TWI550121B - SiCOH低K膜之氣相沈積法 - Google Patents
SiCOH低K膜之氣相沈積法 Download PDFInfo
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- TWI550121B TWI550121B TW100105218A TW100105218A TWI550121B TW I550121 B TWI550121 B TW I550121B TW 100105218 A TW100105218 A TW 100105218A TW 100105218 A TW100105218 A TW 100105218A TW I550121 B TWI550121 B TW I550121B
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- 238000000034 method Methods 0.000 title claims description 24
- 238000007740 vapor deposition Methods 0.000 title description 6
- 239000002243 precursor Substances 0.000 claims description 78
- 239000000758 substrate Substances 0.000 claims description 24
- 238000000151 deposition Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical class C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 8
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 8
- LBIHNTAFJVHBLJ-UHFFFAOYSA-N 3-(triethoxymethyl)undec-1-ene Chemical compound C(=C)C(C(OCC)(OCC)OCC)CCCCCCCC LBIHNTAFJVHBLJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- BFBJEVRUJAGFOH-UHFFFAOYSA-N C(=C)C(C(OCC)(OCC)OCC)CCCCCCC Chemical compound C(=C)C(C(OCC)(OCC)OCC)CCCCCCC BFBJEVRUJAGFOH-UHFFFAOYSA-N 0.000 claims 2
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- 101100504388 Arabidopsis thaliana GFS12 gene Proteins 0.000 description 29
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 27
- 229920002554 vinyl polymer Polymers 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000012159 carrier gas Substances 0.000 description 8
- 229910052734 helium Inorganic materials 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
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- 239000000460 chlorine Substances 0.000 description 7
- -1 decane compound Chemical class 0.000 description 7
- 239000001307 helium Substances 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 7
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- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- GJEZBVHHZQAEDB-UHFFFAOYSA-N 6-oxabicyclo[3.1.0]hexane Chemical compound C1CCC2OC21 GJEZBVHHZQAEDB-UHFFFAOYSA-N 0.000 description 3
- KJKCNRWXADKKRU-UHFFFAOYSA-N C(=C)CC(CCCCCCCCC)(OCC)OCC Chemical compound C(=C)CC(CCCCCCCCC)(OCC)OCC KJKCNRWXADKKRU-UHFFFAOYSA-N 0.000 description 3
