TW201026880A - Method for depositing Si-containing film, insulator film, and semiconductor device - Google Patents
Method for depositing Si-containing film, insulator film, and semiconductor device Download PDFInfo
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- TW201026880A TW201026880A TW098130545A TW98130545A TW201026880A TW 201026880 A TW201026880 A TW 201026880A TW 098130545 A TW098130545 A TW 098130545A TW 98130545 A TW98130545 A TW 98130545A TW 201026880 A TW201026880 A TW 201026880A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000004065 semiconductor Substances 0.000 title claims description 10
- 238000000151 deposition Methods 0.000 title abstract 3
- 239000012212 insulator Substances 0.000 title description 2
- -1 silane compound Chemical class 0.000 claims abstract description 77
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 18
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 18
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 15
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 37
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 35
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 33
- 229910052799 carbon Inorganic materials 0.000 claims description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 21
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 150000001721 carbon Chemical group 0.000 claims description 11
- 125000004429 atom Chemical group 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 150000002923 oximes Chemical class 0.000 claims description 4
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims 3
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 15
- 239000000126 substance Substances 0.000 abstract description 11
- 230000009257 reactivity Effects 0.000 abstract description 8
- 238000007344 nucleophilic reaction Methods 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 5
- 229910000077 silane Inorganic materials 0.000 abstract 2
- 230000008021 deposition Effects 0.000 abstract 1
- 229910052710 silicon Inorganic materials 0.000 abstract 1
- 230000001629 suppression Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 229910052707 ruthenium Inorganic materials 0.000 description 18
