JP2010141335A - 有機シリケート材料からの炭素の除去方法 - Google Patents
有機シリケート材料からの炭素の除去方法 Download PDFInfo
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- JP2010141335A JP2010141335A JP2009280416A JP2009280416A JP2010141335A JP 2010141335 A JP2010141335 A JP 2010141335A JP 2009280416 A JP2009280416 A JP 2009280416A JP 2009280416 A JP2009280416 A JP 2009280416A JP 2010141335 A JP2010141335 A JP 2010141335A
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- organic silicate
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- 238000000034 method Methods 0.000 title claims abstract description 96
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 92
- 239000000463 material Substances 0.000 title abstract description 52
- 239000000126 substance Substances 0.000 claims abstract description 89
- 239000007800 oxidant agent Substances 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims description 79
- 239000002131 composite material Substances 0.000 claims description 68
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 57
- 239000002243 precursor Substances 0.000 claims description 53
- 239000000203 mixture Substances 0.000 claims description 47
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 46
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- 239000003361 porogen Substances 0.000 claims description 33
- 239000011148 porous material Substances 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 20
- 230000008033 biological extinction Effects 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 18
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- 239000010703 silicon Substances 0.000 claims description 17
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 14
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 9
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- 238000010894 electron beam technology Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- NBBQQQJUOYRZCA-UHFFFAOYSA-N diethoxymethylsilane Chemical group CCOC([SiH3])OCC NBBQQQJUOYRZCA-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 5
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- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- PXRCIOIWVGAZEP-UHFFFAOYSA-N Primaeres Camphenhydrat Natural products C1CC2C(O)(C)C(C)(C)C1C2 PXRCIOIWVGAZEP-UHFFFAOYSA-N 0.000 claims description 4
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 4
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 claims description 4
- 229930006739 camphene Natural products 0.000 claims description 4
- ZYPYEBYNXWUCEA-UHFFFAOYSA-N camphenilone Natural products C1CC2C(=O)C(C)(C)C1C2 ZYPYEBYNXWUCEA-UHFFFAOYSA-N 0.000 claims description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical class C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
