KR100508900B1 - Organic silicate polymer and insulation film comprising the same - Google Patents
Organic silicate polymer and insulation film comprising the same Download PDFInfo
- Publication number
- KR100508900B1 KR100508900B1 KR10-2002-0021140A KR20020021140A KR100508900B1 KR 100508900 B1 KR100508900 B1 KR 100508900B1 KR 20020021140 A KR20020021140 A KR 20020021140A KR 100508900 B1 KR100508900 B1 KR 100508900B1
- Authority
- KR
- South Korea
- Prior art keywords
- formula
- carbon atoms
- fluorine
- straight
- insulating film
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 40
- 238000009413 insulation Methods 0.000 title abstract description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title description 8
- 238000000034 method Methods 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 claims abstract description 26
- 229910000077 silane Inorganic materials 0.000 claims abstract description 24
- -1 silane compound Chemical class 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 21
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000011737 fluorine Substances 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 8
- 150000002221 fluorine Chemical class 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 239000008119 colloidal silica Substances 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000000412 dendrimer Substances 0.000 claims description 3
- 229920000736 dendritic polymer Polymers 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 8
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical group [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 claims 2
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 35
- 150000001875 compounds Chemical class 0.000 abstract description 21
- 238000000576 coating method Methods 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000006482 condensation reaction Methods 0.000 abstract description 11
- 239000011229 interlayer Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 4
- 239000010408 film Substances 0.000 description 73
- 238000006243 chemical reaction Methods 0.000 description 33
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- 239000012153 distilled water Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000003377 acid catalyst Substances 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 239000002274 desiccant Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N Valeric acid Natural products CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropyl acetate Chemical compound CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N propyl acetate Chemical compound CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- PVMMVWNXKOSPRB-UHFFFAOYSA-N 1,2-dipropoxypropane Chemical compound CCCOCC(C)OCCC PVMMVWNXKOSPRB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- DMFAHCVITRDZQB-UHFFFAOYSA-N 1-propoxypropan-2-yl acetate Chemical compound CCCOCC(C)OC(C)=O DMFAHCVITRDZQB-UHFFFAOYSA-N 0.000 description 1
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- XWERKWVETTXNQX-UHFFFAOYSA-N 2,3-dimethyl-1,4-dioxine Chemical compound CC1=C(C)OC=CO1 XWERKWVETTXNQX-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OPFTUNCRGUEPRZ-QLFBSQMISA-N Cyclohexane Natural products CC(=C)[C@@H]1CC[C@@](C)(C=C)[C@H](C(C)=C)C1 OPFTUNCRGUEPRZ-QLFBSQMISA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- QQQCWVDPMPFUGF-ZDUSSCGKSA-N alpinetin Chemical compound C1([C@H]2OC=3C=C(O)C=C(C=3C(=O)C2)OC)=CC=CC=C1 QQQCWVDPMPFUGF-ZDUSSCGKSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229960004050 aminobenzoic acid Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- IFDFMWBBLAUYIW-UHFFFAOYSA-N ethane-1,2-diol;ethyl acetate Chemical compound OCCO.CCOC(C)=O IFDFMWBBLAUYIW-UHFFFAOYSA-N 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N iso-pentane Natural products CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- ZIYVHBGGAOATLY-UHFFFAOYSA-N methylmalonic acid Chemical compound OC(=O)C(C)C(O)=O ZIYVHBGGAOATLY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N n-hexanoic acid Natural products CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
Landscapes
- Chemical & Material Sciences (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Power Engineering (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Formation Of Insulating Films (AREA)
- Silicon Polymers (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
본 발명은 기계적 특성과 저유전 특성이 우수한 유기실리케이트 중합체에 관한 것으로, 특히 하이드로 실란화합물을 물 또는 알코올 존재하에서 산화반응시키는 단계, 및 산화된 하이드로 실란화합물을 단독으로 가수분해 및 축합반응시키거나, 실란화합물 또는 실란 올리고머과의 가수분해 및 축합반응시키는 단계를 포함하는 유기실리케이트 중합체의 제조방법과 이 제조방법으로 제조되는 유기실리케이트 중합체를 이용하는 반도체 소자의 절연막 형성용 조성물, 이 조성물이 도포되어 경화된 반도체 소자의 절연막의 제조방법, 및 이 제조방법에 의해 제조되는 절연막을 포함하는 반도체 소자에 관한 것이다.The present invention relates to an organosilicate polymer having excellent mechanical and low dielectric properties, in particular, oxidizing a hydrosilane compound in the presence of water or alcohol, and hydrolyzing and condensing the oxidized hydrosilane compound alone, A method for producing an organosilicate polymer comprising the step of hydrolyzing and condensation reaction with a silane compound or a silane oligomer and a composition for forming an insulating film of a semiconductor device using the organosilicate polymer prepared by the production method, the semiconductor to which the composition is applied and cured A semiconductor device comprising a method for producing an insulating film of a device, and an insulating film produced by the method.
본 발명에 따라 제조한 유기실리케이트 중합체는 반도체 소자의 고속화와 소비전력량을 감소시킬 수 있고, 금속 배선의 상호 간섭 현상을 현저히 저하시킬 수 있는 저유전 배선 층간 절연막으로 사용할 수 있을 뿐만 아니라, 이를 절연막에 적용하면 얻어지는 막은 절연성이 우수하고, 도막의 균일성, 유전율 특성, 도막의 기계적 물성이 모두 우수하다.The organosilicate polymer prepared according to the present invention can not only be used as a low dielectric wiring interlayer insulating film which can reduce the speed and power consumption of semiconductor devices and significantly reduce the mutual interference phenomenon of metal wiring, When applied, the film obtained is excellent in insulation and excellent in both uniformity, dielectric constant, and mechanical properties of the coating film.
Description
본 발명은 기계적 특성과 저유전 특성이 우수한 유기실리케이트 중합체에 관한 것으로, 더욱 상세하게는 기계적 특성과 저유전 특성이 우수한 유기실리케이트 중합체의 제조방법, 이로부터 제조되는 유기실리케이트 중합체와 이를 이용하는 반도체 소자의 절연막 형성용 조성물, 이 조성물을 적용한 절연막의 제조방법, 및 이로부터 제조되는 절연막을 포함하는 반도체 소자에 관한 것이다.The present invention relates to an organosilicate polymer having excellent mechanical and low dielectric properties, and more particularly, to a method for preparing an organosilicate polymer having excellent mechanical and low dielectric properties, and an organosilicate polymer prepared therefrom and a semiconductor device using the same. A semiconductor device comprising a composition for forming an insulating film, a method for producing an insulating film to which the composition is applied, and an insulating film produced therefrom.
최근 반도체 소자의 집적도가 증가하면서 소자 내부를 연결하는 도선의 선폭이 급속하게 줄어들고 있으며, 2003 년경에는 0.1 ㎛의 회로 선폭을 이용한 고밀도의 소자가 개발될 것으로 예상된다.With the recent increase in the degree of integration of semiconductor devices, the line widths of the wires connecting the inside of the devices are rapidly decreasing. In 2003, high density devices using a circuit line width of 0.1 μm are expected to be developed.
일반적으로 반도체 소자의 속도는 트랜지스터의 스위칭 속도와 시그널(signal)의 전달 속도에 비례하고, 시그널의 전달 속도는 배선물질의 저항과 층간 절연막의 정전용량의 곱으로 표시되는 RC 지연(delay)에 의하여 결정된다. 반도체 소자의 집적도가 높아지면 소자내부를 연결하는 금속선간의 폭이 좁아지고, 굵기는 가늘어짐과 동시에 길이는 기하급수적으로 증가하여, 고밀도 칩상의 속도는 스위칭 속도보다는 고밀도 칩상의 RC 지연에 의하여 결정된다. 따라서 고속의 칩을 제조하기 위해서는 저항이 작은 도체와 유전율이 낮은 절연물질을 사용하여야 한다. 또한 저유전 물질의 사용은 반도체 소자의 속도 증가뿐만 아니라, 소비전력을 낮출 수 있고, 금속 배선 사이의 상호 간섭(cross-talk) 현상을 현저히 감소시킬 수 있는 잇점이 있다. In general, the speed of a semiconductor device is proportional to the switching speed of a transistor and the transmission speed of a signal, and the transmission speed of the signal is represented by an RC delay expressed as a product of the resistance of the wiring material and the capacitance of the interlayer insulating film. Is determined. As the degree of integration of semiconductor devices increases, the width between metal lines connecting the inside of the device becomes narrower, and the thickness becomes thinner and the length increases exponentially. The speed on the high density chip is determined by the RC delay on the high density chip rather than the switching speed. . Therefore, in order to manufacture a high speed chip, a low resistance conductor and a low dielectric constant insulating material should be used. In addition, the use of a low dielectric material may not only increase the speed of the semiconductor device, but also may reduce power consumption, and may significantly reduce cross-talk between metal wires.