- 239000007818 Grignard reagent Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 150000004795 grignard reagents Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JZHKIUBMQMDQRG-UHFFFAOYSA-N C(=C)C(C(OC)(OC)OC)CCCCCCCC Chemical compound C(=C)C(C(OC)(OC)OC)CCCCCCCC JZHKIUBMQMDQRG-UHFFFAOYSA-N 0.000 description 2
- QRCXDXYGNVQYNX-UHFFFAOYSA-N C(=C)C(CCCCCCCCC)(OC)OC Chemical compound C(=C)C(CCCCCCCCC)(OC)OC QRCXDXYGNVQYNX-UHFFFAOYSA-N 0.000 description 2
- HNXIPHKHJIMQOY-UHFFFAOYSA-N C(C)OC(CCCCCCCCC)(C=C)OCC Chemical compound C(C)OC(CCCCCCCCC)(C=C)OCC HNXIPHKHJIMQOY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000854291 Dianthus carthusianorum Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000005670 ethenylalkyl group Chemical group 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- VXLHENRCUVMBIR-UHFFFAOYSA-N C(=C)C(C(OC)(OC)C)CCCCCCCC Chemical compound C(=C)C(C(OC)(OC)C)CCCCCCCC VXLHENRCUVMBIR-UHFFFAOYSA-N 0.000 description 1
- CYOXKCUGRLNSCA-UHFFFAOYSA-N C(=C)C(C(OCC)(OCC)C)CCCCCCCC Chemical compound C(=C)C(C(OCC)(OCC)C)CCCCCCCC CYOXKCUGRLNSCA-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910019001 CoSi Inorganic materials 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910005883 NiSi Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 229910004200 TaSiN Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- 229910008482 TiSiN Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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- 229910003460 diamond Inorganic materials 0.000 description 1
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- 239000003989 dielectric material Substances 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000005195 poor health Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01L21/02112—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
-
- 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
- C23C16/06—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 metallic material
- C23C16/18—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 metallic material from metallo-organic compounds
-
- 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