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 15
- 238000003786 synthesis reaction Methods 0.000 description 15
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001273 butane Substances 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000011229 interlayer Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000002309 gasification Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 2
- FBJUQTUWWCVIDH-UHFFFAOYSA-N 1,1-dimethoxyundecane Chemical compound CCCCCCCCCCC(OC)OC FBJUQTUWWCVIDH-UHFFFAOYSA-N 0.000 description 2
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000013590 bulk material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 229910052805 deuterium Inorganic materials 0.000 description 2
- 125000004431 deuterium atom Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 238000001947 vapour-phase growth Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CWZQYRJRRHYJOI-UHFFFAOYSA-N 1,1,1-trimethoxydecane Chemical compound CCCCCCCCCC(OC)(OC)OC CWZQYRJRRHYJOI-UHFFFAOYSA-N 0.000 description 1
- MBNMGGKBGCIEGF-UHFFFAOYSA-N 1,1-diethoxypropane Chemical compound CCOC(CC)OCC MBNMGGKBGCIEGF-UHFFFAOYSA-N 0.000 description 1
- GCYUJISWSVALJD-UHFFFAOYSA-N 1,1-diethylcyclohexane Chemical compound CCC1(CC)CCCCC1 GCYUJISWSVALJD-UHFFFAOYSA-N 0.000 description 1
- DPGQSDLGKGLNHC-UHFFFAOYSA-N 1,1-diethylcyclopentane Chemical compound CCC1(CC)CCCC1 DPGQSDLGKGLNHC-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- GEFAWXQACXMZBX-UHFFFAOYSA-N 2,2-dimethoxyethanimidamide Chemical compound COC(OC)C(N)=N GEFAWXQACXMZBX-UHFFFAOYSA-N 0.000 description 1
- QDKSGHXRHXVMPF-UHFFFAOYSA-N 2,2-dimethylundecane Chemical compound CCCCCCCCCC(C)(C)C QDKSGHXRHXVMPF-UHFFFAOYSA-N 0.000 description 1
- NXNJMRHHFGMODS-UHFFFAOYSA-N 3,5-dimethoxyheptan-4-one Chemical compound CCC(OC)C(=O)C(CC)OC NXNJMRHHFGMODS-UHFFFAOYSA-N 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- AYWXDPHRLSGVBS-UHFFFAOYSA-N C(=C)CC(CCCCCCCCC)(OC)OC Chemical compound C(=C)CC(CCCCCCCCC)(OC)OC AYWXDPHRLSGVBS-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- SZKKRCSOSQAJDE-UHFFFAOYSA-N Schradan Chemical group CN(C)P(=O)(N(C)C)OP(=O)(N(C)C)N(C)C