최근 IBM에서 종래의 알루미늄 배선을 사용하지 않고, 전기 전도도가 높은 구리 배선을 사용하여 20 % 이상의 성능 향상을 보인 반도체 시제품을 출시한 바 있다. 반면에 저유전 물질을 적용한 반도체 소자는 적절한 소재 개발의 미비로 아직 시제품이 출시되어 있지 않은 상태이다.IBM has recently released a prototype of a semiconductor that does not use traditional aluminum wiring and improves performance by more than 20 percent using copper wiring with high electrical conductivity. On the other hand, semiconductor devices using low dielectric materials have not yet been prototyped due to the lack of proper material development.
종래의 IC, LSI 등의 반도체 소자의 층간 절연 재료는 유전상수가 4.0인 SiO2가 대부분이며, 저유전 물질로 플루오린이 도핑된 실리케이트(F-SiO2)가 일부 소자에 적용되고 있다. 그러나 F-SiO2의 경우 플루오린의 함량이 6 % 이상일 경우 열적으로 불안정한 상태가 되어 이 방법으로는 유전상수를 3.5 이하로 낮추기 어려운 문제점이 있다. 최근에 이러한 문제점을 해결하기 위하여 극성이 낮고 열적으로 안정한 여러 가지 유기 및 무기 고분자들이 제시되고 있다.In the conventional interlayer insulating materials of semiconductor devices such as IC and LSI, SiO 2 having a dielectric constant of 4.0 is mostly used, and silicate (F-SiO 2 ) doped with fluorine as a low dielectric material is applied to some devices. However, in the case of F-SiO 2 content of more than 6% fluorine is a thermally unstable state has a problem that it is difficult to lower the dielectric constant below 3.5 by this method. Recently, in order to solve these problems, various organic and inorganic polymers having low polarity and thermal stability have been proposed.
저유전 상수를 갖는 유기 고분자는 플루오린을 함유하거나 또는 함유하지 않은 폴리이미드 수지, 폴리 아릴렌 에테르 수지, 아로마틱 하이드로카본, 및 퍼플루오로 시클로 부탄 함유 수지 등이 알려져 있다. 이들 유기 고분자들은 대부분 유전상수가 3.0 이하이나, 일반적으로 유리 전이 온도가 낮아서 고온에서의 탄성률이 현저히 떨어지고 선팽창 계수가 매우 높다는 문제점이 있다. 또한 플루오린을 함유한 유기 고분자는 이러한 물성들이 더욱 저하된다. 반도체 제조 공정 및 패키징 공정은 공정 중에 200∼450 ℃의 고온까지 올라가, 이러한 낮은 열적 안정성과 탄성률 및 높은 선팽창 계수를 가지는 유기 고분자는 소자 또는 배선판의 신뢰성을 저하시킬 수가 있다.Organic polymers having a low dielectric constant include polyimide resins, polyarylene ether resins, aromatic hydrocarbons, perfluoro cyclobutane-containing resins and the like with or without fluorine. Most of these organic polymers have a dielectric constant of 3.0 or less, but in general, the glass transition temperature is low, so the elastic modulus at the high temperature is significantly decreased and the coefficient of linear expansion is very high. In addition, the organic polymer containing fluorine is further reduced these properties. The semiconductor manufacturing process and the packaging process rise to a high temperature of 200 to 450 ° C. during the process, and the organic polymer having such low thermal stability, elastic modulus and high linear expansion coefficient can lower the reliability of the device or the wiring board.
최근에는 유기 고분자의 열적 안정성 문제를 해결하기 위하여 알콕시실란계 화합물을 이용한 유기실리케이트 중합체 개발이 최근에 진행중이다. 이 방법은 유기 실란을 가수분해, 축합반응시킨 후 경화 공정을 통하여 유기 실리케이트 막을 형성하는 방법이다. 이러한 재료로서 메틸 또는 수소 실세스 퀴옥산은 3.0 이하의 비교적 낮은 유전 상수를 갖고 450 ℃에서 열적으로 안정하다. 그러나, 상기 폴리 실세스 퀴옥산은 경화 공정 중에 발생하는 수축 응력으로 1 ㎛ 이상의 두께에서 크랙이 발생하기 쉽다는 문제점이 있다. 또한 상기 폴리 실세스 퀴옥산은 유기 고분자에 비해 상대적으로 높은 기계적 강도를 갖으나, 유전 상수 2.5 이하를 구현하기 위해 가공을 도입할 경우 기계적 물성이 저하된다는 문제점이 있다.Recently, in order to solve the thermal stability problem of the organic polymer, development of an organosilicate polymer using an alkoxysilane-based compound has been recently underway. This method is a method of forming an organic silicate film through a curing process after hydrolyzing and condensing the organic silane. As such a material, methyl or hydrogen silses quoxane has a relatively low dielectric constant of 3.0 or less and is thermally stable at 450 ° C. However, the polysilses quoxane has a problem in that cracks are likely to occur at a thickness of 1 μm or more due to shrinkage stress generated during the curing process. In addition, the polysilses quoxane has a relatively high mechanical strength compared to the organic polymer, but there is a problem that the mechanical properties are lowered when processing is introduced to implement a dielectric constant of 2.5 or less.
따라서, 저유전성을 유지하면서 더욱 높은 기계적 물성을 갖는 유기실리케이트에 대한 연구가 더욱 요구되는 실정이다.Therefore, there is a need for further studies on organosilicates having higher mechanical properties while maintaining low dielectric properties.
상기와 같은 문제점을 해결하고자, 본 발명은 반도체 소자의 고속화와 소비전력량을 감소시킬 수 있고, 금속 배선의 상호 간섭 현상을 현저히 저하시킬 수 있는 저유전 배선 층간 절연막으로 사용할 수 있는 저유전 물질을 제공하는 것을 목적으로 한다.In order to solve the above problems, the present invention provides a low-k dielectric material that can be used as a low-k dielectric interlayer insulating film that can reduce the speed and power consumption of the semiconductor device, significantly reducing the mutual interference phenomenon of the metal wiring. It aims to do it.
본 발명의 다른 목적은 기계적 물성이 우수하면서 동시에 저유전 특성이 우수한 유기실리케이트 고분자와 그의 제조방법, 이를 이용하는 반도체 소자의 절연막 형성용 조성물, 이 조성물을 적용한 절연막의 제조방법, 및 이로부터 제조되는 절연막을 포함하는 반도체 소자를 제공하는 것이다. Another object of the present invention is an organic silicate polymer having excellent mechanical properties and excellent low dielectric properties, a method for producing the same, a composition for forming an insulating film for a semiconductor device using the same, a method for preparing an insulating film using the composition, and an insulating film prepared therefrom. It is to provide a semiconductor device comprising a.
상기 목적을 달성하기 위하여, 본 발명은 유기실리케이트 중합체의 제조방법에 있어서,In order to achieve the above object, the present invention provides a method for producing an organosilicate polymer,
a) 하이드로 실란화합물을 제공하는 단계;a) providing a hydro silane compound;
b) 상기 a)단계의 하이드로 실란화합물을 물 또는 알코올 존재하에서 산화반b) oxidation of the hydrosilane compound of step a) in the presence of water or alcohol
응시키는 단계; 및 Coagulating; And
c) 용매에c) in solvent
ⅰ) 상기 b)단계의 산화된 하이드로 실란화합물 단독; 또는 V) oxidized hydrosilane compound of step b) alone; or
ⅱ) 상기 b)단계의 산화된 하이드로 실란화합물, 및 실란화합물 또는 실 Ii) the oxidized hydrosilane compound, and silane compound or yarn of step b)
란 올리고머 Column oligomer
를 혼합한 후, 물 및 촉매를 가하여 가수분해 및 축합반응시키는 단계 After mixing the step of hydrolysis and condensation by adding water and a catalyst
를 포함하는 유기실리케이트 중합체의 제조방법을 제공한다.It provides a method for producing an organosilicate polymer comprising a.
