CN100460468C - 用于制备含有新型成孔材料之多孔电介质薄膜的组合物 - Google Patents
用于制备含有新型成孔材料之多孔电介质薄膜的组合物 Download PDFInfo
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- CN100460468C CN100460468C CNB2003101248190A CN200310124819A CN100460468C CN 100460468 C CN100460468 C CN 100460468C CN B2003101248190 A CNB2003101248190 A CN B2003101248190A CN 200310124819 A CN200310124819 A CN 200310124819A CN 100460468 C CN100460468 C CN 100460468C
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- 239000000463 material Substances 0.000 title claims abstract description 101
- 239000000203 mixture Substances 0.000 title claims abstract description 63
- 239000002243 precursor Substances 0.000 claims abstract description 80
- 239000011159 matrix material Substances 0.000 claims abstract description 40
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000011229 interlayer Substances 0.000 claims abstract description 6
- -1 alkyl quaternary ammonium salts Chemical class 0.000 claims description 26
- 239000000178 monomer Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 125000005843 halogen group Chemical group 0.000 claims description 18
- 230000031709 bromination Effects 0.000 claims description 16
- 238000005893 bromination reaction Methods 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 229910008051 Si-OH Inorganic materials 0.000 claims description 9
- 229910006358 Si—OH Inorganic materials 0.000 claims description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical group [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 125000005401 siloxanyl group Chemical group 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical class O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 6
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- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical group OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 238000006884 silylation reaction Methods 0.000 claims description 3
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 claims description 3
- 238000004528 spin coating Methods 0.000 claims description 3
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical group CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 claims description 2
- 239000005453 ketone based solvent Substances 0.000 claims description 2
- 229920003209 poly(hydridosilsesquioxane) Polymers 0.000 claims description 2
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims 2
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- 239000011148 porous material Chemical group 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 3
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- 125000005210 alkyl ammonium group Chemical group 0.000 abstract description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
