第１項又は第２項記載の耐熱性樹脂を半導
体素子表面に塗布し、加熱硬化して半導体素子表
面に被着することを特徴とする半導体装置の製造
方法。[Claims] 1. General formula (R 1 is benzene ring, fused benzene ring) Tetracarboxylic dianhydride (A)99-80
Mol% and general formula (X 1 is -CO-, -O-, -SO 2 -, -S-,
-CH 2 -, [Formula] [Formula]) Tetracarboxylic dianhydride (B) 1 to 20
Tetracarboxylic acid dianhydride consisting of mol% and diamine (C) 99 to 60 mol% represented by the general formula H 2 N—R 2 —NH 2 ( R 2 is a benzene ring or fused benzene ring) and the general formula (X 2 is -CO-, -O-, -SO 2 -, -S-,
—CH 2 —, [Formula] [Formula]) A diamine (D) represented by 1 to 40 mol% is added under anhydrous conditions in an inert gas atmosphere in an organic polar solvent to 0. The intrinsic viscosity of the polyamic acid product reacted at ~100℃ is 0.5~2.5, and the thermal decomposition onset temperature of the cured product after imidization is 480~580℃.
1. A method for manufacturing a semiconductor device, which comprises applying a heat-resistant resin at a temperature of 0.degree. 2. The heat-resistant resin according to claim 1, in which (A) is pyromellitic dianhydride and (B) is benzophenonetetracarboxylic dianhydride, is applied to the surface of a semiconductor element and cured by heating. 1. A method for manufacturing a semiconductor device, characterized in that the method of manufacturing a semiconductor device comprises depositing the same on the surface of a semiconductor element. 3 (C) is paraphenylenediamine and (D) is 4,
A semiconductor characterized in that the heat-resistant resin according to claim 1 or 2, which is 4'-diaminodiphenyl ether, is applied to the surface of a semiconductor element, and is cured by heating to adhere to the surface of the semiconductor element. Method of manufacturing the device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032610A JPS60177659A (en) | 1984-02-24 | 1984-02-24 | Manufacture of semiconductor device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59032610A JPS60177659A (en) | 1984-02-24 | 1984-02-24 | Manufacture of semiconductor device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60177659A JPS60177659A (en) | 1985-09-11 |
| JPH0122308B2 true JPH0122308B2 (en) | 1989-04-26 |
Family
ID=12363621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59032610A Granted JPS60177659A (en) | 1984-02-24 | 1984-02-24 | Manufacture of semiconductor device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60177659A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2811066B2 (en) * | 1985-12-28 | 1998-10-15 | 宇部興産株式会社 | Preparation of dope solution for polyimide film production |
| FR2620453B1 (en) * | 1987-09-14 | 1993-08-13 | Gen Electric | POLYETHERIMIDE PRECURSOR COMPOSITION, POLYETHERIMIDE AND METHODS FOR THEIR PREPARATION |
| US5196500A (en) * | 1990-12-17 | 1993-03-23 | E. I. Du Pont De Nemours And Company | Tetrapolyimide film containing benzophenone tetracarboxylic dianhydride |
| JPH06334204A (en) * | 1993-05-21 | 1994-12-02 | Ind Technol Res Inst | Preparation of flexible amorphous silicon solar cell |
| JP4642664B2 (en) * | 2006-01-17 | 2011-03-02 | 新日鐵化学株式会社 | Laminate for wiring board |
| JP6733220B2 (en) * | 2016-03-03 | 2020-07-29 | 日立化成デュポンマイクロシステムズ株式会社 | Resin composition and polyimide resin film |
-
1984
- 1984-02-24 JP JP59032610A patent/JPS60177659A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60177659A (en) | 1985-09-11 |
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