WO2004040635A1 - 低誘電率非晶質シリカ系被膜の形成方法および該方法より得られる低誘電率非晶質シリカ系被膜 - Google Patents
低誘電率非晶質シリカ系被膜の形成方法および該方法より得られる低誘電率非晶質シリカ系被膜 Download PDFInfo
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- WO2004040635A1 WO2004040635A1 PCT/JP2003/013691 JP0313691W WO2004040635A1 WO 2004040635 A1 WO2004040635 A1 WO 2004040635A1 JP 0313691 W JP0313691 W JP 0313691W WO 2004040635 A1 WO2004040635 A1 WO 2004040635A1
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- Prior art keywords
- coating
- film
- forming
- amorphous silica
- substrate
- Prior art date
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- 238000000576 coating method Methods 0.000 title claims abstract description 295
- 239000011248 coating agent Substances 0.000 title claims abstract description 279
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 274
- 238000000034 method Methods 0.000 title claims abstract description 111
- 239000000758 substrate Substances 0.000 claims abstract description 169
- 239000007788 liquid Substances 0.000 claims abstract description 106
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims abstract description 104
- 239000000203 mixture Substances 0.000 claims abstract description 98
- 239000011148 porous material Substances 0.000 claims abstract description 52
- 238000010438 heat treatment Methods 0.000 claims abstract description 49
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 107
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 53
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000004065 semiconductor Substances 0.000 claims description 39
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 37
- 239000012535 impurity Substances 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 29
- 239000011734 sodium Substances 0.000 claims description 25
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 22
- 229910052801 chlorine Inorganic materials 0.000 claims description 22
- 238000002441 X-ray diffraction Methods 0.000 claims description 21
- 238000004528 spin coating Methods 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 17
- 230000003746 surface roughness Effects 0.000 claims description 17
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- 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 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 14
- 229910052794 bromium Inorganic materials 0.000 claims description 14
- 230000003301 hydrolyzing effect Effects 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000011229 interlayer Substances 0.000 claims description 5
- 229910002026 crystalline silica Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims 1
- 238000011282 treatment Methods 0.000 abstract description 48
- 238000010304 firing Methods 0.000 abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 90
- 239000000243 solution Substances 0.000 description 61
- 239000011259 mixed solution Substances 0.000 description 54
- 239000003960 organic solvent Substances 0.000 description 48
- 239000007864 aqueous solution Substances 0.000 description 42
- 238000003756 stirring Methods 0.000 description 39
- 235000019441 ethanol Nutrition 0.000 description 32
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 30
- 239000000126 substance Substances 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 27
- 229920001296 polysiloxane Polymers 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- -1 or the like Substances 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 238000002156 mixing Methods 0.000 description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 17
- 239000010703 silicon Substances 0.000 description 17
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 15
- 238000006460 hydrolysis reaction Methods 0.000 description 14
- 229910021536 Zeolite Inorganic materials 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 239000010457 zeolite Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 229910000077 silane Inorganic materials 0.000 description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000004756 silanes Chemical class 0.000 description 8
- 230000005856 abnormality Effects 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 239000003729 cation exchange resin Substances 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 239000003957 anion exchange resin Substances 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000006884 silylation reaction Methods 0.000 description 3
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-N tetrapropylazanium;hydrate Chemical compound O.CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-N 0.000 description 3
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical compound CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
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- 239000005858 Triflumizole Substances 0.000 description 1
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- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
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- 238000003795 desorption Methods 0.000 description 1
- ZXPDYFSTVHQQOI-UHFFFAOYSA-N diethoxysilane Chemical compound CCO[SiH2]OCC ZXPDYFSTVHQQOI-UHFFFAOYSA-N 0.000 description 1
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- LJLOWWWTZWZHAZ-UHFFFAOYSA-N difluoro(dimethoxy)silane Chemical compound CO[Si](F)(F)OC LJLOWWWTZWZHAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011737 fluorine 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
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- 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 1
- 229940057867 methyl lactate Drugs 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
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- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 229940095070 tetrapropyl orthosilicate Drugs 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 125000005208 trialkylammonium group Chemical group 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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- HSMVPDGQOIQYSR-KGENOOAVSA-N triflumizole Chemical compound C1=CN=CN1C(/COCCC)=N/C1=CC=C(Cl)C=C1C(F)(F)F HSMVPDGQOIQYSR-KGENOOAVSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- ZASZWSTYEJKHIN-UHFFFAOYSA-N tripropylazanium;hydroxide Chemical compound [OH-].CCC[NH+](CCC)CCC ZASZWSTYEJKHIN-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
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- 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
- H01L21/02214—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 oxygen
- H01L21/02216—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 oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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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
- C09D183/02—Polysilicates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
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- 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
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- 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
- H01L21/02203—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 porous
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- 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
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- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02337—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a gas or vapour
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
Definitions
- the present invention relates to a method for forming a smooth low dielectric constant amorphous silica-based film having a low dielectric constant (2.5) or less, high film strength and excellent hydrophobicity on a substrate. And a low dielectric constant amorphous silica-based film obtained by the method.
- the interlayer insulating film provided for the above purpose is generally formed on a semiconductor substrate by using a vapor deposition method such as a chemical vapor deposition (CVD) method or a coating method such as a spin coating method.
- a vapor deposition method such as a chemical vapor deposition (CVD) method
- a coating method such as a spin coating method.
- silica-based coatings obtained using the latest technology of CVD can achieve a dielectric constant of 3 or less, but have a dielectric constant of about 2.5. It is said that the formation of a film is the limit, and as in the case of the conventional coating method, there is a drawback that the film strength of the film decreases with a decrease in the relative dielectric constant.
- a CVD film of a polyaryl resin, a fluorine-added polyimide resin, a fluorine resin, or the like, or a film formed using these coating solutions has a relative dielectric constant of about 2, but has poor adhesion to the substrate surface.
- the relative dielectric constant can be reduced by using a coating liquid for forming a low dielectric constant silica-based film containing an alkoxysilane and / or a halogenated silane or a hydrolyzate thereof and an organic template material (described in Patent Document 5, etc.).
- Chemical resistance such as adhesion to coating surface, coating strength, alkali resistance, etc. ⁇ Excellent crack resistance and smoothness of coating surface, as well as oxygen plasma resistance and etching resistance It has been found that a film excellent in process suitability can be formed.
- the present inventors have repeatedly conducted a test for forming a low dielectric constant silica-based film on various semiconductor substrates using these coating solutions and a conventionally known film forming method (spin coating method or other coating methods).
- spin coating method or other coating methods As a result, although a film having the above-mentioned characteristics was obtained, the film strength was reduced when a film having a relative dielectric constant of 2.5 or less was formed. It has been found that it is difficult to stably obtain a material having a Young's Modulus higher than GPa (gigapascal).
- tetraethyl orthosilicate dissolved in ethyl alcohol TEOS
- TPAOH tetrapropylammonium hydroxide
- the zeolite coating obtained by this method has a Young's modulus of 16 to 18 GPa, it has a high hygroscopicity, so it absorbs moisture in the air and the relative dielectric constant increases rapidly (for example, there is a problem that the relative dielectric constant is increased to 2.3, and to 3.9), which makes it unsuitable for practical use. Therefore, a method has been proposed in which the zeolite film obtained in this manner is subjected to silane treatment (Silylation) to make the surface hydrophobic, and the dielectric constant of the film is kept at 2. "! To 2.3. (Described in Non-Patent Document 1 and Patent Document 6, etc.)