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- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 claims description 3
- ZXLUFQJSMQSMTR-AATRIKPKSA-N (4e)-2-methylhepta-2,4-diene Chemical compound CC\C=C\C=C(C)C ZXLUFQJSMQSMTR-AATRIKPKSA-N 0.000 claims description 2
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 claims description 2
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- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
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- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
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- 150000001993 dienes Chemical class 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004678 hydrides Chemical class 0.000 claims description 2
- 229940087305 limonene Drugs 0.000 claims description 2
- 235000001510 limonene Nutrition 0.000 claims description 2
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 claims description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003606 tin compounds Chemical class 0.000 claims description 2
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims 3
- VCJPCEVERINRSG-UHFFFAOYSA-N 1,2,4-trimethylcyclohexane Chemical compound CC1CCC(C)C(C)C1 VCJPCEVERINRSG-UHFFFAOYSA-N 0.000 claims 2
- YQQFFTNDQFUNHB-UHFFFAOYSA-N 1,1-dimethylsiletane Chemical compound C[Si]1(C)CCC1 YQQFFTNDQFUNHB-UHFFFAOYSA-N 0.000 claims 1
- WSPOQKCOERDWJQ-UHFFFAOYSA-N 2-methyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound C[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 WSPOQKCOERDWJQ-UHFFFAOYSA-N 0.000 claims 1
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- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 claims 1
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- 150000002429 hydrazines Chemical class 0.000 claims 1
- 230000001035 methylating effect Effects 0.000 claims 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
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- OJAJJFGMKAZGRZ-UHFFFAOYSA-N trimethyl(phenoxy)silane Chemical compound C[Si](C)(C)OC1=CC=CC=C1 OJAJJFGMKAZGRZ-UHFFFAOYSA-N 0.000 claims 1
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- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 1
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- FENFUOGYJVOCRY-UHFFFAOYSA-N 1-propoxypropan-2-ol Chemical compound CCCOCC(C)O FENFUOGYJVOCRY-UHFFFAOYSA-N 0.000 description 1
- WBRUCSICGDSGEV-UHFFFAOYSA-N 2,2-dimethylpropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CC(C)(C)C WBRUCSICGDSGEV-UHFFFAOYSA-N 0.000 description 1