SZKKRCSOSQAJDE-UHFFFAOYSA-N 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000000423 heterosexual effect Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HPICRATUQFHULE-UHFFFAOYSA-J uranium(4+);tetrachloride Chemical compound Cl[U](Cl)(Cl)Cl HPICRATUQFHULE-UHFFFAOYSA-J 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
-
- 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
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
-
- 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
-
- 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
- H01L21/02205—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
-
- 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
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Description
201026880 ψ 六、發明說明: 【發明所屬之技術領域】 本發明係關於一種特別在邏輯u L S I之多層配線技術 上爲有用之低介電率層間絕緣膜材料,且以CVD法而成 膜之含矽膜之成膜方法、以該方法所得到之絕緣體、以及 半導體裝置。 φ 【先前技術】 在電子產業之積體電路領域之製造技術中,越來越被 要求須高集中且高速化。在矽ULSI,尤其是邏輯ULSI中 ’相較於MOSFET之微細化之功能而言,反而是將其等 連結起來之配線之功能更成爲課題。亦即,爲解決伴隨著 多層配線化而來之配線遲延的問題起見,越來越被要求須 減低其配線之電阻以及減低配線間與層間之容量。 由於此等之情事,現在,在積體電路之大部分被使用 ® 之鋁配線,就必須改以電阻更低,且具遷移抗性之銅配線 ’另在機鍍法之種子(seed)形成後,銅電鍍之步驟也已 實用化。 爲達成減低配線間與層間容量之低介電率層間絕緣膜 材料,已有各種各樣之提案。傳統上,在無機系,有二氧 化矽(Si02 )、氮化矽、磷矽酸玻璃,在有機系,則係使 用聚醯亞胺,惟最近則基於得到更爲均一之層間絕緣膜之 目的,而事先將四乙氧基矽烷單體進行加水分解,亦即使 其聚縮合後而得到Si〇2,而作成稱爲Spin on Glass (無 201026880 機SOG)之塗佈材料來使用(之提案),以及,使有機烷 氧基矽烷單體進行重縮合而得到之聚矽氧烷作爲有機SOG 來使用(之提案)。 再者,絕緣膜形成方法,以大分類而言,有將絕緣膜 聚合物溶液以旋轉塗佈法等進行塗佈、成膜之塗佈型;以 及,化學氣相成長(CVD )法,尤其是在電漿中使原料被 激化、反應所成膜之電漿化學氣相成長(Plasma Enhanced Chemical Vapor D e p o s i t i ο η :以下,簡稱爲電發 CVD、或PECVD )法之兩種方法(之提案)。 電漿CVD法之提案,例如,在專利文獻1 (特開 2 002-1 1 0670號公報)中,藉由三甲基矽烷及氧而來之電 漿CVD法,而能形成氧化三甲基矽烷薄膜之方法,還有 ,在專利文獻2 (特開平11-288931號公報)中,藉由具 有甲基、乙基、η-丙基等之直鏈狀烷基、乙烯基苯基等之 鏈烯基及芳基之烷氧基矽烷而來之電漿CVD法,所形成 之氧化烷基矽烷薄膜之方法。 此外,用以得到更低介電率之新穎電漿C VD之含矽 膜之形成方法,例如有使用在側鏈上具有自由基聚合性有 機基之矽烷化合物,並在C V D條件下,使聚合性有機基 發生聚合而形成含矽膜之形成方法(專利文獻4:國際公 開第2005/53009號冊子)’以及,將矽原子間以烴基連 結之矽烷類作爲原料使用之方法(專利文獻5 :美國專利 申請案公開第2005/0194619號說明書)等提案。 專利文獻1 :特開2 0 02 - 1 1 0 6 7 0號公報 -6 - 201026880 專利文獻2:特開平11—288931號公報 專利文獻3 :特開2000-302791號公報 專利文獻4:國際公開第2005/53009號冊子 專利文獻5 :美國專利申請案公開第2005/0 1 946 1 9號 說明書 【發明內容】 ❿ 發明之揭示 發明所欲解決之課題 然而’在爲得到更低介電率而將空孔率提高所設計之 膜上,其蝕刻步驟或洗淨步驟之流程上破壞則成爲問題。 