CN101120436A - 改性多孔质二氧化硅膜的制造方法、由该制造方法得到的改性多孔质二氧化硅膜、及含有该改性多孔质二氧化硅膜的半导体装置 - Google Patents
改性多孔质二氧化硅膜的制造方法、由该制造方法得到的改性多孔质二氧化硅膜、及含有该改性多孔质二氧化硅膜的半导体装置 Download PDFInfo
- Publication number
- CN101120436A CN101120436A CNA2006800050220A CN200680005022A CN101120436A CN 101120436 A CN101120436 A CN 101120436A CN A2006800050220 A CNA2006800050220 A CN A2006800050220A CN 200680005022 A CN200680005022 A CN 200680005022A CN 101120436 A CN101120436 A CN 101120436A
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- China
- Prior art keywords
- film
- group
- modified porous
- porous silica
- silicon dioxide
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- Granted
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 237
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 118
- 239000004065 semiconductor Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims description 48
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 31
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 235000012239 silicon dioxide Nutrition 0.000 claims description 57
- 238000004519 manufacturing process Methods 0.000 claims description 27
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 19
- 229920006254 polymer film Polymers 0.000 claims description 8
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000012685 gas phase polymerization Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000012159 carrier gas Substances 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229920001600 hydrophobic polymer Polymers 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 137
- 238000005245 sintering Methods 0.000 description 32
- 239000000758 substrate Substances 0.000 description 24
- -1 siloxanes Chemical class 0.000 description 22
- 239000004094 surface-active agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 16
- 210000000170 cell membrane Anatomy 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- WZJUBBHODHNQPW-UHFFFAOYSA-N 2,4,6,8-tetramethyl-1,3,5,7,2$l^{3},4$l^{3},6$l^{3},8$l^{3}-tetraoxatetrasilocane Chemical compound C[Si]1O[Si](C)O[Si](C)O[Si](C)O1 WZJUBBHODHNQPW-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- RSNQKPMXXVDJFG-UHFFFAOYSA-N tetrasiloxane Chemical compound [SiH3]O[SiH2]O[SiH2]O[SiH3] RSNQKPMXXVDJFG-UHFFFAOYSA-N 0.000 description 9
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 230000006978 adaptation Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003595 mist Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000012545 processing Methods 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
