KR100422916B1 - Organic silicate polymer and low dielectric insulation film comprising the same - Google Patents
Organic silicate polymer and low dielectric insulation film comprising the same Download PDFInfo
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- KR100422916B1 KR100422916B1 KR10-2001-0036783A KR20010036783A KR100422916B1 KR 100422916 B1 KR100422916 B1 KR 100422916B1 KR 20010036783 A KR20010036783 A KR 20010036783A KR 100422916 B1 KR100422916 B1 KR 100422916B1
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- South Korea
- Prior art keywords
- formula
- straight
- carbon atoms
- substituted
- fluorine
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- 229920000642 polymer Polymers 0.000 title claims abstract description 42
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title claims description 14
- 238000009413 insulation Methods 0.000 title abstract description 8
- -1 hydride silane compound Chemical class 0.000 claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 32
- 239000004065 semiconductor Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 25
- 229910000077 silane Inorganic materials 0.000 claims abstract description 20
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 37
- 229910052731 fluorine Inorganic materials 0.000 claims description 30
- 239000011737 fluorine Substances 0.000 claims description 30
- 125000001153 fluoro group Chemical group F* 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 25
- 125000003118 aryl group Chemical group 0.000 claims description 25
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 25
- 229920002554 vinyl polymer Polymers 0.000 claims description 25
- 125000003545 alkoxy group Chemical group 0.000 claims description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 20
- 229910052801 chlorine Inorganic materials 0.000 claims description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229920000620 organic polymer Polymers 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 239000000412 dendrimer Substances 0.000 claims description 5
- 229920000736 dendritic polymer Polymers 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 150000004756 silanes Chemical class 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000000443 aerosol Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000008119 colloidal silica Substances 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 10
- 239000010408 film Substances 0.000 description 62
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000011229 interlayer Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 239000003989 dielectric material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
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- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000013522 chelant 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
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- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
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- 230000007935 neutral effect Effects 0.000 description 3
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- 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
- 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
- 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-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
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
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- 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
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- 229940043237 diethanolamine Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 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
- 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
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
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- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 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
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 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
- 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 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
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- HAMKTYUJQJZOMY-UHFFFAOYSA-N piperidine;1h-pyrrole Chemical compound C=1C=CNC=1.C1CCNCC1 HAMKTYUJQJZOMY-UHFFFAOYSA-N 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003457 sulfones Chemical group 0.000 description 1
- 150000003462 sulfoxides Chemical group 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- 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
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- 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
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- 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
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Abstract
본 발명은 유기실리케이트 중합체에 관한 것으로, 특히 열적으로 안정한 동시에 성막성이 양호하고, 기계적 특성과 유전특성이 우수한 1 종 이상의 하이드리드 실란화합물과 일반 실란화합물의 가수분해 축중합물의 유기실리케이트 중합체, 및 이의 제조방법과 이를 이용하는 반도체 소자의 절연막 형성용 조성물, 및 이를 적용한 절연막, 및 그의 제조방법을 제공한다.The present invention relates to an organosilicate polymer, in particular an organosilicate polymer of hydrolyzed condensation polymers of at least one hydride silane compound and a general silane compound, which is thermally stable and has good film forming properties and excellent mechanical and dielectric properties, and Provided are a manufacturing method thereof, a composition for forming an insulating film for a semiconductor device using the same, an insulating film using the same, and a manufacturing method thereof.
본 발명의 유기실리케이트 중합체를 절연막에 적용하면 얻어지는 막은 절연성, 탄성률이 우수하고, 또한 도막의 기계적 특성이 우수하다.When the organosilicate polymer of the present invention is applied to an insulating film, the film obtained is excellent in insulation and elastic modulus and excellent in mechanical properties of the coating film.
Description
본 발명은 유기실리케이트 중합체에 관한 것으로, 특히 열적으로 안정한 동시에 성막성이 양호하고, 기계적 특성과 유전 특성이 우수한 저유전 유기실리케이트 중합체, 및 이의 제조방법과 이를 이용하는 반도체 소자의 절연막 형성용 조성물, 및 이를 적용한 절연막, 및 그의 제조방법에 관한 것이다.The present invention relates to an organosilicate polymer, and in particular, a low dielectric organosilicate polymer which is thermally stable and has a good film forming property, and has excellent mechanical and dielectric properties, a method for preparing the same, and a composition for forming an insulating film of a semiconductor device using the same, and The present invention relates to an insulating film and a method of manufacturing the same.
최근 반도체 소자의 집적도가 증가하면서 소자 내부를 연결하는 도선의 선폭이 급속하게 줄어들고 있으며, 2003년경에는 0.1 ㎛의 회로 선 폭을 이용한 고밀도의 소자가 개발될 것으로 예상된다. 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 저 유전 물질의 사용은 반도체 소자의 속도 증가 뿐만 아니라, 소비전력을 낮출 수 있고, 금속 배선 간의 상호 간섭(cross-talk) 현상을 현저히 감소시킬 수 있는 이점이 있다.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. 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 dense chip is determined by the RC delay on the dense chip rather than the switching speed. do. 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 30 % 이상의 성능 향상을 보인 반도체 시제품을 출시한 바 있다. 반면에 저유전 물질을 적용한 반도체 소자는 적절한 소재 개발의 미비로 상업화에 어려움을 겪고 있다.IBM has recently released a prototype of a semiconductor that does not use traditional aluminum wiring, but uses a high-conductivity copper wiring that improves performance by more than 30 percent. On the other hand, semiconductor devices using low dielectric materials are having difficulty in commercialization due to insufficient development of appropriate materials.