-
- 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
- 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
- C23C16/44—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 method of coating
- C23C16/50—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 method of coating using electric discharges
-
- 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
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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
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Description
本申請案主張2010年2月17日申請之美國臨時申請案第61/305,491號的權益,該臨時申請案之全部內容係以引用的方式併入本文中。
本發明揭示用於製造半導體、光伏打、LCD-TFT或平板型器件之在基板上形成SiCOH層的氣相沈積法。
JSR公司之EP2264219揭示一種具有下式之有機矽烷化學氣相沈積化合物:
其中R1及R2個別地表示氫原子、具有1至4個碳原子之烷基、乙烯基或苯基,R3及R4個別地表示具有1至4個碳原子之烷基、乙醯基或苯基,m為0至2之整數,且n為1至3之整數。
JSR公司揭示170種以上滿足該式之特定化合物,且彼等化合物可能並非該式之可用迭代之全部。JSR公司在0033段、0045段及0052段揭示:根據易於合成、純化及處理之觀點,具有所揭示式之化合物在R1及R2中包括0至1個H原子;或者,根據降低化合物沸點且增加機械強度之觀點,該化合物在R1及R2中包括1至2個H原子。
JSR公司進一步揭示170種以上特定化合物與致孔劑(porogen)及具有式R6 aSi(OR7)4-a、R8 b(R9O)3-bSi-Oe-Si(OR10)3-cR11 c及-[R13 f(R14O)2-fSi-(R15)g]-之另一矽烷化合物的組合,其中R6、R8至R11、R13及R14個別地表示H原子、F原子或單價有機基團,R7個別地表示單價有機基團,R15表示O原子、伸苯基或由-(CH2)n-所示之基團,a為0至4之整數,b及c個別地為0至3之整數,e為0或1,f為0至2,g為0或1,h為2至3之整數,且n為1至6之整數(0062段)。成孔劑可為具有環結構之任何化合物(0094段)。據稱數值上有希望之組合產生展現「更優良」機械強度及低相對介電常數之絕緣膜(0067段)。
使用前驅體之組合進行沈積可提供介電常數及楊氏模數(Young's Modulus)為單獨由前驅體產生之膜的介電常數及楊氏模數之近似平均值的膜。此現象部分說明於本申請案之比較實施例1中,其概述EP2264219之實施例2及14-18。
另外,楊氏模數結果之任何改良通常導致介電常數降低。此現象亦部分說明於本申請案之比較實施例1中,其概述EP2264219之實施例1、5-9、組成物1及組成物3。
仍需要具有低介電常數及高機械強度之絕緣膜。
本發明揭示在一或多個安置於反應腔室內之基板上形成SiCOH膜層的方法。將含Si-(CH2)n-Si之前驅體(其中n=1或2)引入反應腔室中。該含Si-(CH2)n-Si之前驅體係選自由以下組成之群:
(式I,其中n=1)
及
(式2,其中n=2)
其中R1至R4各自獨立地選自由H、甲基、乙基、丙基、乙烯基及C1-C3烷氧基組成之群;R5係選自由甲基、乙基及丙基組成之群;R1至R4中較佳至少一者為甲基、乙基或丙基;且R1至R3中至少一者為烷氧基,其可與-OR5相同或不同。將含乙烯基之前驅體引入反應腔室中。該含乙烯基之前驅體具有式Si(R1)x(O(R2))4-x,其中至少一個R1為乙烯基,視情況存在之第二R1為氫或烷基,較佳為甲基或乙基;各R2係獨立地選自烷基,較佳為甲基或乙基;且x為1或2。將致孔劑引入反應腔室中。使Si-(CH2)n-Si前驅體、含乙烯基之前驅體、致孔劑及基板接觸以使用沈積方法、較佳化學氣相沈積在基板之至少一表面上形成SiCOH膜。該方法可進一步包括一或多個以下態樣:
‧ 含乙烯基之前驅體係選自由乙烯基二乙氧基矽烷、乙烯基二甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷及乙烯基甲基二乙氧基矽烷組成之群;
‧ 含乙烯基之前驅體係選自由乙烯基三乙氧基矽烷或乙烯基甲基二乙氧基矽烷組成之群;
‧ 致孔劑為經取代或未經取代之雙環[2.2.1]庚-2,5-二烯;
‧ 沈積方法為單頻率PECVD;
‧ 使SiCOH膜變得多孔;
‧ R1至R4不為H;
