JP2007016177A - シリカ系被膜形成用材料、シリカ系被膜及びその製造方法、多層配線及びその製造方法、並びに、半導体装置及びその製造方法 - Google Patents
シリカ系被膜形成用材料、シリカ系被膜及びその製造方法、多層配線及びその製造方法、並びに、半導体装置及びその製造方法 Download PDFInfo
- Publication number
- JP2007016177A JP2007016177A JP2005200967A JP2005200967A JP2007016177A JP 2007016177 A JP2007016177 A JP 2007016177A JP 2005200967 A JP2005200967 A JP 2005200967A JP 2005200967 A JP2005200967 A JP 2005200967A JP 2007016177 A JP2007016177 A JP 2007016177A
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- Prior art keywords
- bis
- silica
- film
- based film
- ethane
- Prior art date
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 623
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 312
- 239000000463 material Substances 0.000 title claims abstract description 90
- 238000004519 manufacturing process Methods 0.000 title claims description 99
- 239000004065 semiconductor Substances 0.000 title claims description 95
- 238000005530 etching Methods 0.000 claims abstract description 64
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 57
- 239000000126 substance Substances 0.000 claims abstract description 39
- 229920005573 silicon-containing polymer Polymers 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 229910002808 Si–O–Si Inorganic materials 0.000 claims abstract description 12
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 9
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims description 98
- 239000011248 coating agent Substances 0.000 claims description 96
- 238000000034 method Methods 0.000 claims description 84
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000011229 interlayer Substances 0.000 claims description 26
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 25
- 229930195733 hydrocarbon Natural products 0.000 claims description 24
- 150000002430 hydrocarbons Chemical class 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 230000001681 protective effect Effects 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 15
- 238000001312 dry etching Methods 0.000 claims description 14
- 238000000059 patterning Methods 0.000 claims description 13
- 238000012643 polycondensation polymerization Methods 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 238000005498 polishing Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 abstract 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract 3
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- -1 1,3-bis (trimethoxymethylsilyl) propane Chemical compound 0.000 description 105
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 68
- 239000010410 layer Substances 0.000 description 64
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 56
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 52
- 239000010949 copper Substances 0.000 description 38
- 230000008569 process Effects 0.000 description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 30
- 229910052802 copper Inorganic materials 0.000 description 30
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 29
- 239000001273 butane Substances 0.000 description 27
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 27
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 27
- 239000001294 propane Substances 0.000 description 26
- 239000007789 gas Substances 0.000 description 19
- 230000003071 parasitic effect Effects 0.000 description 19
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 15
- 230000009467 reduction Effects 0.000 description 15
- 238000012545 processing Methods 0.000 description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- 239000004020 conductor Substances 0.000 description 13
- 229910052710 silicon Inorganic materials 0.000 description 13
- 239000010703 silicon Substances 0.000 description 13
- 230000004888 barrier function Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 12
- 238000010586 diagram Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- 238000007747 plating Methods 0.000 description 10
- 238000009713 electroplating Methods 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 230000004044 response Effects 0.000 description 8
- 229910000077 silane Inorganic materials 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- 238000002955 isolation Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 238000001039 wet etching Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 6
- 230000002265 prevention Effects 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000005055 methyl trichlorosilane Substances 0.000 description 5
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 5
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 5
- BVNZLSHMOBSFKP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxysilane Chemical compound CC(C)(C)O[SiH3] BVNZLSHMOBSFKP-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- JCZAJKHHBXAQDG-UHFFFAOYSA-N ethoxy-phenyl-propylsilane Chemical compound CCC[SiH](OCC)c1ccccc1 JCZAJKHHBXAQDG-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QQPIVGWMQIQARD-UHFFFAOYSA-N 2-phenylethoxy(propyl)silane Chemical compound C(CC)[SiH2]OCCC1=CC=CC=C1 QQPIVGWMQIQARD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- COFLYCFUVHLITN-UHFFFAOYSA-N chloro-[4-[chloro(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound C[Si](C)(Cl)C1=CC=C([Si](C)(C)Cl)C=C1 COFLYCFUVHLITN-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- UHJWZLRWUMOYIJ-UHFFFAOYSA-N ethoxy-[4-[ethoxy(dimethyl)silyl]phenyl]-dimethylsilane Chemical compound CCO[Si](C)(C)C1=CC=C([Si](C)(C)OCC)C=C1 UHJWZLRWUMOYIJ-UHFFFAOYSA-N 0.000 description 3