종래의 IC, LSI 등의 반도체 소자의 층간 절연 재료는 유전상수가 4.0인 SiO2가 대부분이며, 저유전 물질로 플로린이 도핑된 실리케이트(F-SiO2)가 일부 소자에 적용되고 있다. 그러나 F-SiO2의 경우 플로린의 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.Most of the interlayer insulating materials of semiconductor devices such as ICs and LSIs are SiO 2 having a dielectric constant of 4.0, and silicate (F-SiO 2 ) doped with florin as a low dielectric material is applied to some devices. However, in the case of F-SiO 2 , when the content of florin is 6% or more, the state becomes thermally unstable, and there is a problem in that the dielectric constant is less than 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 플로린을 함유하거나 또는 함유하지 않은 폴리 이미드 수지, 폴리 아릴렌 에테르 수지, 및 퍼플로로 사이클로 부탄 함유 수지 등이 알려져 있다. 이들 유기 고분자들은 대부분 유전상수가 3.0 이하이지만 일반적으로 유리 전이 온도가 낮아서 고온에서의 탄성률이 현저히 떨어지고 선팽창 계수가 매우 높은 문제점이 있다. 또한 플로린을 함유한 유기 고분자는 이러한 물성들이 더욱 저하된다. 반도체 제조 공정 및 패키징 공정은 공정 중에 200 내지450 ℃의 높은 온도까지 올라갈 수 있다. 그러므로 이와 같이 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, perfluoro cyclobutane-containing resins, and the like with or without florin. Most of these organic polymers have a dielectric constant of 3.0 or less, but generally have a low glass transition temperature, which significantly reduces the elastic modulus at high temperatures and has a very high coefficient of linear expansion. In addition, the organic polymer containing florin is further reduced these properties. The semiconductor manufacturing process and the packaging process can be elevated to high temperatures of 200-450 ° C. during the process. Therefore, the organic polymer having such low thermal stability, elastic modulus and high linear expansion coefficient can reduce the reliability of the device or the wiring board.
상기에서 설명한 유기 고분자의 열적 안정성 문제를 해결하기 위하여 솔-젤(sol-gel) 공정을 이용한 유기실리케이트 고분자 개발이 최근에 진행중이다. 이 방법은 유기 실란을 가수분해, 축합반응 후 경화 공정을 통하여 유기 실리케이트 막을 형성하는 방법이다. 이러한 방법으로 실세스 퀴옥산은 3.0 이하의 낮은 유전 상수를 갖고 450 ℃에서 열적으로 안정하다. 그러나 상기 유기실리케이트 고분자는 경화 공정 중에 발생하는 수축 응력이 매우 커서 1 ㎛ 이상의 두께에서 크랙이 발생하기 쉽고, 알킬기의 도입으로 기계적 강도가 낮고, 최종 경화 후 미 반응 관능기가 잔존하는 경우가 있다.In order to solve the thermal stability problem of the organic polymer described above, the development of an organosilicate polymer using a sol-gel process is recently underway. This method is a method of forming an organic silicate film through a curing process after hydrolysis and condensation reaction of the organic silane. In this way, silses quoxane has a low dielectric constant of 3.0 or less and is thermally stable at 450 ° C. However, the organosilicate polymer is very large in shrinkage stress generated during the curing process, so that cracks are likely to occur at a thickness of 1 μm or more, the mechanical strength is low due to the introduction of alkyl groups, and unreacted functional groups may remain after the final curing.
본 발명은 상기 종래 기술의 문제점을 고려하여, 반도체 소자의 고속화와 소비 전력량 감소가 가능하며, 금속 배선의 상호 간섭 현상을 현저히 줄일 수 있는 초저유전 배선 층간 절연막으로 사용될 수 있는 저유전 물질을 제공하는 것을 목적으로 한다.SUMMARY OF THE INVENTION In view of the problems of the prior art, the present invention can provide a low dielectric material that can be used as an ultra-low dielectric wiring interlayer insulating film capable of speeding up a semiconductor device and reducing power consumption and significantly reducing mutual interference of metal wiring. For the purpose of
본 발명의 다른 목적은 성막 특성이 양호하고, 기계적 특성 및 유전 특성이 우수한 실리카계 중합체와 그의 제조방법, 및 이 중합체를 함유하는 절연막, 및 그의 제조방법을 제공하는 것이다.Another object of the present invention is to provide a silica-based polymer having good film forming properties, excellent mechanical and dielectric properties, a method for producing the same, an insulating film containing the polymer, and a method for producing the same.
본 발명은 상기 목적을 달성하기 위하여, 유기 실리케이트 중합체에 있어서,The present invention, in order to achieve the above object, in the organic silicate polymer,
a) 1 종 이상의 하기 화학식 1로 표시되는 하이드리드 실란화합물; 및a) at least one hydride silane compound represented by Formula 1; And
b) 하기 화학식 2로 표시되는 화합물, 하기 화학식 3으로 표시되는 화합물,b) a compound represented by formula 2, a compound represented by formula 3,
및 하기 화학식 4로 표시되는 화합물의 군으로부터 1 종 이상 선택되는And at least one selected from the group of compounds represented by the following general formula (4):
실란화합물Silane compound
의 가수분해 축합물의 유기실리케이트 중합체를 제공한다:An organosilicate polymer of hydrolysis condensation of is provided:
[화학식 1][Formula 1]
상기 화학식 1의 식에서,In the formula of Formula 1,
R1은 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이며,R 1 is aryl, vinyl, allyl, or unsubstituted or substituted with fluorine, straight or branched alkyl of 1 to 4 carbon atoms,
R2는 염소, 아세톡시, 하이드록시, 또는 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알콕시이며, p는 0 내지 2의 정수이다.R 2 is chlorine, acetoxy, hydroxy, or straight or branched alkoxy having 1 to 4 carbon atoms, and p is an integer of 0 to 2;
[화학식 2][Formula 2]
상기 화학식 2의 식에서,In the formula (2),
R3는 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이며,R 3 is aryl, vinyl, allyl, or unsubstituted or substituted with fluorine, straight or branched alkyl of 1 to 4 carbon atoms,
R4는 염소, 아세톡시, 하이드록시, 또는 직쇄 또는 분지쇄 상의 탄소수 1 내지 4의 알콕시이며, q는 0 내지 3의 정수이다.R 4 is chlorine, acetoxy, hydroxy, or straight or branched alkoxy having 1 to 4 carbon atoms, and q is an integer of 0 to 3;
[화학식 3][Formula 3]
상기 화학식 3의 식에서,In the formula (3),
R5및 R7은 각각 독립적으로 수소, 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄 상의 탄소수 1 내지 4의 알킬이며,R 5 and R 7 are each independently hydrogen, aryl, vinyl, allyl, unsubstituted or substituted with fluorine, straight or branched alkyl of 1 to 4 carbon atoms,
R6및 R8은 각각 독립적으로 염소, 아세톡시, 하이드록시, 또는 직쇄 또는 분지쇄 상의 탄소수 1 내지 4의 알콕시이며,R 6 and R 8 are each independently chlorine, acetoxy, hydroxy, or straight or branched alkoxy having 1 to 4 carbon atoms,
r, 및 s는 각각 독립적으로 0 내지 2의 정수이다.r, and s are each independently an integer of 0-2.