- 238000011282 treatment Methods 0.000 description 3
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000007914 intraventricular administration Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- KOJCPAMHGPVAEW-UHFFFAOYSA-N 2,4,6,8-tetraethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[SiH]1O[SiH](CC)O[SiH](CC)O[SiH](CC)O1 KOJCPAMHGPVAEW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XUYGCLPHGGZAJP-UHFFFAOYSA-N C(C)[SiH3].COC=1C(=C(C=CC1)OC)OC Chemical compound C(C)[SiH3].COC=1C(=C(C=CC1)OC)OC XUYGCLPHGGZAJP-UHFFFAOYSA-N 0.000 description 1
- OJIKWFOITYJUSO-UHFFFAOYSA-N CC(C)[SiH2]O[SiH3] Chemical compound CC(C)[SiH2]O[SiH3] OJIKWFOITYJUSO-UHFFFAOYSA-N 0.000 description 1
- CWNXOPXKENEODI-UHFFFAOYSA-N C[SiH]1O[SiH](C)O[Si](C)(CCC(F)(F)F)O1 Chemical compound C[SiH]1O[SiH](C)O[Si](C)(CCC(F)(F)F)O1 CWNXOPXKENEODI-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- JWVHPGDCFVOYMQ-UHFFFAOYSA-N [dimethoxy(methyl)silyl]oxy-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)O[Si](C)(OC)OC JWVHPGDCFVOYMQ-UHFFFAOYSA-N 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- HOARHIIWXZMCMV-UHFFFAOYSA-N bis[[ethoxy(dimethyl)silyl]oxy]-dimethylsilane Chemical class CCO[Si](C)(C)O[Si](C)(C)O[Si](C)(C)OCC HOARHIIWXZMCMV-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical class CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- OLSXJZGGKBQREO-UHFFFAOYSA-N butoxy(trifluoro)silane Chemical class CCCCO[Si](F)(F)F OLSXJZGGKBQREO-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- VEEVJGGLMCRPMO-UHFFFAOYSA-N chloro-(2,3,4-triethoxyphenyl)silane Chemical compound C(C)OC1=C(C(=C(C=C1)[SiH2]Cl)OCC)OCC VEEVJGGLMCRPMO-UHFFFAOYSA-N 0.000 description 1
- YZPKMQUUTFLIRN-UHFFFAOYSA-N chloro-(2,3,4-trimethoxyphenyl)silane Chemical compound COC1=C(C(=C(C=C1)[SiH2]Cl)OC)OC YZPKMQUUTFLIRN-UHFFFAOYSA-N 0.000 description 1
- HAURRGANAANPSQ-UHFFFAOYSA-N cis-2,4,6-Trimethyl-2,4,6-triphenylcyclotrisiloxane Chemical compound O1[Si](C)(C=2C=CC=CC=2)O[Si](C)(C=2C=CC=CC=2)O[Si]1(C)C1=CC=CC=C1 HAURRGANAANPSQ-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 125000004983 dialkoxyalkyl group Chemical group 0.000 description 1