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- 238000006243 chemical reaction Methods 0.000 description 9
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 229960004853 betadex Drugs 0.000 description 8
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical group COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 7
- 239000012895 dilution Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 4
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 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
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 229920000592 inorganic polymer Polymers 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ULZCNCRJRBXLJW-UHFFFAOYSA-N [chloromethyl(methyl)silyl]oxy-trimethylsilane Chemical class ClC[SiH](O[Si](C)(C)C)C ULZCNCRJRBXLJW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
- 229950010007 dimantine Drugs 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000686 lactone group Chemical group 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- KRPAJLYSLFNDOA-UHFFFAOYSA-N mephenesin carbamate Chemical compound CC1=CC=CC=C1OCC(O)COC(N)=O KRPAJLYSLFNDOA-UHFFFAOYSA-N 0.000 description 1
- 229950006838 mephenesin carbamate Drugs 0.000 description 1
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- 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
- H01L21/02112—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 characterised by the material of the layer
- H01L21/02123—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 characterised by the material of the layer the material containing silicon
- H01L21/02126—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 characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- 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
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Abstract
本发明提供一种制备含有成孔材料的多孔电介质薄膜的组合物,所述组合物含有双向洗涤剂,烷基季铵,热稳定有机或无机基质前体以及用于溶解所述两种固体组分的溶剂。本发明还提供一种用于半导体器件,具有良好机械性能,例如硬度,模量和吸湿性的夹层绝缘薄膜。
Description
优先权
按照35U.S.C.§119(a),该非临时申请要求2002年12月3日提交的韩国专利申请第2002-762725号的优先权,该申请引入本文作为参考。
技术领域
本发明涉及一种用于制备含有新型成孔材料之多孔电介质薄膜的组合物。更具体地,本发明涉及一种组合物,其包含硅氧烷基双向洗涤剂(Geminidetergent),烷基季铵(fourth alkyl ammonium)或它们的混合物,作为成孔材料,从而形成具有良好机械性能和耐湿性的多孔夹层电介质薄膜。
背景技术
已经知道含有纳米微孔的物质可在各种领域中用于吸附剂,催化剂载体,绝热体和电绝缘体。特别地,近来有报道在半导体器件中把它们用作互连层之间的绝缘薄膜材料。由于半导体器件集成水平的提高,电线的传输速率决定了器件的性能。因而,需要降低互连薄膜的存储量以减小电线中的电阻和电容。为此,尝试在绝缘薄膜中使用具有低介电常数的材料。例如,美国专利3,615,272,4,399,266和4,999,397中公开的能够用于自旋沉积(Spin onDeposition,SOD)的介电常数为2.5~3.1的聚倍半硅氧烷,可作为用于化学气相沉积(CVD)中介电常数为4.0的SiO2的替代品。另外,美国专利5,965,679中描述了介电常数为2.65~2.70的有机高分子,聚亚苯基。然而,上述基质的介电常数不足够低,以达到高速器件所需的低于2.50的极低介电常数。