- the surface of the obtained zeolite coating is considerably rough because the zeolite particles contained in the coating are as large as about 20 nm, and means such as a polishing operation are required to smooth the surface. It has been. Further, since only the surface of the hydrophobized zeolite film is hydrophobized, if the film is subjected to fine processing such as resist coating or etching treatment to form a wiring pattern or a through hole, the surface is hydrophobized.
- the exposed portion may be exposed and absorb moisture from that portion, resulting in problems such as degrading the relative dielectric constant of the coating (ie, increasing the relative dielectric constant).
- the inventors of the present application have conducted intensive studies with the aim of solving the above-mentioned problems, and prepared a coating liquid for forming a film having a novel composition and properties as shown below.
- the present invention was completed.
- Patent Document 2 Japanese Patent Application Laid-Open No. 9-315812
- Patent Document 3 International Application Publication WO OOZ1 8847
- Patent Document 4 International Application Publication WOOOZ1 26'40
- Patent Document 6 United States Patent Application Publication US 2000/0060364 A1
- Non-Patent Document 1 Advanced Material 2001, 13, No.19, October 2, Page 1453
- the present invention is intended to solve the above-mentioned problems, and has a characteristic that the relative dielectric constant is as small as 2.5 or less, and the Young's elastic modulus representing the film strength is 6.0 GPa or more.
- An object of the present invention is to provide a method for forming a smooth, low-dielectric-constant amorphous silica-based coating having excellent hydrophobicity on a substrate and a low-dielectric-constant amorphous silica-based coating obtained by the method.
- the first method for forming a low dielectric constant amorphous silica-based coating according to the present invention
- a method of forming a smooth, low-dielectric-constant amorphous silica-based coating having high film strength and excellent hydrophobicity on a substrate
- Gaylin obtained by hydrolyzing tetraalkylorthosilicate (TA0S) and alkoxysilane (AS) represented by the following general formula (I) in the presence of tetraalkylammonium hydroxide-containing oxide (TAA0H) Preparing a liquid composition containing the compound,
- X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- n is an integer of 0 to 3.
- the second method for forming a low dielectric constant amorphous silica-based film according to the present invention comprises forming a flat low dielectric constant amorphous silica-based film having high film strength and excellent hydrophobicity on a substrate.
- the tetraalkyl orthosilicate (TAOS) used in the preparation step (a) is tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TEOS). TMOS) or a mixture thereof.
- the alkoxysilane used in the preparation step (a) is preferably methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES) or a mixture thereof.
- MTMS methyltrimethoxysilane
- MTES methyltriethoxysilane
- the tetraalkyl ammonium hydroxide mouth oxide (TAAOH) used in the preparation step (a) is tetrapropyl ammonium hydroxide mouth oxide (TPAOH), tetrabutyl ammonium hydroxide mouth oxide (TBAOH) or a mixture thereof. It is preferable that there is.
- bromine (Br), chlorine (CI) and the like contained in the tetraalkyl ammonium hydroxide (TAAOH) used in the preparation step (a) are used.
- the content of impurities composed of compounds of any halogen group elements is based on the respective elements.
- the molar ratio of tetraalkyl ortho silicate are one bets to be used in the preparation process (a) (TAOS) and the alkoxysilane (AS) (TAOSZAS) is, Si0 2 in terms of criteria 6 4-2 8 Is preferably within the range.
- the molar ratio (TAAOH / CTAOS + AS) of the tetraalkylammonium hydroxide (TAAOH) and the silica-based film forming component (TAOS + AS) used in the preparation step (a) is Si0 It is preferably in the range of 110 to 710 on a 2 conversion basis.
- each operation of the coating step (b), the heat treatment step (c), and the baking treatment step () is performed using the following method.
- the operation of the coating step (b) is performed by a spin coating method.
- the low-dielectric-constant amorphous silica-based coating according to the present invention is a coating obtained by the above-described coating forming method, and has a relative dielectric constant of 2.5 or less and a Young's modulus (Young's Modulus) of 6.0 GPa or more. It is characterized by having a high film strength. Further, the coating is an amorphous silica-based coating having no X-ray diffraction peak such as an MFI crystal structure.
- the coating preferably has an average pore diameter of pores contained in the coating of 3 nm or less and a pore volume content of micropores of 2 nm or less of 70% or more.
- the coating preferably has a smooth surface with a surface roughness (Rms) of 1 nm or less.
- the surface roughness is a root mean square roughness of a value measured by an atomic force microscope AFM.
- a preferable use of the coating is an interlayer insulating film formed on a semiconductor substrate.
- Fig. 1 shows the results of X-ray diffraction of the silica-based coating (amorphous coating) formed on the substrate 1-2 of the example
- Fig. 2 shows the silica-based coating formed on the substrate 3 of the comparative example.
- the result of X-ray diffraction of the (crystalline film) is shown.
- the X-ray diffraction peaks (peaks at 2 ° to 8 °, 9 °, and 23 °) in FIG. 2 indicate that the film has a crystal structure (ie, a ZSM-5 type zeolite film). Is shown.
- a tetraalkyl orthosilicate (TAOS) and an alkoxysilane represented by the following general formula (I) are used as a coating solution for forming a film.
- TAOS tetraalkyl orthosilicate
- I alkoxysilane represented by the following general formula (I)
- a liquid composition containing a gay compound obtained by hydrolyzing AS) in the presence of a trialkylammonium hydroxide (TAAOH) is used as a coating solution for forming a film.
- X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- n is an integer of 0 to 3.
- the tetraalkyl orthosilicate includes tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetraisopropylorthosilicate, tetrabutylorthosilicate, and the like.
- TAOS tetraalkyl orthosilicate
- TEOS tetraethylorthosilicate
- TMOS tetramethylorthosilicate
- alkoxysilane examples include methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, octyltrimethoxysilane, and Octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, trimethoxysilane, triethoxysilane, triisopropoxysilane, fluorotrimethoxysilane, fluorotriethoxysilane , Dimethyldimethoxysilane, dimethyljetoxysilane, ethisoresylmethoxysilane, getyljetoxysilane, dimethoxysilane, diethoxysilane, di
- the tetraalkyl ammonium hydroxide oxide includes tetramethyl ammonium hydroxide oxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide oxide, tetrabutyl ammonium hydroxide. Mouth oxide, tetra-n-octylammonium hydride mouth oxide, n-hexadecyltrimethylammonium hydride mouth oxide, n-octadecyltrimethylammonium hydride mouth oxide, and the like.
- TPAOH tetrapropyl ammonium hydroxide mouth oxide
- TAAOH pertrapyl ammonium hydroxide mouth oxide
- TAAOH tetraalkylammonium hydroxide
- TAAOH tetraalkylammonium hydroxide
- impurities composed of compounds of alkali metal elements such as sodium (Na) and potassium (K) are contained in amounts of more than 50 ppb on an element basis, the impurities diffuse into the transistor portion of the semiconductor substrate and deteriorate. May cause.