- YHLRENUMYCBJKT-UHFFFAOYSA-N ethyl(2-phenylethoxy)silane Chemical compound C(C)[SiH2]OCCC1=CC=CC=C1 YHLRENUMYCBJKT-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000005054 phenyltrichlorosilane Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical compound OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CNOSLBKTVBFPBB-UHFFFAOYSA-N [acetyloxy(diphenyl)silyl] acetate Chemical compound C=1C=CC=CC=1[Si](OC(C)=O)(OC(=O)C)C1=CC=CC=C1 CNOSLBKTVBFPBB-UHFFFAOYSA-N 0.000 description 2
- KXJLGCBCRCSXQF-UHFFFAOYSA-N [diacetyloxy(ethyl)silyl] acetate Chemical compound CC(=O)O[Si](CC)(OC(C)=O)OC(C)=O KXJLGCBCRCSXQF-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- UQFDPFMHQDISLB-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](OC(C)(C)C)(OC(C)(C)C)C1=CC=CC=C1 UQFDPFMHQDISLB-UHFFFAOYSA-N 0.000 description 2
- VSCMNSZBNLOXNR-UHFFFAOYSA-N bromo(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 VSCMNSZBNLOXNR-UHFFFAOYSA-N 0.000 description 2
- XIHJSYLELOWZFE-UHFFFAOYSA-N butyl(propan-2-yloxy)silane Chemical compound CCCC[SiH2]OC(C)C XIHJSYLELOWZFE-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- VGQOKOYKFDUPPJ-UHFFFAOYSA-N chloro-[2-[chloro(dimethyl)silyl]ethyl]-dimethylsilane Chemical compound C[Si](C)(Cl)CC[Si](C)(C)Cl VGQOKOYKFDUPPJ-UHFFFAOYSA-N 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DBUGVTOEUNNUHR-UHFFFAOYSA-N dibromo(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Br)(Br)C1=CC=CC=C1 DBUGVTOEUNNUHR-UHFFFAOYSA-N 0.000 description 2
- OSMIWEAIYFILPL-UHFFFAOYSA-N dibutoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCCCC)(OCCCC)C1=CC=CC=C1 OSMIWEAIYFILPL-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 2
- BOMPXIHODLVNMC-UHFFFAOYSA-N difluoro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](F)(F)C1=CC=CC=C1 BOMPXIHODLVNMC-UHFFFAOYSA-N 0.000 description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- YLDKQPMORVEBRU-UHFFFAOYSA-N diphenoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1O[Si](C=1C=CC=CC=1)(C=1C=CC=CC=1)OC1=CC=CC=C1 YLDKQPMORVEBRU-UHFFFAOYSA-N 0.000 description 2
- QAPWZQHBOVKNHP-UHFFFAOYSA-N diphenyl-di(propan-2-yloxy)silane Chemical compound C=1C=CC=CC=1[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 QAPWZQHBOVKNHP-UHFFFAOYSA-N 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- UAPXIVAOXRNIFF-UHFFFAOYSA-N ethoxy-[2-[ethoxy(dimethyl)silyl]ethyl]-dimethylsilane Chemical compound CCO[Si](C)(C)CC[Si](C)(C)OCC UAPXIVAOXRNIFF-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- HTCTWQJVXUXJLI-UHFFFAOYSA-N methoxy(propan-2-yl)silane Chemical compound CO[SiH2]C(C)C HTCTWQJVXUXJLI-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- RBCYCMNKVQPXDR-UHFFFAOYSA-N phenoxysilane Chemical compound [SiH3]OC1=CC=CC=C1 RBCYCMNKVQPXDR-UHFFFAOYSA-N 0.000 description 2
- 239000005360 phosphosilicate glass Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 description 2
- 230000007261 regionalization Effects 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent 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
- JXXQPVMVSMWLGZ-UHFFFAOYSA-N tributoxy(tributoxysilylmethyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C[Si](OCCCC)(OCCCC)OCCCC JXXQPVMVSMWLGZ-UHFFFAOYSA-N 0.000 description 2
- ABDDAHLAEXNYRC-UHFFFAOYSA-N trichloro(trichlorosilylmethyl)silane Chemical compound Cl[Si](Cl)(Cl)C[Si](Cl)(Cl)Cl ABDDAHLAEXNYRC-UHFFFAOYSA-N 0.000 description 2
- DJYGUVIGOGFJOF-UHFFFAOYSA-N trimethoxy(trimethoxysilylmethyl)silane Chemical compound CO[Si](OC)(OC)C[Si](OC)(OC)OC DJYGUVIGOGFJOF-UHFFFAOYSA-N 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- LGPDWVZQGAULHL-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy-[2-[(2-methylpropan-2-yl)oxy-di(propan-2-yl)silyl]ethyl]-di(propan-2-yl)silane Chemical compound CC(C)(C)O[Si](C(C)C)(C(C)C)CC[Si](OC(C)(C)C)(C(C)C)C(C)C LGPDWVZQGAULHL-UHFFFAOYSA-N 0.000 description 1
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- KKEPAEPHHNNTFJ-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-(2-phenylethyl)silane Chemical compound C1(=CC=CC=C1)CC[SiH](OC(C)(C)C)OC(C)(C)C KKEPAEPHHNNTFJ-UHFFFAOYSA-N 0.000 description 1
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- CGMNWEJTNCSUOL-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-(4-phenylbutyl)silane Chemical compound C1(=CC=CC=C1)CCCC[SiH](OC(C)(C)C)OC(C)(C)C CGMNWEJTNCSUOL-UHFFFAOYSA-N 0.000 description 1
- GEVFICDEOWFKDU-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-di(propan-2-yl)silane Chemical compound CC(C)(C)O[Si](C(C)C)(OC(C)(C)C)C(C)C GEVFICDEOWFKDU-UHFFFAOYSA-N 0.000 description 1
- NZJRLFDIDIUMPD-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-dipropylsilane Chemical compound CCC[Si](CCC)(OC(C)(C)C)OC(C)(C)C NZJRLFDIDIUMPD-UHFFFAOYSA-N 0.000 description 1
- COIKARXZTHWZEO-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-phenyl-propan-2-ylsilane Chemical compound CC(C)(C)O[Si](C(C)C)(OC(C)(C)C)C1=CC=CC=C1 COIKARXZTHWZEO-UHFFFAOYSA-N 0.000 description 1
- WELYMSVAYLOFER-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[SiH](OC(C)(C)C)OC(C)(C)C WELYMSVAYLOFER-UHFFFAOYSA-N 0.000 description 1
- DMAVYNCFCVFOQF-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]methyl-[2-[bis[(2-methylpropan-2-yl)oxy]methylsilyl]ethyl]silane Chemical compound CC(C)(C)OC(OC(C)(C)C)[SiH2]CC[SiH2]C(OC(C)(C)C)OC(C)(C)C DMAVYNCFCVFOQF-UHFFFAOYSA-N 0.000 description 1
- RWZGYVLZALWKEB-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]methyl-[3-[bis[(2-methylpropan-2-yl)oxy]methylsilyl]propyl]silane Chemical compound C(C)(C)(C)OC(OC(C)(C)C)[SiH2]CCC[SiH2]C(OC(C)(C)C)OC(C)(C)C RWZGYVLZALWKEB-UHFFFAOYSA-N 0.000 description 1