또한 본 발명은 상기 제조방법으로 제조되는 유기실리케이트 중합체를 포함하는 반도체 소자의 절연막 형성용 조성물, 및 이 조성물이 도포되어 경화된 반도체 소자의 절연막을 제공한다.The present invention also provides a composition for forming an insulating film of a semiconductor device comprising an organosilicate polymer produced by the above method, and an insulating film of a semiconductor device to which the composition is applied and cured.
구체적으로는, 반도체 소자의 절연막 형성용 조성물에 있어서,Specifically, in the composition for insulating film formation of a semiconductor element,
a) 상기 유기실리케이트 중합체의 제조방법으로 제조되는 유기실리케이트 중a) among the organosilicates prepared by the method for preparing the organosilicate polymer
합체; 및 coalescence; And
b) 유기용매b) organic solvent
를 포함하는 절연막 형성용 조성물을 제공한다.It provides a composition for forming an insulating film comprising a.
또한 상기 절연막 형성용 조성물은 In addition, the composition for forming an insulating film
c) 유기분자, 유기폴리머, 유기 덴드리머, pH 조정제, 콜로이드상 실리카, 및 계면활성제로 이루어지는 군으로부터 1 종 이상 선택되는 첨가제를 추가로 포함할 수 있다.c) an additive selected from the group consisting of organic molecules, organic polymers, organic dendrimers, pH adjusters, colloidal silica, and surfactants.
또한 본 발명은 반도체 소자의 절연막의 제조방법에 있어서,In addition, the present invention is a method of manufacturing an insulating film of a semiconductor device,
a) 상기 유기실리케이트 중합체의 제조방법으로 제조되는 유기실리케이트 중a) among the organosilicates prepared by the method for preparing the organosilicate polymer
합체를 제공하는 단계; Providing coalescence;
b) 상기 a)단계의 유기실리케이트 중합체, 및 필요시 첨가제를 용매에 용해b) dissolving the organosilicate polymer of step a) and, if necessary, an additive in a solvent
하는 단계; Making;
c) 상기 b)단계의 유기실리케이트 중합체의 용액을 반도체 소자의 기재에 도c) applying the solution of the organosilicate polymer of step b) to the substrate of the semiconductor device.
포하는 단계; 및 Including; And
d) 상기 c)단계의 도포되는 절연막을 건조 및 소성하는 단계d) drying and baking the insulating film applied in step c)
를 포함하는 절연막의 제조방법 및 이 제조방법으로 제조되는 절연막을 포함하는 반도체 소자를 제공한다.It provides a method for manufacturing an insulating film comprising a and a semiconductor device comprising an insulating film produced by the manufacturing method.
이하 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 기계적 물성과 저유전 특성이 우수한 물질에 대하여 연구하던 중, 하이드로 실란화합물을 산화반응시키고, 산화된 실란화합물을 단독으로, 또는 실란화합물 또는 실란 올리고머과 함께 가수분해 및 축합반응시켜 유기실리케이트 중합체를 제조한 결과, 기계적 물성과 저유전 특성이 동시에 우수할 뿐만 아니라, 이를 적용한 절연막의 절연성이 우수하고, 도막의 균일성, 유전율 특성, 도막의 기계적 물성이 우수함을 확인하고, 이를 토대로 본 발명을 완성하게 되었다.The inventors of the present invention, while studying a material having excellent mechanical properties and low dielectric properties, oxidized the hydrosilane compound and hydrolyzed and condensed the silane compound alone or together with the silane compound or the silane oligomer to organosilicate polymer. As a result, the mechanical properties and the low dielectric properties were not only excellent at the same time, but also excellent in insulation properties of the insulating film to which the applied, and uniformity of the coating film, dielectric properties, mechanical properties of the coating film was confirmed, and based on the present invention It was completed.
본 발명은 하이드로 실란화합물을 산화시키고, 이 산화물을 가수분해 및 축합하여 유기실리케이트 중합체를 제조하는 방법, 이를 함유하는 절연막 형성용 조성물, 이 조성물을 도포하고 경화하여 제조되는 절연막의 제조방법, 및 이로부터 제조되는 절연막을 포함하는 반도체 소자를 제공하는 것이다.The present invention provides a method for producing an organosilicate polymer by oxidizing a hydrosilane compound and hydrolyzing and condensing the oxide, a composition for forming an insulating film containing the same, a method for preparing an insulating film prepared by applying and curing the composition, and a It is to provide a semiconductor device including an insulating film manufactured from.
본 발명은 물 또는 알코올 존재하에서 하이드로 실란화합물을 산화시키고, 상기 산화된 실란화합물을 용매의 존재하에서 물과 촉매를 첨가하고 가수분해 및 축중합 반응시키는 방법으로 일정한 분자량의 유기실리케이트 중합체를 얻을 수 있다. 또한 본 발명은 물 또는 알코올 존재하에서 하이드로 실란화합물을 산화시키고, 상기 산화된 실란화합물과 실리콘, 산소, 탄소, 수소로 구성된 실란화합물 또는 실란올리고머를 혼합하여 용매의 존재하에서 물과 촉매를 첨가하고 가수분해, 축중합 반응시키는 방법으로 일정한 분자량의 유기실리케이트 중합체를 얻을 수 있다.The present invention can obtain an organosilicate polymer having a constant molecular weight by oxidizing a hydrosilane compound in the presence of water or an alcohol, and adding the catalyst with water in the presence of a solvent, followed by hydrolysis and polycondensation. . The present invention also oxidizes the hydrosilane compound in the presence of water or alcohol, and mixes the oxidized silane compound with a silane compound or silane oligomer composed of silicon, oxygen, carbon, and hydrogen to add water and a catalyst in the presence of a solvent. An organosilicate polymer having a constant molecular weight can be obtained by a decomposition and polycondensation reaction.
본 발명에서 사용되는 상기 하이드로 실란화합물은 하이드로겐을 함유하는 유기 실란올리고머이면 어느 것이나 사용가능하며, 특히 하기 화학식 1로 표시되는 하이드로 실란올리고머, 또는 하기 화학식 2로 표시되는 사이클릭 하이드로 실란 올리고머인 것이 바람직하다.The hydrosilane compound used in the present invention may be any organic silane oligomer containing a hydrogen, in particular, a hydrosilane oligomer represented by the following formula (1), or a cyclic hydrosilane oligomer represented by the following formula (2) desirable.
[화학식 1][Formula 1]
상기 화학식 1의 식에서,In the formula of Formula 1,
R1은 각각 독립적으로 수소, 불소, 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이고,Each R 1 is independently hydrogen, fluorine, aryl, vinyl, allyl, or unsubstituted or substituted fluorine, straight or branched alkyl having 1 to 4 carbon atoms,
m은 1 내지 20의 정수이고,m is an integer from 1 to 20,
n은 1 내지 20의 정수이다.n is an integer from 1 to 20.
[화학식 2][Formula 2]
상기 화학식 2의 식에서,In the formula (2),
R2는 각각 독립적으로 수소, 불소, 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이고,Each R 2 is independently hydrogen, fluorine, aryl, vinyl, allyl, or unsubstituted or substituted fluorine, straight or branched alkyl having 1 to 4 carbon atoms,
k, 및 l은 각각 3 내지 10의 정수이다.k and l are each an integer of 3-10.
상기 하이드로 실란화합물은 하이드록시 또는 알콕시 관능기를 갖지 않는 것이 일반적이나, 산화반응 전에 일정량의 하이드록시 또는 알콕시 관능기를 포함할 수도 있다. The hydrosilane compound generally does not have a hydroxy or alkoxy functional group, but may include a certain amount of hydroxy or alkoxy functional group before the oxidation reaction.
본 발명의 하이드로 실란화합물의 산화반응는 촉매, 또는 산화제를 추가로 사용할 수 있다. 상기 촉매는 Pd, Pt, 또는 Rh 등의 금속 촉매를 사용할 수 있으며, 상기 산화제는 당량을 사용하는 산화제인 페록사이드(peroxide)류를 사용할 수 있다. 상기 페록사이드류는 제한 없이 사용가능하며, 그 예로는 다이메틸다이옥시레인 등의 옥시레인류 등이 있다.The oxidation reaction of the hydrosilane compound of the present invention may further use a catalyst or an oxidizing agent. The catalyst may be a metal catalyst such as Pd, Pt, or Rh, and the oxidizing agent may use peroxides, which are oxidizing agents using equivalents. The peroxides can be used without limitation, and examples thereof include oxiranes such as dimethyldioxylane.