- SGFGWXCJHHZQBS-UHFFFAOYSA-N diethylsilyloxy(diethyl)silane Chemical compound CC[SiH](CC)O[SiH](CC)CC SGFGWXCJHHZQBS-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SCTQCPWFWDWNTC-UHFFFAOYSA-N diphenylsilyloxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[SiH](C=1C=CC=CC=1)O[SiH](C=1C=CC=CC=1)C1=CC=CC=C1 SCTQCPWFWDWNTC-UHFFFAOYSA-N 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XZFFGKZBTQABBO-UHFFFAOYSA-N ethoxy(dimethyl)silane Chemical compound CCO[SiH](C)C XZFFGKZBTQABBO-UHFFFAOYSA-N 0.000 description 1
- NPOYZXWZANURMM-UHFFFAOYSA-N ethoxy-[ethoxy(dimethyl)silyl]oxy-dimethylsilane Chemical compound CCO[Si](C)(C)O[Si](C)(C)OCC NPOYZXWZANURMM-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- JKGQTAALIDWBJK-UHFFFAOYSA-N fluoro(trimethoxy)silane Chemical compound CO[Si](F)(OC)OC JKGQTAALIDWBJK-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000011221 initial treatment Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XKINWJBZPLWKCW-UHFFFAOYSA-N methoxy-[methoxy(dimethyl)silyl]oxy-dimethylsilane Chemical compound CO[Si](C)(C)O[Si](C)(C)OC XKINWJBZPLWKCW-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000000711 polarimetry Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- ZBYSWWMOCOYCFE-UHFFFAOYSA-N propan-2-yl(silyloxysilyloxy)silane Chemical class C(C)(C)[SiH2]O[SiH2]O[SiH3] ZBYSWWMOCOYCFE-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- REWDXIKKFOQRID-UHFFFAOYSA-N tetrabutylsilane Chemical compound CCCC[Si](CCCC)(CCCC)CCCC REWDXIKKFOQRID-UHFFFAOYSA-N 0.000 description 1
- VBSUMMHIJNZMRM-UHFFFAOYSA-N triethoxy(2-phenylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC1=CC=CC=C1 VBSUMMHIJNZMRM-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- WZOKLTDCMZSBQL-UHFFFAOYSA-N trifluoro(propan-2-yloxy)silane Chemical class C(C)(C)O[Si](F)(F)F WZOKLTDCMZSBQL-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- 229940030010 trimethoxybenzene Drugs 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76826—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by contacting the layer with gases, liquids or plasmas
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- 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
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Abstract
本发明提供一种改性多孔质二氧化硅膜,其对多孔质二氧化硅膜,在减压(30kPa以下)下使具有至少各1个的疏水性基团(碳数1~6的烷基或C6H5基团)和可聚合性基团(氢原子、羟基或卤原子)的疏水性化合物进行气相聚合反应,使该膜中的空孔内壁生成疏水性聚合薄膜,由此得到该改性多孔质二氧化硅膜。该多孔质二氧化硅膜具有低介电常数及低折射率,且机械强度及疏水性得到改良。本发明还提供一种使用该多孔质二氧化硅膜的半导体装置。
Description
技术领域
本发明涉及一种改性多孔质二氧化硅膜的制造方法、由该制造方法得到的改性多孔质二氧化硅膜及含有该改性多孔质二氧化硅膜的半导体装置,特别是涉及一种具有低介电常数和低折射率、且机械强度及疏水性优良的改性多孔质二氧化硅膜的制造方法、由该制造方法得到的改性多孔质二氧化硅膜及含有该改性多孔质二氧化硅膜的半导体装置。
背景技术