舉例而言,在專利文獻4所提案之材料,雖可得到具 有能良好保存其有機側鏈之低介電率之膜,惟膜中所殘存 之不飽和鍵卻有會在後面步驟產生流程上破壞,從而使得 膜之物性成爲不安定化之問題。 φ 此外,在高空孔率之材料上,特別容易因爲鹼性水處 理而產生破壞,此破壞情形被認爲係絕緣膜表面之親水化 而擴大,並因爲對於具有Si-O鍵結之Si進行親核攻擊, 所以介電率得以上升所致者。 本發明有鑑於上述情事,其目的係藉由使用在傳統 CVD法之氧化矽系膜之成膜上從未利用之含Si膜形成材 料,而提供一種新穎的含Si膜之成膜方法、以該成膜方 法所得到之含Si膜所成之絕緣膜以及使用該絕緣膜之半 導體裝置。 201026880 解決課題之手段 本發明者們,爲達成上述目的而進行努力檢討之結果 ,發現了藉由:在扣除結合於砂原子之反應性基(院氧基 )所含之碳原子的碳原子數[C]及Si原子數[Si]之比[C]/ [Si]爲3以上,且將:除在含有2個以上之矽原子以外’ 並具有全部之矽原子具有2以上之與碳原子的直接鍵結之 矽烷化合物,作成電漿CVD法之原料而使用,可得到具 有有效之成膜速度,且相較於傳統之膜而言,其疏水性提 高,且化學安定性亦提高之含Si膜,從而完成了本發明 〇 亦即,本發明係一種以電漿CVD法進行之含Si膜之 成膜方法,其特徵爲在以電漿CVD法進行之含Si膜之成 膜方法中,作爲成膜原料使用之矽烷化合物,使用其反應 性基除具有氫原子或烷氧基以外,並在分子中含有2個以 上之矽原子,且2個以上之矽原子係介由亦可含有環狀構 造之直鏈狀、分枝狀或環狀之飽和烴基而結合,且扣除烷 氧基所含之碳原子之碳原子數[C]及Si原子數[Si]之比[C] / [Si]係3以上,且全部之矽原子具有2以上之與碳原子 的直接鍵結之矽烷化合物。(申請專利範圍第1項) 使用此種矽烷化合物並利用電漿CVD法對於氧化矽 膜進行成膜時,可得到:不會使膜之成長速度降低,其疏 水性高,且對於後續步驟之安定之氧化矽膜。 上述矽烷化合物係以1分子中所含之碳原子數在20 -8- 201026880 以下者爲較佳。(申請專利範圍第2項) 藉由將碳數控制在20以下者作爲目標,即可在CVD 步驟時得到有效之蒸氣壓。 上述矽烷化合物之一種較佳態樣,例如下述一般式( 1 )所示之矽烷化合物, 【化1】
(式中,R係各自獨立地爲碳數1〜6之烷基、X係各自 獨立地爲氫原子或碳數1〜4之烷氧基,Y係亦可含有環 狀構造之碳數2〜10之直鏈狀、分枝狀或環狀之(q+1) 價之飽和烴基,Z係亦可含有環狀構造之碳數2〜1〇之直 鏈狀、分枝狀或環狀之2價之飽和烴基;此外,m係各自 獨立地爲1或2,η係各自獨立地爲1或2,p爲0〜2之 整數,q爲1〜3之整數;惟分子整體所含之碳數不超過 ® 20,且R、Y、Z所含之碳數及全矽原子數之比在3以上 )。(申請專利範圍第3項) 此外,更具體之態樣,例如有下述一般式(2 )所示 之矽烷化合物, x3.brb s i - (ch2) k- S i r„x (式中’ R、X、m之定義係與一般式(1)之定義爲相同 者,k爲2〜6之整數,同時R與矽間之伸甲基鏈所含之 全碳數與分子所含之全矽數之比在3以上’且全碳數爲 -9 - 201026880 2 0以下)。(申請專利範圍第4項) 此外’本發明並係一種絕緣膜,其特徵係使用上述之 含Si膜之成膜方法進行成膜者(申請專利範圍第5項) 〇 以本發明之成膜方法所得到之絕緣膜,其化學上的安 定性高,尤其是對於鹼性之洗淨液等具有耐性。 進一步’本發明另係一種半導體裝置,其特徵係具有 上述之絕緣膜(申請專利範圍第6項)。 具有上述之絕緣膜之半導體裝置,由於在製造步驟中 其絕緣膜不容易產生物性變化之故,而成爲具有高信賴性 之半導體裝置。 發明之效果 根據本發明,無須大幅變更傳統之CVD法,除可得 到有效之成膜速度以外,並可同時達成確保膜之疏水性, 以及抑制對於矽原子之親核反應之反應性,而確保膜之化 學安定性。 此外,藉由將本發明之成膜方法作爲多層配線絕緣膜 之成長方法而利用時,可安定地製造配線訊號遲延少之半 導體積體電路。 用以實施發明之最佳型態 以下,茲詳細說明本發明。 在本發明之含Si膜形成方法上使用之成膜材料即矽 -10- 201026880 烷化合物,其反應性基除具有氫原子或烷氧基以外,並在 分子中含有2個以上之矽原子,且2個以上之矽原子係介 由亦可含有環狀構造之直鏈狀、分枝狀或環狀之飽和烴基 而結合,且扣除烷氧基所含之碳原子之碳原子數[C]及Si 原子數[Si]之比[C]/[Si]係3以上,且全部之矽原子具有 2以上之與碳原子的直接鍵結之矽烷化合物。 如上所述,已有提案使用各種材料之CVD法而進行 φ 之含Si膜形成方法,惟此等幾乎皆係介由氧而將矽原子 間加以結合所設計者。此被認爲係矽-氧間之結合能較大 之故,使得在CVD步驟中,容易得到安定且有效之成膜 速度。 相對於此,專利文獻5所提案者,係爲得到較低介電 率而使用將複數之矽原子間以烴基加以連結之化合物,惟 本發明者認爲此種在矽間具有烴基鍵結之骨架亦可利用作 爲化學上安定性之確保之用。亦即,爲形成膜之三次元構 Q 造起見,膜中之主要矽原子有必要具有3或4個結合,而 如上所述,此一般係氧原子之鍵結。