- VULIOKFBTJUTKC-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]methyl-[4-[bis[(2-methylpropan-2-yl)oxy]methylsilyl]butyl]silane Chemical compound C(C)(C)(C)OC(OC(C)(C)C)[SiH2]CCCC[SiH2]C(OC(C)(C)C)OC(C)(C)C VULIOKFBTJUTKC-UHFFFAOYSA-N 0.000 description 1
- CYOAYOCWEAJBAG-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]methyl-[4-[bis[(2-methylpropan-2-yl)oxy]methylsilyl]phenyl]silane Chemical compound C(C)(C)(C)OC(OC(C)(C)C)[SiH2]C1=CC=C(C=C1)[SiH2]C(OC(C)(C)C)OC(C)(C)C CYOAYOCWEAJBAG-UHFFFAOYSA-N 0.000 description 1
- HDKPWMFTHXIDPW-UHFFFAOYSA-N bromo(3,3-diphenylpropyl)silane Chemical compound C1(=CC=CC=C1)C(CC[SiH2]Br)C1=CC=CC=C1 HDKPWMFTHXIDPW-UHFFFAOYSA-N 0.000 description 1
- PZDCBRNVONKWOQ-UHFFFAOYSA-N bromo(methyl)silane Chemical compound C[SiH2]Br PZDCBRNVONKWOQ-UHFFFAOYSA-N 0.000 description 1
- RGGVPEYOIBUFPY-UHFFFAOYSA-N bromo(phenyl)silane Chemical compound Br[SiH2]C1=CC=CC=C1 RGGVPEYOIBUFPY-UHFFFAOYSA-N 0.000 description 1
- HFMYSRHRBCIWFA-UHFFFAOYSA-N bromo(propan-2-yl)silane Chemical compound CC(C)[SiH2]Br HFMYSRHRBCIWFA-UHFFFAOYSA-N 0.000 description 1
- UCKORWKZRPKRQE-UHFFFAOYSA-N bromo(triethyl)silane Chemical compound CC[Si](Br)(CC)CC UCKORWKZRPKRQE-UHFFFAOYSA-N 0.000 description 1
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 description 1
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- JGXWBSJNJRDQQF-UHFFFAOYSA-N bromo-[2-[bromo(dibutyl)silyl]ethyl]-dibutylsilane Chemical compound CCCC[Si](Br)(CCCC)CC[Si](Br)(CCCC)CCCC JGXWBSJNJRDQQF-UHFFFAOYSA-N 0.000 description 1
- GYEOTFVABVWJFG-UHFFFAOYSA-N bromo-[2-[bromo(diethyl)silyl]ethyl]-diethylsilane Chemical compound CC[Si](Br)(CC)CC[Si](Br)(CC)CC GYEOTFVABVWJFG-UHFFFAOYSA-N 0.000 description 1
- VKSREWXQBUQJCH-UHFFFAOYSA-N bromo-[2-[bromo(dimethyl)silyl]ethyl]-dimethylsilane Chemical compound C[Si](C)(Br)CC[Si](C)(C)Br VKSREWXQBUQJCH-UHFFFAOYSA-N 0.000 description 1
- BELZHZCGIJFLSF-UHFFFAOYSA-N bromo-[2-[bromo(diphenyl)silyl]ethyl]-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Br)CC[Si](Br)(C=1C=CC=CC=1)C1=CC=CC=C1 BELZHZCGIJFLSF-UHFFFAOYSA-N 0.000 description 1
- KHNFTVNPPRTKQG-UHFFFAOYSA-N bromo-[2-[bromo(dipropyl)silyl]ethyl]-dipropylsilane Chemical compound CCC[Si](Br)(CCC)CC[Si](Br)(CCC)CCC KHNFTVNPPRTKQG-UHFFFAOYSA-N 0.000 description 1
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- CXRQDGATOVWLNB-UHFFFAOYSA-N bromo-[3-[bromo(diethyl)silyl]propyl]-diethylsilane Chemical compound CC[Si](Br)(CC)CCC[Si](Br)(CC)CC CXRQDGATOVWLNB-UHFFFAOYSA-N 0.000 description 1
- UQQPGWLIXQJUOV-UHFFFAOYSA-N bromo-[3-[bromo(dimethyl)silyl]propyl]-dimethylsilane Chemical compound C[Si](C)(Br)CCC[Si](C)(C)Br UQQPGWLIXQJUOV-UHFFFAOYSA-N 0.000 description 1
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- PQVPWZHUJMEZSA-UHFFFAOYSA-N triethoxy(4-triethoxysilylbutyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCC[Si](OCC)(OCC)OCC PQVPWZHUJMEZSA-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
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- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
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- UCUKUIPXDKEYLX-UHFFFAOYSA-N triethyl(propan-2-yloxy)silane Chemical compound CC[Si](CC)(CC)OC(C)C UCUKUIPXDKEYLX-UHFFFAOYSA-N 0.000 description 1
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- JGHTXIKECBJCFI-UHFFFAOYSA-N trifluoro(propyl)silane Chemical compound CCC[Si](F)(F)F JGHTXIKECBJCFI-UHFFFAOYSA-N 0.000 description 1
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- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
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- NNLPAMPVXAPWKG-UHFFFAOYSA-N trimethyl(1-methylethoxy)silane Chemical compound CC(C)O[Si](C)(C)C NNLPAMPVXAPWKG-UHFFFAOYSA-N 0.000 description 1
- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 description 1
- PHPGKIATZDCVHL-UHFFFAOYSA-N trimethyl(propoxy)silane Chemical compound CCCO[Si](C)(C)C PHPGKIATZDCVHL-UHFFFAOYSA-N 0.000 description 1
- PGZGBYCKAOEPQZ-UHFFFAOYSA-N trimethyl-[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(C)C PGZGBYCKAOEPQZ-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- QHUNJMXHQHHWQP-UHFFFAOYSA-N trimethylsilyl acetate Chemical compound CC(=O)O[Si](C)(C)C QHUNJMXHQHHWQP-UHFFFAOYSA-N 0.000 description 1
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- OAKRVFBXZCHVCL-UHFFFAOYSA-N triphenoxy(3-triphenoxysilylpropyl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)CCC[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 OAKRVFBXZCHVCL-UHFFFAOYSA-N 0.000 description 1
- FNNJGIKXHZZGCV-UHFFFAOYSA-N triphenoxy(propan-2-yl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(C(C)C)OC1=CC=CC=C1 FNNJGIKXHZZGCV-UHFFFAOYSA-N 0.000 description 1
- AMUIJRKZTXWCEA-UHFFFAOYSA-N triphenoxy(propyl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(CCC)OC1=CC=CC=C1 AMUIJRKZTXWCEA-UHFFFAOYSA-N 0.000 description 1
- AABYOUNGNSKTRH-UHFFFAOYSA-N triphenoxy(triphenoxysilylmethyl)silane Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)C[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 AABYOUNGNSKTRH-UHFFFAOYSA-N 0.000 description 1
- PCNSFYCYEXDHHE-UHFFFAOYSA-N triphenoxy-(4-triphenoxysilylphenyl)silane Chemical compound C=1C=CC=CC=1O[Si](C=1C=CC(=CC=1)[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 PCNSFYCYEXDHHE-UHFFFAOYSA-N 0.000 description 1
- APTHFTIZBJWVSX-UHFFFAOYSA-N triphenyl(propan-2-yloxy)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OC(C)C)C1=CC=CC=C1 APTHFTIZBJWVSX-UHFFFAOYSA-N 0.000 description 1
- QDOHRQCMIFOPEY-UHFFFAOYSA-N tripropoxy(2-tripropoxysilylethyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)CC[Si](OCCC)(OCCC)OCCC QDOHRQCMIFOPEY-UHFFFAOYSA-N 0.000 description 1