본 발명에 사용되는 상기 실란화합물 또는 실란올리고머는 실리콘, 산소, 탄소, 수소로 구성된 실란화합물 또는 실란올리고머이면 어느 것이나 사용가능하고, 특히 하기 화학식 3 또는 하기 화학식 4로 표시되는 실란화합물을 사용하는 것이 바람직하다.The silane compound or silane oligomer used in the present invention may be any silane compound or silane oligomer composed of silicon, oxygen, carbon, hydrogen, and in particular, to use a silane compound represented by the following formula (3) or (4): desirable.
[화학식 3][Formula 3]
상기 화학식 3의 식에서,In the formula (3),
R3는 각각 독립적으로 수소, 아릴, 비닐, 알릴, 또는 불소로 치환되거나 치환되지 않은 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이고,Each R 3 is independently straight or branched alkyl having 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine,
R4는 각각 독립적으로 아세톡시, 하이드록시, 또는 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알콕시이고,Each R 4 is independently acetoxy, hydroxy, or straight or branched alkoxy having 1 to 4 carbon atoms,
p는 0 내지 2의 정수이다.p is an integer of 0-2.
[화학식 4][Formula 4]
상기 화학식 4의 식에서,In the formula (4),
R5 및 R7는 각각 독립적으로 수소, 아릴, 비닐, 알릴, 또는 불소로 치환되거나 치환되지 않은 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이고,R 5 and R 7 are each independently straight or branched alkyl having 1 to 4 carbon atoms, optionally substituted with hydrogen, aryl, vinyl, allyl, or fluorine,
R6 및 R8는 각각 독립적으로 아세톡시, 하이드록시, 또는 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알콕시이고,R 6 and R 8 are each independently acetoxy, hydroxy, or straight or branched alkoxy having 1 to 4 carbon atoms,
M은 탄소수 1 내지 6의 알킬렌 또는 페닐렌이고,M is alkylene or phenylene having 1 to 6 carbon atoms,
q, 및 r은 각각 0 내지 2의 정수이다.q and r are each an integer of 0-2.
본 발명의 유기실리케이트 중합체 제조에 사용된 용매는 산화된 실란화합물, 물, 및 촉매를 적절히 혼합하거나, 또는 상분리 상태에서 가수분해, 축합반응에 지장을 초래하지 않으면 큰 제한은 없다. 그 예로는, n-펜탄, i-펜탄, n-헥산, i-헥산, 2,2,4-트리메틸펜탄, 시클로 헥산, 또는 메틸시클로 헥산 등의 지방족 탄화 수소계 용매; 벤젠, 톨루엔, 크실렌, 트리메틸 벤젠, 에틸 벤젠, 또는 메틸 에틸 벤젠 등의 방향족 탄화 수소계 용매; 메틸알콜, 에틸알콜, n-프로판올, i-프로판올, n-부탄올, i-부탄올, sec-부탄올, t-부탄올, 4-메틸 2-펜탄올, 시클로 헥사놀, 메틸시클로 헥사놀, 또는 글리세롤 등의 알코올계 용매; 아세톤, 메틸에틸케톤, 메틸-n-프로필케톤, 메틸-n-부틸케톤, 메틸-i-부틸케톤, 디에틸케톤, 시클로헥사논, 메틸시클로헥사논, 또는 아세틸아세톤 등의 케톤계 용매; 테트라하이드로퓨란, 2-메틸 테트라하이드로 퓨란, 에틸에테르, n-프로필에테르, i-프로필에테르, n-부틸에티르, 디글라임, 디옥신, 디메틸디옥신, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜모노에틸에테르, 에틸렌글리콜-n-프로필에테르, 에틸렌글리콜 디메틸에테르, 에틸렌글리콜 디에틸에테르, 프로필렌글리콜 모노메틸에테르, 프로필렌글리콜 모노에틸에테르, 프로필렌글리콜 모노프로필에테르, 프로필렌글리콜 디메틸에테르, 프로필렌글리콜 디에틸에테르, 또는 프로필렌글리콜 디프로필에테르 등의 에테르계 용매; 디에틸카보네이트, 메틸아세테이트, 에틸아세테이트, n-프로필아세테이트, i-프로필아세테이트, n-부틸아세테이트, 에틸락테이트, 에틸렌글리콜 모노메틸에테르아세테이트, 에틸렌글리콜 모노에틸아세테이트, 프로필렌글리콜 모노메틸에테르아세테이트, 프로필렌글리콜 모노에틸에테르아세테이트, 프로필렌글리콜 모노프로필에테르아세테이트, 에틸렌글리콜 디아세테이트, 또는 프로필렌글리콜 디아세테이트 등의 에스테르계 용매; 또는 N-메틸피롤리돈, 포름아마이드, N-메틸포름아마이드, N-에틸포름아마이드, N,N-디메틸포름아마이드, N,N-디에틸포름아마이드, N-메틸아세트아마이드, N-에틸아세트아마이드, N,N-디메틸아세트아마이드, 또는 N,N-디에틸아세트아마이드 등의 아마이드계 용매 등이 있다.The solvent used in the preparation of the organosilicate polymer of the present invention is not particularly limited unless the oxidized silane compound, water, and catalyst are properly mixed or do not interfere with the hydrolysis and condensation reaction in the phase separation state. Examples thereof include aliphatic hydrocarbon solvents such as n-pentane, i-pentane, n-hexane, i-hexane, 2,2,4-trimethylpentane, cyclo hexane, or methylcyclo hexane; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethyl benzene, ethyl benzene, or methyl ethyl benzene; Methyl alcohol, ethyl alcohol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, 4-methyl 2-pentanol, cyclo hexanol, methylcyclo hexanol, or glycerol Alcohol solvents; Ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, diethyl ketone, cyclohexanone, methylcyclohexanone, or acetylacetone; Tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl ether, n-propyl ether, i-propyl ether, n-butyl ether, diglyme, dioxin, dimethyldioxin, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, ethylene glycol-n-propyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, Or ether solvents such as propylene glycol dipropyl ether; Diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, propylene glycol monomethyl ether acetate, propylene Ester solvents such as glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol diacetate, or propylene glycol diacetate; Or N-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N, N-diethylformamide, N-methylacetamide, N-ethylacetide Amide solvents such as amide, N, N-dimethylacetamide, or N, N-diethylacetamide.
상기 가수분해 및 축합반응에 사용된 용매들은 반응 후 모두 제거하여 유기실리케이트 중합체 오일 또는 분말을 얻고, 다시 이 유기실리케이트 중합체를 막 형성용 유기 용매에 녹여 사용하거나, 또는 가수분해 및 축합반응에 사용된 용매 중 코팅성에 나쁜 영향을 주는 용매, 물, 및 반응 부산물을 모두 또는 일정량 제거한 후 직접 막형성에 사용할 수 있다. 상기 용매들은 1 종 또는 2 종 이상 혼합하여 사용할 수 있다.The solvents used in the hydrolysis and condensation reactions are all removed after the reaction to obtain an organosilicate polymer oil or powder, and then the organosilicate polymer is dissolved in an organic solvent for film formation or used in the hydrolysis and condensation reactions. The solvent, water, and reaction by-products that adversely affect the coating property in the solvent may be removed or used in a certain amount after the removal of a certain amount. The solvent may be used alone or in combination of two or more thereof.