然而,結合於矽原子 之氧原子,卻會因爲分極作用而提高矽原子對於親核反應 之反應性。因此’如將氧原子之鍵結改成烴基之鍵結時, 就可以抑制矽原子對於親核反應之反應性。亦即,作爲成 膜原料所使用之矽烷化合物中,藉由使其在分子中含有2 個以上之矽原子’且2個以上之矽原子介由亦可含有環狀 構造之直鏈狀、分枝狀或環狀之飽和烴基而交聯之構造時 ’就可以在與矽原子所具有之氧之結合數爲2時,亦能使 -11 - 201026880 其形成三次元構造。此外,藉由結合之氧原子數之減少, 就可以使矽原子之分極率減少,並抑制對於親核反應之反 應性。 另一方面,爲確保化學上安定性起見,其塊材之疏水 性設計亦很重要。藉由提升其塊材之疏水性,不僅在與鹼 性水溶液之界面的反應性會降低,而且還可以防止經由空 孔所造成之膜質變化。爲確保此塊材之疏水性,其矽原子 所具有之側鏈及結合取代基如能選擇飽和烴基者將較有利 。此外,藉由選擇飽和烴基,並可由碳與矽之比,來推定 塊材與疏水性相關之大槪物性。 爲確保本發明目的之對於水溶液處理之耐性所必要之 疏水性,其扣除烷氧基所含之碳原子之碳原子數[C]及Si 原子數[Si]之比[C]/ [Si],係以選擇3以上者爲目標,而 如在4以上時就可更確實地確保其疏水性。 再者,在電漿CVD反應中使用之材料,必須具有一 定之蒸氣壓,上述矽烷化合物所具有之碳數如係在20以 下者,就可作爲一般之使用。 此外,在電漿CVD反應中,結合於矽原子之飽和烴 取代基係以保存良好者爲較佳,與矽原子直接鍵結之碳原 子如不具有容易發生自由基之分枝構造者爲較佳。 在本發明之電漿CVD法之成膜方法中使用之矽烷化 合物,例如有下述一般式(1 )所示之矽烷化合物, 201026880 【化2】 X3-mRmSi- _·«i-SiR.Xj—Z^-SiRmX3.m (1) (式中,R係各自獨立地爲碳數1〜6之烷基、X係各自 獨立地爲氫原子或碳數1〜4之烷氧基,γ係亦可含有環 狀構造之碳數2〜10之直鏈狀、分枝狀或環狀之(q+i) 價之飽和烴基’ Z係亦可含有環狀構造之碳數2〜10之直 φ 鏈狀、分枝狀或環狀之2價之飽和烴基;此外,m係各自 獨立地爲1或2,η係各自獨立地爲1或2,p爲0〜2之 整數’ q爲1〜3之整數;惟分子整體所含之碳數不超過 20,且R、Y、Z所含之碳數及全矽原子數之比在3以上 )° 上述一般式(1)中,藉由m及η在1以上,式(1 )中之各矽原子所結合之氧原子數即使最高爲2時,其親 核反應性亦可受到抑制。此外,反應性基X爲烷氧基或 φ 氫原子,惟此等不論何者在以電漿CVD法所作成之膜中 皆係由氧原子交聯所成之部分。再者,分子全體,則可被 設計成R、Υ' ζ所含之碳數及全矽原子數之比爲3以上 者。 如上所述’ R及Υ以及ζ所含之與矽原子直接結合之 碳原子’係以不具有分枝者爲較佳,R及Υ以及Ζ如係碳 數2以上之取代基時,與矽原子直接結合之碳原子,係 以-CH2-之構造與矽原子結合者爲較佳。 R之較佳具體例,有甲基、乙基、丙基、丁基、戊基 -13- 201026880 、己基,又丁基以下不僅爲直鏈,亦可爲具有分枝之異性 體者,惟其與矽直接結合之部分則以伸甲基(-CH2-)之 構造者爲較佳。再者,全部之R如係選擇乙基或含有其以 上碳原子之取代基時,並不依存於Y及Z之構造,其扣 除反應性取代基之碳原子之碳原子數[C]及Si原子數[Si] 之比[c]/ [Si]可選擇3以上者,同樣地如選擇丙基以上者 使其爲4以上亦可。 Y及Z之較佳具體例,例如有二伸甲基、三伸甲基、 四伸甲基 '五伸甲基、六伸甲基、七伸甲基、八伸甲基, 三伸甲基以下者,如整體而言其碳數在10以下時,其碳 上亦可具有烷基取代基,惟與矽直接結合之部分係以伸甲 基(-CH2-)之構造者爲較佳。進一步,例如二伸乙基環 己烷或二伸乙基環戊烷等之在中間具有環狀飽和烴骨架之 取代基爲更佳之取代基。 上述一般式(1)所示之矽烷化合物,其較佳之具體 構造,例如有下述一般式(2 )所示之矽烷化合物, X3-*RnSi - (CH2)k-SiR.Xji (2) (式中’ R、X、m之定義係與一般式(1)之定義爲相同 者,k爲2〜6之整數,同時R與矽間之伸甲基鏈所含之 全碳數與分子所含之全矽數之比在3以上,且全碳數爲 20以下)。 上述一般式(2)所示之矽烷化合物之較佳具體例, 例如有1,2-雙(乙基二甲氧基甲矽烷基)乙烷、1,2-雙( 丙基二甲氧基甲矽烷基)乙烷、1,2-雙(丁基二甲氧基甲 -14 - 201026880 矽烷基)乙烷、1,2-雙(戊基二甲氧基甲矽烷基)乙烷、 I,2-雙(己基二甲氧基甲矽烷基)乙烷、1,2-雙(二甲基 甲氧基甲矽烷基)乙烷、1,2-雙(二乙基甲氧基甲矽烷基 )乙烷、1,2-雙(二丙基甲氧基甲矽烷基)乙烷、l,2-雙 (二丁基甲氧基甲矽烷基)乙烷、1,2-雙(乙基二乙氧基 甲矽烷基)乙烷、1,2-雙(丙基二乙氧基甲矽烷基)乙烷 、1,2-雙(丁基二乙氧基甲矽烷基)乙烷、1,3-雙(乙基 ❿ 二甲氧基甲矽烷基)丙烷、1,3-雙(丙基二甲氧基甲矽烷 基)丙烷、1,3-雙(丁基二甲氧基甲矽烷基)丙烷、1,3_ 