‧ 含Si-(CH2)n-Si之前驅體係選自由(EtO)3Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)HMe、Me2(OEt)Si-CH2-Si(OEt)2H、(EtO)Me2SiCH2Si(OMe)2H、Me2(OEt)Si-CH2-Si(OEt)HMe、(OEt)3Si-CH2-Si(OEt)HMe、(EtO)3Si-CH2-Si(OMe)HMe、Me(OMe)2Si-CH2-Si(OMe)2H、Me(OMe)2Si-CH2-Si(OMe)HMe、Me2(OMe)SiCH2Si(OMe)2H及Me2(OEt)Si-CH2-Si(OMe)HMe組成之群;
‧ 含Si-(CH2)n-Si之前驅體係選自由Me(OEt)2Si-CH2-Si(OEt)2H、Me2(OEt)Si-CH2-Si(OEt)2H及Me(OEt)2Si-CH2-Si(OEt)HMe組成之群;
‧ 含Si-(CH2)n-Si之前驅體係選自由(EtO)3Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)HMe、Me2(OEt)Si-CH2CH2-Si(OEt)2H、(EtO)Me2SiCH2CH2Si(OMe)2H、Me2(OEt)Si-CH2CH2-Si(OEt)HMe、(OEt)3Si-CH2CH2-Si(OEt)HMe、(EtO)3Si-CH2CH2-Si(OMe)HMe、Me(OMe)2Si-CH2CH2-Si(OMe)2H、Me(OMe)2Si-CH2CH2-Si(OMe)HMe、Me2(OMe)SiCH2CH2Si(OMe)2H及Me2(OEt)Si-CH2CH2-Si(OMe)Hme組成之群;
‧ 含Si-(CH2)n-Si之前驅體係選自由Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me2(OEt)Si-CH2CH2-Si(OEt)2H及Me(OEt)2Si-CH2CH2-Si(OEt)HMe組成之群;
‧ R1至R3中僅一者為H;
‧ 含Si-(CH2)n-Si之前驅體係選自由MeH(OMe)Si-CH2-Si(OMe)HMe、(EtO)2HSi-CH2-Si(OEt)2H、(EtO)HMeSi-CH2-Si(OEt)HMe及(iPrO)HMeSi-CH2-Si(OiPr)HMe組成之群;及
‧ SiCOH膜具有低於以下兩者之介電常數:(1)由含Si-(CH2)n-Si之前驅體及致孔劑形成之SiCOH膜的介電常數;及(2)由含乙烯基之前驅體及致孔劑形成之SiCOH膜的介電常數。
亦揭示藉由所揭示方法形成之膜。藉由所揭示方法形成之膜較佳具有在約2.0至約2.7、較佳約2.0至約2.5之範圍內的介電常數,及在約4 GPa至約10 GPa、較佳約5 GPa至約10 GPa之範圍內的楊氏模數。
符號及命名
某些縮寫、符號及術語在整個以下描述及申請專利範圍中使用且包括:縮寫「SiCOH」係指含有Si、C、O及H原子之介電膜;縮寫「pSiCOH」係指已使SiCOH膜變得多孔後之SiCOH膜;縮寫「BCHD」係指雙環[2.2.1]庚-2,5-二烯,亦稱作2,5-降莰二烯;縮寫「PECVD」係指電漿增強化學氣相沈積;縮寫「CVD」係指化學氣相沈積;縮寫「MIM」係指金屬絕緣體金屬(電容器中所用之結構);縮寫「DRAM」係指動態隨機存取記憶體;縮寫「FeRAM」係指鐵電隨機存取記憶體;縮寫「CMOS」係指互補金屬氧化物半導體;縮寫「UV」係指紫外線;且縮寫「RF」係指射頻。
此外,本發明預期使用三種前驅體(Si-(CH2)n-Si前驅體、含乙烯基之前驅體及致孔劑)中各一或多者且互換地以單數或複數形式指代各者,而不意欲藉此限制範疇。
術語「烷基」係指僅含有碳及氫原子的飽和官能基。此外,術語「烷基」係指直鏈、分支鏈或環狀烷基。直鏈烷基之實例包括(不限於)甲基、乙基、丙基、丁基等。分支鏈烷基之實例包括(不限於)第三丁基。環狀烷基之實例包括(不限於)環丙基、環丁基、環戊基、環己基等。
如本文中所用之縮寫「Me」係指甲基;縮寫「Et」係指乙基;縮寫「Pr」係指丙基;縮寫「nPr」係指鏈丙基;縮寫「iPr」係指異丙基;縮寫「Bu」係指丁基(正丁基);縮寫「tBu」係指第三丁基;縮寫「sBu」係指第二丁基;縮寫「iBu」係指異丁基;且縮寫「TMS」係指三甲基矽烷基。
本文中使用來自元素週期表之元素的標準縮寫。應瞭解,元素可由此等縮寫提及(例如,Si係指矽,C係指碳等)。
本申請人已驚訝地發現使用特定含Si-(CH2)n-Si之前驅體(其中n為1或2)、特定乙烯基烷氧基矽烷或乙烯基烷基烷氧基矽烷前驅體及特定致孔劑之組合進行CVD沈積導致SiCOH膜與由單獨任一前驅體/致孔劑組合沈積之SiCOH膜的介電常數及楊氏模數相比具有相同或改良之介電常數及改良之楊氏模數。本申請人認為含Si-(CH2)n-Si之前驅體中的Si-H鍵與乙烯基烷氧基矽烷或乙烯基烷基烷氧基矽烷上之乙烯基反應產生具有較低介電常數及改良機械強度的膜。
使用一或多種下文更詳細描述之含Si-(CH2)n-Si之前驅體、一或多種第二含矽前驅體及一或多種致孔劑,藉由氣相沈積、較佳CVD且更佳PECVD沈積SiCOH膜。該膜較佳係使用紫外光或另一能量源移除致孔劑而固化,以產生具有較低介電常數之pSiCOH膜。