为了解决这个问题,进行了各种试验,以将气泡以纳米级混入这些有机和无机材料中。在此方面,美国专利6,231,989B1中描述了使用内酯基树状(denriric)聚合物作为成孔剂(porogen),该物质可以通过加热分解。而且,美国专利6,107,357和6,093,636中公开了一种制备极低介电常数(k<3.0)的物质的方法,包括下述步骤:混合乙烯基高分子树状聚合物(dendrimer)成孔材料如聚苯乙烯,聚甲基丙烯酸酯和聚酯,其可在加热步骤中降解形成薄膜;通过将这些物质等与有机或无机基质一起混合制备薄膜;及在高温下分解混合物中的成孔材料,以形成纳米微孔。
发明内容
以双向洗涤剂和烷基季铵作为成孔材料,制备具有微孔的材料,我们发现该材料在物理性质和抗吸湿性方面具有足够低的介电常数和令人满意的物理性能,进而完成本发明。
一方面,本发明提供一种用于制备多孔电介质薄膜的组合物,所述组合物包含:(1)成孔材料,其包括下面式(8)所示的双向洗涤剂,下面式(9)所示的烷基季铵盐或它们的混合物;(2)热稳定的有机或无机基质前体;及(3)用于溶解所述成孔材料和基质前体的溶剂,
在上述式(8)中,
R1和R2独立地为甲基或乙基,
R3是C5~40烷基,
X是卤原子,
r独立地为氢原子,甲基或C1~10烷氧基,
j是0或1,
n是1~12的整数,
m是0~10的整数;
NL1L2L3L4X (9)
在上述式(9)中,
N是氮原子,
X是卤原子,
L1,L2,L3和L4独立地为C1~30烷基。
另一方面,本发明提供一种在半导体器件中的互连层之间形成夹层绝缘薄膜的方法,所述方法包括将所述组合物涂布在基材上;从所述基材上蒸发溶剂,并将所述基材在150~600℃的温度下于惰性气氛或真空中加热。
又一方面,本发明提供用所述组合物制得的微孔材料。
再一方面,本发明提供具有微孔的物质作为耐热材料,电绝缘体,吸附剂,催化剂载体等的用途。
具体实施方式
下文中,本发明将通过下述实施例及其参考附图作更详细的解释。
用作本发明组合物的热稳定基质前体可以是具有玻璃化转变温度高于400℃的有机或无机高分子。
无机高分子的例子包括,但不限于,(1)倍半硅氧烷,(2)数均分子量为500~20,000的烷氧基硅烷溶胶,其源于至少是硅烷单体如SiOR4,RSiOR3或R2SiOR2(R是有机取代基)等的部分缩合,(3)数均分子量为1000~1,000,000的聚硅氧烷,其源于至少一种环状或笼形结构的硅氧烷单体如SiOR4,RSiOR3或R2SiOR2(R是有机取代基)的部分缩合。
具体地,倍半硅氧烷的例子可以是氢倍半硅氧烷,烷基倍半硅氧烷,芳基倍半硅氧烷,及这些倍半硅氧烷的共聚物。
另外,优选在高温下固化形成网状结构的有机高分子作为基质前体。有机高分子的非限定例子包括:可以酰亚胺化的聚酰亚胺基聚合物,例如聚(酰胺酸),聚(酰胺酸酯)等;聚苯并环丁烯基聚合物;以及聚亚芳基聚合物,例如聚亚苯基,聚(亚芳基醚)等。
在本发明中,更优选的基质前体是具有良好溶解性的有机聚硅氧烷,其具有至少10mol%,优选25mol%或更多的Si-OH含量。该有机聚硅氧烷是通过环状或笼形结构的硅氧烷单体(选择性地混有多种硅烷单体如SiOR4,RSiOR3或R2SiOR2)在酸性催化剂和溶剂的存在下,于溶剂中的水解和缩聚而制备的。当混有硅烷单体时,具有环状或笼形结构的硅氧烷单体与硅烷单体的比例为0.99:0.01~0.01:0.99,优选为0.8:0.2~0.1:0.9,更优选为0.6:0.4~0.2:0.8。
具有环状结构的硅氧烷单体可以通过式(1)来表示。
在上述式(1)中,
R是氢原子,C1~3烷基,C3~10环烷基,或C6~15芳基;
X1,X2和X3独立地为C1~3烷基,C1~10烷氧基或卤原子;且其中至少一个是可水解的;
p是3~8的整数;及
m是0~10的整数。
从上述式(1)可以看出,硅原子通过氧原子互相连接在一起形成环状结构,每个支链的末端含有构成可水解取代基的有机基团。
制备环状硅氧烷单体的方法没有特别的限定,但是优选使用金属催化剂的硅氢化反应。
具有笼形结构的硅氧烷单体可以通过式(2)~(4)来表示。
在上述式(2)~(4)中,
X1,X2和X3独立地为氢原子,C1~3烷基,C1~10烷氧基或卤原子,并且至少它们之一是可以水解的;
n是1~10的整数。
制备具有笼形结构的硅氧烷单体的方法没有特别的限定,但是使用在本领域中已知的金属催化剂的硅氢化反应制备。
硅烷基单体可以通过式(5)~(7)来表示。
SiX1X2X3X4 (5)
R1SiX1X1X3 (6)
R1R2SiX1X2 (7)
在上述式(5)~(7)中,
R1和R2独立地是氢原子,C1~3烷基,C3~10环烷基或C6~15芳基;及
X1,X2和X3独立地为C1~3烷基,C1~10烷氧基或卤原子。
在制备基质前体的缩合反应中使用的催化剂没有特别的限定,但是优选盐酸,苯磺酸,草酸,甲酸或它们的混合物。
在水解和缩聚反应中,加入的水为每当量的单体中的反应基团1.0~100.0当量,优选1.0~10.0当量,然后使反应在0~200℃,优选50~110℃下进行1~100小时,优选5~24小时。
反应中使用的有机溶剂优选是芳香烃溶剂例如甲苯,二甲苯,均三苯等;酮基溶剂例如甲基异丁基酮,丙酮等;醚基溶剂例如四氢呋喃,异丙基醚等;醋酸酯基溶剂例如丙二醇单甲基醚醋酸酯;酰胺基溶剂例如二甲基乙酰胺,二甲基甲酰胺等;γ-丁内酯;硅溶剂或它们的混合物。
本发明中使用的热不稳定成孔材料是式(8)所示的双向洗涤剂,式(9)所示的烷基季铵盐或它们的混合物。
在上述式(8)中,R1和R2独立地为甲基或乙基;
R3是C5~40烷基;
X是卤原子;
r独立地为氢原子,甲基或C1~10烷氧基;
j是0或1;
n是1~12的整数;以及
m是0~10的整数。
NL1L2L3L4X (9)
在上述式(9)中,
N是氮原子;
X是卤原子;及
L1,L2,L3和L4独立地为C1~30烷基。
上述双向洗涤剂通过式(10)和式(11)所示的材料在诸如乙醇,乙腈,甲苯等溶剂中反应1~100小时,优选24~72小时制得,反应温度为30~120℃,优选为60~90℃。
在上述式(10)中,
X是卤原子;
r独立地为氢原子,甲基或C1~10烷氧基,
j是0或1;
n是1~12的整数;以及
m是0~10的整数。
R3R2R1N (11)
在上述式(11)中,
R1和R2独立地为甲基或乙基;和
R3是C5~40烷基。
在该反应中,式(10)和式(11)所示的材料的摩尔比为1:2~1:3。