- impurities composed of compounds of halogen elements such as bromine (Br) and chlorine (CI) are contained in an amount of more than 1 ppm by weight on an element basis, aluminum wiring, copper wiring and the like constituting a semiconductor substrate are not included. Can corrode and cause catastrophic damage.
- the present inventors have found that when the impurities of the alkali metal element compound is contained more than 50 wt PP b, alkoxysilanes represented by the tetraalkyl ortho silicate gate (TAOS) and the general formula (I) (AS) has been found to act as a catalyst for this impurity when hydrolyzing in the presence of tetraalkylammonium hydroxide oxide (TAAOH), and the resulting gay compound becomes zeolite-like crystalline silica.
- TAAOH tetraalkylammonium hydroxide oxide
- the tetraalkylammonium hydroxide mouth oxide (TAAOH) used in the method of the present invention is obtained by treating a commercially available tetraalkylammonium hydroxide mouth oxide with a cation exchange resin treatment step and an anion exchange resin treatment step.
- impurities contained therein such as compounds of alkali metal elements such as sodium (Na) and potassium (K) and compounds of halogen group elements such as bromine (Br) and chlorine (CI), are substantially eliminated. It is preferable to remove the carbon and purify it.
- the tetraalkyl ortho silicate are one preparative (TAOS) and the molar ratio before Symbol alkoxysilane (TAOS / AS) is, Si0 2 equivalent value in 6 4-2 Roh 8, the good Mashiku 5 It is desirable to be in the range of 5 to 3/7.
- TAOS / AS the molar ratio
- the molar ratio exceeds 64, the resulting silica-based coating will have poor water-freeness.
- the molar ratio is less than 2/8, the template effect due to the tetraalkyl ammonium hydroxide oxide (TAAOH) is reduced, so that the fine particles (pore volume) formed in the film are reduced.
- the method for preparing the liquid composition that is, the coating liquid for coating formation (coating liquid A) used in the method of the present invention is as follows.
- the coating solution for forming a film (coating solution A) used in the method of the present invention is:
- the tetraalkyl orthosilicate (TAOS) and It can be prepared as a liquid composition containing a silicon compound which is a hydrolyzate of the alkoxysilane (AS).
- a mixed solution of tetraalkylorthosilicate (TAOS), alkoxysilane (AS) and an organic solvent prepared in G) is mixed under the same conditions as above (temperature: 10 to 30 ° C, stirring speed: 100 ° C). ⁇ 200 rpm) into the aqueous solution of the tetraalkyl ammonium hydroxide (TAAOH) of (ii) above for 30 to 90 minutes.
- TAOS tetraalkyl orthosilicate
- AS alkoxysilane
- TAAOH Tetraalkyl ammonium hydroxide oxide
- Examples of the organic solvent used in the method of the present invention include alcohols, ketones, ethers, esters, and hydrocarbons, and more specifically, for example, methanol, ethanol, propanol, butanol and the like.
- Alcohols, ketones such as methylethyl ketone, methyl isobutyl ketone, glycol ethers such as methyl sorb, ethyl sorb, glycol ether such as propylene glycol monopropyl ether, ethylene glycol, propylene glycol, hexylene glycol, etc.
- Examples include glycols, esters such as methyl acetate, ethyl acetate, methyl lactate, and ethyl lactate; hydrocarbons such as hexane, cyclohexane, and octane; and aromatic hydrocarbons such as toluene, xylene, and mesitylene.
- esters such as methyl acetate, ethyl acetate, methyl lactate, and ethyl lactate
- hydrocarbons such as hexane, cyclohexane, and octane
- aromatic hydrocarbons such as toluene, xylene, and mesitylene.
- it is preferable to use alcohols such as ethanol.
- the amount of the organic solvent used is not particularly limited, but the weight mixing ratio (organic solvent / TTAOS + AS) to the silica-based film forming component (TAOS + AS) is from 1 / ⁇ to It is desirably in the range of 31, preferably 1 Z1 -2.5X1.
- the aqueous solution of tetraalkylammonium hydroxide (TAAOH) dropped into the above-mentioned mixed organic solvent is prepared by adding 5 to 40 tetraalkylammonium hydroxide (TAAOH) in distilled water or ultrapure water. weight 0/0, it is desirable preferably containing at a ratio of 1 0 to 30 by weight%.
- TAOS tetraalkylorthosilicate
- AS alkoxysilane
- TAAOH tetraalkyl ammonium hydroxide oxide
- the reaction conditions of the hydrolysis 30 to 80 ° C, preferably at a temperature of 35 to 60 ° C, with stirring "! ⁇ 72 hours, this preferably is preferably carried out over a period of 1 0 to 48 hours c
- the number average molecular weight of the silicon compound (TAOS and AS hydrolyzate) contained in the liquid composition thus obtained is in the range of 500 to 100,000, preferably 1,000 to 100,000 in terms of polystyrene.
- a coating liquid for forming a coating film that is, the liquid composition
- the coating liquid for forming a film may include, as necessary, at least one silicon selected from the group consisting of an alkoxysilane represented by the following general formula (I) and a halogenated silane represented by the following general formula (II).
- Compound and Z or their hydrolysates It can be included polysiloxane (PS) force is the reaction product of a silica-based fine particles having a particle size of 5 to 50 nm.
- X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- X ′ represents a halogen atom c
- n is an integer of 0 to 3.
- the silica-based fine particles can be obtained by mixing at least one of the alkoxysilanes of the general formula (I) with an organic solvent and subjecting the mixture to hydrolysis and polycondensation in the presence of water and ammonia,
- a silica-based coating is formed on a substrate by using a coating solution containing polysiloxane (PS) obtained by reacting the above-mentioned alkoxysilane and a hydrolyzate of silane or halogenated silane on the surface thereof.
- PS polysiloxane
- the silica-based coating film forming component (TAOS + AS) weight mixing ratio (PSZ (TAOS + AS)) is 1 3 hereinafter with Si0 2 in terms of reference , Preferably 14 or less.
- the film strength of the formed silicon-based film becomes weak, and the film strength consisting of Young's modulus of 6.0 GPa or more Cannot be obtained. Furthermore, the relative dielectric constant increases, and it becomes difficult to obtain a silica-based coating having a relative dielectric constant of 2.5 or less.
- the reason for this is that as the amount of tetraalkyl orthosilicate (TAOS) decreases, the template effect of tetraalkylammonium hydroxide (TAAOH) decreases.
- the silica-based film-forming components thus obtained ie, a) a silicon compound which is a hydrolyzate of tetraalkyl orthosilicate (TAOS) and alkoxysilane (AS), or b) a tetraalkylorthosilicate
- TAOS tetraalkyl orthosilicate
- AS alkoxysilane
- the silica-based film forming component Gay-containing compound, or Kei-containing compounds and PS
- Si0 2 preferably it is desirable to contain in the range of 5 to 20 wt%.
- the liquid composition containing the silica-based film-forming component obtained by the above method may be used as it is as a coating solution for forming a film.
- the concentration of the component for forming the silicic film is adjusted to the above level before use.