本申請人認為所揭示之含Si-(CH2)n-Si之前驅體經改適以沈積含有Si-(CH2)n-Si結構之膜。一般而言,含Si-(CH2)n-Si之前驅體可由下式描述:
(式1)
或
(式2)
其中R1至R4各獨立地選自由H、甲基、乙基、丙基、乙烯基及C1-C3烷氧基組成之群;R5係選自由甲基、乙基及丙基組成之群;R1至R4中較佳至少一者為甲基、乙基或丙基;且R1至R3中至少一者為烷氧基,其可與-OR5相同或不同。較佳地,R1及R2為Me,R3及R4為OEt,且R5為Et。
烷氧基配位體(亦即甲氧基、乙氧基或丙氧基)導致SiCOH膜中產生交聯Si-O-Si結構。因此,至少一個烷氧基配位體應存在於各Si原子處以使得充分交聯。Si-OEt基團為較佳,因為其較Si-OMe基團稍不具反應性,且因此不易導致前驅體在儲存期間自體聚合(self-polymerization)或在環境暴露於前驅體時的不良健康影響。
Si-Me基團將開放體積或超微孔引入結構中且降低介電常數。其亦增加最終膜之碳含量,此舉有助於增加對電漿損壞及濕式蝕刻的抗性。亦咸信高碳含量增加對「翻轉」之抗性。「翻轉」為高縱橫比之緊密間隔特徵坍塌於彼此之上。因此合意的是分子內有至少一個甲基。然而,甲基亦導致交聯降低且因此對機械性質有害。可視低介電常數與所需機械性質之間的平衡而選擇甲基數目。
Si-(CH2)n-Si子結構允許併入碳以提供對電漿損壞及翻轉之良好抗性,同時維持交聯以保持機械性質。
前驅體中之Si-H已展示有利於併入一些致孔劑。然而,膜中之殘餘Si-H趨向於與大氣中之氧及/或水分反應以形成Si-OH,其轉而導致水分吸收入膜中且k增加。因此,具有適當數目個Si-H鍵為重要的。本發明人認為每個前驅體分子一個Si-H鍵可能最佳。
在第一具體實例中,R1至R4不為H,前驅體僅具有一個Si-H鍵。如實施例1及比較實施例4及7中所說明,僅具有一個Si-H鍵之含Si-(CH2)n-Si之前驅體與含乙烯基之前驅體及BCHD的組合(實施例1)產生與由各個別前驅體/BCHD組合(比較實施例4及6)產生之膜相比具有改良之介電常數及楊氏模數結果的膜。與之相比,如比較實施例2、3及5中所說明,不含Si-H鍵之Si-(CH2)n-Si前驅體由於添加含乙烯基之前驅體而不產生具有改良之介電常數或楊氏模數的膜。本申請人認為來自含乙烯基之前驅體的乙烯基與含Si-(CH2)n-Si之前驅體的Si-H基團反應,導致碳併入膜中。
第一具體實例之例示性分子包括(EtO)3Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)2H、Me(OEt)2Si-CH2-Si(OEt)HMe、Me2(OEt)Si-CH2-Si(OEt)2H、(EtO)Me2SiCH2Si(OMe)2H、Me2(OEt)Si-CH2-Si(OEt)HMe、(OEt)3Si-CH2-Si(OEt)HMe、(EtO)3Si-CH2-Si(OMe)HMe、Me(OMe)2Si-CH2-Si(OMe)2H、Me(OMe)2Si-CH2-Si(OMe)HMe、Me2(OMe)SiCH2Si(OMe)2H及/或Me2(OEt)Si-CH2-Si(OMe)HMe,較佳為Me(OEt)2Si-CH2-Si(OEt)2H、Me2(OEt)Si-CH2-Si(OEt)2H及/或Me(OEt)2Si-CH2-Si(OEt)HMe。
或者,第一具體實例之含Si-(CH2)n-Si之前驅體包括(EtO)3Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me(OEt)2Si-CH2CH2-Si(OEt)HMe、Me2(OEt)Si-CH2CH2-Si(OEt)2H、(EtO)Me2SiCH2CH2Si(OMe)2H、Me2(OEt)Si-CH2CH2-Si(OEt)HMe、(OEt)3Si-CH2CH2-Si(OEt)HMe、(EtO)3Si-CH2CH2-Si(OMe)HMe、Me(OMe)2Si-CH2CH2-Si(OMe)2H、Me(OMe)2Si-CH2CH2-Si(OMe)HMe、Me2(OMe)SiCH2CH2Si(OMe)2H及/或Me2(OEt)Si-CH2CH2-Si(OMe)HMe,較佳為Me(OEt)2Si-CH2CH2-Si(OEt)2H、Me2(OEt)Si-CH2CH2-Si(OEt)2H及/或Me(OEt)2Si-CH2CH2-Si(OEt)HMe。
在第二具體實例中,R1、R2、或R3為H,前驅體具有一鍵結至各Si之H。理論上,本申請人認為在第二具體實例中將發生與第一具體實例中所述相同之乙烯基/Si-H反應機制。然而,一特定分子之極小數目個初步測試結果不提供預期協同作用。
第二具體實例之例示性分子包括MeH(OMe)Si-CH2-Si(OMe)HMe、(EtO)2HSi-CH2-Si(OEt)2H、(EtO)HMeSi-CH2-Si(OEt)HMe及(iPrO)HMeSi-CH2-Si(OiPr)HMe。
可使用習知方法根據以下流程達成此等前驅體之合成:
其中R'為乙基或甲基且格林納試劑(Grignard reagent)R1R2R3SiCH2MgCl係以中間物形式形成。可藉由在諸如四氫呋喃(THF)之無水、回流溶劑中逐滴添加起始氯化合物(式3)至鎂屑中來形成格林納試劑。隨後逐滴添加甲氧基或乙氧基化合物(式4)至格林納反應溶液中以形成所需產物(式1)。可藉由過濾移除反應之鎂鹽副產物,接著蒸發溶劑以自溶液中分離所需產物(式1)。關於經由格林納試劑形成Si-(CH2)n-Si鍵聯之程序的其他詳情可見於美國專利第5,296,624號(Larson等人)及美國專利申請公開案第2009/0299086號(Nobe等人)中。應在惰性氛圍下(例如在流動之乾燥氮氣下)進行本文所述之所有反應。
根據上述程序,較佳化合物之起始物質如下:
(EtO)MeHSiCH2SiHMe(OEt) MeH(OEt)2SiCH2Cl+Si(OEt)2MeH(EtO)3Si-CH2-Si(OEt)2H (EtO)3SiCH2Cl+Si(OEt)3HMe(OEt)2Si-CH2-Si(OEt)2H Me(OEt)2SiCH2Cl+Si(OEt)3HMe(OEt)2Si-CH2-Si(OEt)HMeMe(OEt)2SiCH2Cl+Si(OEt)2MeHMe2(OEt)Si-CH2-Si(OEt)2H Me2(OEt) SiCH2Cl+Si(OEt)3HMe2(OEt)Si-CH2-Si(OEt)HMeMe(OEt)2SiCH2Cl+Si(OEt)2MeH(OEt)3Si-CH2-Si(OEt)HMe (OEt)3SiCH2Cl+Si(OEt)2MeH此等起始物質可購得。
另一合成方法(最適用於對稱分子)係根據以下流程:
其中RO為烷氧基。舉例而言,對於R1=R6=H,且R=Et,流程A可用於製備(EtO)2HSiCH2SiH(OEt)2。此等起始物質可購得。應在諸如THF之溶劑中進行反應,其中試劑係在攪拌下緩慢添加。替代RONa,醇ROH可與諸如三烷基胺或吡啶之鹼一起使用。
可根據流程B製備化合物(EtO)MeHSiCH2SiHMe(OEt),其中R=Et,R1=R6=H,R2=R5=Me,且其中起始物質係根據Hemida等人,J. Mat. Sci 32 3485(1997)所述之程序製備。
如上所述之Si-(CH2)n-Si前驅體可彼此組合及與一或多種適於沈積低k SiCOH膜之含乙烯基之前驅體組合。文獻中已知許多含乙烯基之前驅體。該等前驅體之一重要種類由式Si(R1)x(O(R2))4-x描述,其中第一R1為乙烯基且視情況存在之第二R1為氫或烷基,較佳為甲基或乙基;各R2獨立地為烷基;且x為1或2。較佳地,含乙烯基之前驅體為乙烯基二乙氧基矽烷、乙烯基二甲氧基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基甲基二甲氧基矽烷及乙烯基甲基二乙氧基矽烷,且更佳為乙烯基三乙氧基矽烷或乙烯基甲基二乙氧基矽烷。
適合之致孔劑包括不飽和多環烴,諸如2,5-降莰二烯(雙環[2.2.1]庚-2,5-二烯或BCHD)及經取代BCHD。
藉由此項技術中已知之氣相沈積方法,可使用Si-(CH2)n-Si前驅體、含乙烯基之前驅體及致孔劑於基板上形成多孔SiCOH膜,該基板上可能已包括或可能不包括其他層。美國專利第6,312,793號、第6,479,110號、第6,756,323號、第6,953,984號、第7,030,468號、第7,049,427號、第7,282,458號、第7,288,292號、第7,312,524號、第7,479,306號及美國專利申請公開案第2007/0057235號中所揭示之關於氣相沈積方法之例示性、但非限制性參考係以引用的方式併入本文中。
舉例而言,預期本文所揭示之Si-(CH2)n-Si前驅體、含乙烯基之前驅體及致孔劑可用於美國專利第7,479,306號中揭示之沈積SiCOH介電材料的方法中,且更特定言之如實施例6中所揭示。如實施例6中所述,將基板置於PECVD沈積反應腔室中之經加熱基座(亦稱作晶圓夾盤)上。將基座在300℃下加熱至425℃,且較佳在350℃下加熱至400℃,但該溫度亦可介於150℃與300℃之間。前驅體流動速率可在100 mg/min至2000 mg/min之間變化。He氣可在10 sccm至500 sccm之間的速率下流動。致孔劑流動速率可在50 mg/min至2000 mg/min之間變化。前驅體流動經穩定以達到壓力在1-10 Torr(133-1333 Pa)範圍內。將RF輻射施用至簇射頭(shower head),持續5秒至500秒之時間。一般熟習此項技術者將認識到,不同沈積器件可需要不同參數。
當利用BCHD作為致孔劑時,應注意向其中併入聚合抑制劑,諸如由同在申請中之美國專利申請案第12/613,260號所揭示的聚合抑制劑,該專利申請案係以全文引用的方式併入本文中。本文中進一步描述此等方法之常見重點部分。
將基板置於氣相沈積工具之反應腔室中。用於形成絕緣膜之Si-(CH2)n-Si前驅體及含乙烯基之前驅體以及致孔劑可以氣態直接傳遞至反應腔室中,以蒸發之液體形式傳遞且引入反應腔室中,或藉由惰性載氣(包括但不限於氦氣或氬氣)傳輸。較佳地,在引入反應腔室中之前,Si-(CH2)n-Si前驅體、含乙烯基之前驅體及致孔劑在諸如He或Ar之載氣存在下在介於約70℃與約150℃之間的溫度下蒸發。
