WO2005014744A1 - Composition de revetement et materiau siliceux poreux a faible constante dielectrique produit au moyen de ladite composition - Google Patents
Composition de revetement et materiau siliceux poreux a faible constante dielectrique produit au moyen de ladite composition Download PDFInfo
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- WO2005014744A1 WO2005014744A1 PCT/JP2004/011136 JP2004011136W WO2005014744A1 WO 2005014744 A1 WO2005014744 A1 WO 2005014744A1 JP 2004011136 W JP2004011136 W JP 2004011136W WO 2005014744 A1 WO2005014744 A1 WO 2005014744A1
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- WIPO (PCT)
- Prior art keywords
- coating composition
- film
- siliceous
- group
- siliceous material
- Prior art date
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000008199 coating composition Substances 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 19
- 238000010304 firing Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- 239000004065 semiconductor Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 11
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 239000010408 film Substances 0.000 description 115
- 238000000034 method Methods 0.000 description 38
- -1 compound compound Chemical class 0.000 description 34
- 239000011148 porous material Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 26
- 238000010521 absorption reaction Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 15
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 14
- 239000010703 silicon Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 238000004528 spin coating Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005530 etching Methods 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
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- 239000011248 coating agent Substances 0.000 description 5
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- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
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- 239000005055 methyl trichlorosilane Substances 0.000 description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001709 polysilazane Polymers 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 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
- JRKUQQUFMLYTED-UHFFFAOYSA-N 2-methyl-5-trimethylsilyloxypent-2-enoic acid Chemical compound OC(=O)C(C)=CCCO[Si](C)(C)C JRKUQQUFMLYTED-UHFFFAOYSA-N 0.000 description 2
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 description 1
- VIDOPANCAUPXNH-UHFFFAOYSA-N 1,2,3-triethylbenzene Chemical compound CCC1=CC=CC(CC)=C1CC VIDOPANCAUPXNH-UHFFFAOYSA-N 0.000 description 1
- AKHDFTZYLYPQEB-UHFFFAOYSA-N 4-silyloxybutan-2-one Chemical compound CC(=O)CCO[SiH3] AKHDFTZYLYPQEB-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000255925 Diptera Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910014299 N-Si Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910008072 Si-N-Si Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- BTHCBXJLLCHNMS-UHFFFAOYSA-N acetyloxysilicon Chemical group CC(=O)O[Si] BTHCBXJLLCHNMS-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
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- 239000003599 detergent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 125000001303 disiloxanyl group Chemical group [H][Si]([*])([H])O[Si]([H])([H])[H] 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- SENKOTRUJLHKFM-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.CCOC(=O)C(C)=C SENKOTRUJLHKFM-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
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- 125000005647 linker group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 125000005641 methacryl group Chemical group 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000011574 phosphorus Substances 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000011085 pressure filtration Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- QJMMCGKXBZVAEI-UHFFFAOYSA-N tris(trimethylsilyl) phosphate Chemical compound C[Si](C)(C)OP(=O)(O[Si](C)(C)C)O[Si](C)(C)C QJMMCGKXBZVAEI-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02219—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen
- H01L21/02222—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and nitrogen the compound being a silazane
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
Definitions
- the present invention relates to a coating composition. Further, the present invention relates to a method for producing a low dielectric siliceous material using the same, and a low dielectric siliceous film produced using the same. Further, the present invention relates to a semiconductor device comprising the low dielectric siliceous material thus manufactured. Background art
- a method of making an organic siliceous film obtained by firing polyorganosilazane porous can be considered. Since the organic siliceous film thus obtained has a structure in which an organic group is bonded to the silicon atom of silica, the water repellency of the film itself is high and the relative permittivity due to moisture absorption over time is high. In addition to suppressing the rise, it is possible to obtain a porous film having heat resistance and environmental resistance required as an interlayer insulating film for semiconductors.
- Patent Document 1 JP 2002-75982A
- a high-strength porous siliceous film can be obtained by firing a film of a composition containing a polyalkylsilazane and a polyacrylate or a polymethacrylate.
- Patent Document 1 The porous siliceous film described in Patent Document 1 has an effect that a rise in relative dielectric constant over time due to moisture absorption can be suppressed.
- the porous silica film generally has an elastic modulus of 3 GPa or less when the relative dielectric constant is about 2.2, and the film strength is high. It turns out that there is room for improvement in terms of
- the holes formed in the porous film may have smaller diameters, and may have uniform diameters. is important. If the porous insulating film is exposed to an etching gas, a stripping solution, or the like used when forming a multilayer wiring structure, the gas or the stripping solution may enter the large holes and erode. In addition, the stress and heat applied when forming metal wiring and other thin films on the porous film triggers the hole to expand, and furthermore, the local force of the hole becomes S leak purse, and the porous film becomes an insulating film.