본 발명에서는 가수분해, 축합반응을 촉진시키기 위하여 촉매를 사용하는 것이 바람직하다. 가수분해, 축합반응에 사용되는 촉매는 산 촉매, 또는 염기 촉매를 사용할 수 있다. 상기 사용가능한 산촉매로는 큰 제한이 없으며, 예를 들면 염산, 질산, 황산, 인산, 불산, 포름산, 아세트산, 프로피온산, 부탄산, 펜탄산, 헥산산, 모노클로로아세트산, 디클로로아세트산, 트리클로로아세트산, 트리플로로아세트산, 옥살산, 말론산, 술폰산, 프탈산, 푸마르산, 구연산, 말레산, 올레산, 메틸말론산, 아디프산, p-아미노벤조산, 또는 p-톤루엔술폰산 등이 있다. 상기 사용가능한 염기 촉매로는 큰 제한이 없으나, 형성된 절연막이 반도체 소자용으로 사용될 경우, 나트륨, 칼륨 등의 반도체 소자에 악영향을 미치는 금속 이온을 포함하지 않는 것이 좋으며, 바람직하게는 암모니아수, 또는 유기 아민을 사용하는 것이다. 또한, 무기 염기를 사용할 경우에는 가수분해, 축합반응 후 금속이온을 모두 제거한 후 코팅 조성물로 사용한다. 상기 산 촉매, 또는 염기 촉매는 1 종 또는 2 종 이상을 동시에 사용할 수 있다.In the present invention, it is preferable to use a catalyst to promote hydrolysis and condensation reactions. As the catalyst used for the hydrolysis and condensation reaction, an acid catalyst or a base catalyst may be used. The acid catalyst which can be used is not particularly limited, for example, hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrofluoric acid, formic acid, acetic acid, propionic acid, butanoic acid, pentanic acid, hexanoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, Trifluoroacetic acid, oxalic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid, citric acid, maleic acid, oleic acid, methylmalonic acid, adipic acid, p-aminobenzoic acid, or p-tonluenesulfonic acid. The base catalyst that can be used is not particularly limited, but when the insulating film formed is used for a semiconductor device, it is preferable not to include metal ions that adversely affect semiconductor devices such as sodium and potassium, preferably ammonia water or organic amines. Is to use In addition, in the case of using an inorganic base, after removing all metal ions after hydrolysis and condensation reaction, it is used as a coating composition. The acid catalyst or the base catalyst may be used alone or in combination of two or more.
상기 촉매의 첨가량은 반응 조건에 따라 조절이 가능하며, 바람직하게는 사용된 총 실란화합물 1 몰에 대해 0.000001 내지 2 몰을 사용하는 것다. 상기 첨가량이 실란화합물 1 몰 당 2 몰을 초과할 경우에는 낮은 농도에서도 반응 속도가 매우 빨라 분자량 조절이 어렵고, 쉽게 겔이 발생할 우려가 있다. The addition amount of the catalyst can be adjusted according to the reaction conditions, it is preferably to use 0.000001 to 2 mol to 1 mol of the total silane compound used. When the added amount exceeds 2 mol per mol of the silane compound, the reaction rate is very fast even at low concentrations, making it difficult to control the molecular weight, and there is a concern that gel may easily occur.
상기 촉매의 사용방법에 있어서, 조성물을 산 촉매, 또는 염기 촉매를 이용하여 단계적으로 가수분해 축합반응할 수 있다. 일례로, 산으로 가수 분해 축합반응을 행한 후 염기로 다시 반응시키거나, 또는 염기로 먼저 가수분해 축합반응을 행하고 다시 산으로 반응할 수 있다. 또한 산 촉매와 염기 촉매로 각각 반응시킨 후 축합물을 혼합하여 사용할 수도 있다. In the method of using the catalyst, the composition may be subjected to step hydrolysis condensation reaction using an acid catalyst or a base catalyst. For example, the hydrolysis condensation reaction may be performed with an acid, followed by reaction with a base, or the hydrolysis condensation reaction may be performed with a base first, followed by reaction with an acid. The condensates may also be used after reacting with an acid catalyst and a base catalyst, respectively.
상기 가수분해 축합반응시 반응 온도는 0 내지 100 ℃인 것이 바람직하고, 더욱 바람직하게는 15 내지 80 ℃인 것이다. 이때 얻어지는 가수분해 축합물의 중량 평균 분자량은 폴리스틸렌 환산분자량으로 비교하여 500 이상이며, 절연막에 적용시에는 500 내지 1,000,000인 것이 바람직하다.In the hydrolysis condensation reaction, the reaction temperature is preferably 0 to 100 ° C, more preferably 15 to 80 ° C. The weight average molecular weight of the hydrolysis-condensation product obtained at this time is 500 or more compared with the molecular weight of polystyrene conversion, and when applied to an insulating film, it is preferable that it is 500-1,000,000.
본 발명에서 얻어지는 절연막 형성용 코팅 조성물에는 절연막의 밀도를 낮추기 위하여 유기분자, 유기폴리머, 덴드리머를 일정량 첨가해도 좋다. 유기물의 종류에는 큰 제한은 없으며, 200 내지 450 ℃에서 열분해가 가능한 물질로 상기 유기실리케이트 중합체 제조 후 절연막 형성용 조성물에 첨가하여 사용하거나 유기실리케이트 중합체 제조시 첨가할 수 있다.In order to reduce the density of an insulating film, you may add a fixed amount of organic molecules, an organic polymer, and a dendrimer to the coating composition for insulating film formation obtained by this invention. The type of the organic material is not particularly limited, and may be used as a material capable of thermal decomposition at 200 to 450 ° C. and then used in addition to the composition for forming an insulating film after the organosilicate polymer is prepared or at the time of preparing the organosilicate polymer.
본 발명에서 얻어지는 절연막 형성용 조성물에는 그 밖의 첨가제로 pH 조정제, 콜로이드 상태 실리카, 계면활성제 등의 성분을 그 목적에 맞게 일정량 첨가해도 좋다.You may add a fixed amount of components, such as a pH adjuster, colloidal silica, surfactant, etc. to the composition for insulating film formation obtained by this invention according to the objective.
본 발명의 조성물의 전 고형분의 농도는 2 내지 60 중량%, 바람직하게는 5 내지 40 중량%가 절연막의 막 두께와 보전 안정성을 고려하여 적당하다. 여기에서 고형분 농도는 상기 유기용매의 종류 및 사용량에 의하여 조절이 가능하다.The concentration of the total solids of the composition of the present invention is 2 to 60% by weight, preferably 5 to 40% by weight is suitable in consideration of the film thickness and the integrity of the insulating film. The solid content concentration can be adjusted by the type and the amount of the organic solvent.
본 발명의 절연막 형성용 조성물은 실리콘 웨이퍼, SiO2 웨이퍼, SiN 웨이퍼, 화합물 반도체 등의 기재에 도포함으로서 형성된다. 절연막의 형성 방법은 스핀코트법, 침지법, 롤 코트법, 스프레이법 등을 사용할 수 있으며, 이들의 방법을 사용하여 일정 두께의 막을 형성하는 것이 가능하다. 특히, 반도체 장치의 다층회로 층간 절연막을 제조할 경우에는 스핀 코트법을 사용하는 것이 좋다.An insulating film forming composition of the present invention is formed by coating a silicon wafer, SiO 2 wafer, SiN wafer, a compound semiconductor substrate such as. As the method for forming the insulating film, a spin coating method, an immersion method, a roll coating method, a spray method, or the like can be used, and it is possible to form a film having a predetermined thickness using these methods. In particular, when manufacturing a multilayer circuit interlayer insulating film of a semiconductor device, it is preferable to use a spin coat method.
상기 막의 두께는 조성물의 점도와 스핀코우터의 회전 속도를 변화시켜 조절할 수 있으며, 통상적으로 반도체 장치의 다층회로구조의 층간 절연막으로 사용하는 경우에 있어서는 0.1 내지 2 ㎛인 것이 적당하다.The thickness of the film can be adjusted by changing the viscosity of the composition and the rotational speed of the spin coater. In general, when the film is used as an interlayer insulating film of a multilayer circuit structure of a semiconductor device, it is appropriate that it is 0.1 to 2 m.