[화학식 4][Formula 4]
상기 화학식 4의 식에서,In the formula (4),
R9은 수소, 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알킬이며,R 9 is hydrogen, aryl, vinyl, allyl, or unsubstituted or substituted with fluorine, straight or branched alkyl of 1 to 4 carbon atoms,
R10는이고, 여기에서, R10의 R11은 수소, 아릴, 비닐, 알릴, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1내지 4의 알킬이고, R12는 염소, 아세톡시, 하이드록시, 또는 치환되지 않거나 불소로 치환된 직쇄 또는 분지쇄상의 탄소수 1 내지 4의 알콕시이고, a는 1 내지 6의 정수이고, b는 0 내지 2의 정수이며,R 10 is And, in which, in R 10 R 11 is hydrogen, aryl, vinyl, allyl, or is optionally substituted with a straight-chain or alkyl having 1 to 4 carbon atoms, branched chain substituted with fluorine, R 12 is chlorine, acetoxy, hydroxy Or unsubstituted or substituted with fluorine, straight or branched alkoxy having 1 to 4 carbon atoms, a is an integer of 1 to 6, b is an integer of 0 to 2,
n, 및 m은 각각 독립적으로 0 내지 10의 정수이다.n, and m are each independently an integer of 0-10.
또한 본 발명은 유기실리케이트 중합체의 제조방법에 있어서,In addition, the present invention is a method for producing an organosilicate polymer,
a) 유기용매에a) in an organic solvent
ⅰ) 1 종 이상의 상기 화학식 1로 표시되는 하이드리드 실란화합물; 및Iii) at least one hydride silane compound represented by formula (1); And
ⅱ) 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는Ii) a compound represented by Formula 2, represented by Formula 3
화합물, 및 상기 화학식 4로 표시되는 화합물의 군으로부터 1 종1 type from a compound, and the group of a compound represented by the said Formula (4)
이상 선택되는 실란화합물Silane compound selected above
을 혼합하는 단계;Mixing the;
b) 상기 혼합물에 촉매 및 물을 가하고 가수분해 및 축합반응을 시키는 단계b) adding a catalyst and water to the mixture and subjecting it to hydrolysis and condensation
를 포함하는 유기실리케이트 중합체의 제조방법을 제공한다.It provides a method for producing an organosilicate polymer comprising a.
또한 본 발명은 반도체 소자의 절연막 형성용 조성물에 있어서,In addition, the present invention is a composition for forming an insulating film of a semiconductor device,
a) ⅰ) 1 종 이상의 상기 화학식 1로 표시되는 하이드리드 실란화합물; 및a) iii) at least one hydride silane compound represented by formula (1); And
ⅱ) 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는Ii) a compound represented by Formula 2, represented by Formula 3
화합물, 및 상기 화학식 4로 표시되는 화합물의 군으로부터 1 종1 type from a compound, and the group of a compound represented by the said Formula (4)
이상 선택되는 실란화합물Silane compound selected above
의 가수분해 축합물의 유기실리케이트 중합체; 및Organosilicate polymers of hydrolysis condensates of; And
b) 유기 용매b) organic solvents
를 포함하는 절연막 형성용 조성물을 제공한다.It provides a composition for forming an insulating film comprising a.
상기 절연막 형성용 조성물에 있어서,In the composition for forming an insulating film,
c) 유기 분자, 유기폴리머, 유기 덴드리머, 콜로이드상 실리카, 에어로졸, 지오로졸, 및 계면활성제로 이루어진 군으로부터 1 종 이상 선택되는 첨가제를 그 목적에 맞게 더욱 포함할 수 있다.c) an additive selected from the group consisting of organic molecules, organic polymers, organic dendrimers, colloidal silica, aerosols, geosols, and surfactants may be further included for the purpose.
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) ⅰ) ㄱ) 1 종 이상의 상기 화학식 1로 표시되는 하이드리드 실란화합물;a) iii) a) at least one hydride silane compound represented by Formula 1;
및And
ㄴ) 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는B) a compound represented by Formula 2, represented by Formula 3
화합물, 및 상기 화학식 4로 표시되는 화합물의 군으로부터 1 종1 type from a compound, and the group of a compound represented by the said Formula (4)
이상 선택되는 실란화합물Silane compound selected above
의 가수분해 축합물의 유기실리케이트 중합체;Organosilicate polymers of hydrolysis condensates of;
ⅱ) 유기 용매; 및Ii) organic solvents; And
ⅲ) 필요시, 유기 분자, 유기폴리머, 유기 덴드리머, 콜로이드상 실리카,I) organic molecules, organic polymers, organic dendrimers, colloidal silica,
에어로졸, 지오로졸, 및 계면활성제로 이루어진 군으로부터 1 종1 type from the group consisting of aerosol, geosol, and surfactant
이상 선택되는 첨가제More than one additive
를 포함하는 절연막 형성용 조성물 용액을 제공하는 단계:Providing a composition solution for forming an insulating film comprising:
b) 상기 a)단계의 용액을 반도체 소자의 기재에 도포하여 절연막을 형성시b) applying the solution of step a) to the substrate of the semiconductor device to form an insulating film
키는 단계;Keying up;
c) 상기 b)단계에서 형성되는 절연막을 건조, 및 소성하는 단계; 및c) drying and baking the insulating film formed in step b); And
d) 필요시 상기 절연막을 표면 처리하는 단계d) surface treating the insulating film if necessary
를 포함하는 절연막의 제조방법을 제공한다.It provides a method of manufacturing an insulating film comprising a.