烷基季铵盐可以商业得到,具体的例子包括但不限于:溴化四甲铵,溴化四乙铵,溴化四丙铵,溴化四丁铵,溴化四戊铵,溴化四己铵,溴化四庚铵,溴化四辛铵,溴化四(十六烷基)铵,溴化四(十八烷基)铵,二乙基二甲基溴化铵,二丙基二甲基溴化铵,二丁基二甲基溴化铵,二戊基二甲基溴化铵,二己基二甲基溴化铵,二庚基二甲基溴化铵,二辛基二甲基溴化铵和二癸基二甲基溴化铵等。
在本发明的组合物中,除了双向洗涤剂,烷基季铵或它们的混合物,下述式(12)所示的环糊精基衍生物也可以作为成孔剂加入以改善介电常数和提高吸湿性。
在上述式(12)中,
q是6~12的整数;
R1,R2和R3独立地为卤原子,C0~10氨基或叠氮基,C3~20咪唑基或吡啶基,C1~10氰基,C2~10碳酸酯基,C1~10氨甲酸酯基,或-OR4,其中R4是氢原子,C2~30酰基,C1~20烷基,C3~10链烯基,C3~20炔基,C7~20甲苯磺酰基,C1~10甲磺酰基,C0~10亚磷基,C3~10环烷基,C6~30芳基,C1~20羟烷基,或羧基,C1~20羧烷基,葡萄糖基或麦芽糖基,或Sir1r2r3所示的硅化合物,其中r1,r2或r3独立地为C1~5烷基,C1~5烷氧基或C6~20芳基。
在式(13)-(15)中,
R1,R2和R3与式(12)中定义的那些相同。
在上述α-,β-,γ-环糊精衍生物中,R1,R2和R3优选为C2~30的酰基,C1~20烷基,C3~10的链烯基,C3~20的炔基,C3~10的环烷基,C6~30的芳基或Sir1r2r3所示的硅化合物,其中r1,r2和r3独立地为C1~5烷基,C1~5烷氧基或C6~20芳基。
环糊精衍生物的具体例子包括,但不限于:六(2,3,6-三-O-乙酰基)-α-环糊精,七(2,3,6-三-O-乙酰基)-β-环糊精,八(2,3,6-三-O-乙酰基)-γ-环糊精,七(2,3,6-三-O-丙醇基)-β-环糊精,七(2,3,6-三-O-丁醇基)-β-环糊精,七(2,3,6-三-O-戊醇基)-β-环糊精,六(2,3,6-三-O-苯甲酰基)-α-环糊精,七(2,3,6-三-O-苯甲酰基)-β-环糊精,八(2,3,6-三-O-苯甲酰基)-γ-环糊精,六(2,3,6-三-O-甲基)-α-环糊精,七(2,3,6-三-O-甲基)-β-环糊精,六(6-O-甲苯磺酰基)-α-环糊精,六(6-氨基-6-脱氧)-α-环糊精,七(6-氨基-6-脱氧)-β-环糊精,双(6-叠氮基-6-脱氧)-β-环糊精,六(2,3-O-乙酰基-6-溴基-6-脱氧)-α-环糊精,七(2,3-O-乙酰基-6-溴基-6-脱氧)-β-环糊精,单(2-O-磷酰基)-α-环糊精,单(2-O-磷酰基)-β-环糊精,六(6-脱氧-6-(1-咪唑基))-β-环糊精以及单(2,(3)-O-羧基甲基)-α-环糊精,七(2,3,6-三-O-三甲基甲硅烷基)-β-环糊精和七(2,3,6-三-O-三甲基甲硅烷基)-β-环糊精等。
环糊精衍生物的用量优选为全部成孔材料的5.0~95重量%,更优选为20~80重量%。
在本发明中,制备成孔物质的组合物可以通过上述热稳定基质前体和热不稳定成孔材料在适当的溶剂中溶解制备。
所述溶剂的例子包括,但不限于:芳烃如苯甲醚,均三苯和二甲苯;酮例如甲基异丁基酮和丙酮;醚例如四氢呋喃和异丙基醚;醋酸酯例如丙二醇甲基醚醋酸酯;酰胺例如二甲基乙酰胺和二甲基甲酰胺;γ-丁内酯;硅溶剂;以及它们的混合物。
溶剂的用量应足以使得两种固体组分(基质前体+环糊精衍生物)完全涂覆基材,在组合物(基质前体+成孔材料+溶剂)中,用量可以是20~99.9重量%,优选为50~95重量%。存在这样的问题,如果溶剂的用量低于20重量%,由于高粘度,形成的薄膜不均匀,相反地,如果溶剂的用量超过99.9重量%,薄膜的厚度太薄。
而且,成孔材料的用量优选为固体组分(基质前体+成孔材料)的0.1~95重量%,更优选为10~70重量%。存在这样的问题,如果成孔材料的用量超过95重量%,薄膜的机械性能就会变坏。相反,如果成孔材料的用量低于10重量%,由于成孔太差,薄膜的介电常数不会低。
根据本发明,使用本发明的组合物在基材上形成的带孔的薄膜可以作为半导体设备需求的好的夹层绝缘薄膜。本发明的组合物首先通过旋涂,浸涂,喷涂,流涂,丝网印刷等涂覆在基材上。更优选地,涂覆步骤是通过在1000~5000rpm的旋涂进行的。涂覆后,溶剂从基材上蒸发,在基材上沉积一层树脂薄膜。当时,蒸发通过简单的风干或者在固化步骤的开始,在真空或缓慢加热(≤100℃)下,处理基材来进行。
得到的树脂涂覆薄膜可以通过在150~600℃加热来固化,更优选地为200~450℃,其中成孔材料会发生分解,从而提供没有裂缝的不溶性薄膜。在此,“没有裂缝的薄膜”指的是在放大率为1000倍下,用光学显微镜观察不到裂缝。在此“不溶性薄膜”指的是基本上不溶解于任何用作涂覆和沉积硅氧烷基树脂的溶剂的薄膜。涂覆薄膜的热固化可以在惰性气氛或真空条件下持续10小时,优选为30分钟~1小时。固化以后,成孔材料分解形成孔。
上述方法得到的薄膜具有低的介电常数(k≤2.5)。而且,如果使用约30重量份的环糊精基成孔材料与70重量份的基质前体混合(也就是成孔剂的含量为固体混合物的30重量%),也可以得到极低的介电常数(k≤2.2)。
用上述组合物生产的成孔材料可以应用在各个领域中,特别是用于吸附剂,催化剂载体,绝热体和电绝缘体以及低介电材料。
下文中,本发明将结合下述实施例作更详细的描述。然而,这些实施例是用来举例说明的目的,而不是限定本发明的范围。
实施例1-基质单体的合成
实施例1-1:基质单体A的合成
在烧瓶中加入29.014mmol(10.0g)2,4,6,8-四甲基-2,4,6,8-四乙烯基环四硅氧烷和0.164g铂(O)-1,3-二乙烯基-1,1,3,3-四甲基二硅氧烷络合物(溶解于二甲苯中),然后用300ml二乙基醚稀释。接着,烧瓶冷却至-78℃,缓慢加入127.66mmol(17.29g)三氯甲硅烷,将烧瓶慢慢加热至室温。在室温下,反应持续20小时,在压力减至约0.1torr下,从反应混合物中去除任何可挥发材料。在混合物中加入100ml戊烷且搅拌1小时,然后通过C盐过滤得到清澈无色的溶液。所述戊烷在减压至约0.1torr下蒸发得到无色液体化合物,[-Si(CH3)(CH2CH2Cl3)O-]4,产率为95%。