- BKBQKRDWRZADLL-UHFFFAOYSA-N tripropoxy(3-tripropoxysilylpropyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)CCC[Si](OCCC)(OCCC)OCCC BKBQKRDWRZADLL-UHFFFAOYSA-N 0.000 description 1
- BZIXIRYKSIMLOB-UHFFFAOYSA-N tripropoxy(tripropoxysilylmethyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)C[Si](OCCC)(OCCC)OCCC BZIXIRYKSIMLOB-UHFFFAOYSA-N 0.000 description 1
- FOUOZDXPXSKVEL-UHFFFAOYSA-N tripropoxy-(4-tripropoxysilylphenyl)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=C([Si](OCCC)(OCCC)OCCC)C=C1 FOUOZDXPXSKVEL-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- GBGOZMPAPWGNGR-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[2-[tris[(2-methylpropan-2-yl)oxy]silyl]ethyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C GBGOZMPAPWGNGR-UHFFFAOYSA-N 0.000 description 1
- DHUQSOWCGDZWFQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[3-[tris[(2-methylpropan-2-yl)oxy]silyl]propyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DHUQSOWCGDZWFQ-UHFFFAOYSA-N 0.000 description 1
- UINSJWBNIXDRAO-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[4-[tris[(2-methylpropan-2-yl)oxy]silyl]butyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C UINSJWBNIXDRAO-UHFFFAOYSA-N 0.000 description 1
- PITXUFPLSLHXRV-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[4-[tris[(2-methylpropan-2-yl)oxy]silyl]phenyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C1=CC=C([Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C)C=C1 PITXUFPLSLHXRV-UHFFFAOYSA-N 0.000 description 1
- QJJZQRNPNLTSNS-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[tris[(2-methylpropan-2-yl)oxy]silylmethyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C QJJZQRNPNLTSNS-UHFFFAOYSA-N 0.000 description 1
- KGOOITCIBGXHJO-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-phenylsilane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C1=CC=CC=C1 KGOOITCIBGXHJO-UHFFFAOYSA-N 0.000 description 1
- MJIHPVLPZKWFBL-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propan-2-ylsilane Chemical compound CC(C)(C)O[Si](C(C)C)(OC(C)(C)C)OC(C)(C)C MJIHPVLPZKWFBL-UHFFFAOYSA-N 0.000 description 1
- QCKKBOHAYRLMQP-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[SiH](OC(C)(C)C)OC(C)(C)C QCKKBOHAYRLMQP-UHFFFAOYSA-N 0.000 description 1
- DJECDCLXTNZYDL-UHFFFAOYSA-N tritert-butyl(chloro)silane Chemical compound CC(C)(C)[Si](Cl)(C(C)(C)C)C(C)(C)C DJECDCLXTNZYDL-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—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
- H01L21/312—Organic layers, e.g. photoresist
- H01L21/3121—Layers comprising organo-silicon compounds
- H01L21/3122—Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
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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
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—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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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—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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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—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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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
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- H—ELECTRICITY
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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
- H01L21/02164—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 being a silicon oxide, e.g. SiO2
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02203—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
- H01L21/02208—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
- H01L21/02211—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 being a silane, e.g. disilane, methylsilane or chlorosilane
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- H—ELECTRICITY
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Abstract
【解決手段】 本発明のシリカ系被膜形成用材料は、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有するシリコーンポリマーを含む。xは、0〜2の整数を表す。シリコーンポリマーが一般式(1)〜(3)で表されるシリコン化合物と、一般式(4)〜(7)で表されるシリコン化合物とを加水分解縮重合反応させて得られる態様等が好ましい。
【化13】
【化14】
一般式(1)〜(7)中、nは0又は1を表す。R1はn=0のとき、塩素、臭素、フッ素及び水素のいずれかを表し、n=1のとき、炭素数1〜4の炭化水素、芳香族炭化水素、水素、カルボキシル基のいずれかを表す。R2は炭素数1〜4の炭化水素、芳香族炭化水素、及び水素のいずれかを表す。R3は炭素数1〜3の炭化水素及び芳香族炭化水素のいずれかを表す。
【選択図】 なし
Description
本発明のシリカ系被膜形成用材料は、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有するシリコーンポリマーを少なくとも含むことを特徴とする。
ただし、前記xは、0〜2の整数を表す。
該シリコーンポリマーは、下記一般式(1)から(3)で表されるシリコン化合物から選択される少なくとも1種と、下記一般式(4)から(7)で表されるシリコン化合物から選択される少なくとも1種とを、加水分解縮重合反応させて得られるのが好ましい。
該シリカ系被膜形成用材料においては、前記一般式(1)から(3)で表されるシリコン化合物が、優れた耐エッチング性、耐薬品性、及び耐湿性を有し、前記一般式(4)から(7)で表されるシリコン化合物が、優れた密着性を有するため、これらのシリコン化合物が加水分解縮重合反応されて得られたシリコーンポリマーは、耐エッチング性、耐薬品性、耐湿性及び密着性の総てに優れる。このため、シリカ系被膜、多層配線の形成に好適に使用可能であり、各種半導体装置などに好適であり、本発明のシリカ系被膜、本発明の多層配線、及び本発明の半導体装置の製造に特に好適に使用可能である。
従来より、絶縁膜の寄生容量による信号伝播速度の低下が知られていたが、半導体デバイスの配線間隔が1μm以上の世代では配線遅延のデバイス全体への影響は少なかった。近時、半導体集積回路が高集積化され、多層配線構造化されるようになり、配線幅・間隔が狭くなり、特に配線間隔が1μm以下では、配線抵抗の上昇と配線間の寄生容量の増大が問題となってきている。前記半導体集積回路等のデバイスの性能を支配する大きな要素である、前記配線抵抗と前記配線間の寄生容量とによって、該半導体集積回路の多層配線構造における信号伝播速度が決定されることから、該配線抵抗の上昇と該配線間の寄生容量の増大は前記信号伝播速度の低下を招く原因として、克服しなければならない大きな問題である。該信号伝播速度の向上を図るためには、前記配線抵抗の低下と前記配線間の寄生容量(絶縁膜の誘電率)の低下とが必須である。前記配線間の寄生容量は、配線を薄くして断面積を小さくすると低減できるものの、配線を薄くすると前記配線抵抗が上昇してしまう。つまり、前記配線間の寄生容量の低下と前記配線抵抗の低下とは二律背反の関係にあるため、前記信号伝播速度の向上は容易ではない。しかし、低誘電率で、応答速度の高速化に寄与し得る本発明のシリカ系被膜によれば、前記配線間の寄生容量の低下と前記配線抵抗の低下とを達成することができ、前記信号伝播速度の高速化が可能となる。