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- 229910010082 LiAlH Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UMFNUTVBQXZLBL-UHFFFAOYSA-N [[acetyloxy(methyl)silyl]oxy-methylsilyl] acetate Chemical compound CC(=O)O[SiH](C)O[SiH](C)OC(C)=O UMFNUTVBQXZLBL-UHFFFAOYSA-N 0.000 description 1
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- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- LMWRZXGRVUIGGC-UHFFFAOYSA-N bis[(2-methylpropan-2-yl)oxy]methylsilane Chemical compound CC(C)(C)OC([SiH3])OC(C)(C)C LMWRZXGRVUIGGC-UHFFFAOYSA-N 0.000 description 1
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- 239000005388 borosilicate glass Substances 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
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- AONDIGWFVXEZGD-UHFFFAOYSA-N diacetyloxy(methyl)silicon Chemical compound CC(=O)O[Si](C)OC(C)=O AONDIGWFVXEZGD-UHFFFAOYSA-N 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- UCMVNBCLTOOHMN-UHFFFAOYSA-N dimethyl(silyl)silane Chemical compound C[SiH](C)[SiH3] UCMVNBCLTOOHMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
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- ANODDRXPELXJAK-UHFFFAOYSA-N ethoxy-[ethoxy(methyl)silyl]oxy-methylsilane Chemical compound CCO[SiH](C)O[SiH](C)OCC ANODDRXPELXJAK-UHFFFAOYSA-N 0.000 description 1
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- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
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- 230000000670 limiting effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000005055 memory storage Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- IQCYANORSDPPDT-UHFFFAOYSA-N methyl(silyl)silane Chemical compound C[SiH2][SiH3] IQCYANORSDPPDT-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
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- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- RLUCXJBHKHIDSP-UHFFFAOYSA-N propane-1,2-diol;propanoic acid Chemical compound CCC(O)=O.CC(O)CO RLUCXJBHKHIDSP-UHFFFAOYSA-N 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- YOQUCILXQDXKQE-UHFFFAOYSA-N silyl 2-methylpropanoate Chemical compound CC(C)C(=O)O[SiH3] YOQUCILXQDXKQE-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 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
- VIPCDVWYAADTGR-UHFFFAOYSA-N trimethyl(methylsilyl)silane Chemical compound C[SiH2][Si](C)(C)C VIPCDVWYAADTGR-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
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- 239000011800 void material Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/401—Oxides containing silicon
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- 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