- the pore diameter of the pores of the porous membrane is desirably 2 nm or less.
- the conventional method usually produces only a porous film having fine pores having a pore size of 5 to 8 nm, and it is difficult to form a porous film having pores having a uniform pore size of 5 nm or less.
- the present invention provides a polyalkylsilazane conjugate, a siloxy group-containing polymer, and an organic solvent. And a coating composition comprising:
- the siliceous material of the present invention is characterized in that the coating composition is formed by applying the coating composition on a substrate or filling a groove, followed by firing.
- a semiconductor device is characterized in that the above-mentioned siliceous material is included as an interlayer insulating film.
- the above-mentioned coating composition is preliminarily calcined in a steam-containing atmosphere at a temperature of 50 to 300 ° C, and further calcined in a dry atmosphere at a temperature of 300 to 500 ° C. It is characterized by doing.
- the siliceous material according to the present invention is characterized in that it has 0.53 x m micropores inside.
- the present invention solves a problem in the production of a conventional porous material as described above, and provides an excellent mechanical strength that can withstand the latest high integration processes such as the damascene method. easily produce porous siliceous materials with small pores, exhibiting a very low dielectric constant, especially less than 2.5, exhibiting a stable dielectric constant and having chemical resistance to various chemicals. To provide a coating composition that can be used.
- the polyalkylsilazane conjugate in the present invention has an alkyl-substituted silazane bond.
- preferred polyalkylsilazane compounds are preferably those having a repeating unit represented by the following general formula (1) and a unit represented by the general formula (2) or (3). Any of them is included.
- R 1 to R 11 each represent a hydrogen atom or an alkyl group having 13 to 13 carbon atoms.
- R 5 and R 6 , and R 9 —R 11 are not all hydrogen.
- R 1 —R 11 in each formula are as follows.
- R 1 represents a hydrogen atom or an alkyl group having 13 to 13 carbon atoms, but it is not easy for all R 1 of the entire compound to be hydrogen at the same time.
- R 2 — R 4 are each independently a hydrogen atom or a C 1-3 alkyl group R 2 —
- p, q, and r are each 0 or 1, and 0 ⁇ p + q + r ⁇ 3.
- R 1 is a methyl group and R 2 —R 4 are present, it is preferable that all of them are hydrogen.
- R 5 and R 7 are each independently a force S representing a hydrogen atom or an alkyl group having 13 carbon atoms, and all R 5 and R 6 of the whole compound are simultaneously hydrogen. None.
- R 5 and R 6 are a hydrogen atom
- the rest is a methyl group
- R 7 is a hydrogen atom
- R 8 R 11 is a force S independently representing a hydrogen atom or an alkyl group having 13 carbon atoms, and all R 9 R 11 of the whole compound are simultaneously hydrogen. There is no.
- a R 8 is a hydrogen atom, R 9 - that all of R 11 is a methyl group Is preferred.
- a polyalkylsilazane compound compound containing a repeating unit represented by the general formula (1) and at least one of the repeating units represented by the general formula (2) or (3) It is particularly useful in that it can prevent gelling during storage of the tinting composition.
- the number of the repeating units represented by the general formula (1) is 50 mol% or more of the total number of the units represented by the general formulas (1) to (3). More preferably, it is particularly preferably at least 90 mol%.
- the repeating unit force of the general formula (1) is at least 50 mol% with respect to the total number of the repeating units of the general formula (1)-(3), problems such as uneven repelling and coating unevenness are less likely to occur during film formation. It is.
- the polysilazane compound according to the present invention preferably has a number average molecular weight of 100 or more in order to improve the coating properties of the coating composition, particularly the coating properties when applying by a spin coating method.
- the polysilazane conjugate according to the present invention preferably has a number average molecular weight of 50,000 or less in order to suppress the gelation of the composition by appropriately setting the number of crosslinking groups.
- a particularly preferred polyalkylsilazane conjugate comprises a repeating unit of the general formula (1) and at least one unit of the general formula (2) or (3). .
- the number average molecular weight of the polyalkylsilazane conjugate is preferably from 100 to 50,000, more preferably from 1,000 to 20,000.
- polyalkylsilazane conjugates can be used in the case of a polyalkylsilazane containing a repeating unit of the general formula (1) in an ammonolysis process for synthesizing a normal polysilazane, which is obvious to those skilled in the art.
- (R iCl) is represented by the repeating unit of the general formula (2).
- the coating compositions according to the invention comprises a siloxy group-containing polymer c
- the union contains a siloxy group (one Si—o —)-containing monomer as a polymerized unit, and has a main chain
- a side chain, or a terminal unit contains a siloxy group.