本発明の多層配線の製造方法は、本発明の前記多層配線を製造する方法であって、シリカ系被膜形成工程と配線形成工程とを、少なくとも含むことを特徴とする。該多層配線の製造方法では、前記シリカ系被膜形成工程において、本発明の前記シリカ系被膜形成用材料が前記被加工面上に塗布された後、熱処理が行われて前記シリカ系被膜が形成される。前記配線形成工程において、前記配線が形成される。そして、前記シリカ系被膜形成工程及び前記配線形成工程を含む一連の工程を繰り返し行うことにより、本発明の多層配線が効率的に形成される。該多層配線の製造方法は、本発明の前記多層配線の製造に特に好適である。
従来、半導体装置の製造は、低誘電率絶縁膜(層間絶縁膜)の形成、プラズマCVDによる保護層の形成、及びエッチングストッパ層の形成により行われているが、該製造方法では、層間絶縁膜を真空チャンバとキュア炉とを往復させて形成する必要があり、製造コストが高いという問題があった。しかし、本発明の半導体装置の製造方法によれば、本発明の前記シリカ系被膜を形成する工程を含むので、絶縁膜積層コストの低減と、低誘電率化による寄生容量の低減とを実現することができ、信号伝播速度の高速化が可能となる。また、前記シリカ系被膜は、耐エッチング性等に優れるので、ドライエッチングにおけるハードマスクとして用いることができ、微細パターンの形成に有効であり、より効率よく半導体装置が製造される。
本発明のシリカ系被膜形成用材料は、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有するシリコーンポリマーを少なくとも含んでなり、更に必要に応じて、有機溶剤、その他の成分等を含んでなる。
前記シリコーンポリマーは、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有することが必要である。ただし、前記xは、0〜2の整数を表す。この場合、耐エッチング性、耐薬品性、耐湿性、及び密着性の総てに優れたシリカ系被膜形成用材料が得られる。
前記シリコーンポリマーにおける、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合の存在を確認する方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、赤外分光分析を用いて吸収ピークを測定することにより、これらの構造を総て含んでいることを分析することができる。
下記一般式(1)から(3)で表されるシリコン化合物は、骨格に炭化水素又は芳香族炭化水素を有し、耐エッチング性、耐薬品性、耐湿性などを付与することができ、下記一般式(4)から(7)で表されるシリコン化合物は、機械的強度、下地層との密着性などを付与することができる。
、1,3−ビス(ジアセトキシイソプロピルシリル)プロパン、1,4−ビス(ジアセトキシイソプロピルシリル)ブタン、1,4−ビス(ジアセトキシイソプロピルシリル)ベンゼン、ビス(ジフェノキシイソプロピルシリル)メタン、1,2−ビス(ジフェノキシイソプロピルシリル)エタン、1,3−ビス(ジフェノキシイソプロピルシリル)プロパン、1,4−ビス(ジフェノキシイソプロピルシリル)ブタン、1,4−ビス(ジフェノキシイソプロピルシリル)ベンゼン、ビス(ジブトキシブチルシリル)メタン、1,2−ビス(ジブトキシブチルシリル)エタン、1,3−ビス(ジブトキシブチルシリル)プロパン、1,4−ビス(ジブトキシブチルシリル)ブタン、1,4−ビス(ジブトキシブチルシリル)ベンゼン、ビス(ジtertブトキシブチルシリル)メタン、1,2−ビス(ジtertブトキシブチルシリル)エタン、1,3−ビス(ジtertブトキシブチルシリル)プロパン、1,4−ビス(ジtertブトキシブチルシリル)ブタン、1,4−ビス(ジtert)ブトキシブチルシリル)ベンゼン、ビス(ジアセトキシブチルシリル)メタン、1,2−ビス(ジアセトキシブチルシリル)エタン、1,3−ビス(ジアセトキシブチルシリル)プロパン、1,4−ビス(ジアセトキシブチルシリル)ブタン、1,4−ビス(ジアセトキシブチルシリル)ベンゼン、ビス(ジフェノキシブチルシリル)メタン、1,2−ビス(ジフェノキシブチルシリル)エタン、1,3−ビス(ジフェノキシブチルシリル)プロパン、1,4−ビス(ジフェノキシブチルシリル)ブタン、1,4−ビス(ジフェノキシブチルシリル)ベンゼン、1,2−ビス(ジブトキシフェニルシリル)メタン、1,2−ビス(ジブトキシフェニルシリル)エタン、1,2−ビス(ジブトキシフェニルシリル)プロパン、1,2−ビス(ジブトキシフェニルシリル)ブタン、1,2−ビス(ジブトキシフェニルシリル)ベンゼン、1,2−ビス(ジtertブトキシフェニルシリル)メタン、1,2−ビス(ジtertブトキシフェニルシリル)エタン、1,2−ビス(ジtertブトキシフェニルシリル)プロパン、1,2−ビス(ジtertブトキシフェニルシリル)ブタン、1,2−ビス(ジtertブトキシフェニルシリル)ベンゼン、ビス(ジアセトキシフェニルシリル)メタン、1,2−ビス(ジアセトキシフェニルシリル)エタン、1,3−ビス(ジアセトキシフェニルシリル)プロパン、1,4−ビス(ジアセトキシフェニルシリル)ブタン、1,4−ビス(ジアセトキシフェニルシリル)ベンゼン、ビス(ジフェノキシフェニルシリル)メタン、1,2−ビス(ジフェノキシフェニルシリル)エタン、1,3−ビス(ジフェノキシフェニルシリル)プロパン、1,4−ビス(ジフェノキシフェニルシリル)ブタン、1,4−ビス(ジフェノキシフェニルシリル)ベンゼン、などが挙げられる。これらは1種単独で使用してもよいし、2種以上を併用してもよい。
1,3−ビス(ジイソプロピルアセトキシシリル)プロパン、1,4−ビス(ジイソプロピルアセトキシシリル)ブタン、1,4−ビス(ジイソプロピルアセトキシシリル)ベンゼン、ビス(ジイソプロピルフェノキシシリル)メタン、1,2−ビス(ジイソプロピルフェノキシシリル)エタン、1,3−ビス(ジイソプロピルフェノキシシリル)プロパン、1,4−ビス(ジイソプロピルフェノキシシリル)ブタン、1,4−ビス(ジイソプロピルフェノキシシリル)ベンゼン、ビス(ジブチルブトキシシリル)メタン、1,2−ビス(ジブチルブトキシシリル)エタン、1,3−ビス(ジブチルブトキシシリル)プロパン、1,4−ビス(ジブチルブトキシシリル)ブタン、1,4−ビス(ジブチルブトキシシリル)ベンゼン、ビス(ジブチルtertブトキシシリル)メタン、1,2−ビス(ジブチルtertブトキシシリル)エタン、1,3−ビス(ジブチルtertブトキシシリル)プロパン、1,4−ビス(ジブチルtertブトキシシリル)ブタン、1,4−ビス(ジブチルtertブトキシシリル)ベンゼン、ビス(ジブチルアセトキシシリル)メタン、1,2−ビス(ジブチルアセトキシシリル)エタン、1,3−ビス(ジブチルアセトキシシリル)プロパン、1,4−ビス(ジブチルアセトキシシリル)ブタン、1,4−ビス(ジブチルアセトキシシリル)ベンゼン、ビス(ジブチルフェノキシシリル)メタン、1,2−ビス(ジブチルフェノキシシリル)エタン、1,3−ビス(ジブチルフェノキシシリル)プロパン、1,4−ビス(ジブチルフェノキシシリル)ブタン、1,4−ビス(ジブチルフェノキシシリル)ベンゼン、ビス(ジtertブチルブトキシシリル)メタン、1,2−ビス(ジtertブチルブトキシシリル)エタン、1,3−ビス(ジtertブチルブトキシシリル)プロパン、1,4−ビス(ジtertブチルブトキシシリル)ブタン、1,4−ビス(ジtertブチルブトキシシリル)ベンゼン、ビス(ジtertブチルtertブトキシシリル)メタン、1,2−ビス(ジtertブチルtertブトキシシリル)エタン、1,3−ビス(ジtertブチルtertブトキシシリル)プロパン、1,4−ビス(ジtertブチルtertブトキシシリル)ブタン、1,4−ビス(ジtertブチルtertブトキシシリル)ベンゼン、ビス(ジtertブチルアセトキシシリル)メタン、1,2−ビス(ジtertブチルアセトキシシリル)エタン、1,3−ビス(ジtertブチルアセトキシシリル)プロパン、1,4−ビス(ジtertブチルアセトキシシリル)ブタン、1,4−ビス(ジtertブチルアセトキシシリル)ベンゼン、ビス(ジtertブチルフェノキシシリル)メタン、1,2−ビス(ジtertブチルフェノキシシリル)エタン、1,3−ビス(ジtertブチルフェノキシシリル)プロパン、1,4−ビス(ジtertブチルフェノキシシリル)ブタン、1,4−ビス(ジtertブチルフェノキシシリル)ベンゼン、ビス(ジブトキシtertブチルシリル)メタン、1,2−ビス(ジブトキシtertブチルシリル)エタン、1,3−ビス(ジブトキシtertブチルシリル)プロパン、1,4−ビス(ジブトキシtertブチルシリル)ブタン、1,4−ビス(ジブトキシtertブチルシリル)ベンゼン、ビス(ジtertブトキシtertブチルシリル)メタン、1,2−ビス(ジtertブトキシtertブチルシリル)エタン、1,3−ビス(ジtertブトキシtertブチルシリル)プロパン、1,4−ビス(ジtertブトキシtertブチルシリル)ブタン、1,4−ビス(ジtertブトキシtertブチルシリル)ベンゼン、ビス(ジアセトキシtertブチルシリル)メタン、1,2−ビス(ジアセトキシtertブチルシリル)エタン、1,3−ビス(ジアセトキシtertブチルシリル)プロパン、1,4−ビス(ジアセトキシtertブチルシリル)ブタン、1,4−ビス(ジアセトキシtertブチルシリル)ベンゼン、ビス(ジフェノキシtertブチルシリル)メタン、1,2−ビス(ジフェノキシtertブチルシリル)エタン、1,3−ビス(ジフェノキシtertブチルシリル)プロパン、1,4−ビス(ジフェノキシtertブチルシリル)ブタン、1,4−ビス(ジフェノキシtertブチルシリル)ベンゼン、ビス(ジフェニルブトキシシリル)メタン、1,2−ビス(ジフェニルブトキシシリル)エタン、1,3−ビス(ジフェニルブトキシシリル)プロパン、1,4−ビス(ジフェニルブトキシシリル)ブタン、1,4−ビス(ジフェニルブトキシシリル)ベンゼン、ビス(ジフェニルtertブトキシシリル)メタン、1,2−ビス(ジフェニルtertブトキシシリル)エタン、1,3−ビス(ジフェニルtertブトキシシリル)プロパン、1,4−ビス(ジフェニルtertブトキシシリル)ブタン、1,4−ビス(ジフェニルtertブトキシシリル)ベンゼン、ビス(ジフェニルアセトキシシリル)メタン、1,2−ビス(ジフェニルアセトキシシリル)エタン、1,3−ビス(ジフェニルアセトキシシリル)プロパン、1,4−ビス(ジフェニルアセトキシシリル)ブタン、1,4−ビス(ジフェニルアセトキシシリル)ベンゼン、1,2−ビス(ジフェニルフェノキシシリル)メタン、1,2−ビス(ジフェニルフェノキシシリル)エタン、1,2−ビス(ジフェニルフェノキシシリル)プロパン、1,2−ビス(ジフェニルフェノキシシリル)ブタン、1,2−ビス(ジフェニルフェノキシシリル)ベンゼン、などが挙げられる。これらは1種単独で使用してもよいし、2種以上を併用してもよい。
前記pHの水溶液が、11を超えると、シロキサン結合が分解することがある。
なお、前記酸性又はアルカリ性の水溶液としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、塩酸、硝酸、硫酸、トルエンスルホン酸、シュウ酸、マレイン酸、蟻酸、酢酸、アンモニア、テトメチルアンモニウムハイドロオキサイド、テトラエチルアンモニウムオキサイド、テトラプロピルアンモニウムオキサイド、テトラブチルアンモニウムオキサイドなどが挙げられる。なお、前記酸性の水溶液としては、シロキサン結合が分解されるため、フッ化水素酸を用いないのが好ましい。
前記シリカ系被膜形成用材料を用いて前記シリカ系被膜を形成する場合、成膜が容易な点で、塗布により行うのが好ましく、該シリカ系被膜形成用材料が有機溶剤を含むのが好ましい。
前記有機溶剤としては、前記シリコーンポリマーが溶解可能であれば特に制限はなく、目的に応じて適宜選択することができ、例えば、メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、イソブチルアルコール、tert-ブチルアルコール等のアルコール系;フェノール、クレゾール、ジエチルフェノール、トリエチルフェノール、プロピルフェノール、ノニルフェノール、ビニルフェノール、アリルフェノール、ノニルフェノール等のフェノール系;シクロヘキサノン、メチルイソブチルケトン、メチルエチルケトン等のケトン系、メチルセロソルブ、エチルセロソルブ等のセロソルブ系;ヘキサン、オクタン、デカン等の炭化水素系;プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート等のグリコール系などが挙げられる。これらは1種単独で使用してもよいし、2種以上を併用してもよい。