上面將要沈積SiCOH層之基板之類型將視預期最終用途而變化。基板可包括摻雜或未摻雜含矽材料(諸如SiCN),視情況塗佈有二氧化矽層及在該等應用中用作導電材料之金屬,諸如鎢、鈦、鉭、釕或銅。或者,基板可包括銅互連及絕緣區(諸如另一低k材料),視情況塗佈有諸如SiO2或SiN之密封層。上面可塗佈pSiCOH膜之基板之其他實例包括(但不限於)固體基板,諸如金屬基板(例如,Ru、Al、Ni、Ti、Co、Pt及金屬矽化物,諸如TiSi2、CoSi2及NiSi2);含金屬氮化物之基板(例如,TaN、TiN、WN、TaCN、TiCN、TaSiN及TiSiN);半導體材料(例如,Si、SiGe、GaAs、InP、鑽石、GaN及SiC);絕緣體(例如,SiO2、Si3N4、HfO2、Ta2O5、ZrO2、TiO2、Al2O3及鈦酸鋇鍶);或包括此等材料之任何數目個組合的其他基板。所用實際基板亦將取決於所用SiCOH層。
將含Si-(CH2)n-Si之前驅體、含乙烯基之前驅體及致孔劑同時或以脈衝順序引入膜沈積腔室中且與基板接觸以在基板之至少一表面上形成絕緣層。普遍地,將前驅體及致孔劑同時引入PECVD腔室中。膜沈積腔室可為進行沈積方法之器件之任何封閉空間或腔室,諸如(不限於)平行板型反應器、冷壁型反應器、熱壁型反應器、單晶圓反應器、多晶圓反應器或其他該等類型之沈積系統。
一般熟習此項技術者應能夠容易地選擇在低k膜沈積期間控制之製程變量的適當值,包括RF功率、前驅體混合物及流動速率、反應腔室中之壓力及基板溫度。
隨後可藉由額外加工使SiCOH層變得多孔以降低絕緣層之介電常數。該加工包括(但不限於)退火、UV光或電子束。
所得膜較佳具有低於以下兩者之介電常數:(1)由含Si-(CH2)n-Si之前驅體及致孔劑形成之SiCOH膜的介電常數;及(2)由含乙烯基之前驅體及致孔劑形成之SiCOH膜的介電常數。所得膜較佳具有在約2.0至約2.7之範圍內的介電常數及在約4至約10之範圍內的楊氏模數。
實施例
提供以下非限制性實施例以進一步說明本發明之具體實例。然而,該等實施例不意欲全部包括在內且不意欲限制本文所述本發明之範疇。
在以下實施例中,使用配備有DxZ沈積腔室及TEOS套組之Applied Materials P5000電漿增強化學氣相沈積裝置來沈積SiCOH膜。藉由經TEOS或DMDMOS校準之質量流量控制器來控制前驅體之流動速率。藉由關於BCHD校準之質量流量控制器來控制致孔劑之流動速率。
沈積後,使膜在另一訂製腔室(亦基於DxZ腔室)中固化,該腔室經改進以包括於腔室蓋中之一熔融二氧化矽窗及一透過該窗照射晶圓之UV燈。膜在1 Torr壓力、1 slm氮氣流速及400℃基座溫度下固化3至30分鐘。
為評估除比較實施例1以外之以下實施例中沈積膜之介電常數,用汞探針測定介電常數。
為評估除比較實施例1以外之以下實施例中沈積膜之機械效能,藉由奈米壓痕(nanoindentation)測定其楊氏模數。為達成代表性量測,各膜厚度為奈米壓痕尖端之特徵尺寸的約10倍或大於10倍。此厚度係選以消除基板之影響。對各樣品在此深度測定之楊氏模數一般為其最小值。
比較實施例1
表1概述JSR公司在EP2264219之實施例中獲得之結果。
實施例2及14-18之結果似乎說明所提出之含Si-(CH2)n-Si之前驅體與第二前驅體及致孔劑之組合對介電常數及楊氏模數結果不產生任何顯著改變。不幸的是,由於未提供(CH3CH2O)2CH3SiH+成孔劑之結果,因此未明確說明由於將兩種前驅體(亦即,Si-(CH2)n-Si前驅體及含乙烯基之前驅體)混合而出現之平均效應。然而,由於由含Si-(CH2)n-Si之前驅體與BCHD形成之膜的大部分介電常數結果及所有楊氏模數結果優於由含Si-(CH2)n-Si之前驅體、含乙烯基之前驅體及BCHD形成之膜的結果,因此一般技術者將推斷出,由含乙烯基之前驅體與BCHD之組合形成之膜的楊氏模數將低於由含Si-(CH2)n-Si之前驅體及BCHD形成之膜的楊氏模數。
實施例1、3-6及比較實施例1及2概述使用BCHD作為致孔劑形成之膜的結果。實施例10、12、13及比較實施例5及6概述使用對二甲苯作為致孔劑所形成之膜的結果。實施例7-9及11及比較實施例3及4概述使用環戊烯氧化物作為致孔劑所形成之膜的結果。除實施例11以外,使用BCHD或對二甲苯作為致孔劑所形成之膜與使用環戊烯氧化物作為致孔劑所形成之膜相比具有較低介電常數。在特定致孔劑之結果內,楊氏模數結果變化極大(亦即,楊氏模數在9.3至16.5之範圍內(對於BCHD),在11.2至14.4之範圍內(對於環戊烯氧化物),及在9.1至14.2之範圍內(對於對二甲苯))。最終,實施例3、4及13之結果似乎表明向沈積方法中添加氧氣導致膜具有較高楊氏模數。
請注意,EP2264219中之例示性沈積方法利用雙頻率電漿CVD裝置,而本申請人在以下實施例中利用單頻率電漿。因此,在以下表1中由JSR公司提供之實施例所獲得的結果無法與本申請人之以下實施例相比。