- Examples of the group containing a siloxy group include a trimethylsiloxy group, a dimethylbutylsiloxy group, a methylhydrosiloxy group, a dimethylsiloxy group, a phenylmethylsiloxy group, a diphenylsiloxy group, a methylvinylsiloxy group, and a phenyl group.
- the siloxy group-containing polymer according to the present invention contains the above-mentioned siloxy group, it may or may not contain a polymer unit containing no siloxy group.
- a siloxy group-free polymerized unit examples include methyl (meth) acrylic acid, isobutyl (meth) acrylic acid, ⁇ -butyl (meth) acrylic acid, tert-butyl (meth) acrylic acid, polyethylene glycol Forces such as side, polypropylene oxide, polypropylene glycol (meth) acrylic acid and the like are not limited to these.
- the siloxy group-containing polymer is preferably a polymer containing a polymer unit selected from the group consisting of acrylic acid, methacrylic acid, and a polyethylene oxide compound.
- R ′ is an arbitrary substituent such as hydrogen, an alkyl group, an alkoxy group and the like, and R ′ in one molecule may be a mixture of a plurality of types.
- R ′ is a polymerizable group, and can be polymerized with another monomer unit.
- L is a linking group, for example, a single bond, an alkylene group, or the like.
- n and n are numbers representing the degree of polymerization.
- the molecular weight of the siloxy group-containing polymer can be arbitrarily selected as long as the effect of the present invention is not impaired. Or steam It is preferable that the molecular weight of the polymer is not less than a certain value so as to form a porous film by being emitted, but is not more than a certain value from the viewpoint of preventing the generation of voids and a decrease in film strength due to the void. Is preferred. These lower and upper limits are appropriately selected depending on the type of the siloxy group-containing polymer used. When the siloxy group-containing polymer used in the present invention contains a polyethylene oxide compound as a polymerized unit, its molecular weight is preferably 100 5,000, more preferably 500 2,000. .
- the siloxy group-containing polymer contains acrylic acid or methacrylic acid as a polymerized unit
- the molecular weight thereof is preferably 1,000, 80,000, and the molecular weight is preferably 10,000, 20,000 to 20,000. Reason better than mosquito.
- More preferred siloxy group-containing polymers are polymers containing 2- (trimethylsiloxy) ethyl methacrylic acid in the polymerized units and polymers containing hydroxy (polyethyleneoxy) propyl / polydimethylsilicone in the polymerized units. .
- siloxy group-containing polyethylene oxide compound examples include ⁇ - [3- [1,1,3,3-tetramethyl-11-[(trimethylsilyl) oxy] disiloxanyl] propynole] — ⁇ -hydroxy-poly (oxy) 2,3-ethanexyl), hydroxy (polyethyleneoxy) propyl polydimethyl silicone, and MCR-C13 manufactured by Gelest (Pennsylvania, USA).
- the structure of the polyethylene oxide is not particularly limited, but from the viewpoint of appropriately maintaining the viscosity, the weight of the ethyleneoxy moiety is 30 to 90% relative to the weight of the molecule.
- the weight of the siloxy group in the polysiloxy structure is preferably 10 to 40%.
- the hydroxyl group-terminated polyethylene oxide structure crosslinks with the above-mentioned polyalkylsilazane compound. It is thought to increase the pore size and make the pores more porous. Furthermore, the siloxy group-containing polyethylene oxide has an effect that, when sublimated by heating, a part of the siloxy group remains in the fired film of polyalkylsilazane as a matrix, thereby producing a silica material having higher strength. Play.
- the siloxy group-containing polymer in the present invention contains a siloxy group.
- the proportion of the polymerized unit containing a xy group is preferably 1% or more, more preferably 10% or more, more preferably 30%, based on the total number of polymerized units constituting the siloxy group-containing polymer. It is especially preferred that it is more than.
- the coating composition according to the present invention is obtained by dissolving or dispersing the above-mentioned polyalkylsilazane conjugate and acetylethoxysilane conjugate, and, if necessary, other additives described later in an organic solvent. At this time, it is preferable to use an inert organic solvent having no active hydrogen as the organic solvent.
- Such organic solvents include aromatic hydrocarbon solvents such as benzene, tolylene, xylene, ethylbenzene, getylbenzene, trimethylbenzene, and triethylbenzene; cyclohexane, cyclohexene, decahydronaphthalene, ethylcyclohexane, and methylcyclohexane.
- Aromacyclic hydrocarbon solvents such as hexane, p-menthine, dipentene (limonene); ether solvents such as dipropyl ether and dibutyl ether; ketone solvents such as methyl isobutyl ketone; propylene glycol monomethyl ether acetate And the like.
- the coating composition according to the present invention can also contain other additive components as required.
- examples of such a component include a siloxy group-free polymer.