前記その他の成分としては、本発明の効果を害しない限り特に制限はなく、目的に応じて適宜選択することができ、例えば、公知の各種添加剤などが挙げられる。
前記その他の成分の前記シリカ系被膜形成用材料における含有量としては、前記一般式(1)から(7)で表されるシリコン化合物、前記有機溶剤等の種類や含有量などに応じて適宜決定することができる。
本発明のシリカ系被膜は、本発明のシリカ系被膜の製造方法により得られる。
本発明のシリカ系被膜の製造方法においては、本発明の前記シリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことを少なくとも含み、更に必要に応じて、その他の工程を含む。
以下、本発明のシリカ系被膜の製造方法の説明を通じて、本発明のシリカ系被膜の詳細も明らかにする。
前記塗布工程は、本発明の前記シリカ系被膜形成用材料を被加工面上に塗布する工程である。
なお、前記シリカ系被膜形成用材料の詳細については、上述した通りである。
前記塗布の方法としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、スピンコート法、ディップコート法、ニーダーコート法、カーテンコート法、ブレードコート法、などが挙げられる。これらの中でも、塗布効率等の点で、スピンコート法、ディップコート法等が好ましい。該スピンコート法の場合、その条件としては例えば、回転数が100〜10,000rpm程度であり、800〜5,000rpmが好ましく、時間が1秒〜10分程度であり、10〜90秒が好ましい。
以上の工程により、本発明の前記シリカ系被膜形成用材料が前記被加工面上に塗布される。
前記熱処理工程は、前記被加工面上に塗布された本発明の前記シリカ系被膜形成用材料に対して熱処理を行う工程である。
前記熱処理としては、特に制限はなく、目的に応じて適宜選択することができるが、前記有機溶剤を乾燥させ、前記シリカ系被膜形成用材料を焼成するのが好ましい。この場合、前記シリカ系被膜形成用材料中の前記シリコーンポリマーの骨格や側鎖に導入された炭化水素や芳香族炭化水素などの酸化を抑制することができる。
前記熱処理は、目的に応じて適宜その温度、雰囲気等の条件を選択することができるが、前記温度としては、50〜400℃が好ましく、80〜350℃がより好ましい。
前記温度が、50℃未満であると、前記有機溶剤が膜中に残留し、充分な強度が得られないことがあり、400℃を越えると、前記シリコーンポリマーの骨格や側鎖の珪素−炭化水素結合が分解してしまうことがある。
前記雰囲気としては、大気中では酸素の取り込みによる誘電率の上昇が懸念されるため、不活性ガスの存在下、減圧下、などが好ましく、前記不活性ガスとしては、例えば、窒素などが好適に挙げられる。
なお、前記熱処理工程は、前記シリカ系被膜の下地層が、例えばスピンコート法により成膜される多孔質シリカ膜である場合には、該多孔質シリカ膜を形成する材料を塗布し、溶媒乾燥を行った後、この上に前記シリカ系被膜形成用材料を塗布し、一括で前記熱処理工程を行ってもよい。この場合、成膜コストの低減を図ることができる。
前記その他の工程としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、パターン形成工程、などが好適に挙げられる。
前記パターン形成工程は、前記塗布工程及び前記熱処理工程により形成した前記シリカ系被膜に対し選択露光及び現像を行ってパターンを形成する工程である。
前記パターン形成工程は、公知のパターン形成方法に従って行うことができる。
なお、前記露光と前記現像との間で、反応を促進させる観点からベーク処理を行ってもよい。
前記ベタの膜形状を有するシリカ系被膜の形成方法としては、例えば、本発明の前記シリカ系被膜形成用材料に前記被加工面を有する基材を浸漬し、該基材表面(被加工面)の全面にベタのシリカ系被膜を形成する方法、などが挙げられる。
前記パターン状のシリカ系被膜の形成方法としては、例えば、前記被加工面上にレジストでパターン(例えば、ライン状)を形成して前記シリカ系被膜形成用材料を塗布し、パターン状のシリカ系被膜を形成する方法、ベタ膜のシリカ系被膜を形成後にレジストを塗布し所望のパターンを形成した後に、ウェット又はドライでエッチングする方法などが挙げられる。
前記シリカ系被膜が、前記パターン状である場合、及び前記積層構造を有する場合、各パターン及び各層における誘電率は、同一であってもよいし、それぞれ異なっていてもよい。
前記大きさとしては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、前記シリカ系被膜を多層配線、半導体装置などに使用する場合には、既存の半導体装置の大きさに対応した大きさが好ましい。
前記厚みが、10nm未満であると、ピンホール等の構造欠陥が発生することがあり、500nmを超えると、特にドライエッチングで加工する際に、レジストパターンとの選択比が取り難いことがある。
なお、前記誘電率は、例えば、シリカ系被膜上に金電極を形成し、誘電率測定器等を用いて測定することができる。
なお、前記エッチング速度は、例えば、公知のエッチング装置を用いて所定時間エッチング処理を行い試料の減膜量を測定し、単位時間当たりの減膜量を算出することにより測定することができる
前記耐湿性としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、前記シリカ系被膜を室温にて1週間放置し、1MHz、1Vの交流電源を接続したプローバを用いて容量を測定し、該容量と前記シリカ系被膜の膜厚とから算出した誘電率変化が、0.3以内であるのが好ましく、0.2以内であるのがより好ましい。
前記密着強度としては、特に制限はなく、目的に応じて適宜選択することができるが、例えば、密着強度測定装置(「セバスチャンファイブ」;クアッドグループ社製)により測定した強度が、5.88GPa(600kgf/mm2)より大きいのが好ましい。
また、優れた耐薬品性を有する前記シリカ系被膜は、化学的機械研磨(CMP)の際の保護膜として好適に使用することができる。この場合、研磨の対象となる部分以外の部位を保護し、高精細な研磨を行うことができる。
本発明の多層配線は、本発明の前記シリカ系被膜を少なくとも有する。
本発明の多層配線の製造方法は、本発明の前記多層配線を製造する方法であって、シリカ系被膜形成工程と配線形成工程とを少なくとも含み、更に必要に応じて適宜選択した、その他の工程を含む。
以下、本発明の多層配線の製造方法の説明を通じで、本発明の多層配線の詳細も明らかにする。
前記シリカ系被膜形成工程は、本発明の前記シリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことによりシリカ系被膜を形成する工程である。
前記シリカ系被膜形成工程は、本発明の前記シリカ系被膜の製造方法により好適に行うことができる。
なお、前記被加工面、前記塗布、などの詳細については、上述した通りである。
前記熱処理は、目的に応じて適宜その温度、雰囲気等の条件を選択することができるが、前記温度としては、50〜400℃が好ましく、80〜350℃がより好ましい。
前記温度が、50℃未満であると、前記有機溶剤が膜中に残留してしまい、充分な強度が得られないことがあり、400℃を越えると、前記シリコーンポリマーの骨格や側鎖の珪素−炭化水素結合が分解するしてしまうことがある。
前記雰囲気としては、大気中では酸素の取り込みによる誘電率の上昇が懸念されるため、不活性ガスの存在下、減圧下、などが好ましく、前記不活性ガスとしては、例えば、窒素などが好適に挙げられる。
なお、前記熱処理工程は、前記シリカ系被膜の下地層が、例えばスピンコート法により成膜される膜(例えば、多孔質シリカ膜等の低誘電率膜)である場合には、該低誘電率膜を形成する材料を塗布し、溶媒乾燥を行った後、この上に前記シリカ系被膜形成用材料を塗布し、一括で前記熱処理工程を行ってもよい。この場合、成膜コストの低減を図ることができる。
前記配線形成工程は、配線を形成する工程である。
前記多層配線を形成する場合、前記配線形成工程は、スルービア形成工程、導体メッキ工程などの適宜選択したその他の工程を含むのが好ましい。
前記スルービア形成工程は、前記被加工面上に形成された前記シリカ系被膜の最上層に形成される配線と接続するためにスルービアを形成する工程である。
前記スルービアの形成は、例えば、前記スルービア部分に適当な露光量のレーザ光を照射することにより行う。
前記レーザ光としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、炭酸ガスレーザ、エキシマレーザ、YAGレーザなどが挙げられる。
前記導体メッキ工程は、前記被加工面上に形成された前記シリカ系被膜上に、配線前駆体としての導体を全面に被覆し、導体メッキ層を形成する工程である。
前記導体メッキの方法としては、例えば、無電解メッキ、電解メッキなどの常用メッキ法を用いて行うことができる。
前記エッチングの方法としては、特に制限はなく、目的に応じて適宜選択することができ、常用のエッチング法を使用することができる。
前記シリカ系被膜形成工程及び前記配線形成工程(前記スルービア形成工程、前記導体メッキ工程を含む)の一連の工程は、必要に応じて繰り返し行うことにより、回路の集積度の高い多層配線を製造することができる。
本発明の多層配線は、耐エッチング性、耐薬品性、及び耐湿性に優れ、密着性が良好であり、誘電率が低い、本発明の前記シリカ系被膜を低誘電率膜上に有するので、寄生容量が低減され、信号伝播速度の高速化が可能であり、応答速度の高速化が要求される、半導体集積回路等の半導体装置に好適であり、以下の本発明の半導体装置に特に好適である。
本発明の半導体装置は、本発明の前記シリカ系被膜を層間絶縁膜及び該層間絶縁膜の表面に形成される保護膜のいずれかとして有する。
本発明の半導体装置の製造方法は、本発明の前記半導体装置を製造する方法であって、シリカ系被膜形成工程と、パターニング工程とを少なくとも含み、更に必要に応じて適宜選択したその他の工程を含む。
以下、本発明の半導体装置の製造方法の説明を通じて、本発明の半導体装置の詳細も明らかにする。
前記シリカ系被膜形成工程は、前記被加工面上に本発明の前記シリカ系被膜形成用材料を用いてシリカ系被膜を形成する工程である。
なお、前記被加工面、前記シリカ系被膜形成用材料などの詳細については、上述した通りである。
前記熱処理は、目的に応じて適宜その温度、雰囲気等の条件を選択することができるが、前記温度としては、50〜400℃が好ましく、80〜350℃がより好ましい。
前記温度が、50℃未満であると、前記有機溶剤が膜中に残留してしまい、充分な強度が得られないことがあり、400℃を越えると、前記シリコーンポリマーの骨格や側鎖の珪素−炭化水素結合が分解してしまうことがある。
前記雰囲気としては、大気中では酸素の取り込みによる誘電率の上昇が懸念されるため、不活性ガスの存在下、減圧下、などが好ましく、前記不活性ガスとしては、例えば、窒素などが好適に挙げられる。
なお、前記熱処理工程は、前記シリカ系被膜の下地層が、例えばスピンコート法により成膜される膜(例えば、多孔質シリカ膜等の低誘電率膜)である場合には、該低誘電率膜を形成する材料を塗布し、溶媒乾燥を行った後、この上に前記シリカ系被膜形成用材料を塗布し、一括で前記熱処理工程を行ってもよい。この場合、成膜コストの低減を図ることができる。
前記パターニング工程は、前記シリカ系被膜形成工程により得られた前記シリカ系被膜をマスクとして、エッチングにより前記被加工面をパターニングする工程である。
前記パターニング工程においては、前記シリカ系被膜に対し選択露光及び現像を行って所望のパターンを形成した後、該パターンを用いてエッチングするのが好ましい。この場合所望のパターン状に容易にエッチングを行うことができる。
前記パターンは、公知のパターン形成方法に従って形成することができる。
なお、前記露光と前記現像との間で、反応を促進させる観点からベーク処理を行ってもよい。
前記その他の工程としては、特に制限はなく、目的に応じて適宜選択することができ、例えば、配線形成工程が挙げられる。
前記配線形成工程は、配線を形成する工程であり、その詳細については、前記多層配線の製造方法の説明において、詳述した通りである。
前記シリカ系被膜形成工程、前記パターニング工程、及び前記配線形成工程(前記スルービア形成工程、前記導体メッキ工程を含む)の一連の工程は、必要に応じて繰り返し行うことにより、回路の集積度の高い多層配線を有する半導体装置を製造することができる。