加入500ml四氢呋喃和136.71mmol(13.83g)三乙基胺稀释11.28mmol(10.0g)该化合物。接着,混合物冷却至-78℃,慢慢加入136.71mmol(4.38g)甲醇,将混合物缓慢加热至室温。在室温下反应持续15小时,通过C盐过滤,在减压至约0.1torr下,可挥发物质从滤液中蒸发。随即加入100ml戊烷且搅拌1小时,然后混合物通过C盐过滤得到清澈无色溶液。所述戊烷在减压至0.1torr下从溶液中蒸发得到下式(11)所示的单体A,产物为无色液体,产率为94%。
实施例2-基质前体的合成
实施例2-1
前体A:单体A的均聚
在烧瓶中加入9.85mmol(8.218g)单体A,然后用90ml四氢呋喃稀释。接着,在-78℃下,通过8.8ml浓盐酸(35重量%的氯化氢)与100ml去离子水混合得到的稀释的盐酸溶液(1.18mmol氯化氢)慢慢加入至烧瓶中,随后加入更多的去离子水,使得包括上述稀释盐酸溶液中的水在内的水的总量达到393.61mmol(7.084g)。随后,烧瓶缓慢加热至70℃,反应持续16小时。然后反应混合物转移至分液漏斗中,加入90ml二乙基醚,接着用5×100ml去离子水清洗。随后,加入5g无水硫酸钠,在室温下搅拌10小时去除微量的水,过滤得到清澈无色溶液。在减压至约0.1torr下,从该溶液蒸发掉任何可挥发的物质,得到5.3g白色粉末状的前体A。
实施例2-2
前体B:单体A和甲基三甲氧基硅烷共聚
在烧瓶中加入37.86mmol(5.158g)甲基三甲氧基硅烷和3.79mmol(3.162g)单体A,然后用100ml四氢呋喃稀释。接着,在-78℃下,通过用100ml去离子水稀释0.12ml浓盐酸(35重量%的氯化氢)得到的稀释的盐酸溶液(0.0159mmol氯化氢)慢慢加入至烧瓶中,随后加入更多的去离子水,使得包括上述稀释盐酸溶液中的水在内的水的总量达到529.67mmol(9.534g)。随后,烧瓶缓慢加热至70℃,反应持续16小时。然后反应混合物转移至分液漏斗中,加入100ml二乙基醚,接着用5×100ml去离子水清洗。随后,加入5g无水硫酸钠,在室温下搅拌10小时去除微量的水,过滤得到清澈无色溶液。在减压至约0.1torr下,从该溶液蒸发任何可挥发的物质,得到5.5g白色粉末状的前体B。
实施例3:基质前体的分析
通过凝胶渗透色谱仪(Waters Co.)来分析制备的硅氧烷基树脂前体的分子量(以下简称“MW”)和分子量分布(以下称为“MWD”),通过NMR(BrukerCo.)来分析终端基团的Si-OH,Si-OCH3和Si-CH3含量。结论见下表1。
表1
前体 | MW | MWD | Si-O(mol%) | Si-OCH<sub>3</sub>(mol%) | Si~CH<sub>3</sub>(mol%) |
前体(A) | 60800 | 6.14 | 35.0 | 1.2 | 63.8 |
前体(B) | 4020 | 2.77 | 39.8 | 0.5 | 59.7 |
·Si-OH(%)=(Si-OH)面积÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100
·Si-OCH3(%)=(Si-OCH3)面积÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100
·Si-CH3(%)=(Si-CH3)面积÷[(Si-OH)面积+(Si-OCH3)面积/3+(Si-CH3)面积/3]×100
实施例4:成孔材料的制备
实施例4-1:双向洗涤剂成孔材料(a-1)
在烧瓶中混合100ml乙腈和10.0g双(氯甲基)四甲基二硅氧烷(A),然后加入21.4g十四烷基二甲基胺(n=14,B)。A和B的摩尔比为1:2.05。将所得的溶液在82℃下加热回流24小时。用旋转蒸发器去除溶剂(乙腈)得到固态产物。向固态产物中加入2ml氯仿并溶解,然后加入500ml的乙酸乙酯。接着,将溶液在0℃下保持12小时至重结晶。过滤重结晶的材料,用乙酸乙酯洗涤三次。将重结晶,过滤和清洗再重复两次。通过在真空烘箱中于50℃下干燥12小时,将溶剂完全从上述材料中蒸除,制得C14H29N(CH3)2CH2Si(CH3)2OSi(CH3)2CH2N(CH3)2C14H29Cl。
实施例4-2:双向洗涤剂成孔材料(a-2)
在烧瓶中混合200ml乙醇和7.24g BrCH2CH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2CH2Br(A),然后加入9.15g十八烷基二甲基胺(B)。反应物中A和B的摩尔比为1:2.05。将所得的溶液在回流条件下加热48小时。用旋转蒸发器去除溶剂乙醇,得到固态产物。在固态产物中加入2ml氯仿且溶解,然后加入500ml的乙酸乙酯。接着,在0℃下将溶液保持12小时至重结晶。过滤重结晶的材料,用乙酸乙酯洗涤。将重结晶,过滤和清洗再重复两次。通过在真空烘箱中于50℃下干燥12小时,将溶剂完全从上述材料中蒸出,制得C18H37N(CH3)2BrCH2CH2CH2OSi(CH3)2OSi(CH3)2OSi(CH3)2OCH2CH2CH2BrN(CH3)2C18H37。
实施例5:测定含有纳米微孔物质的薄膜的厚度和折射率
按照下表2中的比例,混合实施例2中制得的硅氧烷基树脂基质前体,成孔材料和丙二醇甲基醚醋酸酯(PGMEA)获得用于制备薄膜的组合物。以3000rpm将所述组合物旋涂到掺硼p型硅片上。被涂覆的基材在电热板上经过一系列的软烘烤,在150℃烘烤1分钟,在250℃再烘烤1分钟,这样有机溶剂或许可以完全去除。然后,在真空条件下将基材在Linberg加热炉中420℃固化60分钟。随后,每一个所得的低电介质薄膜的厚度和折射率通过棱镜耦合器来确定。结果见下表2。
表2
·Mat.(1)(重量%)=[基质前体的重量(g)+成孔材料的重量(g)]/[PGMEA的重量(g)+基质前体的重量(g)+成孔材料的重量(g)]×100
·成孔材料(2)(重量%)=成孔材料的重量(g)/[成孔材料的重量(g)+基质前体的重量(g)]×100
·成孔材料(b-1):四己基溴化铵,购自Sigma Aldrich Co.且无任何提纯,直接使用。
·成孔材料(b-2):二癸基二甲基溴化胺,购自Sigma Aldrich Co.且无任何提纯,直接使用。
·成孔材料(c):七(2,4,6-三-O-甲基)-β-环糊精,购自Sigma Aldrich Co.,且无任何提纯,直接使用.