雙(戊基二甲氧基甲矽烷基)丙烷、1,3-雙(己基二甲氧 基甲矽烷基)丙烷' 1,3-雙(二甲基甲氧基甲矽烷基)丙 烷、1,3-雙(二乙基甲氧基甲矽烷基)丙烷、丨,3_雙(二 丙基甲氧基甲矽烷基)丙烷、I,3-雙(乙基二乙氧基甲矽 烷基)丙烷、1,3 -雙(丙基二乙氧基甲矽烷基)丙烷、 I,3-雙(丁基二乙氧基甲砂院基)丙院、1,4_雙(甲基二 ❿甲氧基甲砂院基)丁院、1,4_雙(乙基二甲氧基甲砂院基 )丁烷、I,4-雙(丙基二甲氧基甲矽烷基)丁院、丨,4_雙 (丁基二甲氧基甲矽烷基)丁烷、I,4 -雙(戊基二甲氧基 甲矽烷基)丁烷、1,4 -雙(己基二甲氧基甲矽烷基)丁烷 、I,4 -雙(一甲基甲氧基甲砂院基)丁院、•雙(二乙 基甲氧基甲矽院基)丁烷、1,4-雙(二丙基甲氧基甲矽烷 基)丁烷、I,4-雙(甲基二乙氧基甲矽烷基)丁烷、n 雙(乙基二乙氧基甲砍院基)丁院' ;[,4_雙(丙基二乙氧 基甲矽烷基)丁烷、1,4-雙(丁基二乙氧基甲矽烷基)丁 -15- 201026880 烷、1,5-雙(甲基二甲氧基甲矽烷基)戊烷、1,5-雙(乙 基二甲氧基甲矽烷基)戊烷、1,5_雙(丙基二甲氧基甲矽 烷基)戊烷、1,5-雙(丁基二甲氧基甲矽烷基)戊烷、 1.5- 雙(戊基二甲氧基甲矽烷基)戊烷、1,5-雙(二甲基 甲氧基甲矽烷基)戊烷、1,5-雙(二乙基甲氧基甲矽烷基 )戊烷、1,5-雙(二戊基甲氧基甲矽烷基)戊烷、1,5-雙 (甲基二乙氧基甲矽烷基)戊烷、1,5-雙(乙基二乙氧基
甲矽烷基)戊烷、1,5-雙(丙基二乙氧基甲矽烷基)戊烷 A 、1,6-雙(甲基二甲氧基甲矽烷基)己烷、1,6-雙(乙基 二甲氧基甲矽烷基)己烷、1,6_雙(丙基二甲氧基甲矽烷 基)己烷、1,6-雙(丁基二甲氧基甲矽烷基)己烷、1,6-雙(戊基二甲氧基甲矽烷基)己烷、i,6·雙(己基二甲氧 基甲矽烷基)己烷、1,6-雙(二甲基甲氧基甲矽烷基)己 烷、1,6-雙(二乙基甲氧基甲矽烷基)己烷、1,6-雙(二 丙基甲氧基甲矽烷基)己烷、丨,6·雙(甲基二乙氧基甲矽 烷基)己烷、1,6-雙(乙基二乙氧基甲矽烷基)己烷、 @ 1.6- 雙(丙基二乙氧基甲矽烷基)己烷、1,7-雙(甲基二 甲氧基甲矽烷基)庚烷、1,7_雙(乙基二甲氧基甲矽烷基 )庚烷、1,7-雙(丙基二甲氧基甲矽烷基)庚烷、1,7-雙 (丁基二甲氧基甲矽烷基)庚烷、1,7-雙(戊基二甲氧基 甲矽烷基)庚烷、1,7-雙(二甲基甲氧基甲矽烷基)庚烷 、1,7-雙(二乙基甲氧基甲矽烷基)庚烷、1,7-雙(甲基 二乙氧基甲矽烷基)庚烷、1,7-雙(乙基二乙氧基甲矽烷 基)庚烷、1,8-雙(甲基二甲氧基甲矽烷基)辛烷、I,8- -16- 201026880 雙(乙基二甲氧基甲矽烷基)辛烷、1,8-雙(丙基二甲氧 基甲矽烷基)辛烷、1,8-雙(丁基二甲氧基甲矽烷基)辛 烷、1,8-雙(戊基二甲氧基甲矽烷基)辛烷、1,8-雙(二 甲基甲氧基甲矽烷基)辛烷、1,8-雙(二乙基甲氧基甲矽 烷基)辛烷、1,8-雙(甲基二乙氧基甲矽烷基)辛烷、 1,8-雙(乙基二乙氧基甲矽烷基)辛烷。 在本發明中,係將上述之矽烷化合物作爲原料,並在 φ CVD反應裝置內導入氣體,而以CVD法,尤其是電漿激 態化學氣相成長法形成含Si膜。此時,係以有機基被良 好地保存,而僅反應性基之烷氧基或氫原子被活性化之情 形下,選擇略低之能量區域者爲較佳。又使用3 00 mm晶 圓之平行平板型之電漿CVD裝置時,施加於電極間之高 頻率電力,亦即 RF Power (電漿激態電力),一般係 3 00W以下,較佳係200W以下,最佳則係100W以下進 行者爲理想。此被認爲係在低能量下之反應越多,越容易 φ 反應出原料中所包含之各自結合強度之不同,而用以提高 對於反應性基之選擇性。此外,其下限一般爲20W以上 ,尤其爲50W以上者。 關於其他之條件,可使用一般習知之CVD法,例如 上述之矽烷化合物之氣化方法,例如使用減壓之方法、以 載體氣體打氣泡送氣之方法或使用氣化裝置之方法等,可 由此等加以選擇’或亦可組合而進行者。爲控制矽烷化合 物之供應量’其係藉由液體質量流動等以一定流量送液至 氣化裝置’並以氣化裝置進行氣化者爲較佳。 -17- 201026880 此外,反應裝置內之壓力及溫度或被成膜基板之溫度 ,可根據原料或原料氣體之組成等適當地選擇,一般是在 減壓下,尤其是0.01〜1,000 Pa之範圍爲較佳,且被成膜 基板係於-50 °C〜500°C成膜者爲較佳。成膜時間,可根據 上述反應條件或目標膜厚度而適當地選擇,以20〜2,000 秒爲較佳,且以可形成厚度50〜2,000 nm,特別是100〜 3 00 rim之含Si膜(絕緣膜)者爲較佳。 電漿源,已知有高頻率電漿、微波電漿、電子迴旋共 振電漿、誘導結合電漿、螺旋波電漿等之電漿源,不論何 者皆可使用。 在形成含Si膜之時,係使上述之矽烷化合物進行氣 化所生成之氣體,並導入CVD反應裝置內,惟此時亦可 連同該氣體以外之氣體一倂導入。