-
- 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
- H01L21/02214—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
-
- 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
- H01L21/02296—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
- H01L21/02334—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment in-situ cleaning after layer formation, e.g. removing process residues
-
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Abstract
【解決手段】本明細書中に記載されているのは、酸化剤等の、しかし酸化剤に限られない薬品を用いてOSG膜を処理する工程、OSG膜紫外線を含むエネルギー源に曝す工程、またはOSG膜を薬品で処理する工程およびOSG膜をエネルギー源に曝す工程により、有機シリケート(OSG)膜内の炭素含有種の少なくとも一部分を除去するための方法である。
【選択図】なし
Description
表I:例示的な化学処理条件
Cs=CSi(CT−Cb)/[CSi−(CT−Cb)] 式(1)
によって計算した。
それぞれの膜の誘電率を、式(2):
(式中、dは、膜厚であり、Aは、水銀電極面積であり、そしてε0は、真空中での誘電率である。)
によって計算した。
膜の誘電率の全誤差を6%未満と予期した。
表II:例示的ウェハーを処理するための化学組成物(すべてのパーセンテージは、重量%で提供され、そして100重量%まで加えられる)
ジメチルアセトアミド(DMAC)
テトラヒドロフリルアルコール(THFA)
脱イオン化水(DIW)
酢酸アンモニウム(アンモニウムアセテート)
フッ化アンモニウム(AF)
グリセロール(Gly)
ヒドロキシルアミン(50%溶液)(HA)
メタノールアミン(MEA)
29Si MAS NMRを、ネットワーク構造を評価するために使用し、そして13C MAS NMRを、膜内の炭素含有種を評価するために使用した。1超タイプの炭素、例えば、共有結合でSiに結合したCH3および残留する炭素含有種が、これらの膜の中にありそうである証拠として、表IIIに200mmウェハーからすくい取った粉末の29Si MAS NMRおよび13C MAS NMRをまとめる。表IIIは、膜内の存在する異なるSi種および炭素含有種が存在することを示す。表IIIはまた、膜内の存在する2つのタイプの炭素含有種:Si原子またはネットワーク末端炭素基に結合したメチル基およびアルケンのような炭素相に関連したものを示す。後者の炭素は、膜の誘電率の増加および機械的特性の低下に寄与しそうである。これが、本明細書中に記載された方法が損傷を与えるシリケートネットワークまたは膜を疎水性にする末端基に損傷を与えることなく、除去しようとするこのアルケンのような炭素種である。好ましくない炭素含有種が膜ネットワーク等の材料を著しく劣化させることなく膜から除去できる場合、得られた膜において改善された電気的特性または機械的特性があることができる。
表III:200mmの硬化したPDEMS(商標)2.5ATRPウェハーからすくい取った粉末の29Si MAS NMR および13C MAS NMR。
表IV:種々の処理後の誘電率および機械的特性への影響
表V、VI、およびVIIに提供した種々の処理条件下で硬化し、そして未硬化のPDEMS(商標)2.5ATRPウェハーを(上記表II中に提供された)種々の化学組成物で処理した。表V、VI、およびVIIは、種々のクリーニング組成物で処理した後のそれぞれの例示的なウェハーについて、反射率計によって得た厚さ、屈折率、および吸光係数をさらに提供する。PDEMS(商標)2.5ATRPウェハーを、20℃〜80℃の範囲の種々の温度で、湿式薬品を含有する容器内で接触させるか、または容器内に浸した。種々の化学組成物への基材の暴露の典型的な時間は、例えば、1〜120分の範囲であることができる。化学組成物での処理後に、ウェハーを脱イオン水ですすぎ、そして次に乾燥した。乾燥を不活性雰囲気下で行った。
表V:化学組成物Hを用いた処理
硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、ウェハーがオゾンを含むガス状の雰囲気に曝されるUV−オゾン乾燥洗浄機、または紫外線オゾン洗浄システム、UVOCS Inc.、モデルT10X10/OES、Serial no.1034中で処理した。表VIIIは、それぞれの例示的なウェハーの、反射率計で得られた処理条件および厚さ、屈折率、および吸光係数を提供する。反射率計のデータは、表VIIIに提供され、そしてO3曝露後に、632nmにおける屈折率および240nmにおける吸光係数が、厚さの変化なく著しく減少したことを示す。さらなる湿式化学処理を、UV硬化の前にO3に暴露したウェハーを洗浄するために使用した。湿式薬品は、中性から酸性の半水性溶媒および水混合物またはC=Oを含有する有機溶媒であった。種々の湿式薬品の調合物を上記表IIに示す。O3で処理した基材を20℃〜80℃の範囲の温度で種々の化学組成物に接触させるか、種々の化学組成物を含有する容器に浸した。化学組成物での基材の典型的な処理時間は、例えば、1〜120分間である。化学組成物との接触後に、基材を脱イオン水ですすぎ、そして次に乾燥させることができる。乾燥は、典型的には、不活性な雰囲気下で行う。化学組成物を用いた追加の処理の後で、屈折率および吸光係数は、さらに低下した(例10を参照のこと)。