实施例6:制备介电常数确定的薄膜和介电常数的确定
为了确定多孔薄膜的介电常数,在掺硼p型硅片上热氧化一层3000厚度的硅膜,然后通过金属蒸发器沉积100的钛,2000的铝,然后,表3中的低介电常数的薄膜以与实施例5相同的方法涂覆。此后,利用设计为1mm电极直径的硬质面罩沉积2000厚的直径为1mm的圆形铝薄膜,以完成这些薄膜的MIM(金属-绝缘体-金属)-介电常数决定电容,利用带探针控制台(显微操作器6200探针控制台)的精确LCR测试仪(HP4284A)测试,测试频率为100HZ。也使用棱镜耦合器对薄膜的厚度进行了测试。介电常数按照下述方程式测定。
K=(C×d)/(ε0×A)
K:介电常数
C:电容
A:电极的接触面积
ε0:真空介电常数
d:低电介质薄膜的厚度
表3
实施例编号 | 前体 | 成孔材料 | Mat.<sup>(1)</sup>(重量%) | 成孔材料<sup>(2)</sup>(重量%) | 介电常数 |
实施例6-1 | 前体(A) | - | 25.0 | - | 2.715 |
实施例6-2 | 前体(A) | (a-1) | 25.0 | 20重量% | 2.398 |
实施例6-3 | 前体(A) | (a-2) | 25.0 | 20重量% | 2.369 |
实施例6-4 | 前体(A) | (a-1)+(b-2) | 25.0 | (a-1):10重量%+(b-2):20重量% | 2.226 |
实施例6-5 | 前体(A) | (a-1)+(c) | 25.0 | (a-1):20重量%+(c):10重量% | 2.201 |
实施例6-6 | 前体(A) | (a-1)+(c) | 25.0 | (a-1):10重量%+(c):20重量% | 2.196 |
实施例6-7 | 前体(A) | (a-2)+(c) | 25.0 | (a-2):10重量%+(c):20重量% | 2.237 |
实施例6-8 | 前体(B) | - | 30.0 | - | 3.653 |
实施例6-9 | 前体(B) | (a-1) | 30.0 | 20重量% | 2.353 |
实施例6-10 | 前体(B) | (a-1) | 30.0 | 30重量% | 2.202 |
实施例6-11 | 前体(B) | (a-1)+(b-1) | 30.0 | (a-1):10重量%+(b-1):20重量% | 2.184 |
实施例6-12 | 前体(B) | (a-1)+(c) | 30.0 | (a-1):10重量%+(c):20重量% | 2.102 |
实施例6-13 | 前体(B) | (a-1)+(c) | 30.0 | (a-1):20重量%+(c):10重量% | 2.178 |
实施例6-14 | 前体(A) | (b-1) | 30.0 | 20重量% | 2.314 |
实施例6-15 | 前体(A) | (b-1)+(c) | 30.0 | (b-1):10重量%+(c):20重量% | 2.204 |
实施例6-16 | 前体(B) | (b-1) | 30.0 | 20重量% | 2.317 |
实施例6-17 | 前体(B) | (b-1)+(c) | 30.0 | (b-1):10重量%+(c):20重量% | 2.191 |
·Mat.(1)(重量%)=[基质前体的重量(g)+成孔材料的重量(g)]/[PGMEA的重量(g)+基质前体的重量(g)+成孔材料的重量(g)]×100
·成孔材料(2)(重量%)=成孔材料的重量(g)/[成孔材料的重量(g)+基质前体的重量(g)]×100
实施例7:薄膜吸湿性的测定
为了测量多孔薄膜的吸水程度,将上述实施例5中制备的薄膜置于去离子水中4天,取出薄膜,用氮气吹1分钟,从薄膜上把水分移走。此后,通过电容的变化确定吸湿性,所述电容在100kHz下,利用带探针控制台(显微操作器6200探针控制台)的精确LCR测试仪(HP4284A)测试。
通常,如果发生吸附,浸入水之后与浸入水之前相比,电容吸附测试增加超过10%。但是在本发明中,从电容变化非常小来看,可以认为没有发生吸附。
表4
实施例编号 | 前体 | 成孔材料 | Mat.<sup>(1)</sup>(重量%) | 成孔材料<sup>(2)</sup>(重量%) | 浸入前的CP(pF) | 浸入后的CP(pF) |
实施例7-1 | 前体(A) | - | 25.0 | - | 22.14 | 22.72 |