本発明の半導体装置は、例えば、以下のようにして得られる。即ち、まず、図1に示すような、素子間分離膜2で分離され、ソース拡散層5aとドレイン拡散層5b、サイドウォール絶縁膜3を有するゲート電極4を形成したトランンジスタ層が形成されたシリコンウェハー1に、図2に示すように、層間絶縁膜6(リンガラス)及びストッパー膜7(SiC)を形成した後、電極取り出し用のコンタクトホールを形成する。図3に示すように、スパッタ法によりこのコンタクトホ−ルにバリア膜8(TiN)を厚みが50nmとなるように形成した後、WF6と水素とを混合し、還元することにより、Wによる導体プラグ9(ブランケット)を該コンタクトホールに埋め込み、ビアを形成すると共に、化学的機械研磨法(CMP)により該ビア以外の部分を除去する。
ここで、図9に示すように、これらの絶縁層に対し、ビアパターンを形成したレジスト層をマスクとして用い、CF4/CHF3ガスを原料としたFプラズマ法にてガス組成及び圧力を変えることにより、シリカ系被膜19、多孔質シリカ膜18、シリカ系被膜17、及び多孔質シリカ膜16の順に加工を行いビアを形成する。次いで、第2層目配線パターンを施したレジスト層をマスクとして用い、CF4/CHF3ガスを原料としたFプラズマ法にて加工を行い、配線溝を形成する。図10に示すように、形成したビアと配線溝とに対し、スパッタ法により、配線材料(銅)が多孔質シリカ膜18へ拡散するのを防ぐバリア膜20(TaN)を厚みが10nmとなるように形成する。続いて、前記配線溝に形成したバリア膜20の表面に、電解メッキの際に電極として機能するシード層(Cu)を厚みが10nmとなるように形成する。次に、電解メッキ法により、銅配線21(Cu)を厚み1,400nm程度積層した後、化学的機械研磨法(CMP)により配線パターン部以外の銅を除去し、図11に示すように、プラズマCVD法によりSiC:O:H膜22を30nmの厚みとなるように形成し、第2層目のビア及び配線層(銅)を形成する。
以下、前記第2層目のビア及び配線層(銅)の形成を再度行うことにより、3層目のビア及び配線層(銅)を有する3層構造の銅配線(該銅配線は、本発明の前記多層配線に相当する)を有する半導体装置を製造することができる。
本発明の半導体装置は、例えば、フラッシュメモリ、DRAM、FRAM、MOSトランジスタ、などに特に好適である。
−シリカ系被膜形成用材料の調製−
前記構造式(3)で表されるシリコン化合物としての、1,2−ビス(ジメチルエトキシシリル)エタン(1,2−DMESE)、及び1,4−ビス(ジメチルエトキシシリル)ベンゼン(1,4−DMESB)、前記構造式(4)で表されるシリコン化合物としてのテトラエトキシシラン(TEOS)、前記構造式(5)で表されるシリコン化合物としての、メチルトリエトキシシラン(MTEOS)、及びフェニルトリエトキシシラン(PTEOS)、更に500ppm硝酸水、並びに前記有機溶剤としてのプロピレングリコールモノメチルエーテルを、それぞれ表1〜3に示す分量で四ツ口フラスコに仕込み、50℃で2時間にわたって加水分解縮重合反応を行い、シリカ系被膜形成用材料を調製した。
得られたシリカ系被膜形成用材料を、シリコンウェハー上にスピンコート法により、回転数1,500rpm、塗布時間1分間で、厚みが1μmとなるように塗布した。次いで、該シリコンウェハーを150℃に設定したホットプレートに載せ、N2ガス中にて3分間、前記有機溶剤の乾燥を行った。更に、400℃に設定した電気炉を用い、N2ガス中にて30分間焼成し、シリカ系被膜を作製した。
得られたシリカ系被膜中のシリコーンポリマーの存在を、赤外分光分析により確認した。実施例1のシリカ系被膜におけるポリマーの組成を、図12に示す。図12より、実施例1のシリカ系被膜中には、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合の存在が確認され、これらの構造を総て有するシリコーンポリマーが含まれていることが判った。
得られたシリカ系被膜上に直径1mmの金属極を作製し、1MHz、1Vの交流電源を接続したプローバを用いて容量を測定し、該容量と前記膜厚とから誘電率を算出した。結果を表1〜3に示す。
−積層膜の作製−
多孔質シリカ膜(低誘電率膜、「セラメート NCS」;触媒化成工業製)をシリコン基板上に成膜し、次いで、実施例1〜27のシリカ系被膜形成用材料をスピンコート法により、回転数1,500rpm、塗布時間1分間で、0.2μmの厚みとなるように塗布した。次いで、前記シリコン基板を150℃に設定したホットプレートに載せ、N2ガス中にて3分間、前記有機溶剤の乾燥を行った。更に、400℃に設定した電気炉を用い、N2ガス中にて30分間焼成し、多孔質シリカ膜上にシリカ系被膜が積層された積層膜を作製した。
得られた積層膜における、多孔質シリカ膜とシリカ系被膜との密着強度を、密着強度測定器(「セバスチャンファイブ」;クアッドグループ社製)を用いて測定した。結果を表1〜3に示す。
得られた積層膜に対し、CF4/CHF3ガスを原料としたFプラズマによりドライエッチングを行い、多孔質シリカ膜とシリカ系被膜とのエッチングレート比を測定した。結果を表1〜3に示す。
シリコン基板上にノボラック樹脂を150nmの厚みで成膜した後、実施例1〜27のシリカ系被膜形成用材料を用い、厚み400nmのシリカ系被膜を作製した。該シリカ系被膜上に、ArFレジストを用いて200nmピッチの配線パターンを露光及び現像し、断面を走査型電子顕微鏡(SEM)(日立製作所製)を用いて観察し、レジストパターンの形状を確認した。結果を表1〜3に示す。
次いで、レジストパターンの形状が良好であったシリカ系被膜に対し、CF4/CHF3ガスを原料としたFプラズマによりドライエッチングを行い、エッチングシフト量を前記SEMにより測定した。結果を表1〜3に示す。
なお、前記エッチングシフト量は、所定のエッチングサイズに対する、実際のエッチングサイズの変位量を表す。
前記耐薬品性の評価は、0.5質量%HFに対するエッチングレートを測定することにより行った。即ち、実施例1〜27のシリカ系被膜形成用材料をスピンコート法により、回転数1,500rpm、塗布時間1分間で、1μmの厚みとなるように塗布した。次いで、前記シリコン基板を150℃に設定したホットプレートに載せ、N2ガス中にて3分間、前記有機溶剤の乾燥を行った。更に、400℃に設定した電気炉を用い、N2ガス中にて30分間焼成し、シリカ系被膜を作製した。該シリカ系被膜が形成されたシリコン基板を、0.5質量%HFに1分間浸漬してウェットエッチングを行い、減膜量を測定することによりエッチングレートを算出した。
前記耐湿性の評価は、誘電率の変化(7日間放置後の誘電率)を測定することにより行った。即ち、前記耐薬品性の評価におけるシリカ系被膜の形成方法と同様にして、実施例1〜27のシリカ系被膜形成用材料を用い、150nmの厚みのシリカ系被膜を作製した。該シリカ系被膜を、室温にて7日間放置した後、1MHz、1Vの交流電源を接続したプローバを用いて容量を測定した。該容量とシリカ系被膜の膜厚とから誘電率を算出した。結果を表1〜3に示す。
前記構造式(3)で表されるシリコン化合物としての、1,2−ビス(ジメチルエトキシシリル)エタン(1,2−DMESE)及び1,4−ビス(ジメチルエトキシシリル)ベンゼン(1,4−DMESB)と、前記構造式(4)で表されるシリコン化合物としてのテトラエトキシシラン(TEOS)、前記構造式(5)であらわされる化合物としての、メチルトリエトキシシラン(MTEOS)、及びフェニルトリエトキシシラン(PTEOS)との加水分解縮合反応を行わず、いずれか一方のシリコン化合物を、表4に示す分量で使用した以外は、実施例1と同様にして、シリカ系被膜形成用材料を調製し、シリカ系被膜を作製した。また、シリカ系被膜の諸物性を実施例1と同様にして評価し、表4に併せて示した。
なお、得られたシリカ系被膜中のシリコーンポリマーの存在を、赤外分光分析により確認した。比較例4のシリカ系被膜におけるポリマーの組成を、図12に示す。図12より、比較例4のシリカ系被膜中には、Si−CHx−結合の存在が確認されず、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合の総ての構造を有するシリコーンポリマーが含まれていないことが判った。
−シリカ系被膜形成用材料の調製−
前記構造式(10)で表されるシリコン化合物としての、1,2−ビス(ジメチルクロロシリル)エタン(1,2−DMCSE)、及び1,4−ビス(ジメチルクロロシリル)ベンゼン(1,4−DMCSB)、前記構造式(11)で表されるシリコン化合物としての、テトラクロロシラン(TCS)、前記構造式(12)で表されるシリコン化合物としての、メチルトリクロロシラン(MTCS)及びフェニルトリクロロシラン(PTCS)、更に500ppm硝酸水、並びに前記有機溶剤としてのプロピレングリコールモノメチルエーテルを、それぞれ表5〜7に示す分量で四ツ口フラスコに仕込み、50℃で2時間にわたって加水分解縮重合反応を行い、シリカ系被膜形成用材料を調製した。
なお、得られたシリカ系被膜中のシリコーンポリマーの存在を、赤外分光分析により確認した。実施例28のシリカ系被膜におけるポリマーの組成を、図12に示す。図12により、実施例28のシリカ系被膜中には、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合の存在が確認され、これらの構造を総て有するシリコーンポリマーが含まれていることが判った。
前記構造式(10)で表されるシリコン化合物としての、1,2−ビス(ジメチルクロロシリル)エタン(1,2−DMCSE)及び1,4−ビス(ジメチルクロロシリル)ベンゼン(1,4−DMCSB)と、前記構造式(11)で表されるシリコン化合物としてのテトラクロロシラン(TCS)、前記構造式(12)で表されるシリコン化合物としての、メチルトリクロロシラン(MTCS)及びフェニルトリクロロシラン(PTCS)との加水分解縮合反応を行わず、いずれか一方のシリコン化合物を、表8に示す分量で使用した以外は、実施例1と同様にして、シリカ系被膜形成用材料を調製し、シリカ系被膜を作製した。また、シリカ系被膜の諸物性を実施例1と同様にして評価し、表8に併せて示した。
なお、得られたシリカ系被膜中のシリコーンポリマーの存在を、赤外分光分析により確認した。比較例12のシリカ系被膜におけるポリマーの組成を、図12に示す。図12より、比較例12のシリカ系被膜中には、Si−CHx−結合の存在が確認されず、CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合の総ての構造を有するシリコーンポリマーが含まれていないことが判った。
−多層配線及び半導体装置の製造−
本発明の多層配線及び半導体装置を以下のようにして製造した。まず、図1に示すように、素子間分離膜2で分離され、ソース拡散層5aとドレイン拡散層5b、サイドウォール絶縁膜3を有するゲート電極4を形成したトランンジスタ層が形成されたシリコンウェハー1に、図2に示すように、層間絶縁膜6(リンガラス)及びストッパー膜7(SiC)を形成した後、電極取り出し用のコンタクトホールを形成した。図3に示すように、スパッタ法によりこのコンタクトホ−ルにバリア膜8(TiN)を厚みが50nmとなるように形成した後、WF6と水素とを混合し、還元することにより、Wによる導体プラグ9(ブランケット)を該コンタクトホールに埋め込み、ビアを形成すると共に、化学的機械研磨法(CMP)により該ビア以外の部分を除去した。
ここで、図9に示すように、これらの絶縁層に対し、ビアパターンを形成したレジスト層をマスクとして用い、CF4/CHF3ガスを原料としたFプラズマ法にてガス組成及び圧力を変えることにより、シリカ系被膜19、多孔質シリカ膜18、シリカ系被膜17、及び多孔質シリカ膜16の順に加工を行いビアを形成した。次いで、第2層目配線パターンを施したレジスト層をマスクとして用い、CF4/CHF3ガスを原料としたFプラズマ法にて加工を行い、配線溝を形成した。図10に示すように、形成したビアと配線溝とに対し、スパッタ法により、配線材料(銅)が多孔質シリカ膜18へ拡散するのを防ぐバリア膜20(TaN)を厚みが10nmとなるように形成した。続いて、前記配線溝に形成したバリア膜20の表面に、電解メッキの際に電極として機能するシード層(Cu)を厚みが10nmとなるように形成した。次に、電解メッキ法により、銅配線21(Cu)を厚み1400nm程度積層した後、化学的機械研磨法(CMP)により配線パターン部以外の銅を除去し、図11に示すように、プラズマCVD法によりSiC:O:H膜22を30nmの厚みとなるように形成し、第2層目のビア及び配線層(銅)を形成した。