- the organic solvent and water contained in the liquid composition, and alcohols by-produced by hydrolysis of alkoxysilane (AS) and the like are separated and removed.
- the liquid composition is included before being subjected to the process. It is desirable that the organic solvent and water are kept in the range of 0.1 to 40% by weight, preferably 1 to 30% by weight, respectively, based on the total amount of the liquid composition.
- Coating solution B This makes it possible to obtain a coating liquid for forming a smooth low dielectric constant amorphous silica-based film having high film strength and excellent hydrophobicity.
- a tetraalkyl orthosilicate is used as a coating liquid for forming a film.
- AS alkoxysilane
- AS alkoxysilane
- a liquid composition containing a silicon compound obtained by hydrolyzing the whole is used.
- X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- n is an integer of 0 to 3.
- TAOS tetraalkyl orthosilicate
- AS alkoxysilane
- TAAOH tetraalkylammonium hydride oxide
- TAAOH tetraalkylammonium hydroxide mouth oxide
- impurities such as compounds of alkali metal elements such as sodium (Na) and potassium (K) and compounds of halogen group elements such as bromine (Br) and chlorine (CI) contained therein Must be removed beforehand.
- the content of impurities composed of compounds of alkali metal elements such as sodium (Na) and potassium (K) contained therein should be set to 50 wt ppb or less on an element basis, and bromine (Br) or chlorine (GI ) And other halogen elements It is necessary that the content of impurities consisting of the above compounds be 1 ppm by weight or less on an elemental basis.
- This liquid composition (coating solution B) is prepared by hydrolyzing or partially hydrolyzing a tetraalkylorthosilicate (TAOS), and then mixing the alkoxysilane (AS) or its hydrolyzate or partial hydrolyzate, Further, if necessary, some or all of them are hydrolyzed.
- TAOS tetraalkylorthosilicate
- the alkoxysilane (AS) is preliminarily hydrolyzed or partially hydrolyzed) and then mixed, the tetraalkylorthosilicate (TAOS) is hydrolyzed (or partially hydrolyzed).
- TAOS tetraalkylorthosilicate
- the tetraalkyl ammonium hydroxide mouth oxide (TAAOH) is used for each of the silica-based film forming components, that is, the tetraalkyl orthosilicate (TAOS) and the alkoxysilane (AS).
- the method for preparing the liquid composition that is, the coating solution for coating formation (coating solution B) used in the present invention is as follows.
- coating solution B is
- TAAOH tetraalkylammonium hydroxide
- the coating solution for forming a film (coating solution B) used in the present invention is:
- Tetraalkyl orthosilane KTA0S
- organic solvent e.g., benzyl alcohol
- tetraalkylammonium hydroxide is added to the mixed solution under stirring.
- the aqueous solution of the side (TAAOH) is added dropwise over 5 to 20 minutes, the mixture is further stirred at a temperature of 10 to 30 ° C for 30 to 90 minutes at a speed of 100 to 200 rpm,
- TAA0H of (ii) above is added dropwise to the mixed solution of TAOS and the organic solvent prepared in (i) above, (V) in a mixed solution of AS and organic solvent
- TAOS tetraalkyl orthosilicate
- an organic solvent is added under the same conditions as above (at a temperature of 10 to 30 ° C).
- stirring speed is 100-200 rpm) in the aqueous solution of tetraalkylammonium hydroxide (TAA0H) of ((1)) for 30-90 minutes.
- TAA0H tetraalkylammonium hydroxide
- AS alkoxysilane
- AS alkoxysilane
- the tetraalkylammonium hydroxide (TAAOH) of (V) may be slowly dropped into the aqueous solution of the tetraalkylammonium hydroxide (TAAOH) of (V) for 30 to 90 minutes.
- TAAOH tetraalkylammonium hydroxide
- the tetraalkyl orthosilicate (TAOS), the alkoxysilane (AS) and The tetraalkyl ammonium hydroxide (TAAOH) is used by being mixed or added so as to have the above molar ratio, respectively.
- the organic solvent the same organic solvents as those exemplified for preparing the coating liquid A can be used.
- the respective organic solvents to be mixed with the tetraalkylorthosilicate (TAOS) and the above-mentioned alkoxysilane (AS) may be different as long as their types (for example, alcohols) are the same, It is desirable that they be the same.
- the amount of the organic solvent to be used is not particularly limited, but as in the case of the coating solution A, the weight mixing ratio (organic solvent ZCTAOS + AS)) is in the range of 1/1 to 3Z1, preferably 1Z1 to 2.5 / 1. Therefore, the weight mixing ratio (organic solvent / (TAOS + AS)) of the organic solvent and the silica-based film forming component (TAOS + AS) after mixing them is 1 / ⁇ , as in the case of the coating solution A. 331, preferably 11 12.5 / 1.
- the aqueous solution of the tetraalkyl ammonium hydroxide (TAAOH) dropped into the mixed organic solvent is a tetraalkyl ammonium hydroxide in distilled water or ultrapure water. It is desirable to contain 5 to 40% by weight, preferably 10 to 30% by weight, of a hydroxide (TAAOH).
- the tetraalkyl orthosilicide (TAOS) or the alkoxysilicone may be used.
- the time for hydrolyzing the orchids (AS) alone may be short, it is desirable that the next step be performed for a time sufficient to completely hydrolyze them (for example, 10 to 30 hours).
- the number average molecular weight of the silicon compound (the hydrolyzate of TAOS and AS) contained in the liquid composition thus obtained is 500 to 10000000 in terms of polyethylene oxide, similarly to the case of the coating solution A. And preferably in the range of 1,000 to 100,000.
- the coating solution for forming a film may be formed from an alkoxysilane represented by the following general formula (I) and a halogenated silane represented by the following general formula (II), if necessary.
- PS polysiloxane which is a reaction product of at least one silicon compound selected from the group consisting of and / or a hydrolyzate thereof and silica-based fine particles having a particle size of 5 to 50 nm can be contained. .
- X represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 8 carbon atoms, a fluorine-substituted alkyl group, an aryl group or a vinyl group
- R represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- X ′ represents a halogen atom c
- n is an integer of 0 to 3.
- the content of the polysiloxane (PS) is such that the weight mixing ratio (PSZ (TAOS + AS)) with respect to the silica-based film-forming component (TAOS + AS) is Si0 2 It is desirably 13 or less, preferably 14 or less on a conversion basis.
- the silica-based film-forming components thus obtained ie, a) a tetraalkyl orthosilicide (TA0S) and a silicon compound which is a hydrolyzate of alkoxysilane (AS), or b) a tetraalkyl orthosilicate
- a liquid composition containing a hydrolyzate of a TA0S) and an alkoxysilane (AS) and a polysiloxane (PS) is used as a coating liquid for forming a film, similar to the case of the coating liquid A
- the silica-based film-forming component a gay compound or a gay compound and The PS 2 to 40% by weight Si0 2 in terms of standards, it is desirable that preferably contains in the range of 5 to 20 wt%.
- the liquid composition containing the silica-based film-forming component obtained by the above method is used as it is as a coating liquid for forming a film.
- the organic solvent component contained in the liquid composition may be converted to propylene glycol monopropyl ether (PGP), propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether acetate (PGMEA) using a rotary evaporator or the like.