導入之氣體,例如有單 矽烷、二矽烷等之氫化矽烷、四乙氧基矽烷、三甲氧基矽 烷等之烷氧基矽烷、六甲基二矽氧烷等之直鏈狀矽氧烷、 1,3,5,7-四甲基環四矽氧烷等之環狀矽氧烷、六甲基二矽 氨烷等之矽氨烷、三甲基矽烷醇等之矽烷醇、氧、氮、氨 、氬•氦等之稀有氣體、一氧化碳、二氧化碳、二氧化氮 、臭氧、一氧化二氮、單甲基胺等之胺等。此等之氣體, 相對於上述之矽烷化合物,可使其含有1〇〜99質量%者 〇 以上述之方法所成膜之含Si膜,可作爲低介電率絕 緣膜而使用。如上所述,本發明之含Si膜,雖然具有多 孔質性,惟其塊材之疏水性高,且膜中之矽原子之分極很 -18 - 201026880 小,因此對於親核反應具有被抑制之反應性,故其係化學 上安定性高,尤其是在使用鹼性之洗淨液時亦不容易發生 物性變化之材料。從而,藉由將本發明之含Si膜作爲絕 緣膜使用,其對於後續步驟之流程上破壞之問題,就可製 造高信賴性之半導體裝置。 【實施方式】 Φ 實施發明之最佳型態 實施例 以下’茲舉出合成例 '實施例及比較例,惟本發明並 不限於此等之實施例範圍。 (合成例1) 1,2 -雙(二甲氧基甲基甲矽烷基)乙烷 之合成 在乙烯基甲基二甲氧基矽烷198 g中事先添加氯化鈾 φ 酸之丁烷溶液’再慢慢地滴入二甲氧基甲基矽烷159 g。 因爲產生生熱反應’將滴入速度調整到使反應混合物之溫 度成爲80°C。在滴入終了後,藉由減壓蒸餾,製得n 雙(二甲氧基甲基甲矽烷基)乙烷。其沸點在8·7χ103 Pa 下爲1 2 6 °C。 (合成例2) 1,2 -雙(甲氧基甲基丙基甲矽烷基)乙 烷之合成 在THF (四氫呋喃)中由丙基氯4 7.1 g及金屬鎂 -19- 201026880 14.6 g事先調整丙基格利雅,再滴入準備於另一燒瓶中之 1,2-(雙甲基二甲氧基甲矽烷基)乙烷71.5 g之THF溶 液中。在3小時加熱熟成之後,將生成之鹽濾掉,濃縮後 ,藉由減壓蒸餾,製得1,2-雙(甲氧基甲基丙基甲矽烷基 )乙烷。其沸點在〇.13xl 03 Pa下爲105 °C。 (合成例3) 1,6-雙(二甲氧基甲基甲矽烷基)己烷 之合成 將氯化鉑酸之丁醇溶液添加於1,5 -己二烯4 1 · 1 g,再 慢慢地滴入二甲氧基甲基矽烷106.2 g。因爲產生生熱反 應,將滴入速度調整到使反應混合物之溫度成爲8 0 °C。 在滴入終了後,藉由減壓蒸餾,製得1,6-雙(二甲氧基甲 基甲矽烷基)己烷。其沸點在0.13x1 03 Pa下爲120 °C。 (實施例1) 1,2-雙(甲氧基甲基丙基甲矽烷基)乙 烷之電漿CVD成膜 使用圖1所示之平行平板容量結合型PECVD裝置, 使在合成例2合成之1,2-雙(甲氧基甲基丙基甲矽烷基) 乙烷在矽基板上成膜。 此外,在圖1中,1爲裝置本體(小室),2爲原料 氣體導入管,3爲不活性氣體導入管,4爲樣品,5爲上 部電極,6爲下部電極,7爲排氣管。 成膜條件,係以1 0 m 1 / m i η供給不活性氣體之氬氣, 再將已被氣化之1,2-雙(甲氧基甲基丙基甲矽烷基)乙烷 201026880 持續供給至小室內壓成爲5 P a爲止,並以基板溫度1 5 〇 °C 、RF電源電力3〇w、RF電源頻率13·56ΜΗζ之條件使其 成膜。其結果,成膜速度爲5 nm/min。 (實施例2、3 ) 實施例1之條件中,除將小室內壓力各自調整爲20 Pa (實施例2) 、50 Pa (實施例3 )以外,其餘均以與實 φ 施例1同樣之條件,進行1,2-雙(甲氧基甲基丙基甲矽烷 基)乙烷之成膜。其結果,實施例2之成膜速度爲12 nm/min,實施例3之成膜速度爲20 nm/min。 (實施例4及比較例1 ) 將在實施例2進形成膜之原料,改以合成例3所調製 之I,6-雙(二甲氧基甲基甲矽烷基)己烷(實施例2)、 合成例1所調製之1,2-雙(二甲氧基甲基甲矽烷基)乙烷 φ (比較例1 )以外,其餘均以與實施例2同樣之條件進行 成膜。其結果,實施例4之成膜速度爲13 nm/min,比較 例1之成膜速度爲15 nm/min。 此外’所得到之膜之物性測定,其相對介電率係使用 49 5-CV系統(日本SSm公司製),並以使用自動水銀探 針之CV法加以測定。彈性率(楊氏率)則使用奈米壓印 機(奈米儀器公司製)加以測定。 此外,對於各膜,使用 UV照射裝置(Axcelis Technology 公司製 Rapid Cure UV Source),在照射 300 -21 - 201026880 秒之UV後測定該膜之機械強度。 上述測定結果示於表1中。 [表1] 樣品 小室內壓力 (Pa) 成膜速度 (nm/min) 相對介 電率 楊氏率 成膜後 (GPa) 楊氏率UV 照射後 (GPa) 實施例1 合成例2 5 5 2.7 5.3 9.7 實施例2 合成例2 20 12 2.6 4.7 8.3 實施例3 合成例2 50 20 2.5 4.2 7.7 實施例4 合成例3 20 13 2.6 4.5 8.2 比較例1 合成例1 20 15 2.8 8.3 9.2 根據表1所示之結果,得知:使用本發明之電漿 CVD法進行之成膜方法,具有低介電率之含Si膜可以實 用之速度成膜,且機械強度雖然因爲略大之烷基被導入之 故而在成膜後之膜上呈現略低之値,惟藉由倂用紫外線等 高能量射線照射仍而得到(該値爲)充分高者。