近年来,在LSI领域正在积极研究开发与铜配线一起的以介电常数(k)≤2.5的低介电常数为特征的层间绝缘膜的引入。作为该层间绝缘膜,提案有将具有低介电常数的氧化物膜做成多孔质,但由于通过做成多孔质,产生了如下问题:(1)机械强度急剧下降、(2)空孔内吸附空气中的水分、(3)由于为防止该吸附而引入的CH3基团等疏水性基团而导致多孔质膜与相接的膜的密合性下降等。因此,在多孔质膜向半导体装置的实用化工艺、特别是铜双镶嵌配线结构中的CMP(化学机械抛光)或引线接合工艺等中产生如下问题:由机械强度下降引起的多孔质膜的破裂、由吸湿引起的介电常数上升、由密合性降低引起的层叠膜和多孔质绝缘膜之间产生剥离等,从而造成实用上的很大障碍。
另外确认,为了通过显示器等从发光部以高效率获取光或防止来自外部的光的反射,或为了通过太阳能电池等以高效率射入来自外部的光,而通过设置二氧化硅气溶胶薄膜作为低折射率层,并在其上设置透明导电膜,从而可以以高辉度获取光。然而,即使在至今为止提案的二氧化硅气溶胶薄膜中,与上述同样地也存在机械强度下降、空孔内吸附水分、与相接的膜的密合性降低等问题。
为了解决现有技术的问题点,已知有如下方法:在表面活性剂和环状硅氧烷(例如:四甲基环四硅氧烷)的存在下,将烷氧基硅烷类进行水解缩合而配制涂敷液,将该涂敷液涂敷于基板表面,然后将形成于基板表面的涂敷膜进行加热,由此制造多孔质二氧化硅膜(例如,参照专利文献1)。但是,此时,在常压下的加热处理中存在如下问题:例如,(4)由通过四甲基环四硅氧烷的聚合反应生成的聚甲基硅氧烷构成的微粒附着在多孔质二氧化硅膜表面及处理室内,污染了多孔质二氧化硅膜、(5)在制造大面积的多孔质二氧化硅膜时难以得到均匀的效果。
专利文献1:日本特开2004-210579号公报(权利要求书)
发明内容
发明要解决的问题
本发明的课题在于,解决现有技术问题,提供一种具有低介电常数、低折射率,且机械强度和疏水性得到改良的改性多孔质二氧化硅膜的制造方法及由该方法得到的改性多孔质二氧化硅膜以及使用有该改性多孔质二氧化硅膜的半导体装置。
解决问题的方法
本发明人等为了制作具有低介电常数、低折射率且机械强度及疏水性得到改良的改性多孔质二氧化硅膜而进行了深入地研究开发,结果发现,通过对原料多孔质二氧化硅膜,使用特定的硅氧烷那样的疏水性化合物,在规定的减压条件下进行气相聚合反应,由此可以解决现有技术的上述问题点(1)~(5)的方法,至此完成了本发明。
本发明的改性多孔质二氧化硅膜的制造方法的特征在于,对多孔质二氧化硅膜,在减压条件下,使具有至少各1个的疏水性基团和可聚合性基团的疏水性化合物进行气相聚合反应,使聚合物薄膜生成于该膜中的空孔内壁上。如上所述,通过在减压下,在气相状态下将疏水性化合物引入多孔质二氧化硅膜中的空孔内,且在空孔内产生气相聚合反应,可以在空孔内壁上形成疏水性聚合物薄膜,并使该薄膜与空孔内壁结合。由此,可以对改性多孔质二氧化硅膜本身赋予良好的疏水性,同时,通过结合于空孔内壁上的聚合物薄膜的作用,可以加固多孔质膜的空孔结构,其结果可以提高多孔质二氧化硅膜的机械强度(弹性模量及硬度)。
上述疏水性基团是碳数1~6的烷基或C6H5基团,上述可聚合性基团优选氢原子、羟基或卤原子。当烷基的碳数超过6时,存在分子尺寸大、影响其向空孔内扩散的问题。
上述疏水性化合物优选有机硅化合物,所述有机硅化合物具有至少1个Si-X-Si键合单元(X为氧原子、NR基团、CnH2n基团或C6H4基团,R为CmH2m+1基团或C6H5基团,n为1或2,m为1~6的整数),还具有至少2个Si-A键合单元(A为氢原子、羟基、OCeH2e+1基团或卤原子,同一分子内的A可以相同或不同,e为1~6的整数)。
上述疏水性化合物优选为环状硅氧烷类。
上述减压优选为1×10-5Pa~30kPa。当室内压为30kPa以下时,疏水性化合物向室内的扩散性变好,空孔内的该化合物的浓度均匀,可以有效地生成所希望的聚合物薄膜。但是,当超过30kPa时,存在如下问题:由通过聚合反应生成的聚合物(例如聚甲基硅氧烷等)构成的微粒附着于多孔质二氧化硅膜表面及处理室内,污染了作为目标物的多孔质二氧化硅膜。
另外,本发明改性多孔质二氧化硅膜的特征在于通过上述制造方法得到。
近而,本发明半导体材料的特征在于使用上述的改性多孔质二氧化硅膜。
本发明半导体装置的特征在于使用上述半导体材料。
发明效果
根据本发明的制造方法,实现了如下效果:可以制造具有低的介电常数、低折射率,且机械强度及疏水性得到改良的改性多孔质二氧化硅膜,而且,由于可以提供具有这种特性的改性多孔质二氧化硅膜,故也可以提供使用有该改性多孔质二氧化硅膜的有用的半导体材料及使用有该半导体材料的有用的半导体装置。
具体实施方式
用作本发明改性多孔质二氧化硅膜原料的多孔质二氧化硅膜,只要具有规定的空孔就没有特别限制。例如,可以是通过如下方法制造,将作为多孔质二氧化硅材料前体的有机硅烷即烷氧基硅烷的溶液进行酸解或碱解而得到的溶液进行加热处理,蒸发该前体溶液中的水、酸或碱催化剂、表面活性剂、根据需要添加的醇等溶剂,同时,在反应体系中含有其它有机物时除去该物质;另外,也可以通过如下方法来制造,将具有烷基那样的疏水基团的含硅有机化合物添加到上述烷氧基硅烷溶液中,将该溶液进行酸解或碱解而得到的溶液进行加热处理,蒸发该前体溶液中的水、酸或碱催化剂、表面活性剂、根据需要添加的醇等溶剂,同时,在反应体系中含有其它有机物时除去该物质。
作为上述有机硅烷,例如可以使用四乙氧基硅烷(TEOS)、四甲氧基硅烷(TMOS)等之类的可水解的烷氧基硅烷类。此外,可以列举:四异丙氧基硅烷、四丁基硅烷等四烷氧基硅烷;三甲氧基氟硅烷、三乙氧基氟硅烷、三异丙氧基氟硅烷、三丁氧基氟硅烷等三烷氧基氟硅烷;三甲氧基甲基硅烷、三乙氧基甲基硅烷、三甲氧基乙基硅烷、三乙氧基乙基硅烷、三甲氧基丙基硅烷、三乙氧基丙基硅烷等三烷氧基烷基硅烷;三甲氧基苯基硅烷、三乙氧基苯基硅烷、三甲氧基氯苯基硅烷、三乙氧基氯苯基硅烷等三烷氧基芳基硅烷;三甲氧基苯乙基硅烷、三乙氧基苯乙基硅烷等三烷氧基苯乙基硅烷;二甲氧基二甲基硅烷、二乙氧基二甲基硅烷等二烷氧基烷基硅烷等。其中,当使用四乙氧基硅烷时,容易控制室温下的水解反应,故优选。上述烷氧基硅烷类可以使用选自上述中的1种或组合使用其中的2种以上。