表VIII:O3、種々のクリーニング組成物およびUV曝露を用いた処理後の硬化したPDEMS(商標)2.5ATRP膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMSウェハーを、約21.8℃で水中に30(ppm)オゾンを含むオゾン水(O3/H2O)に表XIおよびXIIに示した種々の時間浸した。反射率計データ(表XI)は、オゾン水への浸漬の後で、浸漬時間を増やすにつれて、632nmでの屈折率および240nmでの吸光係数が著しく減少することを示す。ウェハーの厚さは、本質的に変わっていない。
表XI: O3/H2Oを用いた処理後の例示的OSG膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、SPM(10:1モル比率の98%硫酸:30%H2O2)中に120℃で表XIIIおよびXIVに示した種々の時間浸漬した。反射率計データ(表XIII)は、浸漬時間が増えるにつれて、SPMへの浸漬後に、632nmでの屈折率はわずかに低下し;240nmでの吸光係数は著しく低下し;そしてウェハーの厚さは、わずかに変化したことを示す。
表XIII:SPMへの浸漬後の硬化した多孔質OSG膜の反射率計データ
未硬化のPDEMS(商標)2.5ATRPウェハーを、ウェハーがオゾンを含有するガス雰囲気に曝されるUVオゾン乾燥洗浄機(UVOC)中で処理した。反射率計データ(表XV)は、O3曝露後に、厚さのわずかな減少を伴いながら632nmでの屈折率および240nmでの吸光係数は、著しく低下したことを示す。UV硬化の前にO3に暴露されたウェハーを洗浄するために追加の湿式化学処理を使用した。湿式薬品は、中性から酸性の半水性溶媒および水混合物またはC=Oを含有する有機溶媒である。薬品の例は、組成物AからCであり、本明細書中の表IIに提供されている。
表XV:O3曝露および湿式化学的クリーニング後の未硬化のOSG膜の反射率計データ
未硬化のPDEMS(商標)2.5ATRPウェハーを、約21.8℃で水中に30(ppm)オゾンを含むオゾン水(O3/H2O)に、表XVIIおよびXVIIIに示した種々の時間浸した。反射率計データ(表XVII)は、オゾン水への浸漬後に、浸漬時間が増えるにつれて240nmでの吸光係数が、著しく減少したことを示す。ウェハーの屈折率および厚さがわずかに変化した。
表XVII:オゾン水への浸漬後の未硬化のPDEMS2.5膜の反射率計データ
未硬化のPDEMS2.5ウェハーを、120℃でSPM(98%硫酸:30%H2O2=10:1)に種々の時間浸漬した。反射率計データ(表XVIX)は、浸漬時間が増えるにつれて、SPMへの浸漬後に、632nmでの屈折率および240nmでの吸光係数著しく低下したことを示す。浸漬時間が増えるにつれて、ウェハーの厚さのわずかな減少がある。
表XVIX:SPMへの浸漬後の未硬化のPDEMS2.5膜の反射率計データ
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、70℃でヒドラジン溶液(水中35wt%ヒドラジン)に、1、5、10、および30分間浸漬した。反射率計データは、ヒドラジン溶液への浸漬後に、632nmでの屈折率が減少するであろうし;240nmでの吸光係数が低下するであろうし;そして浸漬時間が増加するにつれて、ウェハーの厚さがわずかに変化するであろうことを示す。
2.5の誘電率を有する硬化した多孔質PDEMS(商標)2.5ATRPウェハーを、シュウ酸溶液に、1、5、10、および30分間浸漬した。反射率計データは、シュウ酸溶液への浸漬後に、632nmでの屈折率が減少するであろうし;240nmでの吸光係数が低下するであろうし;そして浸漬時間が増加するにつれて、ウェハーの厚さがわずかに変化するであろうことを示す。
例10は、材料の孔サイズがUV−硬化した多孔質PDEMS膜からの非骨格炭素の改変および除去で変化することを具体的に示す。これらの結果は、未処理のPDEMS2.5膜と比較して、膜の増加した機械的特性および等しい誘電率を説明できる。
表XXI:O3への暴露後の硬化したPDEMS2.5膜のEPデータ
Claims (27)
- 複合有機シリケート膜を用意する工程、
該複合有機シリケート膜は、少なくとも1種のケイ素含有前駆体および少なくとも1
種のポロゲン含有前駆体を含む組成物から堆積され、そして該複合有機シリケート膜
は、炭素含有種を含む;
該複合有機シリケート膜を、紫外線を含むエネルギー源に曝す工程;および
膜に含まれる炭素含有種の少なくとも一部分を除去し、そして多孔質有機シリケート膜を提供するために、酸化剤、フッ素化試薬、メチル化試薬、還元剤、およびそれらの組み合わせから選択される少なくとも1種を含む薬品を用いて、該複合有機シリケート膜を処理する工程、
を含んで成る、多孔質有機シリケート膜の生成方法。 - 該多孔質有機シリケート膜を、該エネルギー源に曝すことをさらに含む、請求項1に記載の方法。
- 該エネルギー源が、熱源、α−粒子、β−粒子、γ−線、X線、高エネルギー電子、電子ビーム、可視光、赤外光、マイクロ波、ラジオ周波数波長、およびそれらの組み合わせから選択された少なくとも1種をさらに含む、請求項1に記載の方法。
- 該薬品が、酸化剤を含む、請求項1に記載の方法。
- 該酸化剤が、酸素、オゾン、オゾン水、SPM、酸素原子、O2またはO3のラジカル、O2またはO3の帯電種、およびそれらの組み合わせから選択された少なくとも1種を含む、請求項4に記載の方法。
- 該酸化剤が、オゾンを含む、請求項4に記載の方法。
- 該酸化剤が、オゾン水を含む、請求項4に記載の方法。
- 該酸化剤が、SPMを含む、請求項4に記載の方法。
- 該薬品が、還元剤を含む、請求項1に記載の方法。
- 該還元剤が、ヒドラジン、ヒドラジンの塩、水素化物、カルボン酸、炭化水素、水素、スズ化合物、第一鉄化合物、一酸化炭素、およびそれらの組み合わせから選択される少なくとも1種である、請求項9に記載の方法。