- the siloxy group-free polymer that can be used in the coating composition according to the present invention includes a homopolymer and a copolymer of a (meth) acrylic acid ester that can use any polymer. Those selected from the group and containing a carboxyl group or a hydroxyl group in a part of the side groups are preferable. Such a polymer has the effect of making the pores of the formed siliceous material small and uniform.
- Examples of such a polymer include a homopolymer of an acrylate ester such as polymethyl acrylate and polyethyl acrylate; and a homopolymer of a methacrylate ester such as polymethyl methacrylate and polyethyl methacrylate; Ester copolymers, such as poly (methyl acrylate-co-ethyl acrylate); methacrylate copolymers, such as poly (methyl methacrylate-co-ethyl methacrylate); acrylate esters and methacrylate esters And copolymers such as poly (methyl acrylate) -Ethyl methacrylate).
- the polymer is a copolymer, a random copolymer, a block copolymer or any other sequence having no restriction on the monomer sequence can be used.
- the monomers constituting the homopolymer and copolymer of the (meth) acrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, Forces include, but are not limited to, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, and the like.
- methyl methacrylate and n-butyl methacrylate and n-butyl acrylate and i-butyl acrylate are more preferred from the viewpoint of compatibility with polyalkylsilazane.
- the carboxyl group and the hydroxyl group contained in such a (meth) acrylic acid ester polymer form a cross-link with the polyalkylsilazane conjugate. Since the cross-linking reaction affects the final strength and structure of the siliceous material, the amount of carboxyl groups and hydroxyl groups is important. In order to obtain a sufficient crosslinked structure, the amount of the carboxyl group and the hydroxyl group is preferably at least 0.01 mol%, more preferably at least 0.1 mol%, based on the total number of monomers constituting the polymer component. Is more preferred. Further, in order to prevent gelling by excessive crosslinking, the content is preferably 50 mol% or less, more preferably 30 mol% or less.
- the polymer When a polymer containing no siloxy group is used, the polymer has a molecular weight of 1,000 or more so that the polymer sublimates, decomposes, or evaporates at an appropriate temperature to form a porous film. More preferably, it is more preferably 10,000 or more. On the other hand, the molecular weight of the polymer is preferably 800,000 or less, more preferably 200,000 or less, from the viewpoint of preventing voids and the resulting decrease in film strength.
- the coating composition according to the present invention can also contain other additive components as necessary.
- a component include a viscosity modifier, a crosslinking accelerator, and the like.
- a phosphorus compound for example, tris (trimethylsilyl) phosphate can be contained for the purpose of gettering effect of sodium when used in a semiconductor device.
- a reaction accelerator for example, an acetooxysilane compound, may be added. Acetoxysilane compound
- the material sometimes exerts an action to make the fine pores formed in the calcined siliceous material small and uniform.
- the polymerizable composition according to the present invention is obtained by dissolving or dispersing the polyalkylsilazane compound, the siloxy group-containing polymer, and other additives as necessary in the organic solvent, and reacting the components.
- the order of dissolving each component in the organic solvent is not particularly limited, and two or more solutions, for example, a solution of the polyalkylsilazane conjugate and a solution of the siloxy group-containing polymer are mixed. You can.
- the mixture is physically stirred while heating, whereby a homogeneous coating composition having a cross-linked bond can be obtained.
- heating it is generally heated at 3080 ° C, but this temperature varies depending on the type of components used. Care must be taken especially when the temperature is excessively high because the composition may gel.
- the stirring time depends on the type and temperature of the components to be reacted, but is generally about 124 hours. Further, it is preferable to perform ultrasonic dispersion treatment in a hot water bath at 30-80 ° C for about 5 to 90 minutes, because it accelerates the reaction.
- the solvent can be replaced after the components are reacted.
- the amount of the siloxy group-containing polymer according to the present invention when used, is preferably based on the weight of the polyalkylsilazane compound in order to effectively realize a porous silica material. Is used in an amount of 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more. On the other hand, in order to prevent a decrease in film strength due to generation of voids or cracks, it is preferable to use the polyalkylsilazane conjugate in an amount of preferably not more than 50% by weight.
- the content of each of the above components varies depending on the intended use of the coating composition.
- the solid content is not less than 5% by weight in order to form a siliceous material having a sufficient thickness.
- it is preferably 50% by weight or less. That is, it is generally preferable that the solid content is 5 to 50% by weight based on the whole coating composition. Is more preferable.
- a generally preferable film thickness for example, 2000 to 8000 A, can be obtained.
- the coating composition according to the present invention is applied onto a substrate or filled in a mold or groove, and then dried as necessary to remove excess organic solvent, and then calcined to obtain a siliceous material. be able to.