水解既可以是利用酸的水解,也可以是利用碱的水解,为了该水解,可以使用盐酸、氢溴酸、硝酸、硫酸等无机酸;甲酸等有机酸;氨水等碱。
上述溶剂可以列举:甲醇、乙醇、1-丙醇等伯醇;2-丙醇、2-丁醇等仲醇;叔丁醇等叔醇;丙酮、乙腈等。溶剂可以使用选自这些溶剂中的1种或组合使用其中的2种以上。
在用于制造本发明原料多孔质二氧化硅膜的涂敷液的配制中使用的表面活性剂,优选使用具有聚环氧烷结构的化合物。聚环氧烷结构可以列举聚环氧乙烷结构、聚环氧丙烷结构、聚四氢呋喃结构、聚环氧丁烷结构等。
作为具有这种聚环氧烷结构的化合物,例如,可以列举:聚氧乙烯聚氧丙烯嵌段共聚物、聚氧乙烯聚氧丙烯烷基醚、聚乙烯烷基醚、聚氧乙烯烷基苯基醚等醚型化合物;聚氧乙烯甘油脂肪酸酯、聚氧乙烯山梨糖醇酐脂肪酸酯、聚乙烯山梨糖醇脂肪酸酯、山梨糖醇酐脂肪酸酯、丙二醇脂肪酸酯、蔗糖脂肪酸酯等醚酯型化合物。
上述表面活性剂可以使用选自上述这些表面活性剂中的1种或组合使用其中的2种以上,表面活性剂只要是在上述所示范围内添加,表面活性剂的状态就无特殊限定,可以是固体状态、溶解于溶剂的状态的任一种状态。
上述表面活性剂在水中形成胶束并规则地排列。以该胶束为模型,制作与二氧化硅的复合体,当除去模型时,可以制成具有均匀而规则的细孔的多孔质二氧化硅膜。
作为上述具有烷基那样的疏水基的含硅有机化合物,例如可以使用六甲基二硅烷、二甲基二乙氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、三乙氧基硅烷、二甲基二甲氧基硅烷那样的具有甲基的硅烷化合物、或六甲基二硅氮烷那样的具有甲基的二硅氮烷化合物、或六甲基二硅氧烷那样的具有甲基的硅氧烷化合物。
原料多孔质二氧化硅膜例如可以通过下述方法得到:将上述多孔质二氧化硅材料的前体溶液利用通常的涂敷方法涂敷于基板上后,使用公知的红外线加热炉等进行加热处理,使水-醇系溶剂、酸或碱催化剂、表面活性剂、其它物质等蒸发,在基板上形成多孔质二氧化硅膜。此时的加热处理条件,只要是可以使溶剂、酸或碱催化剂、表面活性剂等蒸发、且可以形成所希望的多孔质二氧化硅膜的条件,就没有特别限制。为了得到介电常数低的多孔质二氧化硅膜,优选:首先,在空气中、在50~350℃左右的温度下进行处理,主要使溶剂等蒸发,接着,例如在100~10-5Pa左右的真空中,在可以使表面活性剂及其他有机物质等蒸发的温度(例如250~500℃)下进行中间处理,其处理时间以不破坏所得多孔质二氧化硅膜的空孔结构为宜。当然,当氧化等成为问题时,需要完全在惰性气体或真空中进行处理。
或者,也可以使用如下所述的涂敷液得到原料多孔质二氧化硅膜。这种涂敷液例如可以通过配混上述烷氧基硅烷类、表面活性剂、催化剂、水、以及根据需要的溶剂,搅拌规定的时间而得到;另外,也可以通过添加上述烷氧基硅烷类、催化剂、水、以及根据需要的溶剂,搅拌规定的时间,使烷氧基硅烷类部分水解、脱水缩合,再根据需要添加溶解于溶剂中的表面活性剂,进一步搅拌规定时间而得到。通常认为,在由此得到的涂敷液中,由于表面活性剂的疏水基团进行排列,故胶束的直径变大。因此,由含有这种胶束的涂敷液得到的多孔质二氧化硅膜的空孔直径变大、空隙率增加,故可以得到介电常数小的多孔质二氧化硅膜。将如上所述配制成的涂敷液涂敷于基板,使形成于基板表面的涂敷膜干燥后,通过烧结除去表面活性剂等,由此可以制造原料多孔质二氧化硅膜。
上述基板只要是通常使用的基板,任何基板都可以使用。例如可举出玻璃、石英、硅片、不锈钢等。其形状可以是板状、盘状等均可。
在上述中,在基板上涂敷涂敷液的方法例如有:旋转涂敷法、流延法、浸渍涂敷法等通常的方法。旋转涂敷法的情况如下进行:将基板放置于旋转器上,在该基板上滴下试剂,以500~10000rpm使其旋转。
根据本发明,对如上所得的原料多孔质二氧化硅膜,使疏水性化合物进行气相聚合反应,在空孔内壁生成聚合物薄膜,该疏水性化合物是具有至少各1个的包括碳数1~6的烷基或C6H5基团的疏水性基团和包括氢原子、羟基或卤原子的可聚合性基团的化合物,例如可以列举:1,2-双(四甲基二硅氧烷基)乙烷、1,3-双(三甲基甲硅烷氧基)-1,3-二甲基二硅氧烷、1,1,3,3-四异丙基二硅氧烷、1,1,3,3-四苯基二硅氧烷、1,1,3,3-四乙基二硅氧烷、1,1,4,4-四甲基亚乙二硅烷、1,1,3,3,5,5-六甲基三硅氧烷、1,1,3,3,5,5-六异丙基三硅氧烷、1,1,3,3,5,5,7,7-八甲基四硅氧烷、1,1,1,3,5,5-六甲基三硅氧烷、1,1,1,3,3,5,7,7-八甲基四硅氧烷、1,3-二甲基四甲氧基二硅氧烷、1,1,3,3-四甲基-1,3-二乙氧基二硅氧烷、1,1,3,3,5,5-六甲基二乙氧基三硅氧烷、四甲基-1,3-二甲氧基二硅氧烷等。
另外,在本发明中可用的疏水性化合物是有机硅化合物,所述有机硅化合物具有至少1个Si-X-Si键合单元(X为氧原子、NR基团、CnH2n基团或C6H4基团,R为CmH2m+1基团或C6H5基团,n为1或2,m为1~6的整数)和至少2个Si-A键合单元(A为氢原子、羟基、OCeH2e+1基团或卤原子,同一分子内的A可以相同或不同,e为1~6的整数)。例如,可以列举:1,2,3,4,5,6-六甲基环三硅氮烷、1,3,5,7-四乙基-2,4,6,8-四甲基环四硅氮烷、1,2,3-三乙基-2,4,6-三乙基环三硅氮烷等。
上述疏水性化合物只要是能在原料多孔质二氧化硅膜的空孔内壁生成聚合物薄膜的充分的量即可。例如优选在气体中的浓度为0.1vol%以上。
另外,根据本发明,作为疏水性化合物,可以使用环状硅氧烷,此时,在多孔质二氧化硅膜的空孔内壁可以生成该环状硅氧烷的聚合物。