- the silica-based film-forming component is used after adjusting the concentration of the silica-based film-forming component to the above-mentioned level after the step of solvent replacement with an organic solvent selected from the above.
- the organic solvent and water contained in the liquid composition, and alcohols by-produced by hydrolysis of alkoxysilane (AS) and the like are separated and removed.
- the liquid composition the total amount in pairs respectively 0.1 to 40 weight 0/0 of the liquid composition and the organic solvent and moisture contained in before being subjected to the process, preferably 1 to 30 wt% It is desirable to keep them within the range.
- a spin coating method In general, as a method for applying such a coating solution, a spin coating method, a dip coating method, a roll coating method, a transfer method, or the like is adopted. In the present invention, such a conventionally known method is used. A low dielectric constant amorphous silica-based coating can be formed. Among them, when a coating liquid for forming a coating is applied on a semiconductor substrate or the like, the spin coating method is preferable, and is excellent in uniformity of the coating film thickness and low dust generation. Therefore, in the present invention, it is desirable to employ the coating method by the spin coating method. However, when the coating method is applied on a large-diameter semiconductor substrate, a transfer method may be employed. .
- this heat treatment is desirably performed by increasing the temperature stepwise within the range of 80 to 350 ° C as necessary. Furthermore, if this heat treatment is performed at a temperature lower than 80 ° C, most of the organic solvent contained in the above-mentioned coating film often remains in the coating film without evaporating. In addition to not being able to achieve the object, there is a case where unevenness occurs in the film thickness of the formed film.
- the heat treatment varies depending on the thickness of the coating film, but it is preferable to perform the heat treatment over a period of 10 minutes, preferably 2 to 5 minutes.
- it is preferable to perform the treatment under an air atmosphere because the treatment is performed at a relatively low temperature of 350 ° C. or less. Since it is performed for a short time under the conditions, even if the heat treatment is performed in an air atmosphere containing a relatively large amount of oxygen, the metal wiring provided on the semiconductor substrate will not be damaged by metal oxidation or the like.
- the organic solvent contained in the above-mentioned coating film evaporates, and the polyalkylammonium hydroxide oxide (TAAOH) contained in the coating film is decomposed and desorbed.
- TAAOH polyalkylammonium hydroxide oxide
- the polymerization of the silica-based film-forming component which is a solid component, progresses and cures, the melt viscosity of the polymer decreases in the process of heating, and the reflow property of the film increases. The result is improved.
- this heat treatment is preferably performed by placing the substrate obtained in the coating step on a single-wafer hot plate. (d) Firing process
- the film subjected to the heat treatment is calcined (cured) at a temperature of 350 to 450 ° C. in an atmosphere of an inert gas.
- an inert gas it is desirable to use nitrogen gas.
- an oxygen gas or air is added to the inert gas to contain a small amount of oxygen (for example, about 500 to 10,000 ppm by volume of oxygen).
- An inert gas may be used. (Described in International Application Publication WO 01/48806, etc.)
- the firing temperature is determined based on the type and amount of tetraalkylammonium hydroxide (TAAOH) used in preparing the coating solution for forming a film, or the gay compound contained in the coating solution (that is, a silica-based coating). Although it depends on the properties of the (forming component), in order to obtain a low dielectric constant amorphous silica-based film with moisture absorption resistance (hydrophobicity) and high film strength, select from a temperature range of 350 to 450 ° C. It is desired to do. Here, if the temperature of the baking treatment is lower than 350 ° C., it is difficult to crosslink the precursor of the silica-based film-forming component, so that a film having sufficient film strength cannot be obtained. If the temperature exceeds ° C, aluminum wiring and copper wiring constituting the semiconductor substrate may be oxidized or melted, and may cause fatal damage to the wiring layer.
- TAAOH tetraalkylammonium hydroxide
- the baking treatment varies depending on the type of the coating solution for forming the film, the film thickness of the film, and the like, but is preferably performed for 5 to 90 minutes, preferably 10 to 60 minutes. Further, this baking treatment is preferably performed by placing the substrate on a single-wafer hot plate, as in the case of the heating step.
- the thickness of the silica-based coating obtained in this way varies depending on the semiconductor substrate on which the coating is formed and its purpose. For example, it is usually 100 to 600 nm on a silicon substrate (silicon wafer) in a semiconductor device. The thickness is usually 100 to 1,000 nm between wiring layers of the multilayer wiring.
- the low dielectric constant amorphous silica-based coating according to the present invention is a coating obtained by the above-described coating forming method, and has a relative dielectric constant of 2.5 or less and a Young's modulus (Young's modulus) of 6.0 GPa or more. Modulus). Further, according to the above-mentioned method for forming a film, a silica-based film having an average pore diameter of pores contained in the film of 3 nm or less and a pore content of 70% or more of micropores of 2 nm or less is used. Can be easily formed. These physical properties are one of the important factors in providing the low relative dielectric constant and high film strength. Therefore, in the present invention, it is possible to provide a silica-based coating that meets the demands of the recent semiconductor manufacturing industry.
- a silica-based film having a smooth surface with a surface roughness (Rms) of 1 nm or less can be easily formed.
- This surface roughness is the root-mean-square of the value measured by an atomic force microscope AMF.
- the silica-based coating according to the present invention is an amorphous silica-based coating having no X-ray diffraction peak such as the MFI crystal structure of a zeolite coating.
- the silica-based coating according to the present invention is formed on a conductive substrate, between wiring layers of a multilayer wiring structure, on a substrate provided with an element surface and / or a PN junction, or between multilayer wiring layers provided on the substrate.
- the silica-based coating according to the present invention is preferably used as an interlayer insulating film formed on a semiconductor substrate or the like. According to the method of the present invention, even if the surface of the coating is not subjected to silane treatment or the like, the relative dielectric constant is as small as 2.5 or less and the coating has a Young's modulus of at least 6.0 GPa.
- a low dielectric constant amorphous silica-based coating having a smooth surface with a surface roughness (Rms) of 1 nm or less can be obtained without polishing the surface of the coating. Can be formed on.
- the silica-based coating obtained by the method of the present invention is excellent in chemical resistance such as adhesion to a coating surface such as a semiconductor substrate, alkali resistance and the like, crack resistance, and oxygen resistance. It has excellent characteristics in process suitability such as plasma properties and etching processability. That is, the silica-based coating according to the present invention has a relative permittivity as small as 2.5 or less and a Young's value of 6.0 GPa or more, in addition to those achieved by the inventions filed by the present inventors in the past. An effect having both high film strength consisting of an elastic modulus and moisture absorption resistance (hydrophobicity) can be obtained.
- the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
- Ultrapure water was added to the obtained aqueous solution of tetrapropyl ammonium hydroxide (TPAOH) to adjust the concentration to 10% by weight, and sodium (Na) and potassium (K) contained as impurities in the aqueous solution were adjusted.
- TPAOH tetrapropyl ammonium hydroxide
- Na sodium
- K potassium
- the compounds of the halogen group elements of bromine (Br) and chlorine (CI) were determined by the atomic absorption method (AAS method, polarized Zeeman atomic absorption spectrophotometer Z-5710 manufactured by Hitachi, Ltd.).