- the siliceous material according to the present invention is applied to an electronic component such as a semiconductor device, usually, the coating composition applied on the substrate is baked into a siliceous material, so that the silica material is directly formed on the semiconductor device. It is common to form porous materials
- Examples of a method of applying the coating composition to the substrate surface include a conventionally known method, for example, a spin coating method, a dip method, a spray method, a transfer method, and the like.
- the coating film formed on the substrate surface is preliminarily fired in a steam atmosphere after removing (drying) an excess organic solvent as necessary.
- steam atmosphere refers to an atmosphere in which the relative humidity at 23 ° C is 40% or more.
- gases other than water vapor forming the atmosphere are air, nitrogen, helium, argon, and the like.
- Precalcination is performed at a temperature of 50-350 ° C, preferably 100-300 ° C. This preliminary firing can be performed stepwise or continuously while increasing the temperature.
- the dry atmosphere is an atmosphere containing almost no water vapor such as dry air, dry nitrogen, and dry helium, and an atmosphere having a relative humidity at 25 ° C of 10% or less.
- the calcination temperature is 300 to 500 ° C, preferably 350 to 450 ° C, and the calcination and firing time varies depending on the calcination temperature and the components, but is generally 1 minute to 1 hour.
- the firing temperature is preferably 300 ° C or higher to complete the firing step in as short a time as possible, but 500 ° C or lower to maintain the quality of the formed siliceous material. It is preferable that
- SiH, SiR (R: hydrocarbon group) and Of the SiN bonds only the SiN bonds are oxidized and converted into SiO bonds, forming a siliceous material having unoxidized SiH and SiR bonds.
- the SiO bond formed by selectively oxidizing the SiN bond and the unoxidized SiH and SiR bonds can be present.
- the siliceous material according to the present invention containing SiH or SiR bonds, since these bonds have water repellency, it is possible to prevent the adsorption of water at a low density even at a low density. Therefore, the siliceous material according to the present invention has a great advantage that the dielectric constant of the siliceous material hardly increases even when it is exposed to an atmosphere containing water vapor. Further, since the siliceous material according to the present invention has a low density, there is an advantage that the internal stress of the film is small and cracks are hardly generated.
- fine pores having a pore diameter of 0.5 to 3 nm are mainly formed inside the siliceous material.
- this siliceous material has substantially no micropores with a pore diameter exceeding 5 nm.
- the diameter of these micropores can be measured by the X-ray diffuse scattering method.
- ATX-G type multifunctional X-ray diffractometer manufactured by Rigaku Denki Co., Ltd. S is used. It is considered that these fine pores are formed by the decomposition of the acetoxysilane bonded product and the decomposition product being evaporated or sublimated. Due to the presence of the micropores, the density of the siliceous material further decreases, and as a result, the relative dielectric constant of the siliceous material further decreases.
- the porous siliceous material according to the present invention has excellent mechanical strength because extremely fine pores can be formed. Specifically, the porous siliceous material according to the present invention exhibits remarkably high mechanical strength as a porous material having an elastic modulus of 3 GPa or more, and in some cases, 5 GPa or more by a nanoindentation method described later. .
- the siliceous material in order to have both mechanical strength and various chemical resistances that can withstand the wiring material removal process by the CMP method, it is used as an interlayer insulating film compatible with the latest high integration processes such as the damascene method. It is possible. Further, since the water-repellent groups derived from the polyalkylsilazane compound which is a matrix component of the siliceous material according to the present invention sufficiently remain after calcination, the siliceous material can be left in an atmosphere containing water vapor even if it is left in an atmosphere containing water vapor. The rate hardly rises.
- the lowering of the density of the siliceous material (SiH, SiR) due to the binding components (SiH, SiR) and the lowering of the density of the entire film due to the micropores are combined with less than 2.5, A porous siliceous material that can stably maintain an extremely low relative dielectric constant of 2.0 or less, or about 1.6 in some cases, can be obtained.
- the porous siliceous material according to the present invention, its density is 0.5 to 1.6 g / cm 3 , preferably 0.8 to 1.4 gZcm 3 , and its crack limit film thickness is 1. Ozm or more, preferably 5 xm or more, and its internal stress is 80 MPa or less, preferably 50 MPa or less.
- the Si-containing group present as SiH or SiR (R: hydrocarbon group) bond contained in the siliceous material is 10 to 100 atomic%, preferably 10 to 100 atomic%, based on the number of S ⁇ g elements contained in the material. Is 25 75 atomic%. The content of Si present as SiN bonds is 5 atomic% or less.
- the thickness of the porous siliceous material obtained after the calcination varies depending on the use of the surface of the substrate, and is usually 0.01-1 ⁇ ⁇ , preferably 0.1-2 ⁇ . In particular, when it is used as an interlayer insulating film of a semiconductor device, the thickness is preferably 0.1-2 / m.