该环状硅氧烷类优选为下述通式表示的环状硅氧烷化合物的至少1种。
(式中,R1、R2可以相同或不同,分别表示H、C6H5、CaH2a+1、CF3(CF2)b(CH2)c、卤原子,a为1~3的整数,b为0~10的整数,c为0~4的整数,n为3~8的整数)
上式表示的环状硅氧烷化合物优选至少具有2个以上Si-H键,另外,还优选R1、R2的至少一个是H。
当使用这种环状硅氧烷时,由于所得多孔质二氧化硅膜的空孔直径变大、空隙率增加,因此,介电常数下降。
这种环状硅氧烷类具体例如有:三(3,3,3-三氟丙基)三甲基环三硅氧烷、三苯基三甲基环三硅氧烷、1,3,5,7-四甲基环四硅氧烷、八甲基环四硅氧烷、1,3,5,7-四甲基-1,3,5,7-四苯基环四硅氧烷、四乙基环四硅氧烷、五甲基环五硅氧烷等。本发明中可以使用的环状硅氧烷类,可以从中选择1种或组合2种以上使用。上述环状硅氧烷中,优选1,3,5,7-四甲基环四硅氧烷。
另外,上述环状硅氧烷类可以是下述通式表示的环状硅氧烷化合物的至少1种。
(式中,R3、R4、R5、R6、R7、R8可以相同或不同,分别表示H、C6H5、CaH2a+1、CF3(CF2)b(CH2)c、卤原子,a为1~3的整数,b为0~10的整数,c为0~4的整数,L为0~8的整数,m为0~8的整数,n为0~8的整数,且3≤L+m+n≤8,至少含有2个以上Si-H键)
而且,上述环状硅氧烷类也可以是下述通式表示的环状硅氧烷化合物的至少1种。
(式中,R9表示H、C6H5、CaH2a+1、CF3(CF2)b(CH2)c、卤原子,a为1~3的整数、b为0~10的整数、c为0~4的整数,n为3~8的整数)
根据本发明的改性多孔质二氧化硅膜的制造方法,如上所述,通过在减压下使用环状硅氧烷那样的有机硅化合物,与不使用环状硅氧烷类制造成的多孔质二氧化硅膜相比,可以得到介电常数降低的疏水性改性多孔质二氧化硅膜。而且,通过在规定的减压条件下进行处理,环状硅氧烷类在多孔质二氧化硅膜的空孔内壁聚合,内壁面被具有疏水性官能团的聚合物的薄膜覆盖,可以得到疏水性优良的多孔质二氧化硅膜。因此,根据本发明,在制造成改性多孔质二氧化硅膜后,无须再进行疏水化处理,即可得到介电常数及疏水性等优良的多孔质二氧化硅膜。
如上所述,根据本发明的改性多孔质二氧化硅膜的制造方法,通过在减压下、在多孔质二氧化硅膜中的空孔内发生聚合反应,在空孔内壁生成聚硅氧烷类那样的疏水性聚合物薄膜,使该薄膜与空孔内壁结合,由此可以赋予改性多孔质二氧化硅膜本身良好的疏水性。同时,利用聚合物薄膜的作用,多孔质膜的空孔结构得到加强,其结果可以提高多孔质二氧化硅膜的机械强度。
另外,由于处理后的多孔质二氧化硅膜中存在疏水性化合物的未聚合残基,故在所得改性多孔质二氧化硅膜上层叠有其他的金属薄膜或绝缘膜等时,通过该未聚合残基可提高这些膜之间的密合性。
近而,根据本发明的改性多孔质二氧化硅膜的制造方法,可以在将疏水性化合物的蒸汽引入处理室内之前,一次性将室内压进行减压(例如30kPa以下的真空),然后引入疏水性化合物的蒸汽,在维持该减压的情况下进行聚合反应,从而,疏水性化合物向室内的扩散性变好,空孔内的浓度变得均匀。
近而,由于可以在预先除去存在于多孔质二氧化硅膜中的空孔内的气体分子及水分子等后引入疏水性化合物的气体分子,故该化合物向空孔内的扩散性良好。其结果,可以使该疏水性化合物在短时间内均匀地向多孔质二氧化硅膜中的空孔内扩散,并引发聚合反应,因此,可以解决对大面积多孔质二氧化硅膜的处理效果的均匀性的问题。
近而,由于在30kPa以下的减压下,引入的疏水性化合物蒸汽的浓度十分稀薄,故不会发生过度的聚合反应,因此,不会引起聚合反应生成物污染膜表面、室内的问题。
如上所述,本发明的改性多孔质二氧化硅膜的介电常数和疏水性两方面均优良,故可以用作层间绝缘膜、配线间绝缘膜等半导体材料;分子记录介质、透明导电性膜、固体电解质、光波导、LCD用彩色构件等光功能材料、电子功能材料。特别是对于半导体材料的层间绝缘膜或配线间绝缘膜,可寻求低介电常数和疏水性,优选使用这种低介电常数和疏水性优良的本发明的改性多孔质二氧化硅膜。
下面对使用本发明的改性多孔质二氧化硅膜作为配线间绝缘膜的半导体装置进行具体说明。
首先,如上所述,在基板表面上形成改性多孔质二氧化硅膜。依据本发明的改性多孔质二氧化硅膜的制造方法,可以得到低介电常数的疏水性优良的配线间绝缘膜。然后,在该改性多孔质二氧化硅膜上形成硬掩膜和光致抗蚀剂,按照光致抗蚀剂的图案进行蚀刻。蚀刻后,利用化学气相成长法(CVD)在该多孔质二氧化硅膜表面形成由氮化钛(TiN)或氮化钽(TaN)等构成的阻挡膜。
在本发明的多孔质二氧化硅膜表面形成阻挡膜后,利用金属CVD法、溅射法或电镀法形成铜配线,进一步利用CMP法将膜平滑化。然后,在该膜表面形成覆膜。近而根据需要形成硬掩膜,通过反复进行上述工序,可以实现多层化,可以制造本发明的半导体装置。
需要说明的是,在本实施方式中,作为优选例而例举了半导体电路元件的绝缘膜材料,但本发明的应用并不限制于该用途,例如,也可以应用于在水溶液中进行表面加工所需要的防水膜电绝缘材料、催化剂材料、滤波器材料等用途。
下面,对使用有机硅化合物的原料多孔质二氧化硅膜的制造例进行说明。
制造例1
作为配制用于制造多孔质二氧化硅膜的反应液的原料,相对于TEOS1摩尔,使用硝酸0.7摩尔、H2O12摩尔、乙醇15摩尔、规定量的表面活性剂(0.2摩尔),配制成多孔质膜制造用涂敷液。在3000转/分钟的条件下将该涂敷液旋转涂敷于基板上。使用公知的红外线加热炉,将涂敷好的基板首先在空气中、在200~400℃下进行处理,然后在100~10-5Pa的气氛中、在400℃下进行烧结处理,得到原料多孔质二氧化硅膜。此时,将从最初的处理温度200℃升温到后续工序的处理温度400℃的时间设定为60分钟。该升温速度原则上没有特别限制,但就得到的膜的膜质而言,只要是使废膜少,且漏电量也小的值的范围即可。另外,真空烧结中的保持时间只要使膜结构不被破坏的范围即可,因此保持30分钟进行烧结。对这样得到的多孔质二氧化硅膜,用扫描电子显微镜拍摄其截面照片,观察多孔质膜的膜质状态,由其SEM像可知,存在大量微小的空孔。