- ion chromatography DIONEX 2020i).
- ultrapure water is added to the tetrapropylammonium hydroxide aqueous solution (commercially available) before the above-mentioned ion exchange treatment to adjust the concentration to 10% by weight.
- the content of the contained impurities was measured.
- the amount of impurities contained in the aqueous solution before the ion exchange treatment was 50 ppm by weight of sodium, 2500 ppm by weight of potassium, 225 ppm by weight of bromine, and 13 ppm by weight of chlorine on an elemental basis.
- the content of impurities contained in the aqueous solution after the ion-exchange treatment is, on an elemental basis, less than 10% by weight of sodium (detection limit), 10% by weight of potassium (detection limit), 1% by weight of bromine and less than 1% by weight of chlorine.
- the purification of the aqueous solution of tetrapropylammonium hydrate at the mouth could be carried out to a level of not more than ppm by weight c, that is, to the allowable impurity level required in the present invention.
- tetraethyl orthosilane TEOS manufactured by Tama Chemical Industry Co., Ltd.
- MTMS methyltrimethoxysilane
- EOH Wako Pure Chemical Industries, Ltd.
- the highly purified tetrapropylammonium hydride oxide aqueous solution (containing 10% by weight of TPAOH) was dropped into these mixed solutions at a ratio shown in Table 1 over 10 minutes, and further added at 20 ° C. At 200 rpm for 1 hour. Thereafter, the mixture was heated to a temperature of 50 ° C., and the silica-based film forming components (TEOS and MTMS) were hydrolyzed for 20 hours while stirring at a speed of 200 rpm under this temperature condition.
- ethanol (organic solvent) in the mixed solution containing the hydrolyzate of the silica-based film-forming component was mixed with propylene glycol monopropyl ether (PGP, PGP, using a rotary evaporator (R-114 manufactured by Shibata Kagaku Co., Ltd.)).
- PGP propylene glycol monopropyl ether
- R-114 rotary evaporator
- the concentration of the gay compound which consists of the hydrolyzate of tetraethyl orthosilicide (TEOS) and methyltrimethoxysilane (MTMS) was adjusted.
- TEOS tetraethyl orthosilicide
- MTMS methyltrimethoxysilane
- the substrates were baked at 400 ° C. for 30 minutes in a nitrogen gas atmosphere with the substrates placed on a single-wafer hot plate.
- these substrates (Example substrates I-1 to I-8) were cooled to a temperature close to room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained (a spectroscopic ellipsometer-ESVG manufactured by SOPRA) was about 500 nm.
- EMD-1000 Electro Science Co., Ltd.
- Coating strength Young's Modulus, Young's Modulus, nanoindentation method, MTS Systems Corp Nanoindenter — XP
- iv Surface Roughness (Rms, AFM method)
- pore distribution average pore diameter and pore volume content of 2 mri or less: nitrogen adsorption method
- X-ray diffraction peaks crystalline film and amorphous Determination of coating: X-ray diffraction method
- FIG. 1 shows the result of X-ray diffraction of the silica-based film formed on Example substrate I-2.
- Example coating liquid 2 A liquid composition containing 2% by weight (Example coating liquid 2) was obtained.
- the preparation requirements for this liquid composition are as shown in Table 1. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, this substrate (Example substrate 1) was cooled to a temperature close to room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- Example 2 the relative permittivity of the silica-based coating formed on the substrate, the change in the amount of water absorbed by the coating before and after oxygen plasma irradiation, the coating strength, the surface roughness, the pore distribution (average The pore diameter and the pore volume content of 2 nm or less) and the X-ray diffraction peak (determination of crystalline film and amorphous film) were measured.
- TEOS tetraethylorthosilicate
- MTES methyltriethoxysilane
- EOH Wako Pure Chemical Industries, Ltd.
- Example coating solution 3 a liquid composition containing 12% by weight (Example coating solution 3) was obtained.
- the preparation requirements for this liquid composition are as shown in Table 1. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied on an 8-inch silicon L: L substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, the substrate (Example substrate 3) was cooled to a temperature close to room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- TPAOH tetrapropylammonium hydride oxide
- ultrapure water was added to this aqueous solution to adjust the concentration to 10% by weight, and the aqueous solution was contained as an impurity.
- Na sodium
- potassium (K) alkali metal compounds and bromine (Br) and chlorine (CI) halogen compounds are determined by atomic absorption spectrometry (AAS) and ion chromatography, respectively. It was measured by the method.
- ultrapure water is added to the tetrabutylammonium hydroxide aqueous solution (commercially available) before the above-mentioned ion exchange treatment to adjust the concentration to 10% by weight.
- the content of the contained impurities was measured.
- the amount of impurities contained in the aqueous solution before the ion exchange treatment was 50 ppm by weight of sodium, 3000 ppm by weight of potassium, 2500 ppm by weight of bromine, and 14 ppm by weight of chlorine on an elemental basis.
- the content of impurities contained in the aqueous solution after the ion-exchange treatment is, on an elemental basis, less than 10% by weight of sodium (detection limit), 10% by weight of potassium (detection limit), 1% by weight of bromine and less than 1% by weight of chlorine.
- TEOS tetraethyl orthosilicate
- MTMS methyltrimethoxysilane
- Example coating liquid 4 The preparation requirements for this liquid composition (coating solution for forming a film) are as shown in Table 1. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon wafer substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, this substrate (Example substrate 1) was cooled to a temperature close to room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- a highly purified aqueous solution of the above-mentioned tetrapropylammoniumhydroxide (208.8% by weight containing TPAOH) was added dropwise over 10 minutes, and further at 150 ° C. at a temperature of 20 ° C. Stir at speed for 1 hour. Thereafter, the mixture is heated to a temperature of 50 ° C. and stirred at a speed of 200 rpm under this temperature condition for 25 hours, and methyltrimethoxysilane and other components to be hydrolyzed (partial hydrolysis of tetraethylorthosilicate) are performed. Hydrolysis).
- Example coating solution 5 The preparation requirements for this liquid composition (coating solution for forming a film) are as shown in Table 1. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied on an 8-inch silicon substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, this substrate (Example substrate 1) was cooled to a temperature close to room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- Example 2 the relative dielectric constant of the silica-based coating formed on the substrate, the change in the amount of water adsorbed on the coating before and after oxygen plasma irradiation, the coating strength, the surface roughness, the pore distribution (average Pore diameter and pore volume content of 2 nm or less) and X-ray diffraction peak (Determination of a crystalline film or an amorphous film) was performed.
- Table 5 shows the results.
- TEOS tetraethyl orthosilicate
- EOH ethanol
- beat 1 0 component force ⁇ only look quotient a highly purified tetrapropyl ammonium Niu arm Hyde port oxide water ⁇ ml solution 89. 5 g (1 including TPAOH 0 weight 0/0), The mixture was further stirred at a temperature of 20 ° C at a speed of 150 rpm for 5 hours. Thereafter, the mixture was heated to a temperature of 50 ° C., and partially hydrolyzed tetraethyl orthosilicate for 40 hours while stirring at a speed of 200 rpm under this temperature condition.
- methyltrimethoxysilane 127.3 g of methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 342, 1 g of ethanol having a concentration of 99.5% by weight (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. The mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.