이하에서 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail.
본 발명은 유기 실리케이트 중합체로 1 종 이상의 상기 화학식 1로 표시되는 하이드리드 실란화합물, 및 상기 화학식 2로 표시되는 화합물, 상기 화학식 3으로 표시되는 화합물, 및 상기 화학식 4로 표시되는 화합물의 군으로부터 1 종 이상 선택되는 실란화합물을 일정 비율로 혼합하여 제조되는 가수분해 축합물 및 이의 제조방법, 이를 함유하는 막 형성용 조성물 및 이 조성물로 제조되는 공중합 유기실리케이트 고분자 층간 절연막 및 그의 제조방법을 제공하는 것이다.The present invention relates to an organic silicate polymer comprising at least one hydride silane compound represented by Formula 1, and a compound represented by Formula 2, a compound represented by Formula 3, and a compound represented by Formula 4 It is to provide a hydrolysis-condensation product prepared by mixing a silane compound selected from a species or more at a predetermined ratio, a method for producing the same, a film-forming composition containing the same, and a copolymerized organosilicate polymer interlayer insulating film prepared from the composition and a method for producing the same. .
본 발명의 유기실리케이트 중합체는 절연막에 적용하면 저 유전율 특성을 나타내면서 기계적 물성이 우수하다.The organosilicate polymer of the present invention, when applied to an insulating film, exhibits low dielectric constant and is excellent in mechanical properties.
본 발명의 상기 화학식 1의 하이드리드 실란화합물과 상기 화학식 2, 3, 또는 4의 실란화합물군으로 구성된 실란 조성물은 용매의 존재 하에서 물과 촉매를 첨가하고 가수분해 및 축합 반응을 시켜서 일정한 분자량의 유기 실리케이트 고분자를 얻어 절연막 형성용 조성물을 얻는다. 상기 화학식 1의 하이드리드 실란화합물군과 상기 화학식 2, 3, 또는 4의 실란화합물군의 혼합 순서에는 특정한 제한이 없다. 이를테면, 전체 사용량을 처음부터 모두 혼합한 후 가수분해 축합 반응을 하여도 좋고, 전체 사용량 중 일정량을 먼저 가수 분해 축합 반응시켜 일정 분자량으로 키우고 나머지를 후 첨가하여 더욱 반응시켜도 좋다.The silane composition composed of the hydride silane compound represented by Chemical Formula 1 and the silane compound group represented by Chemical Formulas 2, 3, or 4 according to the present invention may be added with water and a catalyst in the presence of a solvent, and subjected to hydrolysis and condensation reactions to produce organic compounds having a constant molecular weight. The silicate polymer is obtained to obtain a composition for forming an insulating film. There is no particular restriction on the mixing order of the hydride silane compound group of Formula 1 and the silane compound group of Formula 2, 3, or 4. For example, hydrolysis condensation reaction may be performed after mixing all the used amounts from the beginning, or a certain amount of the total amount may be first hydrolyzed and condensed to raise to a certain molecular weight, and then the remainder may be further added.
상기 화학식 1의 하이드리드 실란화합물의 사용량은 전체 사용한 실란화합물의 실리콘 원자 1 몰당 실리콘에 붙은 수소원자의 수가 0.001 몰에서 0.5 몰, 바람직하게는 0.005 몰에서 0.2 몰이 되도록 혼합한다.The amount of the hydride silane compound of Formula 1 is mixed so that the number of hydrogen atoms attached to silicon per mol of silicon atoms of the total silane compounds is 0.001 mol to 0.5 mol, preferably 0.005 mol to 0.2 mol.
상기 유기실리케이트 중합체를 제조함에 있어서, 상기 화학식 2로 표기된 화합물 중에서 q가 2 또는 3인 화합물을 사용하는 경우에는 총 실란화합물에 대하여 70 중량% 미만, 바람직하게는 40 중량% 미만을 사용하는 것이 바람직하다. 그 이상 사용할 경우에는 막강도의 저하를 가져올 수 있다.In preparing the organosilicate polymer, when using a compound having q of 2 or 3 in the compound represented by Formula 2, it is preferable to use less than 70% by weight, preferably less than 40% by weight based on the total silane compound. Do. If used more than this, the film strength may be lowered.