- the porous siliceous material according to the present invention has a low density as described above, and has a crack limit film thickness, that is, a maximum film thickness that can be formed without causing film cracking. It also has the advantage of showing a high value of ⁇ or more. In the case of a conventional siliceous material, its crack limit film thickness is about 0.5-1.5 / im.
- the siliceous material according to the present invention has a low dielectric constant, a low density, a high water repellency, a high chemical resistance, and a high mechanical strength as compared with the conventional siliceous material.
- it can maintain a low dielectric constant stably, and is particularly preferable when applied to an interlayer insulating film in a semiconductor device.
- a stainless steel tank with a capacity of 5 liters is equipped with a stainless steel tank for supplying raw materials. I wore it. After the inside of the reactor was replaced with dry nitrogen, 780 g of methyltrichlorosilane was put into the stainless steel for raw material supply, and this was pressure-fed into the reaction tank with nitrogen and introduced. Next, a raw material supply tank containing pyridine was connected to the reactor, and 4 kg of pyridine was similarly pumped and introduced with nitrogen. The pressure of the reactor was adjusted to 1.0 kg / cm 2 , and the temperature of the mixture in the reactor was adjusted to 14 ° C. Ammonia was blown into the reactor with stirring, and when the pressure in the reactor reached 2.0 kg / cm 2 , the supply of ammonia was stopped.
- the reactor pressure was lowered by opening an exhaust line, and then dry nitrogen was blown into the liquid phase for 1 hour to remove excess ammonia.
- the obtained product was subjected to pressure filtration under a dry nitrogen atmosphere using a pressure filter to obtain 3200 ml of a filtrate.
- pyridine was distilled off using an evaporator, about 340 g of polymethylsilazane was obtained.
- the number average molecular weight of the obtained polymethylsilazane was measured by gas chromatography using a chloroform-form developing solution, and was 1800 in terms of polystyrene.
- Infrared absorption scan vectors (hereinafter, referred to as IR spectrum) was measured, 3350Cm- 1 and 1200cm- 1 NH bonded to based absorption around, 2900Cm- 1 and 1250Cm- 1 of Si- C bond to based absorbent, and 1020 Absorption due to Si—N-Si bond of —820 cm— 1 was observed.
- Synthesis was performed in the same manner as in Reference Example 1 except that a mixture of 720 g of methyltrichlorosilane and 656 of dimethyldichlorosilane was used instead of 780 g of methyltrichlorosilane as a raw material.
- the number average molecular weight of the obtained polymethylsilazane was measured by gas chromatography using a chloroform solution as a developing solution, and was found to be 1400 in terms of polystyrene. Infrared absorption spectra were measured to show absorption at 3350 cm- 1 and 1200 cm- 1 due to N--H bonds, absorption at 2900 cm- 1 and 1250 cm- 1 due to SC bonds, and 1020 820 cm- 1 — Absorption due to N—Si bond was observed.
- the filtrate was applied on a silicon wafer having a diameter of 10.2 cm (4 inches) and a thickness of 0.5 mm using a spin coater at 3000 rpm for 20 seconds, and further dried at room temperature for 5 minutes.
- the silicon wafer was heated at 150 ° C for 3 minutes in an air atmosphere (relative humidity 40% at 23 ° C), and then for 3 minutes on a 250 ° C hot plate.
- This film was allowed to stand in an air atmosphere (23 ° C, 40% relative humidity) for 24 hours, and then calcined in a dry nitrogen atmosphere at 400 ° C for 30 minutes to obtain a siliceous film.
- the IR spectrum of the obtained siliceous film is And Si_ ⁇ based on the binding absorption ASOcnT 1, 1270cm- 1 and 780Cm- 1 of Si_C based binding absorption, absorption was observed based on the C-H bond 2970cm- 1, 3350cm- 1 and 1200Cm- 1 of N
- the absorption based on the —H bond and the absorption based on the copolymer of isobutyl methacrylate and 30- (trimethylsiloxy) ethyl methacrylate were lost.
- the relative dielectric constant was 2.20
- the density was 1. lg / cm 3
- the internal stress was 36 MPa
- the crack limit film thickness was 5 / m or more.
- the modulus of elasticity of this film by a nanoindentation method was 4.5 GPa.
- the average pore size was 2 nm.
- Example 2 [0070] to 20% PGMEA solution 160g of polymethyl silazane synthesized in Reference Example 2, a copolymer of Echirenki side 50 mole 0/0 and dimethylsiloxane 50 mole 0/0 (molecular weight: about 1,000) and 8g The solution dissolved in 32 g of PGMEA was mixed and thoroughly stirred. Subsequently, the solution was filtered through a PTFE syringe filter (manufactured by Advantech) having a filtration accuracy of 0.2 micron.