- 208.8 g (containing 10% by weight of TPAOH) of the highly purified aqueous solution of tetrapropylammonium hydroxide was dropped over 10 minutes, and the solution was further added at a temperature of 20 ° C. The mixture was stirred at a speed of 50 rpm for 2 hours. Thereafter, the mixture was heated to a temperature of 50 ° C. and partially hydrolyzed with methyltrimethoxysilane (MTMS) for 5 hours while stirring at a speed of 200 rpm under this temperature condition.
- MTMS
- Example coating solution 6 The preparation requirements for this liquid composition (coating liquid for forming a film) are as shown in Table 1.
- Example 2 Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, this substrate (Example substrate 1) was cooled to a temperature near room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- Tetraethyl orthosilicide 77.1 g (TEOS, manufactured by Tama Chemical Industry Co., Ltd.), methyltrimethoxysilane 14.5 g (MTMS, Shin-Etsu Chemical Co., Ltd.), polysiloxane 80.
- Og PS, 10% by weight of Si02 conversion product, prepared by the method described in JP-A-9-315812
- EOH 99.5% by weight of ethanol
- Example coating solution 7 Si0 liquid composition containing 1 2% by weight 2 equivalent value (example coating solution 7) was obtained.
- the preparation requirements for this liquid composition are as shown in Table 1. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon wafer substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, this substrate (Example substrate 1) was cooled to a temperature near room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- Example coating liquid I-2 5 ml of the coating liquid for forming a film prepared in Example 1 (Example coating liquid I-2) was spin-coated using an 8-inch silicon wafer substrate (semiconductor substrate).
- these substrates were placed on a single-wafer hot plate and subjected to a heat treatment under an air atmosphere under the temperature conditions shown in Table 2 for 3 minutes.
- the organic solvent (PGP) and the like contained in the film evaporate and were discharged out of the system.
- the processing environment was changed from an air atmosphere to a nitrogen gas atmosphere, and the temperature was changed under the temperature conditions shown in Table 2.
- a baking treatment was performed for 30 minutes.
- these substrates (Example substrates # -1 to # -6) were cooled to a temperature near room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- Tetraethyl orthosilicate (TEOS, manufactured by Tama Chemical Industry Co., Ltd.), methyltrimethoxysilane (MTMS, manufactured by Shin-Etsu Chemical Co., Ltd.) and 99.5 wt. (Manufactured by Yakuhin Co., Ltd.) at the ratio shown in Table 3, and the mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.
- a highly purified aqueous solution of the above-mentioned tetrapropylammonium hydroxide (containing 10% by weight of TPAOH) was added dropwise to these mixed solutions over a period of 10 minutes at a ratio shown in Table 1 and further added at 20 ° C.
- the mixture was stirred at a temperature of C at a speed of 250 rpm for 1 hour. Thereafter, the mixture was heated to a temperature of 50 ° C., and the silica-based film-forming components (TEOS and MTMS) were hydrolyzed for 20 hours while stirring at a speed of 250 rpm under this temperature condition.
- TEOS and MTMS silica-based film-forming components
- Example 2 Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon wafer substrate (semiconductor substrate) by spin coating. Next, under the same conditions as in Example 1, these substrates were subjected to a heat treatment step and a baking treatment step. Further, these substrates (comparative substrates # -1 to # -4) were cooled to a temperature near room temperature, and then taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- the relative permittivity of the silica-based coating formed on the substrate (when moisture is adsorbed, the relative permittivity after being left in air for 1 day is also measured), and the oxygen plasma Changes in water adsorption, film strength, surface roughness, pore distribution (average pore diameter and pore volume content of 2 nm or less) before and after irradiation, and X-ray diffraction peaks (determination of crystalline and amorphous films) ) was measured.
- Table 5 shows the results.
- TEOS manufactured by Tama Chemical Industry Co., Ltd.
- MTMS methyltrimethoxysilane
- ethanol 488. 7g were mixed (ETOH, produced by Wako pure Chemical Industries, Ltd.), holding the mixed solution at a temperature of 20 ° C, and stirred for 30 minutes at a speed of 1 50r P m.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, after cooling the substrate (comparative example substrate No. 1) to a temperature near room temperature, it was taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- the relative permittivity of the silica-based coating formed on the substrate (when moisture is adsorbed, the relative permittivity after being left in air for 1 day is also measured), and the oxygen plasma Changes in moisture adsorption of the coating before and after irradiation, coating strength, surface roughness, pore distribution (average pore diameter and pore volume content of 2 nm or less), and X-ray diffraction peaks (determination of crystalline and amorphous coatings) ) was measured.
- Table 5 shows the results.
- Non-Patent Document 1 Using a method similar to that described in the above-mentioned known examples (Non-Patent Document 1, Patent Document 6, etc.), 285.7 g of tetraethyl orthosilicate (TE0S, manufactured by Tama Chemical Industry Co., Ltd.) and 577.3 g (ETOH, manufactured by Wako Pure Chemical Industries, Ltd.) of 99.5% by weight ethanol was mixed, and the mixed solution was kept at a temperature of 20 ° C. and stirred at a speed of 150 rpm for 30 minutes.
- TE0S tetraethyl orthosilicate
- EOH manufactured by Wako Pure Chemical Industries, Ltd.
- Example 3 the ethanol (organic solvent) contained in this mixed solution was subjected to a solvent replacement process with propylene glycol monopropyl ether (PGP) using a rotary evaporator, and at the same time, tetramethyl Orthosilicate
- PGP propylene glycol monopropyl ether
- tetramethyl Orthosilicate By adjusting the concentration of gay-containing compound comprising a hydrolyzate of (TEOS), to give the compound Si0 liquid composition comprising 1 2 wt% in 2 equivalent value (Comparative Example coating liquid 3).
- the preparation requirements for this liquid composition are as shown in Table 3.
- Example 2 Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied onto an 8-inch silicon wafer substrate (semiconductor substrate) by spin coating.
- this substrate was subjected to a heat treatment step and a baking treatment step. Further, after cooling the substrate (comparative substrate 3) to a temperature near room temperature, it was taken out of the system.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- the relative permittivity of the silica-based coating formed on the substrate (when moisture is adsorbed, the relative permittivity after being left in air for 1 day is also measured), and the oxygen plasma Changes in water adsorption, film strength, surface roughness, pore distribution (average pore diameter and pore volume content of 2 nm or less) before and after irradiation, and X-ray diffraction peaks (determination of crystalline and amorphous films) ) was measured.
- Table 5 shows the results.
- Fig. 2 shows the results of X-ray diffraction of the silica-based coating formed on this substrate.
- Example 2 the ethanol (organic solvent) contained in this mixed solution was subjected to a solvent replacement process with propylene glycol monopropyl ether (PGP) using a rotary evaporator, and at the same time, tetramethyl by adjusting the concentration of gay-containing compound comprising a hydrolyzate of ortho silicate gate (TEOS), to give the compound Si0 liquid composition comprising 1 2 wt% in 2 equivalent value (Comparative example coating liquid 4).