코팅 후에는 건조공정과 소성(경화)공정을 거쳐 3차원 구조의 유기실리케이트 고분자 절연막을 형성할 수 있다. 건조공정은 통상적으로 프리베이크(pre-bake) 공정과 소프트베이크(soft-bake) 공정을 포함하는 것을 의미한다. 프리베이크 공정 중에 사용한 유기 용매를 서서히 증발시키고, 소프트베이크 공정 중에 관능기의 일정량을 가교시킨 다음, 소성공정 중 잔류 관능기를 최종적으로 반응시킨다. 상기 건조는 30 내지 350 ℃의 온도에서, 소성은 350 ℃ 이상의 온도에서 실시하는 것이 좋으며, 특히 소성온도는 350 내지 500 ℃의 온도에서 실시하는 것이 바람직하다. 소성온도가 350 ℃ 미만일 경우에는 유리실리케이트 고분자의 축중합이 완전히 일어나지 않아, 막의 강도가 저하되고, 잔류관능기의 존재로 인하여 유전 특성이 저하될 수 있다. 소성온도의 상한은 본 발명의 유기실리케이트 절연막의 열적 안정성과 이를 이용하여 제조된 반도체 소자에 의존한다.After coating, the organic silicate polymer insulating film having a three-dimensional structure may be formed through a drying process and a baking (curing) process. The drying process usually means including a pre-bake process and a soft-bake process. The organic solvent used during the prebaking process is gradually evaporated, a certain amount of functional groups are crosslinked in the softbaking process, and the remaining functional groups are finally reacted during the firing process. The drying is preferably carried out at a temperature of 30 to 350 ℃, firing at a temperature of 350 ℃ or more, in particular the firing temperature is preferably carried out at a temperature of 350 to 500 ℃. If the calcination temperature is less than 350 ° C., the polycondensation of the glass silicate polymer does not occur completely, and thus the strength of the film is lowered and the dielectric properties may be lowered due to the presence of residual functional groups. The upper limit of the firing temperature depends on the thermal stability of the organosilicate insulating film of the present invention and the semiconductor device fabricated using the same.
건조공정과 소성공정은 연속적으로 일정한 속도로 승온시키면서 할 수 있고 또한, 단속적으로 실시할 수도 있다. 단속적으로 실시할 경우, 건조 및 소성 공정을 각각 1 분 내지 5 시간 동안 수행하는 것이 적당하다. 이때 가열방법은 핫플레이트, 오븐, 퍼니스 등을 사용할 수 있고, 가열 분위기는 질소, 아르곤, 헬륨 등과 같은 불활성 기체분위기, 산소함유 기체(예를 들면, 공기 등) 등과 같은 산소 분위기, 진공상태, 또는 암모니아 및 수소를 함유하는 기체 분위기 하에서 수행할 수 있다. 상기 가열방법은 건조공정과 소성공정이 모두 같은 가열방법으로 행하여도 좋고, 각각 다른 방법으로 행하는 것도 가능하다.A drying process and a baking process can be performed continuously, heating up at a constant speed, and can also be performed intermittently. If carried out intermittently, it is appropriate to carry out the drying and firing processes for 1 minute to 5 hours, respectively. In this case, the heating method may be a hot plate, an oven, a furnace, or the like, and the heating atmosphere may be an inert gas atmosphere such as nitrogen, argon or helium, an oxygen atmosphere such as an oxygen-containing gas (for example, air, etc.), a vacuum state, or It can be performed under a gas atmosphere containing ammonia and hydrogen. The heating method may be performed by the same heating method as the drying step and the firing step, or may be performed by different methods, respectively.
건조공정과 소성공정을 거친 후 필요에 따라 절연막 내부의 하이드록시기 양을 최소화하기 위하여 표면처리를 할 수 있다. 표면처리 방법은 일반적으로 알려진 헥사메틸디실라잔, 알킬알콕시실란, 또는 알킬아세톡시실란 등과 같은 실릴화 화합물 사용하거나, 또는 수소와 같은 환원 분위기 또는 플루오린 함유 가스 하에서 소성하면 표면처리가 가능하다. 절연막의 실릴화 처리 방법은 실릴화 화합물 또는 용매에 희석한 실릴화 화합물에 침지 또는 스핀 코팅시키거나, 실릴화 화합물의 증기 분위기에서 행하는 것이 가능하고, 실릴화 처리 후, 절연막을 100 내지 400 ℃에 가열하는 것이 바람직하다.After the drying process and the firing process, the surface treatment may be performed to minimize the amount of hydroxyl groups in the insulating film, if necessary. The surface treatment method can be surface-treated by using generally known silylated compounds, such as hexamethyldisilazane, alkylalkoxysilane, or alkylacetoxysilane, or baking in a reducing atmosphere such as hydrogen or a fluorine-containing gas. The silylation treatment method of the insulating film can be immersed or spin-coated in the silylated compound or the silylated compound diluted in a solvent, or can be performed in the vapor atmosphere of the silylated compound. It is preferable to heat.
이처럼 하여 얻어지는 막은 절연성이 우수하고, 도막의 균일성, 도막의 내크랙성, 도막의 표면 강도가 모두 우수하기 때문에, LSI, 시스템 LSI, DRAM, SDRAM, RDRAM, D-RDRAM 등의 반도체 소자용 층간 절연막, 반도체 소자 층간 캡핑막(capping layer), 하드 마스크막(hard mask layer), 및 에치 스톱막(etch stop layer), 반도체 소자의 표면 코팅막 등의 보호막, 다층배선 기판의 층간 절연막, 액정표시 소자용의 보호막, 절연 방지막 등의 용도로 사용하기에 좋다.The film thus obtained has excellent insulation properties, excellent uniformity of the coating film, crack resistance of the coating film, and excellent surface strength of the coating film. Therefore, the interlayer for semiconductor devices such as LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, etc. Insulating film, semiconductor device interlayer capping layer, hard mask layer, and etch stop layer, protective film such as surface coating film of semiconductor device, interlayer insulating film of multilayer wiring substrate, liquid crystal display device It is suitable for use in applications such as a protective film for insulation and an insulation prevention film.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범위가 하기 실시예에 한정되는 것은 아니다.Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.
[실시예]EXAMPLE
실시예 1Example 1
(하이드로 실란화합물의 산화 반응)(Oxidation reaction of hydrosilane compound)
반응 용기에 증류수 15 g, 테트라하이드로퓨란 30 g, Pd/C(10 %) 파우더 500 ㎎를 넣어 섞은 후, 반응 용기의 온도를 0 ℃로 유지하였다. 상기 용액에 테트라메틸시클로테르라실록산 10 g을 천천히 가하고, 밤샘(overnight) 반응시켰다. 반응 후 용액을 필터하여 금속촉매를 제거하고, 유기용매를 진공에서 제거하여 11 g의 테트라올이 녹아있는 하이드로 실록산 산화반응물 19 g을 수득하였다.15 g of distilled water, 30 g of tetrahydrofuran, and 500 mg of Pd / C (10%) powder were mixed in a reaction vessel, and the temperature of the reaction vessel was maintained at 0 ° C. 10 g of tetramethylcycloterrasiloxane was slowly added to the solution and allowed to react overnight. After the reaction, the solution was filtered to remove the metal catalyst, and the organic solvent was removed in vacuo to obtain 19 g of hydrosiloxane oxidation product in which 11 g of tetraol was dissolved.
(유기실리케이트 중합체 제조)(Organic silicate polymer production)
상기 수득한 하이드로 실록산 산화반응물 8.3 g, 및 테트라하이드로퓨란 12 g을 반응 용기에 넣었다. 상기 용액에 72 ㎎의 염화수소를 녹인 증류수 1.4 g을 천천히 첨가한 후, 온도를 70 ℃로 올려 밤샘(overnight) 반응시켰다. 반응 완료 후, 반응 용액을 에테르로 희석시키고 증류수로 pH가 중성이 될 때까지 씻어주었다. 얻어진 유기층의 물을 건조제를 이용하여 제거한 후, 진공에서 유기용매를 제거하고, 파우더 상태의 생성물을 수득하였다. 8.3 g of the hydrosiloxane oxidation product obtained above and 12 g of tetrahydrofuran were placed in a reaction vessel. After slowly adding 1.4 g of distilled water in which 72 mg of hydrogen chloride was dissolved in the solution, the temperature was raised to 70 ° C. and reacted overnight. After completion of the reaction, the reaction solution was diluted with ether and washed with distilled water until the pH was neutral. After the water of the obtained organic layer was removed using a drying agent, the organic solvent was removed in vacuo to obtain a powdery product.
(절연막의 제조)(Manufacture of insulating film)
상기 수득한 유기실리케이트 중합체를 프로필렌글리콜 모노메틸에테르아세테이트에 용해한 용액을 실리콘웨이퍼 위에 스핀 코팅하여 박막을 얻고, 질소 분위기하에 425 ℃의 온도에서 1 시간 동안 경화하여 절연막을 제조하였다. The solution obtained by dissolving the obtained organosilicate polymer in propylene glycol monomethyl ether acetate was spin coated on a silicon wafer to obtain a thin film, and cured at a temperature of 425 ° C. for 1 hour under a nitrogen atmosphere to prepare an insulating film.