实施例7-2 | 前体(A) | (a-1) | 25.0 | 20重量% | 22.85 | 23.31 |
实施例7-3 | 前体(A) | (a-2) | 25.0 | 20重量% | 27.82 | 27.48 |
实施例7-4 | 前体(A) | (a-1)+(b-2) | 25.0 | (a-1):10重量%+(b-2):20重量% | 27.85 | 24.82 |
实施例7-5 | 前体(A) | (a-1)+(c) | 25.0 | (a-1):20重量%+(c):10重量% | 25.22 | 24.09 |
实施例7-6 | 前体(A) | (a-1)+(c) | 25.0 | (a-1):10重量%+(c):20重量% | 24.43 | 24.90 |
实施例7-7 | 前体(A) | (a-2)+(c) | 25.0 | (a-2):10重量%+(c):20重量% | 9.68 | 9.65 |
实施例7-8 | 前体(B) | - | 30.0 | - | 6.49 | 6.55 |
实施例7-9 | 前体(B) | (a-1) | 30.0 | 20重量% | 5.47 | 5.55 |
实施例7-10 | 前体(B) | (a-1) | 30.0 | 30重量% | 6.04 | 6.12 |
实施例7-11 | 前体(B) | (a-1)+(b-1) | 30.0 | (a-1):10重量%+(b-1):20重量% | 6.64 | 6.72 |
实施例7-12 | 前体(B) | (a-1)+(c) | 30.0 | (a-1):10重量%+(c):20重量% | 8.33 | 8.15 |
实施例7-13 | 前体(B) | (a-1)+(c) | 30.0 | (a-1):20重量%+(c):10重量% | 8.81 | 8.41 |
实施例7-14 | 前体(A) | (b-1) | 25.0 | 20重量% | 22.35 | 22.55 |
实施例7-15 | 前体(A) | (b-1)+(c) | 25.0 | (b-1):10重量%+(c):20重量% | 24.04 | 24.11 |
实施例7-16 | 前体(B) | (b-1) | 30.0 | 20重量% | 5.44 | 5.43 |
实施例7-17 | 前体(B) | (b-1)+(c) | 30.0 | (b-1):10重量%+(c):20重量% | 7.22 | 7.21 |
·Mat.(1)(wt%)=[基质前体的重量(g)+成孔材料的重量(g)]/[PGMEA的重量(g)+基质前体的重量(g)+成孔材料的重量(g)]×100
·成孔材料(2)(重量%)=成孔材料的重量(g)/[成孔材料的重量(g)+基质前体的重量(g)]×100
实施例8:机械性能的测量-薄膜的硬度和模量
利用MS Co.的Nanointender II测量与实施例5相同的方法制备的薄膜的硬度和模量。当目标深度(intent depth)达到整个薄膜厚度的10%时,测量硬度和模量。而且,为了确保可靠,每个薄膜样品压印6个点,取平均值来确定薄膜的厚度和模量。薄膜的厚度通过棱镜耦合器来测量。结果见表5。
表5
·Mat(1)(重量%)=[基质前体的重量(g)+成孔材料的重量(g)]/[PGMEA的重量(g)+基质前体的重量(g)+成孔材料的重量(g)]×100
·成孔材料(2)(重量%)=成孔材料的重量(g)/[成孔材料的重量(g)+基质前体的重量(g)]×100
提供使用本发明的组合物制备的微孔材料,以及它们作为耐热材料,电绝缘体,吸附剂和催化剂载体的应用。特别是,由于介电常数k为2.5或更低,所述物质对半导体设备互连层之间的绝缘薄膜是非常有用的。
具有相关领域普通知识的任何人员可以轻易对本发明作出简单的修改和变化,应该明白,所有的这样的修改和变化包含于本发明的范围内。
Claims (15)
1.一种用于制备多孔电介质薄膜的组合物,所述组合物含有:
(1)成孔材料,其包括下面式(8)所示的双向洗涤剂,下面式(9)所示的烷基季铵盐或它们的混合物;
(2)热稳定的有机或无机基质前体;及
(3)用于溶解所述成孔材料和基质前体的溶剂:
其中,
R1和R2独立地为甲基或乙基;
R3为C5~40烷基;
X为卤原子;
r独立地为氢原子,甲基或C1~10烷氧基;
j是0或1;
n是1~12的整数;及
m是0~10的整数,以及
NL1L2L3L4X (9)
其中,
N是氮原子;
X是卤原子;及
L1,L2,L3和L4独立地为C1~30烷基,