- the preparation requirements for this liquid composition (coating liquid for forming a film) are as shown in Table 3. Under the same conditions as in Example 1, 5 ml of the thus-obtained coating liquid for forming a film was applied to an 8-inch silicon substrate (semiconductor substrate) using a spin coating method.
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- the relative permittivity of the silica-based coating formed on the substrate (when moisture is adsorbed, the relative permittivity after being left in air for 1 day was measured) Changes in moisture adsorption of the coating before and after irradiation, coating strength, pore distribution (average pore size and pore volume content of 2 nm or less), and measurement of X-ray diffraction peaks (determining crystalline and amorphous coatings) was done. Table 5 shows the results.
- Example coating liquid I 5 ml of the coating liquid for forming a film prepared in Example 1 (Example coating liquid I) was coated on an 8-inch silicon wafer substrate (semiconductor substrate) by spin coating. Was applied. Next, these substrates were placed on a single-wafer hot plate and subjected to a heat treatment under an air atmosphere under the temperature conditions shown in Table 4 for 3 minutes. In this heat treatment step, the organic solvent (PGP) and the like contained in the film evaporate and were discharged out of the system. Furthermore, with these substrates placed on a single-wafer hot plate, the processing environment was changed from an air atmosphere to a nitrogen gas atmosphere, and the baking treatment was performed for 30 minutes under the temperature conditions shown in Table 4. gave. Next, after cooling these substrates (comparative example substrates # -1 to # -6) to a temperature near room temperature, they were taken out of the system.
- PGP organic solvent
- the thickness of the silica-based film formed on the substrate thus obtained was about 500 nm.
- the silica-based coating itself has excellent hydrophobicity (moisture absorption resistance)
- the silica-based coating includes a silane treatment recommended in the above-mentioned known examples (Non-Patent Document 1, Patent Document 6, etc.). Even without surface treatment, I can maintain the hydrophobic property for a long time, and as a result, the relative permittivity does not decrease.
- this amorphous silica-based coating is not only superior in hydrophobicity to crystalline coatings such as zeolite coatings, but also has a very smooth surface of 1 nm or less. did.
- the average pore diameter contained in the silica-based coating was 3 nm or less, and the pore volume content of micropores of 2 nm or less was 0% or more.
- sodium (Na), potassium (Na) contained in tetraalkylammonium hydride oxide (TAAOH) used in the preparation step are used.
- TAAOH tetraalkylammonium hydride oxide
- Compounds of alkali metal elements such as K) and bromine (Br), salts It has been found that it is necessary to remove impurities composed of compounds of halogen group elements such as nitrogen (CI) to the above level in advance.
- the coating solution for forming a film When preparing the coating solution for forming a film, it is used in the preparation process.
- the desired relative dielectric constant and a silica-based film having film strength was obtained, a part of the film was crystallized, and a surface roughness (Rms) exceeding 1 nm was observed.
- TPAOH tripropylammonium hydroxide oxide
- a low dielectric constant amorphous silica-based coating with high strength which is small and has a Young's modulus of 6.0 GPa or more, it is not only resistant to adhesion such as adhesion to the coating surface of the substrate and alkali resistance. It is possible to obtain a silica-based coating that has excellent chemical resistance, excellent crack resistance, and excellent process compatibility such as oxygen plasma resistance and etching processability.
- the thickness of the formed film will not be uneven, and aluminum wiring and copper wiring of the semiconductor substrate will be damaged. I will not give it.
- a film is formed on a substrate using the methods of the heat treatment step and the baking treatment step shown in the comparative example, some of the above-mentioned performances can be obtained, but all of the performances or effects cannot be exhibited. There was found.
- the method of the present invention is the most suitable method for forming a smooth low dielectric constant amorphous silica-based film having high film strength and excellent hydrophobicity on a substrate.
- the yank bullet is the rate of change in the amount of adsorbed moisture on the semiconductor substrate.
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- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Wood Science & Technology (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Spectroscopy & Molecular Physics (AREA)
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020057007529A KR100983426B1 (ko) | 2002-10-31 | 2003-10-27 | 저유전율 비정질 실리카계 피막의 형성방법 및 상기 방법에의해 얻을 수 있는 저유전율 비정질 실리카계 피막 |
US10/533,238 US7232769B2 (en) | 2002-10-31 | 2003-10-27 | Method of forming amorphous silica-based coating film with low dielectric constant and thus obtained silica-based coating film |
EP03758926.4A EP1564798B1 (en) | 2002-10-31 | 2003-10-27 | Method of forming low-dielectric-constant amorphous silica coating and low-dielectric-constant amorphous silica coating obtained by the method |
Applications Claiming Priority (2)
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JP2002-318418 | 2002-10-31 | ||
JP2002318418A JP4225765B2 (ja) | 2002-10-31 | 2002-10-31 | 低誘電率非晶質シリカ系被膜の形成方法および該方法より得られる低誘電率非晶質シリカ系被膜 |
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WO2004040635A1 true WO2004040635A1 (ja) | 2004-05-13 |
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PCT/JP2003/013691 WO2004040635A1 (ja) | 2002-10-31 | 2003-10-27 | 低誘電率非晶質シリカ系被膜の形成方法および該方法より得られる低誘電率非晶質シリカ系被膜 |
Country Status (7)
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US (1) | US7232769B2 (ja) |
EP (1) | EP1564798B1 (ja) |
JP (1) | JP4225765B2 (ja) |
KR (1) | KR100983426B1 (ja) |
CN (1) | CN100380608C (ja) |
TW (1) | TWI280263B (ja) |
WO (1) | WO2004040635A1 (ja) |
Cited By (2)
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US7728065B2 (en) | 2006-02-14 | 2010-06-01 | Fujitsu Limited | Material for forming exposure light-blocking film, multilayer interconnection structure and manufacturing method thereof, and semiconductor device |
WO2022196656A1 (ja) | 2021-03-15 | 2022-09-22 | AC Biode株式会社 | 人工鉱物の製造方法及び人工鉱物 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7728065B2 (en) | 2006-02-14 | 2010-06-01 | Fujitsu Limited | Material for forming exposure light-blocking film, multilayer interconnection structure and manufacturing method thereof, and semiconductor device |
US7830012B2 (en) | 2006-02-14 | 2010-11-09 | Fujitsu Limited | Material for forming exposure light-blocking film, multilayer interconnection structure and manufacturing method thereof, and semiconductor device |
WO2022196656A1 (ja) | 2021-03-15 | 2022-09-22 | AC Biode株式会社 | 人工鉱物の製造方法及び人工鉱物 |
Also Published As
Publication number | Publication date |
---|---|
JP4225765B2 (ja) | 2009-02-18 |
EP1564798A4 (en) | 2006-01-18 |
CN100380608C (zh) | 2008-04-09 |
TWI280263B (en) | 2007-05-01 |
US20060084277A1 (en) | 2006-04-20 |
CN1708839A (zh) | 2005-12-14 |
TW200500494A (en) | 2005-01-01 |
US7232769B2 (en) | 2007-06-19 |
EP1564798A1 (en) | 2005-08-17 |
EP1564798B1 (en) | 2017-08-02 |
JP2004153147A (ja) | 2004-05-27 |
KR20050060108A (ko) | 2005-06-21 |
KR100983426B1 (ko) | 2010-09-20 |
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