본 발명의 중합 또는 절연막 형성용 조성물에 사용된 용매는, 예를 들면 n-펜탄, i-펜탄, n-헥산, i-헥산, 2,2,4-트리메틸펜탄, 시클로 헥산, 메틸시클로 헥산 등의 지방족 탄화 수소계 용매; 벤젠, 톨루엔, 크실렌, 트리메틸 벤젠, 에틸 벤젠, 메틸 에틸 벤젠 등의 방향족 탄화 수소계 용매; 메틸알콜, 에틸알콜, n-프로판올, i-프로판올, n-부탄올, i-부탄올, sec-부탄올, t-부탄올, 시클로 헥사놀, 메틸사이클로 헥사놀, 글리세롤 등의 알코올계 용매; 테트라하이드로퓨란, 2-메틸 테트라하이드로 퓨란, 에틸에테르, n-프로필에테르, 이소프로필에테르, 디글라임, 디옥신, 디메틸 디옥신, 에틸렌글리콜모노메틸에테르, 에틸렌글리콜 디메틸에테르, 에틸렌글리콜디에틸에테르, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜 디메틸 에테르 등의 에테르계 용매; 디에틸카보네이트, 메틸아세테이트, 에틸아세테이트, 에틸락테이트, 에틸렌글리콜모노메틸에테르아세테이트, 프로필렌글리콜모노메틸에테르아세테이트, 에틸렌글리콜디아세테이트 등의 에스테르계 용매; N-메틸피롤리돈, 포름아마이드, N-메틸포름아마이드, N-에틸포름아마이드, N,N-디메틸아세트아마이드, N,N-디에틸아세트아마이드 등의 아마이드계 용매 등이 있다.The solvent used for the composition for polymerization or insulating film formation of the present invention is, for example, n-pentane, i-pentane, n-hexane, i-hexane, 2,2,4-trimethylpentane, cyclohexane, methylcyclohexane, and the like. Aliphatic hydrocarbon solvents; Aromatic hydrocarbon solvents such as benzene, toluene, xylene, trimethyl benzene, ethyl benzene and methyl ethyl benzene; Alcohol solvents such as methyl alcohol, ethyl alcohol, n-propanol, i-propanol, n-butanol, i-butanol, sec-butanol, t-butanol, cyclo hexanol, methylcyclo hexanol and glycerol; Tetrahydrofuran, 2-methyl tetrahydrofuran, ethyl ether, n-propyl ether, isopropyl ether, diglyme, dioxin, dimethyl dioxin, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, Ether solvents such as propylene glycol monomethyl ether and propylene glycol dimethyl ether; Ester solvents such as diethyl carbonate, methyl acetate, ethyl acetate, ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and ethylene glycol diacetate; Amide solvents such as N-methylpyrrolidone, formamide, N-methylformamide, N-ethylformamide, N, N-dimethylacetamide, and N, N-diethylacetamide.
가수분해 및 축합반응에 사용된 용매들은 반응 후 모두 제거하여 유기실리케이트 고분자 오일 또는 분말을 얻고, 다시 이 유기실리케이트 고분자를 막 형성용 유기 용매에 녹여 사용하거나, 또는 가수분해 및 축합반응에 사용된 유기 용매 중 코팅성에 나쁜 영향을 주는 특정 용매를 일정량 제거한 후 직접 막형성에 사용할 수 있다. 상기 유기 용매들은 1 종 또는 2 종 이상 혼합하여 사용하는 것이 가능하다.The solvents used in the hydrolysis and condensation reactions are all removed after the reaction to obtain an organosilicate polymer oil or powder, and the organic silicate polymer is dissolved in an organic solvent for film formation, or used in the hydrolysis and condensation reactions. After removing a certain amount of a specific solvent that adversely affects the coating property in the solvent can be used for direct film formation. The said organic solvent can be used 1 type or in mixture of 2 or more types.
본 발명에서는 가수 분해 축합반응을 촉진시키기 위하여 촉매를 사용하는 것이 바람직하다. 가수분해 축합반응에 사용되는 촉매는 산 촉매, 염기 촉매, 금속킬레이트화합물 등이 가능하고 바람직하게는 산 촉매가 적당하다. 예를 들면, 산촉매는 염산, 질산, 황산, 인산, 포름산, 벤젠술폰산, 톨루엔술폰산, 아세트산, 옥살산, 말론산, 말레산, 푸마르산, 구연산, 프로피온산 등이 가능하고, 염기촉매는 암모니아, 수산화나트륨, 수산화칼슘, 수산화칼륨, 트리메틸아민, 트리에틸아민, 디에탄올아민, 트리에탄올아민, 디메틸 에틸알콜 아민, 모노메틸 디에탄올 아민디아자비시클로운데센, 피리딘,피롤피페리딘, 콜린, 피롤리딘, 피페라진 등이 가능하다. 금속킬레이트 화합물은 알루미늄, 티탄, 지르코늄, 주석, 탄타륨 등의 금속으로 이루어진 유기금속 화합물을 들 수 있다. 상기 산, 염기 및 금속킬레이트 화합물은 단독 또는 조합하여 사용할 수 있다. 또한 2 종 이상을 단계적으로 사용하는 것도 가능하다.In the present invention, it is preferable to use a catalyst to promote the hydrolytic condensation reaction. The catalyst used for the hydrolysis condensation reaction may be an acid catalyst, a base catalyst, a metal chelate compound, or the like, and an acid catalyst is preferable. For example, the acid catalyst may be hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, formic acid, benzenesulfonic acid, toluenesulfonic acid, acetic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, citric acid, propionic acid, and the like. Calcium hydroxide, potassium hydroxide, trimethylamine, triethylamine, diethanolamine, triethanolamine, dimethyl ethyl alcohol amine, monomethyl diethanol amine diazabicyclo undecene, pyridine, pyrrole piperidine, choline, pyrrolidine, piperazine Etc. are possible. Examples of the metal chelate compound include organometallic compounds made of metals such as aluminum, titanium, zirconium, tin, and tantalum. The acid, base and metal chelate compounds may be used alone or in combination. It is also possible to use two or more kinds in stages.
이러한 촉매의 첨가량은 사용된 총 실란화합물 1 몰에 대하여 0.0001 내지 1몰을 사용하고, 바람직하게는 0.5 몰 이하를 사용한다. 촉매의 양이 실란화합물 1 몰당 1 몰 이상일 경우에는 반응 속도가 매우 빨라 분자량 조절이 어렵고, 쉽게 겔이 발생할 우려가 있다.The amount of the catalyst added is 0.0001 to 1 mole, preferably 0.5 moles or less, based on 1 mole of the total silane compounds used. When the amount of the catalyst is 1 mol or more per mol of the silane compound, the reaction rate is very fast, so that the molecular weight is difficult to control, and there is a risk of gel generation easily.