此外,該 紫外線照射,明顯可改成電子射線等高能量射線之照射。 (實施例5〜8及比較例2 )洗淨液耐性試驗 使用作爲洗淨液之含有羥基胺之半導體用洗淨液 EKC-518 (杜邦公司製),再將上述得到之實施例1〜4 及比較例1之各成膜基板,於室溫下浸漬1 〇分鐘,進行 對於洗淨液之耐性試驗。 所得到之基板以純水潤濕後,乾燥,測定其相對介電 率,再測定其浸漬前後之相對介電率之變化。 -22- 201026880 在實施例1〜4之膜(實施例5〜8)中,相對介電率 各係 2.7、2.6、2.6、2.6,變化量各係 〇·〇、0·0、0.1' 〇. 〇 ’而相對於此,比較例1之膜(比較例2)中,相對介 電率爲3.2及0·4,明顯有上升之情形。 由此結果可知,以本發明之電漿CVD法所成膜之含 _ Si膜,其形成三次元構造之結合於矽原子之氧數,相較 於傳統爲較低者,且大部分之疏水性爲高者,因此,尤其 φ 在後面步驟中使用上述之洗淨液時,其相對介電率會上升 之問題亦可受到相當之抑制。 【圖式簡單說明】 圖1:平行平板容量結合型PECVD裝置之槪略圖。 【主要元件符號說明】 1 :裝置本體(小室) φ 2:原料氣體導入管 3 :不活性氣體導入管 4 ·樣品 5 :上部電極 6 :下部電極 7 :排氣管
Claims (1)
- 201026880 七、申請專利範圍: 1. 一種以電漿CVD法進行之含Si膜之成膜方法,其 特徵爲在以電漿CVD法進行之含Si膜之成膜方法中,作 爲成膜原料使用之矽烷化合物,使用其反應性基除具有氫 原子或烷氧基以外,並在分子中含有2個以上之矽原子, 且2個以上之矽原子係介由亦可含有環狀構造之直鏈狀、 分枝狀或環狀之飽和烴基而結合,且扣除烷氧基所含之碳 原子之碳原子數[C]及Si原子數[Si]之比[C]/[Si]係3以 上,且全部之矽原子具有2以上之與碳原子的直接鍵結之 矽烷化合物。 2. 如申請專利範圍第1項之含Si膜之成膜方法,其 中該矽烷化合物係1分子中所含之碳原子數在20以下者 3.如申請專利範圍第2項之含Si膜之成膜方法,其 中該矽烷化合物係下述一般式(1)所示之矽烷化合物, 【化1】 SiR, ,X2^rZ~^~SiRmX3-m Ο) ❹ (式中,R係各自獨立地爲碳數1〜6之烷基、X係各自 獨立地爲氫原子或碳數1〜4之烷氧基,Y係亦可含有環 狀構造之碳數2〜10之直鏈狀、分枝狀或環狀之(q+1) 價之飽和烴基,Z係亦可含有環狀構造之碳數2〜〗0之直 鏈狀、分枝狀或環狀之2價之飽和烴基;此外,m係各自 獨立地爲1或2,η係各自獨立地爲1或2,p爲0〜2之 -24- 201026880 楚數’ q為1〜3之整數;惟分子整體所含之碳數不超過 20’且R、Y、Z所食之碳數及全矽原子數之比在3以上 )° 4 -如申請專利範圍第3項之含Si膜之成膜方法,其 中該ί夕院化合物係下述一般式(2)所示之矽烷化合物, X3-BR„Si - (CH2) k-SiR.X3-„ (2) (式中,R、X、m之定義係與一般式(1)之定義爲相同 者,k爲2〜ό之整數,同時R與矽間之伸甲基鏈所含之 全碳數與分子所含之全矽數之比在3以上,且全碳數爲 20以下)。 5. —種絕緣膜,其特徵係使用申請專利範圍第1至4 項中任一項之含Si膜之成膜方法進行成膜所獲得者。 6. —種半導體裝置,其特徵係具有申請專利範圍第5 項之絕緣膜。 -25-
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2009
- 2009-08-26 EP EP09010938A patent/EP2163664A1/en not_active Withdrawn
- 2009-09-10 US US12/557,191 patent/US20100061915A1/en not_active Abandoned
- 2009-09-10 TW TW098130545A patent/TW201026880A/zh unknown
- 2009-09-10 KR KR1020090085215A patent/KR20100031081A/ko not_active Application Discontinuation
- 2009-09-11 CN CN200910169167A patent/CN101671816A/zh active Pending
Also Published As
Publication number | Publication date |
---|---|
CN101671816A (zh) | 2010-03-17 |
US20100061915A1 (en) | 2010-03-11 |
KR20100031081A (ko) | 2010-03-19 |
EP2163664A1 (en) | 2010-03-17 |
JP2010067810A (ja) | 2010-03-25 |
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