其中所述基质前体为倍半硅氧烷、烷氧基硅烷溶胶、硅氧烷基聚合物,或为聚酰亚胺、聚苯并环丁烯、聚亚芳基化合物、或它们的混合物;其中所述溶剂为芳烃基溶剂、酮基溶剂、醚基溶剂、乙酸酯基溶剂、酰胺基溶剂、γ-丁内酯、硅基溶剂、或它们的混合物;其中所述成孔材料的含量为固体组分的0.1~95重量%,该固体组分为成孔材料和基质前体的总和;所述溶剂的含量为组合物的20.0~99.9重量%,该组合物为基质前体、成孔材料和溶剂的总和。
2.根据权利要求1的组合物,其中所述成孔材料还包含下面式(12)所示的环糊精衍生物:
其中,
q是6~12的整数;
R1,R2和R3独立地为卤原子,C0~10氨基或叠氮基,C3~20咪唑基或吡啶基,C1~10氰基,C2~10碳酸酯基,C1~10氨甲酸酯基,或官能团-OR4,其中
R4是氢原子,C2~30酰基,C1~20烷基,C3~10链烯基,C3~20炔基,C7~20甲苯磺酰基,C1~10甲磺酰基,C0~10亚磷基,C3~10环烷基,C6~30芳基,C1~20羟烷基,羧基,C1~20羧烷基,葡萄糖基或麦芽糖基,或Sir1r2r3所示的硅化合物,其中r1,r2和r3独立地为C1~5烷基,C1~5烷氧基或C6~20芳基。
3.根据权利要求2的组合物,其中环糊精衍生物选自下面式(13)-(15)所示的α-,β-或γ-环糊精衍生物:
其中,
R1,R2和R3独立地为卤原子,C0~10氨基或叠氮基,C3~20咪唑基或吡啶基,C1~10氰基,C2~10碳酸酯基,C1~10氨甲酸酯基,或官能团-OR4,其中R4是氢原子,C2~30酰基,C1~20烷基,C3~10链烯基,C3~20炔基,C7~20甲苯磺酰基,C1~10甲磺酰基,C0~10亚磷基,C3~10环烷基,C6~30芳基,C1~20羟烷基,羧基,C1~20羧烷基,葡萄糖基或麦芽糖基,或Sir1r2r3所示的硅化合物,其中r1,r2和r3独立地为C1~5烷基,C1~5烷氧基或C6~20芳基。
4.根据权利要求2的组合物,其中所述环糊精衍生物的含量为全部成孔材料的5~95重量%。
5.根据权利要求1的组合物,其中所述烷基季铵盐选自:溴化四甲铵,溴化四乙铵,溴化四丙铵,溴化四丁铵,溴化四戊铵,溴化四己铵,溴化四庚铵,溴化四辛铵,溴化四(十六烷基)铵,溴化四(十八烷基)铵,二乙基二甲基溴化铵,二丙基二甲基溴化铵,二丁基二甲基溴化铵,二戊基二甲基溴化铵,二己基二甲基溴化铵,二庚基二甲基溴化铵,二辛基二甲基溴化铵,二癸基二甲基溴化铵。
6.根据权利要求1的组合物,其中所述倍半硅氧烷是氢倍半硅氧烷,烷基倍半硅氧烷,芳基倍半硅氧烷或它们的共聚物。
8.根据权利要求1的组合物,其中所述基质前体为硅氧烷基树脂,所述硅氧烷基树脂是在催化剂和水存在下,通过一种或多种选自下列式(1)-(4)所示化合物的具有环状或笼状结构的单体与一种或多种选自下列式(6)-(7)所示化合物的硅烷基单体一起,在有机溶剂中的水解和缩聚而制得:
其中,
R是氢原子,C1~3烷基,C3~10环烷基,或C6~15芳基;
X1,X2和X3独立地为C1~3烷基,C1~10烷氧基,或卤原子,且其中至少一个是可水解的;
p是3~8的整数;及
m是0~10的整数,以及
其中,
X1,X2和X3独立地为氢原子,C1~3烷基,C1~10烷氧基,或卤原子,且其中至少一个是可以水解的;
n是1-10的整数,以及
R1SiX1X1X3 (6)
R1R2SiX1X2 (7)
其中,
R1和R2独立地为氢原子,C1~3烷基,C3~10环烷基,或C6~15芳基;
X1,X2和X3独立地为C1~3烷基,C1~10烷氧基,或卤原子。
9.根据权利要求7的组合物,其中所述基质前体中Si-OH的含量大于10mol%。
10.根据权利要求8的组合物,其中所述基质前体中Si-OH的含量大于10mol%。
11.根据权利要求8的组合物,其中所述具有环状或笼状结构的硅氧烷单体与硅烷基单体的摩尔比为0.99:0.01~0.01:0.99。
12.一种在半导体器件的互连层之间形成夹层绝缘薄膜的方法,所述方法包括:
将权利要求1的组合物涂布在基材上;
从中蒸出溶剂;及
在150~600℃下于惰性气氛或真空条件下加热所涂布的薄膜。
13.根据权利要求12的方法,其中所述涂布是在1000~5000rpm下,通过旋涂法实施的。
14.一种具有纳米微孔的材料,该材料是利用权利要求1的组合物制备的。
15.根据权利要求14的具有纳米微孔的材料作为耐热材料,电绝缘体,吸附剂或催化剂载体的用途。
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