본 발명에서는 실란화합물의 가수 분해를 위하여 물을 첨가한다. 실란화합물의 가수분해에 적합한 물의 양은 사용된 총 실란화합물의 실리콘 원자 1 몰당 0.1 내지 20 몰이 적당하고, 바람직하기로는 1 내지 10 몰이 적당하다. 물의 첨가 방법은 단속적 또는 연속적으로 첨가가 가능하다. 이때 촉매는 유기 용매 중에 미리 첨가해 있어도 좋고, 수 첨가시 용해 또는 분산시키고 있어도 좋다. 이때 반응 온도는, 통상 0 내지 100 ℃에서 반응시키고, 바람직하게는 15 내지 80 ℃에서 반응시키는 것이 바람직하다. 이때 얻어지는 가수분해 축합물의 중량 평균 분자량은 통상 500 내지 1,000,000, 바람직하게는 1000 내지 1,000,000 이다.In the present invention, water is added for hydrolysis of the silane compound. The amount of water suitable for hydrolysis of the silane compound is suitably 0.1 to 20 moles per mole of silicon atoms of the total silane compounds used, and preferably 1 to 10 moles. The addition method of water can be added intermittently or continuously. At this time, the catalyst may be previously added to the organic solvent, or may be dissolved or dispersed at the time of addition. At this time, reaction temperature is made to react at 0-100 degreeC normally, Preferably it is made to react at 15-80 degreeC. The weight average molecular weight of the hydrolyzed condensate obtained at this time is usually 500 to 1,000,000, preferably 1000 to 1,000,000.
본 발명에서 얻어지는 막형성용 조성물에는 절연막의 밀도를 더욱 낮추기 위하여 유기분자, 유기폴리머, 덴드리머를 일정량 첨가해도 좋다. 유기물의 종류에는 큰 제한은 없으며, 200 내지 450 ℃에서 열분해가 가능한 물질로, 예를 들면 알리파틱 하이드로 카본, 아로마틱 하이드로카본, 에테르 관능기 분자, 에스테르 관능기 분자, 안하이드라이드 관능기 분자, 카보네이드 관능기 분자, 아크릴 관능기 분자, 사이오 에테르 관능기 분자, 아이소시아네이트 관능기 분자, 아이소 시아누레이트 관능기 분자, 설폰 관능기 분자, 및 설폭사이드 관능기 분자 등으로 구성된 유기분자 또는 고분자 등이 가능하다. 위의 유기분자 또는 유기 고분자는 유기 실리케이트와 반응할 수 있는 알콕시 실란 관능기를 분자 말단 또는 분자내에 함유하여도 좋다. 유기폴리머, 덴드리머는 유기실리케이트 중합체 제조 후 막형성 조성물에 첨가하여 사용하거나 유기실리케이트 중합체 제조시 첨가 할 수 있다.In order to further lower the density of the insulating film, the film-forming composition obtained in the present invention may be added with a certain amount of organic molecules, an organic polymer, and a dendrimer. There is no big limitation in the kind of organic matter, and it is a material which can be thermally decomposed at 200 to 450 ℃, for example aliphatic hydrocarbon, aromatic hydrocarbon, ether functional molecule, ester functional molecule, anhydride functional molecule, carbonide functional molecule , Organic molecules or polymers composed of an acrylic functional group molecule, a thio ether functional group molecule, an isocyanate functional group molecule, an isocyanurate functional molecule, a sulfone functional group molecule, a sulfoxide functional group molecule, and the like. The above organic molecules or organic polymers may contain an alkoxy silane functional group capable of reacting with an organic silicate at the molecular end or in the molecule. The organopolymer and the dendrimer may be used in addition to the film forming composition after the organosilicate polymer is prepared, or may be added when the organosilicate polymer is prepared.
본 발명에서 얻어지는 막형성용 조성물에는 그 밖의 첨가제로 콜로이드 상태의 실리카, 에어로졸, 지오로졸, 계면활성제 등의 성분을 그 목적에 맞게 일정량 첨가해도 좋다.You may add a fixed amount of components, such as a colloidal silica, an aerosol, a geosol, surfactant, etc. to the film forming composition 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 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 amount of the organic solvent used.
절연막은 본 발명의 조성물을 발명의 실리콘 웨이퍼, SiO2웨이퍼, 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. 그 중에서도 반도체 장치의 다층회로 층간 절연막 제조가 목적일 경우에는 스핀 코트법이 적합하다.The insulating film is formed by coating the composition of the present invention on substrates of the inventive silicon wafer, SiO 2 wafer, SiN wafer, compound semiconductor and the like. 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. Among them, the spin coating method is suitable for the purpose of manufacturing a multilayer circuit interlayer insulating film of a semiconductor device.
막의 두께는 조성물의 점도와 스핀코우터의 회전 속도를 변화시켜 조절할 수 있으며, 통상적으로 반도체 장치의 다층회로구조의 층간 절연막으로 사용하는 경우에 있어서는 0.2 내지 2 ㎛ 이 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, 0.2 to 2 m is appropriate.
코팅 후에는 건조공정과 소성(경화)공정을 거쳐 3차원 구조의 유기실리케이트 고분자 절연막을 형성할 수 있다. 건조 공정은 통상적으로 프리베이크(pre-bake) 공정과 소프트베이크(soft-bake) 공정을 포함하는 것을 의미한다. 프리베이크 공정 중 사용한 유기용매를 서서히 증발시키고, 소프트베이크 공정 중에 관능기의 일정량을 가교 시킨 다음 소성 공정 중 잔류 관능기를 최종적으로 반응시킨다. 건조온도와 소성온도는 각각 30 내지 350 ℃와 350 내지 600 ℃에서 실시하는 것이고, 특히 소성온도는 350 내지 500 ℃에서 실시하는 것이 바람직하다. 소성온도가 600 ℃ 이상인 경우에는 유기실리케이트 고분자의 열정안정성이 떨어지고, 반면에 350 ℃ 이하일 경우에는, 유리실리케이트 고분자의 축중합이 완전히 일어나지 않아, 막의 강도가 저하되고, 잔류관능기의 존재로 인하여 유전 특성이 저하될 가능성이 있다.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 typically 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 the functional group is crosslinked during the softbaking process, and the remaining functional groups are finally reacted during the firing process. Drying temperature and baking temperature are performed at 30-350 degreeC and 350-600 degreeC, respectively, It is preferable to carry out baking temperature especially at 350-500 degreeC. If the firing temperature is higher than 600 ℃, the passion stability of the organosilicate polymer is inferior, whereas if it is less than 350 ℃, the condensation polymerization of the glass silicate polymer does not occur completely, the film strength is lowered, the dielectric properties due to the presence of residual functional groups This may fall.