以下、前記第2層目のビア及び配線層(銅)の形成を再度行うことにより、3層目のビア及び配線層(銅)を有する3層構造の銅配線(該銅配線は、本発明の前記多層配線に相当する)を有する半導体装置を製造した。以上のようにして、ビアと銅配線とが連続した連続ビアを有する半導体装置を100万個製造したところ、該連続ビアの歩留まりは91%あった。また、実効的な誘電率を層間容量により算出したところ、2.6であった。更に200℃の高温にて3,000時間放置後の配線抵抗を、抵抗測定器(「HP4284A」;アジレント製)を用いて測定したところ、抵抗上昇は観られなかった。
実施例55において、実施例1で得られたシリカ系被膜形成用材料を、実施例28で得られたシリカ系被膜形成用材料に代えた以外は、実施例55と同様にしてシリカ系被膜12、17及び19をそれぞれ形成し、多層配線及び半導体装置を製造した。
ビアと銅配線とが連続した連続ビアを有する半導体装置を100万個製造したときの該連続ビアの歩留まりは96%あった。また、実効的な誘電率を層間容量により算出したところ、2.55であった。更に200℃の高温にて3,000時間放置後の配線抵抗を、抵抗測定器(「HP4284A」;アジレント製)を用いて測定したところ、抵抗上昇は観られなかった。
実施例55において、実施例1で得られたシリカ系被膜形成用材料を、比較例1で得られたシリカ系被膜形成用材料に代えた以外は、実施例55と同様にしてシリカ系被膜12、17、及び19をそれぞれ形成し、多層配線及び半導体装置を製造した。
ビアと銅配線とが連続した連続ビアを有する半導体装置を100万個製造したところ、該連続ビアの歩留まりは34%あった。また、実効的な誘電率を層間容量により算出したところ、3.8と高いことが判った。更に200℃の高温にて3,000時間放置後の配線抵抗を、抵抗測定器(「HP4284A」;アジレント製)を用いて測定したところ、抵抗上昇は観られた。
(付記1) CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有するシリコーンポリマーを少なくとも含むことを特徴とするシリカ系被膜形成用材料。
ただし、前記xは、0〜2の整数を表す。
(付記2) シリコーンポリマーが、下記一般式(1)から(3)で表されるシリコン化合物から選択される少なくとも1種と、下記一般式(4)から(7)で表されるシリコン化合物から選択される少なくとも1種とを、加水分解縮重合反応させて得られる付記1に記載のシリカ系被膜形成用材料。
(付記3) 加水分解縮重合反応が、pHが1〜11の水溶液を用いて行われる付記2に記載のシリカ系被膜形成用材料。
(付記4) 付記1から3のいずれかに記載のシリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことを特徴とするシリカ系被膜の製造方法。
(付記5) 熱処理が、50〜400℃で行われる付記4に記載のシリカ系被膜の製造方法。
(付記6) 熱処理が、不活性ガスの存在下にて行われる付記4から5のいずれかに記載のシリカ系被膜の製造方法。
(付記7) 付記4から6のいずれかに記載のシリカ系被膜の製造方法により製造されたことを特徴とするシリカ系被膜。
(付記8) ドライエッチングの際のハードマスクとして用いられる付記7に記載のシリカ系被膜。
(付記9) 化学的機械研磨の際の保護膜として用いられる付記7から8のいずれかに記載のシリカ系被膜。
(付記10) 厚みが0.01〜1μmである付記7から9のいずれかに記載のシリカ系被膜。
(付記11) 付記7から10のいずれかに記載のシリカ系被膜を少なくとも有することを特徴とする多層配線。
(付記12) 付記11に記載の多層配線を製造する方法であって、付記1から2のいずれかに記載のシリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことによりシリカ系被膜を形成するシリカ系被膜形成工程と、配線を形成する配線形成工程と、を少なくとも含むことを特徴とする多層配線の製造方法。
(付記13) 熱処理が、50〜400℃の不活性ガスの存在かにて行われる付記12に記載の多層配線の製造方法。
(付記14) 付記7から10のいずれかに記載のシリカ系被膜を、層間絶縁膜及び該層間絶縁膜の表面に形成される保護膜のいずれかとして有することを特徴とする半導体装置。
(付記15) 付記14に記載の半導体装置を製造する方法であって、被加工面上に付記1から3のいずれかに記載のシリカ系被膜形成用材料を用いてシリカ系被膜を形成するシリカ系被膜形成工程と、該シリカ系被膜をマスクとしてエッチングにより前記被加工面をパターニングするパターニング工程とを含むことを特徴とする半導体装置の製造方法。
(付記16) シリカ系被膜形成工程が、付記1から3のいずれかに記載のシリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことにより行われる付記15に記載の半導体装置の製造方法。
(付記17) 熱処理が、50〜400℃で行われる付記16に記載の半導体装置の製造方法。
(付記18) 熱処理が、不活性ガスの存在下にて行われる付記16から17のいずれかに記載の半導体装置の製造方法。
(付記19) エッチングが、ドライエッチング及びウェットエッチングのいずれかにより行われる付記15から18のいずれかに記載の半導体装置の製造方法。
(付記20) 配線を形成する配線形成工程を含む付記15から19のいずれかに記載の半導体装置の製造方法。
本発明のシリカ系被膜の製造方法は、層間絶縁膜、保護膜等の各種低誘電率膜、特に本発明のシリカ系被膜の製造に好適に用いることができる。
本発明のシリカ系被膜は、耐エッチング性、耐薬品性、及び耐湿性に優れ、しかも下地層との密着性が良好であり、応答速度の高速化が要求される半導体集積回路等に特に好適である。
本発明の多層配線の製造方法は、本発明の多層配線の製造に好適に用いることができる。
本発明の多層配線は、信号伝播速度の高速化が可能であり、応答速度の高速化が要求される半導体集積回路等に特に好適である。
本発明の半導体装置の製造方法は、フラッシュメモリ、DRAM、FRAM、MOSトランジスタ等を初めとする各種半導体装置、特に本発明の半導体装置の製造に好適に用いることができる。
本発明の半導体装置は、配線間の寄生容量の低下と配線抵抗の低下とが達成され、高速で信頼性が高い。
2 素子間分離膜
3 サイドウォール絶縁膜
4 ゲート電極
5a ソース拡散層
5b ドレイン拡散層
6 層間絶縁膜(リンガラス)
7 ストッパー膜
8 バリア膜(TiN)
9 導体プラグ(W)
10,15,22 SiC:O:H膜
11,16,18 多孔質シリカ膜(低誘電率膜;配線分離絶縁膜)
12,17,19 シリカ系被膜
13,20 バリア膜(TaN)
14,21 銅配線
Claims (10)
- CHx、Si−O−Si結合、Si−CH3結合、及びSi−CHx−結合を構造の一部に有するシリコーンポリマーを少なくとも含むことを特徴とするシリカ系被膜形成用材料。
ただし、前記xは、0〜2の整数を表す。 - シリコーンポリマーが、下記一般式(1)から(3)で表されるシリコン化合物から選択される少なくとも1種と、下記一般式(4)から(7)で表されるシリコン化合物から選択される少なくとも1種とを、加水分解縮重合反応させて得られる請求項1に記載のシリカ系被膜形成用材料。
- 請求項1から2のいずれかに記載のシリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことを特徴とするシリカ系被膜の製造方法。
- 熱処理が、50〜400℃の不活性ガスの存在下にて行われる請求項3に記載のシリカ系被膜の製造方法。
- 請求項3から4のいずれかに記載のシリカ系被膜の製造方法により製造されたことを特徴とするシリカ系被膜。
- ドライエッチングの際のハードマスク、及び化学的機械研磨の際の保護膜のいずれかとして用いられる請求項5に記載のシリカ系被膜。
- 請求項5から6のいずれかに記載のシリカ系被膜を少なくとも有することを特徴とする多層配線。
- 請求項7に記載の多層配線を製造する方法であって、請求項1から2のいずれかに記載のシリカ系被膜形成用材料を被加工面上に塗布し、熱処理を行うことによりシリカ系被膜を形成するシリカ系被膜形成工程と、配線を形成する配線形成工程と、を少なくとも含むことを特徴とする多層配線の製造方法。
- 請求項5から6のいずれかに記載のシリカ系被膜を、層間絶縁膜及び該層間絶縁膜の表面に形成される保護膜のいずれかとして有することを特徴とする半導体装置。
- 請求項9に記載の半導体装置を製造する方法であって、被加工面上に請求項1から2のいずれかに記載のシリカ系被膜形成用材料を用いてシリカ系被膜を形成するシリカ系被膜形成工程と、該シリカ系被膜をマスクとしてエッチングにより前記被加工面をパターニングするパターニング工程とを含むことを特徴とする半導体装置の製造方法。
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JP2005200967A JP4860953B2 (ja) | 2005-07-08 | 2005-07-08 | シリカ系被膜形成用材料、シリカ系被膜及びその製造方法、多層配線及びその製造方法、並びに、半導体装置及びその製造方法 |
KR1020050105322A KR100695840B1 (ko) | 2005-07-08 | 2005-11-04 | 실리카계 피막 형성용 재료, 실리카계 피막 및 그의 제조방법, 다층 배선 및 그의 제조 방법과 반도체 장치 및 그의제조 방법 |
TW94139236A TWI283897B (en) | 2005-07-08 | 2005-11-09 | Silica film forming material, silica film and method of manufacturing the same, multilayer wiring structure and method of manufacturing the same, and semiconductor device and method of manufacturing the same |
US11/274,094 US7659357B2 (en) | 2005-07-08 | 2005-11-16 | Silica film forming material, silica film and method of manufacturing the same, multilayer wiring structure and method of manufacturing the same, and semiconductor device and method of manufacturing the same |
CNB2005101289734A CN100535054C (zh) | 2005-07-08 | 2005-12-02 | 二氧化硅膜、该膜的形成材料和相关产品、及其制造方法 |
US12/640,362 US8124239B2 (en) | 2005-07-08 | 2009-12-17 | Silica film forming material, silica film and method of manufacturing the same, multilayer wiring structure and method of manufacturing the same, and semiconductor device and method of manufacturing the same |
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Also Published As
Publication number | Publication date |
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US20100155121A1 (en) | 2010-06-24 |
US8124239B2 (en) | 2012-02-28 |
US7659357B2 (en) | 2010-02-09 |
CN1891757A (zh) | 2007-01-10 |
TWI283897B (en) | 2007-07-11 |
TW200703481A (en) | 2007-01-16 |
US20070026689A1 (en) | 2007-02-01 |
CN100535054C (zh) | 2009-09-02 |
KR100695840B1 (ko) | 2007-03-19 |
KR20070006534A (ko) | 2007-01-11 |
JP4860953B2 (ja) | 2012-01-25 |
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