对这样得到的多孔质二氧化硅膜,只要实施本发明的改性疏水性多孔质二氧化硅膜制造方法,就可以得到具有低介电常数、低折射率,且机械强度及疏水性优良的改性多孔质二氧化硅膜。
实施例1
将Si基板放入处理室内的烧结中的压力可调的公知的长型烧结炉内,加热至400℃后,将1,3,5,7-四甲基环四硅氧烷(TMCTS)0.7g/分钟的蒸汽与载气N2一起作为混和气体引入烧结炉内,设定烧结炉内的压力为500Pa或大气压,一直保持该压力烧结60分钟。此时,TMCTS+N2的混和气体以在烧结炉内不停留的方式在烧结过程中持续流动。烧结后立即抽真空,同时降低温度,取出基板。
测定取出的Si基板上的0.2μm以上的微粒数,结果,如下表所示,在减压下的处理中,0.2μm以上的微粒数与经大气压下的处理相比非常少。
表1
压力 | 大气压 | 500Pa |
微粒数 | 10,000个以上 | 15个 |
实施例2
将四乙氧基硅烷(TEOS)0.85摩尔、H2O11摩尔、二甲基二乙氧基硅烷(DMDEOS)0.15摩尔及非离子性表面活性剂(旭电化社制、P103;平均分子量=4600、OH(CH2CH2O)17(CH(CH3)CH2O)55(CH2CH2O)17H)0.017摩尔,在乙醇中强酸性环境下、在室温下进行搅拌,配制成透明而均匀的涂敷液。
在此,DMDEOS的量没有特别限制,但当不添加DMDEOS时,烧结所得多孔质膜的空孔进行二维六角柱状排列,观测由此产生的X射线衍射峰值,不能得到虫蛀状的空孔结构、即所谓的虫洞(Worm-Hole)状的空孔结构,而且,多孔质膜的介电常数升高。
在1200转/分钟的条件下,将上述涂敷液旋转涂敷于半导体Si基板上。然后,将该基板放入以间歇处理进行热气相法的公知的长型烧结炉内,在干燥的纯空气气氛下、在400℃下烧结处理1小时,得到原料多孔质二氧化硅膜。至400℃的升温时间为15分钟。就该温度、升温时间及保持时间而言,没有特别限制,就得到的多孔质膜的膜质而言,只要适当选择不影响膜的性能(例如空孔没有被破坏等)的范围即可。
如上所述得到多孔质二氧化硅膜后,将长型烧结炉内一直保持在400℃,一次减压到400Pa以下。然后,将1,3,5,7-四甲基环四硅氧烷(TMCTS)0.7g/分钟的蒸汽与载气N2一起作为混和气体引入炉内,一直保持500Pa的压力,烧结30分钟。然后,使炉内压力上升至8kPa,烧结60分钟。此时,TMCTS+N2的混合气体以不在炉内停留的方式在烧结中持续流动。烧结后立即抽真空,同时降低温度,取出基板。
这样得到的改性多孔质二氧化硅膜的空孔内壁面,被疏水性的聚合薄膜(聚甲基硅氧烷)覆盖。
对所得多孔质二氧化硅膜,测定了介电常数(汞探针法)、折射率(波长633nm、分光偏振测定法)、弹性模量及硬度(纳米压痕法)。
将在本实施例中得到的膜(A)的物性值和用来比较的不实施在上述TMCTS+N2的混合气体中的烧结而用六甲基二硅氮烷(HMDS)进行疏水化的膜(B)的物性值示于表2。
表2
多孔质膜种类 | 介电常数 | 折射率 | 弹性模量(GPa) | 硬度(GPa) |
基于实施例2得到的改性多孔质二氧化硅膜(A) | 2.10 | 1.209 | 3.78 | 0.43 |
用HMDS处理得到的膜(B) | 2.11 | 1.210 | 3.58 | 0.33 |
由表2所示表明,在TMCTS+N2中实施过烧结的改性多孔质二氧化硅膜,与不实施该烧结的多孔质二氧化硅膜相比,在保持其介电常数、折射率的值的同时,在机械强度方面弹性模量、硬度均提高,特别是在硬度方面增加显著。
实施例3
将四乙氧基硅烷(TEOS)0.85摩尔、H2O 11摩尔、二甲基二乙氧基硅烷(DMDEOS)0.15摩尔及非离子性表面活性剂(旭电化社制、P450;平均分子量=2300、OH(CH2CH2O)13(CH(CH3)CH2O)20(CH2CH2O)13H)0.12摩尔,在乙醇中强酸性环境下、在室温下进行搅拌,配制成透明而均匀的涂敷液。
在此,与实施例2同样,DMDEOS的量没有特别限制,当不添加DMDEOS时,烧结得到的多孔质膜的空孔进行二维六角柱状排列,观测由此产生的X射线衍射峰值,不能得到所谓的虫洞状的空孔结构,而且,多孔质膜的介电常数升高。
在1200转/分钟的条件下将上述涂敷液旋转涂敷于半导体Si基板上,然后,将该基板放入以间歇处理进行热气相法的公知的长型烧结炉内,在N2∶O2=4∶1的气氛下、在425℃下烧结处理1小时,得到多孔质二氧化硅膜。至425℃的升温时间为25分钟。就该温度、升温时间及保持时间而言,与实施例2同样没有特别限制,就得到的多孔质膜的膜质而言,只要适当选择不影响膜的性能(例如空孔没有被破坏等)的范围即可。
如上所述得到多孔质二氧化硅膜后,将长型烧结炉内一直保持在425℃,一次减压到0.4Pa以下。然后,将1,3,5,7-四甲基环四硅氧烷(TMCTS)0.7g/分钟的蒸汽与载气N2一起作为混和气体引入炉内,一直保持24kPa的压力,烧结30分钟。然后,将TMCTS引入量增加到1.4g/分钟,在相同温度及压力下烧结60分钟。此时,TMCTS+N2的混和气体以不在炉内停留的方式在烧结中持续流动。烧结后立即抽真空,同时降低温度,取出基板。
这样得到的改性多孔质二氧化硅膜的空孔内壁面,被疏水性的聚合薄膜(聚甲基硅氧烷)覆盖。
对所得改性多孔质二氧化硅膜(C),用与实施例2同样的方法测定介电常数、折射率、弹性模量及硬度。
将在本实施例中得到的膜(C)的物性值和用来比较的不实施在上述TMCTS+N2的混合气体中的烧结而用六甲基二硅氮烷(HMDS)进行疏水化的膜(D)的物性值示于表3。