실시예 2Example 2
(하이드로 실란화합물의 산화 반응)(Oxidation reaction of hydrosilane compound)
반응 용기에 메탄올 100 g, Pd/C(10 %) 파우더 300 ㎎를 넣어 섞은 후, 반응 용기의 온도를 0 ℃로 유지하였다. 상기 용액에 테트라메틸시클로테르라실록산 50 g을 천천히 가하고, 밤샘(overnight) 반응시켰다. 반응 후 용액을 필터하여 촉매를 제거하고, 유기용매를 진공에서 제거하여 하이드로 실록산 산화반응물 72 g을 수득하였다.100 g of methanol and 300 mg of Pd / C (10%) powder were added and mixed in the reaction vessel, and the temperature of the reaction vessel was maintained at 0 ° C. 50 g of tetramethylcycloterrasiloxane was slowly added to the solution, followed by overnight reaction. After the reaction, the solution was filtered to remove the catalyst, and the organic solvent was removed in vacuo to give 72 g of hydrosiloxane oxidation.
(유기실리케이트 중합체 제조)(Organic silicate polymer production)
상기 수득한 하이드로 실록산 산화반응물 6.5 g, 테트라하이드로퓨란 16 g, 및 메탄올 4.6 g을 반응 용기에 넣었다. 상기 용액에 75 ㎎의 염화수소를 녹인 증류수 6.5 g을 천천히 첨가한 후, 온도를 70 ℃로 올려 밤샘(overnight) 반응시켰다. 반응 완료 후, 반응 용액을 에테르로 희석시키고 증류수로 pH가 중성이 될 때까지 씻어주었다. 얻어진 유기층의 물을 건조제를 이용하여 제거한 후, 진공에서 유기용매를 제거하고, 파우더 상태의 생성물을 수득하였다. 6.5 g of the hydrosiloxane oxidation product, 16 g of tetrahydrofuran, and 4.6 g of methanol were added to a reaction vessel. 6.5 g of distilled water in which 75 mg of hydrogen chloride was dissolved was slowly added to the solution, and the temperature was raised to 70 ° C. for overnight reaction. After completion of the reaction, the reaction solution was diluted with ether and washed with distilled water until the pH was neutral. After the water of the obtained organic layer was removed using a drying agent, the organic solvent was removed in vacuo to obtain a powdery product.
(절연막의 제조)(Manufacture of insulating film)
상기 실시예 1과 동일한 방법으로 실시하여 절연막을 제조하였다.An insulating film was prepared in the same manner as in Example 1.
실시예 3Example 3
(하이드로 실란화합물의 산화 반응)(Oxidation reaction of hydrosilane compound)
반응용기에 메틸디메톡시 실란 10 g, 메탄올 1.2 g, 및 테트라하이드로퓨란 8.36 g을 넣어 섞은 후, 34 ㎎의 염화수소가 녹아있는 증류수 1.4 g을 0 ℃에서 천천히 첨가한다. 상기 용액을 상온에서 12 시간 동안 반응시키고, 진공에서 물, 용매, 산촉매를 제거하여 5.3 g의 하이드로 실란 부분가수분해 축합물을 수득하였다. 이 부분가수분해 축합물에 증류수 8 g, 테트라하이드로퓨란 16 g, 및 Pd/C(10 %) 파우더 300 ㎎을 혼합한 후, 밤샘(overnight) 반응시켰다. 반응 후 용액을 필터하여 촉매를 제거하고, 유기용매를 진공에 제거하여 8.4 g의 산화반응물을 수득하였다.10 g of methyldimethoxy silane, 1.2 g of methanol, and 8.36 g of tetrahydrofuran are added to the reaction vessel, and 1.4 g of distilled water in which 34 mg of hydrogen chloride is dissolved is slowly added at 0 ° C. The solution was reacted at room temperature for 12 hours, and water, solvent, and acid catalyst were removed in vacuo to obtain 5.3 g of hydrosilane partial hydrolysis condensate. The partially hydrolyzed condensate was mixed with 8 g of distilled water, 16 g of tetrahydrofuran, and 300 mg of Pd / C (10%) powder, followed by overnight reaction. After the reaction, the solution was filtered to remove the catalyst, and the organic solvent was removed in vacuo to obtain 8.4 g of an oxidation reaction product.
(유기실기실리케이트 중합체 제조)(Organic organosilicate polymer production)
상기 수득한 산화반응물을 30 g의 테트라하이드로퓨란에 녹인 후, 여기에 108 ㎎의 염화수소가 녹아있는 증류수 5.3 g을 천천히 가하였다. 첨가 후, 온도를 70 ℃로 올려 12 시간 동안 반응시켰다. 반응 완료 후, 반응용액을 에테르에 희석시키고, 증류수로 pH가 중성이 될 때까지 씻어주었다. 얻어진 유기층의 물을 건조제를 이용하여 제거한 후, 진공에서 유기용매를 제거하고, 파우더 상태의 생성물을 수득하였다. The obtained oxidation product was dissolved in 30 g of tetrahydrofuran, and then 5.3 g of distilled water containing 108 mg of hydrogen chloride was slowly added thereto. After the addition, the temperature was raised to 70 ° C. and reacted for 12 hours. After completion of the reaction, the reaction solution was diluted with ether and washed with distilled water until the pH was neutral. After the water of the obtained organic layer was removed using a drying agent, the organic solvent was removed in vacuo to obtain a powdery product.
(절연막의 제조)(Manufacture of insulating film)
상기 실시예 1과 동일한 조건으로 절연막을 제조하였다.An insulating film was manufactured under the same conditions as in Example 1.
실시예 4Example 4
(유기실기실리케이트 중합체 제조)(Organic organosilicate polymer production)
상기 실시예 1에서 수득한 하이드로 실록산 산화반응물 5.1 g(물 포함), 테트라메톡시실란 1.5 g, 및 테트라하이드로퓨란 9 g을 반응 용기에 넣고, 여기에 256 ㎎의 말론산을 녹인 증류수 2.1 g을 천천히 첨가하였다. 첨가 후, 온도를 70℃로 올려 밤샘(overnight) 반응시켰다. 반응 완료 후, 반응 용액을 에테르로 희석시키고 증류수로 pH가 중성이 될 때까지 씻어주었다. 얻어진 유기층의 물을 건조제를 이용하여 제거한 후, 진공에서 유기용매를 제거하고, 파우더 상태의 생성물을 수득하였다. 5.1 g of the hydrosiloxane oxidation reactant obtained in Example 1 (including water), 1.5 g of tetramethoxysilane, and 9 g of tetrahydrofuran were placed in a reaction vessel, and 2.1 g of distilled water dissolved in 256 mg of malonic acid was added thereto. Added slowly. After the addition, the temperature was raised to 70 ° C. and reacted overnight. After completion of the reaction, the reaction solution was diluted with ether and washed with distilled water until the pH was neutral. After the water of the obtained organic layer was removed using a drying agent, the organic solvent was removed in vacuo to obtain a powdery product.
(절연막의 제조)(Manufacture of insulating film)
상기 실시예 1과 동일한 조건으로 절연막을 제조하였다.An insulating film was manufactured under the same conditions as in Example 1.
비교예Comparative example
(유기실기실리케이트 중합체 제조)(Organic organosilicate polymer production)
반응 용기에 메틸트리메톡시실란 10 g, 및 테트라하이드로퓨란 16.3 g을 넣고, 여기에 80 ㎎의 염화수소를 녹인 증류수 7.93 g을 천천히 첨가하였다. 첨가 후 온도를 70 ℃로 올려 밤샘(overnight) 반응시켰다. 반응 완료 후, 반응 용액을 에테르로 희석시키고 증류수로 pH가 중성이 될 때까지 씻어주었다. 얻어진 유기층의 물을 건조제를 이용하여 제거한 후, 진공에서 유기용매를 제거하고, 파우더 상태의 생성물을 수득하였다. 10 g of methyltrimethoxysilane and 16.3 g of tetrahydrofuran were put into the reaction vessel, and 7.93 g of distilled water dissolved in 80 mg of hydrogen chloride was slowly added thereto. After addition, the temperature was raised to 70 ° C. and reacted overnight. After completion of the reaction, the reaction solution was diluted with ether and washed with distilled water until the pH was neutral. After the water of the obtained organic layer was removed using a drying agent, the organic solvent was removed in vacuo to obtain a powdery product.