- a PTFE syringe filter manufactured by Advantech
- the filtrate was applied on a silicon wafer having a diameter of 20.3 cm (8 inches) and a thickness of lmm using a spin coater at 3500 rpm / 20 seconds, and further dried at room temperature for 5 minutes.
- the silicon wafer was heated at 150 ° C for 3 minutes in an air atmosphere (relative humidity 40% at 23 ° C), and then for 3 minutes on a 250 ° C hot plate.
- This film was left in a humidifier at 70 ° C and a relative humidity of 85% for 3 minutes, and calcined in a dry nitrogen atmosphere at 400 ° C for 10 minutes to obtain a siliceous film.
- the relative dielectric constant was 2.24
- the density was 1.2 g / cm 3
- the internal stress was 35 MPa
- the critical crack thickness was 5 / m or more.
- the modulus of elasticity of this film by the nanoindentation method was 5. OGPa.
- a resistance test of a siliceous film was performed using an etching residue stripping solution ACT-970 (manufactured by Ashland Chemical), ST-210 and ST250 (manufactured by ATMI), EKC265 and EKC640 (manufactured by EKC). And the etching rate was 0.8 A / min or less, respectively, and the increase in the dielectric constant by the test was 1.1% or less.
- the silicon wafer was heated in an air atmosphere (relative humidity at 23 ° C: 40%) at 150 ° C for 3 minutes, and then on a hot plate at 250 ° C for 3 minutes.
- This film was allowed to stand in an air atmosphere (23 ° C., 40% relative humidity) for 24 hours, and then calcined in a dry nitrogen atmosphere at 400 ° C. for 30 minutes to obtain a siliceous film.
- the IR spectrum of the obtained siliceous film is And ASOcnT 1 absorption based on Si_ ⁇ bond, 1270 cm— 1 and 780 cm— 1 absorption based on Si_C bond, 2970 cm 1 absorption based on C—H bond, 3350 cm— 1 and 1200 cm— 1 N— Absorption based on H-bonds and absorption based on poly n-butyl methacrylate were burned out.
- the relative dielectric constant was 2.31
- the density was 1. lg / cm 3
- the internal stress was 35 MPa.
- the elastic modulus of this film by the nanoindentation method was 2.6 GPa, which was lower than that of the siliceous film according to the present invention.
- the average pore size was 7 nm, which was larger than the siliceous film according to the present invention.
- the capacitance is measured at 100 kHz using a 4192ALF impedance analyzer (Yokogawa 'Hyu I Packard).
- the film thickness is measured using an M-44 spectroscopic ellipsometer (A. Woolam, Iowa, USA).
- the relative permittivity is the average of the values calculated by the following formula for all 18 patterns.
- a silicon wafer with a diameter of 10.16 cm (4 inches) and a thickness of 0.5 mm is weighed with an electronic balance.
- the sample composition solution is applied by spin coating to form a film, converted into a siliceous film according to the method of each example, and the weight of the silicon wafer with the film is measured again with an electronic balance.
- the film weight is the difference between the weight of the wafer before and after the film formation.
- the film thickness is measured with an M-44 spectroscopic ellipsometer (JA Woolam).
- the sled of a silicon wafer of 20 ⁇ 32 cm (8 inches) in diameter and lmm thickness is input to a FLX-2320 laser-internal stress measuring instrument (KLA—Tencor, California, USA). Further, a sample composition solution is applied to this silicon wafer by spin coating to form a film, converted into a siliceous film according to the method of each example, and returned to room temperature (23 ° C.). Measure the internal stress with an internal stress meter. The film thickness is measured with an M-44 type spectroscopic ellipsometer (manufactured by J.A. Woolam).
- a sample composition solution is applied to a silicon wafer having a diameter of 10.16 cm (4 inches) and a thickness of 0.5 mm by a spin coating method to form a film, which is converted into a siliceous film according to the method of each example. Adjust the solid concentration of the sample composition solution or the number of revolutions of the spin coater at the time of coating to prepare a sample whose film thickness is changed in the range of about 0.5 zm to about 5 zm. The surface of the film after calcination is observed under a microscope (120x), and the presence or absence of cracks in each sample is examined. The maximum film thickness without cracks is defined as the crack limit film thickness.
- Modulus of elasticity (nanoindentation method) A sample composition solution is applied to a silicon wafer having a diameter of 20.32 cm (8 inches) and a thickness of lmm by spin coating to form a film, which is converted into a siliceous film according to the method of each example. Using the resulting siliceous film, the elastic modulus is measured using a mechanical property evaluation system for thin films (Nano Indenter DCM manufactured by MTS Systems, USA).