- 該少なくとも1種のケイ素含有前駆体が、ジエトキシメチルシラン、テトラエトキシシラン、ジメチルジエトキシシラン、ジメチルジメトキシシラン、ジメチルエトキシシラン、トリエトキシシラン、トリメチルフェノキシシラン、フェノキシシラン、ヘキサメチルジシロキサン、1、1、2、2−テトラメチルジシロキサン、オクタメチルトリシロキサン、メチルトリエトキシシラン、メチルトリアセトキシシラン、テトラアセトキシシラン、ジメチルシラシクロブタン、オクタメチルシクロテトラシロキサン、1、3、5、7−テトラメチルシクロテトラシロキサン、メチルシラン、ジメチルシラン、トリメチルシラン、テトラメチルシラン、メチレン架橋アルコキシシラン、およびそれらの組み合わせから選択される、請求項1に記載の方法。
- 該少なくとも1種のポロゲン前駆体が、α−テルピネン、リモネン、シクロヘキサン、シクロオクタン、ビシクロヘキサジエン、γ−テルピネン、カンフェン、ジメチルヘキサジエン、エチルベンゼン、ノルボルナジエン、シクロペンテンオキシド、1、2、4−トリメチルシクロヘキサン、1、5−ジメチル−1、5−シクロオクタジエン、カンフェン、アダマンタン、1、3−ブタジエン、置換ジエン、デカヒドロナフタレン、トルエン、およびそれらの組み合わせから選択される、請求項1に記載の方法。
- 該少なくとも1種のポロゲン前駆体が、1〜13の炭素原子を有するガス状の炭化水素を含む、請求項1に記載の方法。
- 該処理する工程が、該曝す工程の少なくとも一部の間に行われる、請求項1に記載の方法。
- 該曝す工程が、該処理する工程の前に行われる、請求項1に記載の方法。
- 該処理する工程が、該曝す工程の前に行われる、請求項1に記載の方法。
- 蒸着によって、少なくとも1種のケイ素含有前駆体および少なくとも1種のポロゲン含有前駆体を含む組成物から複合有機シリケート膜を形成させる工程、
該複合有機シリケート膜は、炭素含有種を含む、
該膜に含まれる該炭素含有種の少なくとも一部分を除去するために薬品で、該複合有機シリケート膜を処理する工程;および
膜に含まれる炭素含有種の少なくとも一部分を除去し、そして該多孔質有機シリケート膜を提供するために、紫外線および任意選択的に熱エネルギーを含むエネルギー源に、該複合有機シリケート膜を曝す工程、
を含んで成る、多孔質有機シリケート膜を形成するための方法。 - 該処理する工程中の該薬品が、酸化剤を含む、請求項17に記載の方法。
- 該酸化剤が、酸素、オゾン、オゾン水、SPM、酸素原子、O2またはO3のラジカル、O2またはO3の帯電種およびそれらの組み合わせから選択された少なくとも1種を含む、請求項18に記載の方法。
- 該処理する工程が、該曝す工程の少なくとも一部の間に行われる、請求項17に記載の方法。
- 該曝す工程が、該処理する工程の前に行われる、請求項17に記載の方法。
- 該処理する工程が、該曝す工程の前に行われる、請求項17に記載の方法。
- 複合有機シリケート膜を用意する工程、
該複合有機シリケート膜は、炭素含有種、第1の誘電率、および第1の硬度を含む、
膜中の炭素含有種の少なくとも一部分を除去するために、該複合有機シリケート膜を酸化剤を含む薬品で処理する工程、および、
膜中の炭素含有種の少なくとも一部分を除去し、そして第2の誘電率および第2の硬度を含む該多孔質有機シリケート膜を提供するために、紫外線を含むエネルギー源に該複合有機シリケート膜を曝す工程、
該第2の誘電率は、実質的に、該第1の誘電率以下の誘電率を有し、そして該第2の
硬度は、該第1の硬度より大きい、
を含んで成る、多孔質有機シリケート膜を形成するための方法。 - 該第1の誘電率、該第2の誘電率、または該第1の誘電率および第2の誘電率の両方が、2.7以下である、請求項23に記載の方法。
- 1.2〜2.5の範囲の誘電率、および偏光解析器により240nmで測定して0〜0.03の該膜の吸光係数を含む、多孔質有機シリケート膜。
- 孔の平均サイズが、約100ナノメートル以下である孔を含む、請求項25に記載の多孔質有機シリケート膜。
- 0〜0.025の範囲の240nm測定された該膜の吸光係数を含む、請求項25に記載の多孔質有機シリケート膜。
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KR20120101309A (ko) | 2012-09-13 |
EP3121310B1 (en) | 2018-02-28 |
EP2657365A3 (en) | 2014-01-08 |
EP2657365B1 (en) | 2017-01-18 |
TW201341587A (zh) | 2013-10-16 |
JP6017935B2 (ja) | 2016-11-02 |
EP3211121A2 (en) | 2017-08-30 |
EP2199428B1 (en) | 2018-01-24 |
KR101179167B1 (ko) | 2012-09-03 |
EP2199428A2 (en) | 2010-06-23 |
US20100151206A1 (en) | 2010-06-17 |
EP3121310A1 (en) | 2017-01-25 |
TWI408251B (zh) | 2013-09-11 |
JP2013062530A (ja) | 2013-04-04 |
TWI506164B (zh) | 2015-11-01 |
KR101553308B1 (ko) | 2015-09-16 |
JP2013211592A (ja) | 2013-10-10 |
KR101603265B1 (ko) | 2016-03-14 |
EP3211121A3 (en) | 2017-11-15 |
US20130295334A1 (en) | 2013-11-07 |
JP5775116B2 (ja) | 2015-09-09 |
TW201022472A (en) | 2010-06-16 |
EP2657365A2 (en) | 2013-10-30 |
KR20100067640A (ko) | 2010-06-21 |
EP2199428A3 (en) | 2011-08-17 |
KR20130100252A (ko) | 2013-09-10 |
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