(절연막의 제조)(Manufacture of insulating film)
상기 실시예 1과 동일한 조건으로 절연막을 제조하였다.An insulating film was manufactured under the same conditions as in Example 1.
실험예Experimental Example
상기 실시예 1 내지 4, 및 비교예에서 제조한 절연막의 유전 특성과 기계적 물성을 하기와 같은 방법으로 측정하고, 그 결과를 하기 표 1에 나타내었다.Dielectric properties and mechanical properties of the insulating film prepared in Examples 1 to 4 and Comparative Examples were measured by the following method, and the results are shown in Table 1 below.
ㄱ) 유전 특성 - MIS(Metal/Insulator/Semiconductor) 방식에 의해 유전상수A) dielectric properties-dielectric constant by MIS (Metal / Insulator / Semiconductor) method
를 측정하였다. Was measured.
ㄴ) 기계적 물성 - 하지트론(Hysitron Inc.)의 트리보인덴터(TriboIndenter)B) Mechanical properties-TriboIndenter of Hysitron Inc.
를 사용하여 탄성률과 강도를 측정하였다. The elastic modulus and strength were measured using.
상기 표 1을 통하여, 본 발명에 따라 제조한 실시예 1 내지 4의 절연막은 비교예의 절연막과 비교하여 저유전 특성이 우수하고, 동시에 기계적 물성이 우수함을 확인할 수 있었다.Through Table 1, it was confirmed that the insulating films of Examples 1 to 4 manufactured according to the present invention had superior low dielectric properties and excellent mechanical properties as compared with the insulating films of Comparative Examples.
상기에서 살펴본 바와 같이, 본 발명에 따라 제조한 유기실리케이트 중합체는 반도체 소자의 고속화와 소비전력량을 감소시킬 수 있고, 금속 배선의 상호 간섭 현상을 현저히 저하시킬 수 있는 저유전 배선 층간 절연막으로 사용할 수 있을 뿐만 아니라, 이를 절연막에 적용한 막은 절연성이 우수하고, 도막의 균일성, 유전율 특성, 도막의 기계적 물성이 모두 우수한 효과가 있다.As described above, the organosilicate polymer prepared according to the present invention can be used as a low dielectric wiring interlayer insulating film that can reduce the speed and power consumption of semiconductor devices and significantly reduce the mutual interference of metal wires. In addition, the film applied to the insulating film is excellent in insulating properties, the uniformity of the coating film, dielectric properties, mechanical properties of the coating film is excellent in all.
Claims (11)
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0021140A KR100508900B1 (en) | 2002-04-18 | 2002-04-18 | Organic silicate polymer and insulation film comprising the same |
EP03713057A EP1495066B1 (en) | 2002-04-18 | 2003-03-28 | Organic silicate polymer and insulation film comprising the same |
JP2004511371A JP4142643B2 (en) | 2002-04-18 | 2003-03-28 | Organosilicate polymer and insulating film containing the same |
PCT/KR2003/000634 WO2003104305A1 (en) | 2002-04-18 | 2003-03-28 | Organic silicate polymer and insulation film comprising the same |
CNB038087138A CN100381483C (en) | 2002-04-18 | 2003-03-28 | Organic silicate polymer and insulation film comprising the same |
AU2003218816A AU2003218816A1 (en) | 2002-04-18 | 2003-03-28 | Organic silicate polymer and insulation film comprising the same |
DE60322202T DE60322202D1 (en) | 2002-04-18 | 2003-03-28 | insulating |
AT03713057T ATE401364T1 (en) | 2002-04-18 | 2003-03-28 | ORGANIC SILICATE POLYMER AND COMPREHENSIVE INSULATING FILM |
US10/511,639 US7834119B2 (en) | 2002-04-18 | 2003-03-28 | Organic silicate polymer and insulation film comprising the same |
TW092107963A TWI328017B (en) | 2002-04-18 | 2003-04-02 | Organic silicate polymer and insulation film comprising the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2002-0021140A KR100508900B1 (en) | 2002-04-18 | 2002-04-18 | Organic silicate polymer and insulation film comprising the same |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20030082692A KR20030082692A (en) | 2003-10-23 |
KR100508900B1 true KR100508900B1 (en) | 2005-08-17 |
Family
ID=32379443
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR10-2002-0021140A KR100508900B1 (en) | 2002-04-18 | 2002-04-18 | Organic silicate polymer and insulation film comprising the same |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100508900B1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5548053A (en) * | 1992-05-15 | 1996-08-20 | Wacker-Chemie Gmbh | Process for the preparation of organopolysiloxane resin |
US6232424B1 (en) * | 1999-12-13 | 2001-05-15 | Dow Corning Corporation | Soluble silicone resin compositions having good solution stability |
JP2001237240A (en) * | 2000-02-23 | 2001-08-31 | Hitachi Chem Co Ltd | Low dielectric constant film and semiconductor element with low dielectric constant film |
KR100440488B1 (en) * | 2001-12-27 | 2004-07-14 | 주식회사 엘지화학 | Organic silicate polymer for insulation film of the semiconductor device and low dielectric insulation film comprising the same |
-
2002
- 2002-04-18 KR KR10-2002-0021140A patent/KR100508900B1/en active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5548053A (en) * | 1992-05-15 | 1996-08-20 | Wacker-Chemie Gmbh | Process for the preparation of organopolysiloxane resin |
US6232424B1 (en) * | 1999-12-13 | 2001-05-15 | Dow Corning Corporation | Soluble silicone resin compositions having good solution stability |
JP2001237240A (en) * | 2000-02-23 | 2001-08-31 | Hitachi Chem Co Ltd | Low dielectric constant film and semiconductor element with low dielectric constant film |
KR100440488B1 (en) * | 2001-12-27 | 2004-07-14 | 주식회사 엘지화학 | Organic silicate polymer for insulation film of the semiconductor device and low dielectric insulation film comprising the same |
Also Published As
Publication number | Publication date |
---|---|
KR20030082692A (en) | 2003-10-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4142643B2 (en) | Organosilicate polymer and insulating film containing the same | |
KR100579855B1 (en) | Coating composition for insulating film production, preparation method of insulation film by using the same, insulation film for semi-conductor device prepared therefrom, and semi-conductor device comprising the same | |
EP1328571B1 (en) | A process for preparing organic silicate polymer | |
US7238627B2 (en) | Organosilicate polymer and insulating film therefrom | |
KR100515583B1 (en) | Organic silicate polymer and insulation film comprising the same | |
JP2006514151A (en) | Organosiloxane resin and insulating film using the same | |
KR100508901B1 (en) | Organic silicate polymer and insulation film comprising the same | |
KR100419069B1 (en) | Organic silicate polymer and low dielectric insulation film comprising the same | |
KR100405312B1 (en) | Organic silicate polymer and low dielectric insulation film comprising the same | |
KR100508900B1 (en) | Organic silicate polymer and insulation film comprising the same | |
KR100422916B1 (en) | Organic silicate polymer and low dielectric insulation film comprising the same | |
KR100508903B1 (en) | Composition for low dielectric film and method for forming low dielectric film | |
KR100440488B1 (en) | Organic silicate polymer for insulation film of the semiconductor device and low dielectric insulation film comprising the same | |
KR100515584B1 (en) | Organic silicate polymer and insulation film comprising the same | |
KR100508902B1 (en) | Organic silicate polymer and insulation film comprising the same | |
KR100450257B1 (en) | Organic silicate polymer and low dielectric insulation film comprising the same | |
US20040126595A1 (en) | Nanopore forming material for forming insulating film for semiconductors and low dielectric insulating film comprising the same | |
KR100553203B1 (en) | Organic siloxane resin and film comprising the same | |
KR100490853B1 (en) | Nanopore forming material for forming insulating film for semiconductors and low dielectric insulating film comprising the same | |
KR20040018710A (en) | Method for preparing organic silicate polymer |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20130730 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20140716 Year of fee payment: 10 |
|
FPAY | Annual fee payment |
Payment date: 20150716 Year of fee payment: 11 |
|
FPAY | Annual fee payment |
Payment date: 20160803 Year of fee payment: 12 |
|
FPAY | Annual fee payment |
Payment date: 20170718 Year of fee payment: 13 |
|
FPAY | Annual fee payment |
Payment date: 20180619 Year of fee payment: 14 |
|
FPAY | Annual fee payment |
Payment date: 20190625 Year of fee payment: 15 |