건조공정과 소성공정은 연속적으로 일정한 속도로 승온시키면서 할 수 있고 또한, 단속적으로 실시할 수 있다. 단속적으로 실시할 경우, 건조 및 소성 공정을 각각 1 분 내지 5 시간 동안 수행하는 것이 적당하다. 가열방법은 핫플레이트, 오븐, 퍼니스 등을 사용하는 것이 가능하고, 가열분위기는 질소, 아르곤, 헬륨 등과 같은 불활성 기체분위기에서, 산소함유 기체(예를 들면 공기 등) 분위기 같은 산소분위기, 진공상태 또는 암모니아 및 수소를 함유하는 기체 분위기 하에서 수행하는 것이 가능하다. 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 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. The heating method may be a hot plate, an oven, a furnace, or the like. The heating atmosphere may be an inert gas atmosphere such as nitrogen, argon, helium, or the like, an oxygen atmosphere such as an oxygen-containing gas (for example, air), a vacuum or It is possible to carry out 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 따라서 절연막 내부의 하이드록시기 양을 최소화하기 위하여 표면처리를 한다. 표면처리 방법은 일반적으로 알려진 헥사메틸디실라잔, 알킬클로로실란, 알킬알콕시실란, 알킬아세톡시실란과 같은 실릴화 화합물 사용하거나 또는 수소와 같은 환원 분위기 또는 플러린 함유 가스하에서소성하여 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 drying and firing, surface treatment is performed to minimize the amount of hydroxyl groups in the insulating film. The surface treatment method can be surface treatment by using silylated compounds such as hexamethyldisilazane, alkylchlorosilane, alkylalkoxysilane, alkylacetoxysilane, or baking in a reducing atmosphere such as hydrogen or a fullerene-containing gas. Do. 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, 유전율 특성, 도막의 내크랙성, 도막의 표면 강도가 모두 우수하기 때문에, LSI, 시스템 LSI, DRAM, SDRAM, RDRAM, D-RDRAM 등의 반도체 소자용 층간 절연막, 반도체 소자의 표면 코팅막 등의 보호막, 다층배선 기판의 층간 절연막, 액정표시 소자용의 보호막이나 절연 방지막 등의 용도로 사용하기에 좋다.The film thus obtained is excellent in insulation and excellent in uniformity, dielectric constant characteristics, coating resistance of the coating film, and surface strength of the coating film. Therefore, semiconductors such as LSI, system LSI, DRAM, SDRAM, RDRAM, D-RDRAM, etc. It is suitable for use in applications such as an interlayer insulating film for elements, a protective film such as a surface coating film of a semiconductor device, an interlayer insulating film for a multilayer wiring substrate, a protective film or an insulating film for a liquid crystal display device, and the like.
이하의 실시예 및 비교예를 통하여 본 발명을 더욱 상세하게 설명한다. 단, 실시예는 본 발명을 예시하기 위한 것이지 이들만으로 한정하는 것이 아니다.The present invention will be described in more detail with reference to the following examples and comparative examples. However, an Example is for illustrating this invention and is not limited only to these.
[실시예]EXAMPLE
실시예 1Example 1
(유기실리케이트 축합물의 제조)(Production of Organic Silicate Condensate)
25 ㎖의 테트라하이드로퓨란 용매에 메틸트리메톡시실란 13.6 g, 테트라 에톡시 실란 6.78 g과 메틸디메톡시 실란 0.55 g을 가하고 질소분위기에서 온도를 0 ℃로 낮춘 후 충분히 섞어주었다. 이 혼합용액에 0.78 ㎖의 5.0 N 하이드로 클로린산과 7.74 ㎖의 고순도 수를 천천히 첨가해 준 후, 온도를 70 ℃까지 서서히 올리고 가열환류시켜서 밤새(overnight) 반응시켰다. 반응 후 에테르로 희석시킨 후 물로 pH가 중성이 될 때까지 씻어주고, 얻어진 유기 층은 건조제로 물을 제거한 후에 유기용매를 진공에서 완전히 제거하여 파우더상태로 생성물을 얻었다.13.6 g of methyltrimethoxysilane, 6.78 g of tetraethoxy silane and 0.55 g of methyldimethoxy silane were added to 25 ml of tetrahydrofuran solvent, and the mixture was sufficiently mixed after the temperature was lowered to 0 ° C. in a nitrogen atmosphere. 0.78 mL of 5.0 N hydrochloric acid and 7.74 mL of high purity water were slowly added to the mixed solution, and the temperature was gradually raised to 70 DEG C and heated to reflux for overnight reaction. After the reaction, the mixture was diluted with ether and washed with water until the pH became neutral. The obtained organic layer was dried with a drying agent, and then the organic solvent was completely removed in vacuo to obtain a product in powder form.
(절연막 제조)(Insulation film production)
상기에서 얻어진 파우더 300 ㎎을 메틸이소부틸 케톤에 녹여 전체 용액이 1.5 g이 되게 하였다. 얻어진 용액은 필터를 통하여 불순물을 제거한 후 스핀 코팅하여 박막을 얻고, 질소 분위기 하에서 건조 공정 및 경화 공정을 거쳐 절연막을 제조하였다.300 mg of the powder obtained above was dissolved in methyl isobutyl ketone to make the total solution 1.5 g. The obtained solution was spin-coated after removing impurities through a filter to obtain a thin film, and an insulating film was prepared through a drying process and a curing process under a nitrogen atmosphere.