- a sample composition solution is applied to a silicon wafer having a diameter of 20.32 cm (8 inches) and a thickness of lmm by spin coating to form a film, which is converted into a siliceous film according to the method of each example.
- the pore size of the obtained siliceous film is measured by an X-ray diffuse scattering method using a multifunctional X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd.) for evaluating the surface structure of ATX-G.
- the present invention is to provide a porous siliceous film having a well-balanced combination of stable low dielectric constant, mechanical strength capable of withstanding the latest fine wiring process, and various chemical resistances.
- the porous siliceous film according to the present invention as an interlayer insulating film of a semiconductor device, it is possible to further increase the degree of integration and multilayering of an integrated circuit.
- the present invention is applied to a force that is most preferably applied to form an interlayer insulating film in an electronic material such as a semiconductor, and to other electronic material elements, for example, an insulating film under a metal film. Can be done.
- the use of the coating composition of the present invention can also form a siliceous film on the solid surface of various materials such as metals, ceramics, and wood.
- a metal substrate (silicon, sus, tungsten, iron, copper, zinc, brass, aluminum, etc.) having a siliceous film formed on its surface, or a ceramic substrate having a siliceous film formed on its surface (In addition to metal oxides such as silica, alumina, magnesium oxide, titanium oxide, zinc oxide, and tantalum oxide, metal nitrides such as silicon nitride, boron nitride, and titanium nitride, and silicon carbide).
- metal oxides such as silica, alumina, magnesium oxide, titanium oxide, zinc oxide, and tantalum oxide
- metal nitrides such as silicon nitride, boron nitride, and titanium nitride, and silicon carbide
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
- Silicon Compounds (AREA)
- Formation Of Insulating Films (AREA)
Abstract
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JP2003-292534 | 2003-08-12 | ||
JP2003292534A JP2006188547A (ja) | 2003-08-12 | 2003-08-12 | コーティング組成物、およびそれを用いて製造した低誘電多孔質シリカ質材料 |
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JP (1) | JP2006188547A (fr) |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US8969172B2 (en) | 2010-11-05 | 2015-03-03 | Az Electronic Materials Usa Corp. | Method for forming isolation structure |
JP6475388B1 (ja) * | 2018-07-18 | 2019-02-27 | 信越化学工業株式会社 | ポリシラザン含有組成物 |
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JP5481610B2 (ja) * | 2007-10-18 | 2014-04-23 | 株式会社豊田自動織機 | 塗料組成物、塗料組成物を用いた透明性保護膜の製造方法および透明性保護膜を有する有機ガラス |
Citations (4)
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JPH0673340A (ja) * | 1992-08-26 | 1994-03-15 | Catalysts & Chem Ind Co Ltd | シリカ系被膜形成用塗布液および被膜付基材 |
JPH07292321A (ja) * | 1994-04-28 | 1995-11-07 | Tonen Corp | コーティング用組成物 |
JPH11236533A (ja) * | 1998-02-24 | 1999-08-31 | Hitachi Chem Co Ltd | シリカ系被膜形成用塗布液及びシリカ系被膜 |
JP2002075982A (ja) * | 2000-08-29 | 2002-03-15 | Clariant (Japan) Kk | 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物 |
-
2003
- 2003-08-12 JP JP2003292534A patent/JP2006188547A/ja active Pending
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2004
- 2004-06-28 TW TW093118793A patent/TW200507110A/zh unknown
- 2004-08-04 WO PCT/JP2004/011136 patent/WO2005014744A1/fr not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH0673340A (ja) * | 1992-08-26 | 1994-03-15 | Catalysts & Chem Ind Co Ltd | シリカ系被膜形成用塗布液および被膜付基材 |
JPH07292321A (ja) * | 1994-04-28 | 1995-11-07 | Tonen Corp | コーティング用組成物 |
JPH11236533A (ja) * | 1998-02-24 | 1999-08-31 | Hitachi Chem Co Ltd | シリカ系被膜形成用塗布液及びシリカ系被膜 |
JP2002075982A (ja) * | 2000-08-29 | 2002-03-15 | Clariant (Japan) Kk | 低誘電率多孔質シリカ質膜、半導体装置およびコーティング組成物 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8969172B2 (en) | 2010-11-05 | 2015-03-03 | Az Electronic Materials Usa Corp. | Method for forming isolation structure |
JP6475388B1 (ja) * | 2018-07-18 | 2019-02-27 | 信越化学工業株式会社 | ポリシラザン含有組成物 |
JP2020012059A (ja) * | 2018-07-18 | 2020-01-23 | 信越化学工業株式会社 | ポリシラザン含有組成物 |
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JP2006188547A (ja) | 2006-07-20 |
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