表3
多孔质膜种类 | 介电常数 | 折射率 | 弹性模量(GPa) | 硬度(GPa) |
基于实施例3得到的改性多孔质二氧化硅膜(C) | 2.07 | 1.239 | 8.09 | 1.05 |
用HMDS处理得到的膜(D) | 2.06 | 1.225 | 5.95 | 0.68 |
如表3所示表明,在TMCTS+N2中实施过烧结的改性多孔质二氧化硅膜,与不实施该烧结的多孔质二氧化硅膜相比,在保持其介电常数、折射率值的同时,在机械强度方面,弹性模量、硬度均大大提高。
工业实用性
根据本发明,可以提供具有低介电常数和低折射率,且机械强度及疏水性优良的改性多孔质二氧化硅膜,同时,可以提供使用有该改性多孔质二氧化硅膜的半导体装置,因此,该改性多孔质二氧化硅膜可以用作半导体领域中的低介电常数绝缘膜、显示器领域等中的低折射率膜。
Claims (9)
1.改性多孔质二氧化硅膜的制造方法,其特征在于,对于多孔质二氧化硅膜,在减压下使具有至少各1个的疏水性基团和可聚合性基团的疏水性化合物进行气相聚合反应,使该膜中的空孔内壁生成聚合物薄膜。
2.改性多孔质二氧化硅膜的制造方法,其特征在于,在处理室内引入多孔质二氧化硅膜后将处理室内进行减压,接着,将具有至少各1个的疏水性基团和可聚合性基团的疏水性化合物的蒸汽与载气一起引入,在减压下使该疏水性化合物进行气相聚合反应,使该膜中的空孔内壁生成聚合物薄膜。
3.如权利要求1或2所述的改性多孔质二氧化硅膜的制造方法,其特征在于,上述减压为1×10-5Pa~30kPa。
4.如权利要求1~3中任一项所述的改性多孔质二氧化硅膜的制造方法,其特征在于,上述疏水性基团为碳数1~6的烷基或C6H5基团,上述可聚合性基团为氢原子、羟基或卤原子。
5.如权利要求1~3中任一项所述的改性多孔质二氧化硅膜的制造方法,其特征在于,上述疏水性化合物是有机硅化合物,所述有机硅化合物具有至少1个Si-X-Si键合单元以及至少2个Si-A键合单元,
在Si-X-Si键合单元中,X为氧原子、NR基团、CnH2n基团或C6H4基团,R为CmH2m+1基团或C6H5基团,n为1或2,m为1~6的整数,
在Si-A键合单元中,A为氢原子、羟基、OCeH2e+1基团或卤原子,同一分子内的A可以相同或不同,e为1~6的整数。
6.如权利要求1所述的改性多孔质二氧化硅膜的制造方法,其特征在于,上述疏水性化合物为环状硅氧烷类。
7.改性多孔质二氧化硅膜,其特征在于,由权利要求1~6中任一项所述的制造方法得到。
8.半导体材料,其特征在于,使用权利要求7所述的改性多孔质二氧化硅膜。
9.半导体装置,其特征在于,使用权利要求8所述的半导体材料。
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CN102428145A (zh) * | 2009-03-18 | 2012-04-25 | 巴斯夫欧洲公司 | 改性的二氧化硅粒子和包含它们的防污聚合物组合物 |
CN101983223B (zh) * | 2008-04-02 | 2013-06-05 | 三井化学株式会社 | 组合物及其制造方法、多孔质材料及其形成方法、层间绝缘膜、半导体材料、半导体器件以及低折射率表面保护膜 |
CN113710735A (zh) * | 2019-03-28 | 2021-11-26 | 株式会社尼康 | 多孔质膜、光学元件、光学系统、交换透镜、光学装置和多孔质膜的制造方法 |
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JP5030478B2 (ja) | 2006-06-02 | 2012-09-19 | 株式会社アルバック | 多孔質膜の前駆体組成物及びその調製方法、多孔質膜及びその作製方法、並びに半導体装置 |
US20090026924A1 (en) * | 2007-07-23 | 2009-01-29 | Leung Roger Y | Methods of making low-refractive index and/or low-k organosilicate coatings |
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US6395651B1 (en) * | 1998-07-07 | 2002-05-28 | Alliedsignal | Simplified process for producing nanoporous silica |
CA2413592A1 (en) * | 2000-06-23 | 2002-01-03 | Nigel P. Hacker | Method to restore hydrophobicity in dielectric films and materials |
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CN102428145A (zh) * | 2009-03-18 | 2012-04-25 | 巴斯夫欧洲公司 | 改性的二氧化硅粒子和包含它们的防污聚合物组合物 |
CN102428145B (zh) * | 2009-03-18 | 2014-03-26 | 巴斯夫欧洲公司 | 改性的二氧化硅粒子和包含它们的防污聚合物组合物 |
CN113710735A (zh) * | 2019-03-28 | 2021-11-26 | 株式会社尼康 | 多孔质膜、光学元件、光学系统、交换透镜、光学装置和多孔质膜的制造方法 |
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