비교예 1Comparative Example 1
(유기실리케이트 축합물의 제조)(Production of Organic Silicate Condensate)
25 ㎖의 테트라하이드로퓨란 용매에 메틸트리메톡시실란 13.6 g과 테트라 에톡시 실란 6.78 g을 가하고 질소분위기에서 온도를 0 ℃로 낮춘 후 충분히 섞어주었다. 이 혼합용액에 0.78 ㎖의 5.0 N 하이드로 클로린산과 7.74 ㎖의 고순도 수를 천천히 첨가해 준 후, 온도를 70 ℃까지 서서히 올리고 가열 환류시켜서 밤새(overnight) 반응시켰다. 반응 후 에테르로 희석시킨 후 물로 pH가 중성이 될 때까지 씻어준다. 얻어진 유기 층은 건조제로 물을 제거한 후에 유기용매를 진공에서 완전히 제거하여 파우더상태로 생성물을 얻었다.13.6 g of methyltrimethoxysilane and 6.78 g of tetraethoxy silane were added to 25 ml of tetrahydrofuran solvent, and the mixture was sufficiently mixed after lowering the temperature to 0 ° C. in a nitrogen atmosphere. 0.78 mL of 5.0 N hydrochloric acid and 7.74 mL of high purity water were slowly added to the mixed solution, and the temperature was gradually raised to 70 DEG C and heated to reflux for overnight reaction. After the reaction, dilute with ether and wash with water until the pH is neutral. The obtained organic layer was dried with a drying agent, and then the organic solvent was completely removed in vacuo to obtain a product in powder form.
(절연막 제조)(Insulation film production)
상기에서 얻어진 파우더는 실시예 1의 방법과 마찬가지로 건조 및 경화 공정을 거처 절연막을 제조하였다.The powder thus obtained was subjected to a drying and curing process in the same manner as in Example 1 to prepare an insulating film.
비교예 2Comparative Example 2
(유기실리케이트 축합물의 제조)(Production of Organic Silicate Condensate)
15 ㎖의 테트라하이드로퓨란 용매에 메틸트리메톡시 실란 7.5 g와 4.05 ㎖의 고순도 수를 넣고 온도를 0 ℃로 낮춘 후 충분히 섞어주었다. 이 혼합용액에 2 N 농도의 하이드로클로린산 0.80 ㎖를 천천히 첨가하면서 교반시켰다. 이들을 30 분간 실온에서 반응시킨 후, 온도를 70 ℃까지 서서히 올리고 가열환류시켜서 밤새(overnight) 반응시켰다. 반응 후 에테르로 희석시킨 후 물로 pH가 중성이 될 때까지 씻어주고, 얻어진 유기 층은 건조제로 물을 제거한 후에 유기용매를 진공에서 완전히 제거하여 파우더상태로 생성물을 얻었다.7.5 g of methyltrimethoxy silane and 4.05 ml of high purity water were added to 15 ml of tetrahydrofuran solvent, and the temperature was lowered to 0 ° C. and mixed well. The mixed solution was stirred while slowly adding 0.80 ml of hydrochloric acid at a concentration of 2N. After reacting these at room temperature for 30 minutes, the temperature was gradually raised to 70 ° C and heated to reflux to react overnight. After the reaction, the mixture was diluted with ether and washed with water until the pH became neutral. The obtained organic layer was dried with a drying agent, and then the organic solvent was completely removed in vacuo to obtain a product in powder form.
(절연막 제조)(Insulation film production)
상기에서 얻어진 파우더는 실시예 1의 방법과 같은 방법으로 건조 및 경화 공정을 거쳐서 절연막을 제조하였다.Powder obtained above was dried and cured in the same manner as in Example 1 to prepare an insulating film.
(물성 측정)(Property measurement)
도막의 유전특성은 MIM(metal/insulator/semiconductor) 소자를 Si 웨이퍼 위에 제작하고 HP사의 LCR 미터를 이용하여 1 Mhz에서 측정하였다.The dielectric properties of the coating film were fabricated on a Si wafer using a metal / insulator / semiconductor (MIM) device and measured at 1 Mhz using an HP LCR meter.
절연 박막의 기계적 물성은 2x2 인치 Si 웨이퍼(wafer)에 스핀 코팅한 다음, N2조건 하에 430 ℃에서 1 시간 동안 경화시킨 후 측정하였다.The mechanical properties of the insulating thin film were spin coated on a 2 × 2 inch Si wafer, and then cured at 430 ° C. for 1 hour under N 2 .
절연막의 탄성률은 하지트론(Hysitron Inc.)의 트리보인덴터(TriboIndenter)를 사용하여 측정하였다.The elastic modulus of the insulating film was measured using TriboIndenter of Hysitron Inc.
절연막의 내크랙 특성은 1 ㎛ 두께의 박막을 제작하여 크랙을 내고 크랙의 진행 속도를 측정하여 관찰하였다.The crack resistance of the insulating film was observed by making a thin film having a thickness of 1 μm and measuring the progress of cracking.
상기 각각의 실험 결과는 하기 표 1에 나타내었다.The results of each experiment are shown in Table 1 below.
상기 표 1에서 알 수 있듯이, 본 발명에 의하여 제조되는 유기실리케이트 고분자로 박막을 제조한 경우 절연막의 강도가 높고, 탄성률이 높으며, 절연성이 우수함을 알 수 있다.As can be seen in Table 1, when the thin film is manufactured from the organosilicate polymer prepared according to the present invention, it can be seen that the strength of the insulating film is high, the elastic modulus is high, and the insulation is excellent.
본 발명의 유기실리케이트 중합체는 이를 절연막에 적용하면 얻어지는 막은 절연성, 탄성률이 우수하고, 또한 도막의 기계적 특성이 우수하다.When the organosilicate polymer of the present invention is applied to an insulating film, the film obtained is excellent in insulation and elastic modulus and also excellent in mechanical properties of the coating film.
Claims (14)
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| KR100508902B1 (en) * | 2002-05-06 | 2005-08-17 | 주식회사 엘지화학 | Organic silicate polymer and insulation film comprising the same |
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| KR100450257B1 (en) * | 2001-10-12 | 2004-09-30 | 주식회사 엘지화학 | Organic silicate polymer and low dielectric insulation film comprising the same |
| KR100645682B1 (en) * | 2003-04-17 | 2006-11-13 | 주식회사 엘지화학 | Organic Siloxane Resins and Insulating Film Using the Same |
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