比較實施例2:Me(EtO)2Si-CH2-SiMe(OEt)2
使用Me(EtO)2Si-CH2-SiMe(OEt)2及BCHD沈積SiCOH膜來進行多項測試。Me(EtO)2Si-CH2-SiMe(OEt)2流動速率自300 mg/min變為800 mg/min。BCHD流動速率自300 mg/min變為750 mg/min。氦氣載氣流動速率保持在350 sccm。氧氣流動速率介於5 sccm與30 sccm之間。基座溫度設定為260℃或300℃。電漿功率介於200 W與600 W之間。間隔設定為0.275吋(6.985 mm)或0.500吋(12.7 mm)。「間隔」係指上面停置有晶圓之基座與「簇射頭」之間的間距,「簇射頭」為引入氣體所穿過之上部電極。所得最佳介電常數為約2.5。所得膜在約2.51之k值下具有約4.4 GPa之楊氏模數。
比較實施例3:Me(EtO)2Si-CH2CH2-SiMe(OEt)2
使用Me(EtO)2Si-CH2CH2-SiMe(OEt)2及BCHD沈積SiCOH膜來進行多項測試。Me(EtO)2Si-CH2CH2-SiMe(OEt)2流動速率自300 mg/min變為600 mg/min。BCHD流動速率自300 mg/min變為800 mg/min。氦氣載氣流動速率保持在350 sccm或1000 sccm。氧氣流動速率介於5 sccm與30 sccm之間。基座溫度設定為260℃或300℃。電漿功率介於200 W與500 W之間。間隔設定為0.275吋(6.985 mm)或0.500吋(12.7 mm)。所得最佳介電常數為約2.4。所得膜具有約3.5 GPa之楊氏模數。
比較實施例4:(HC=CH2)(EtO)3Si
使用(HC=CH2)(EtO)3Si及BCHD沈積SiCOH膜來進行多項測試。(HC=CH2)(EtO)3Si流動速率為750 mg/min。BCHD流動速率為800 mg/min。氦氣載氣流動速率保持在750 sccm。氧氣流動速率設定為0 sccm。基座溫度設定為260℃。電漿功率設定為150 W。間隔設定為0.500吋(12.7 mm)。所得最佳介電常數為約2.31。所得膜具有5.5 GPa之楊氏模數。
比 較實施例5:Me(EtO)2Si-CH2-SiMe(OEt)2+(HC=CH2)(EtO)3Si
用Me(EtO)2Si-CH2-SiMe(OEt)2、(HC=CH2)(EtO)3Si及BCHD沈積SiCOH膜來進行測試。Me(EtO)2Si-CH2-SiMe(OEt)2流動速率為200 mg/min。(HC=CH2)(EtO)3Si流動速率為500 mg/min。BCHD流動速率為800 mg/min。氦氣載氣流動速率保持在500 sccm。氧氣流動速率為5 sccm。基座溫度設定為300℃。電漿功率為500 W。間隔設定為0.500吋(12.7 mm)。所得介電常數為約2.41。所得膜具有約3.6 GPa之楊氏模數。
比較實施例6:Me2(EtO)Si-CH2-SiH(OEt)2
使用Me2(EtO)Si-CH2-SiH(OEt)2及BCHD沈積SiCOH膜來進行多項測試。Me2(EtO)Si-CH2-SiH(OEt)2流動速率自300 mg/min變為750 mg/min。BCHD流動速率自300 mg/min變為750 mg/min。氦氣載氣流動速率保持在500 sccm。氧氣流動速率設定為0 sccm、5 sccm、15 sccm、30 sccm或50 sccm。基座溫度設定為260℃或300℃。電漿功率設定為250 W、300 W、400 W或500 W。間隔設定為0.275吋(6.985 mm)或0.500吋(12.7 mm)。所得最佳介電常數為約2.3。所得膜在2.31之k值下在5 sccm O2下具有4.2 GPa之楊氏模數,且在2.39之k值下在30 sccm O2下具有6.5 GPa之楊氏模數。
實施例1:Me2(EtO)Si-CH2-SiH(OEt)2+(HC=CH2)(EtO)3Si
使用Me2(EtO)Si-CH2-SiH(OEt)2、(HC=CH2)(EtO)3Si及BCHD沈積SiCOH膜來進行多項測試。Me2(EtO)Si-CH2-SiH(OEt)2流動速率自250 mg/min變為500 mg/min。(HC=CH2)(EtO)3Si流動速率自250 mg/min變為500 mg/min。BCHD流動速率為800 mg/min。氦氣載氣流動速率保持在500 sccm。氧氣流動速率在介於5 sccm與30 sccm之間變化。基座溫度設定為260℃或300℃。電漿功率設定為300 W或500 W。反應腔室壓力設定為8 Torr。間隔設定為0.500吋(12.7 mm)。所得最佳介電常數為約2.17,其出人意料地優於比較實施例4及6中所得之介電常數。另外,所得膜在2.28之k值下具有6.0 GPa之楊氏模數且在2.23之k值下具有6.1 GPa之楊氏模數。
如表2中所示,除由Me2(EtO)Si-CH2-SiH(OEt)2、(HC=CH2)(EtO)3Si及BCHD之混合物所形成之膜中之一者以外所有的膜之介電常數(k量測值)均低於由Me2(EtO)Si-CH2-SiH(OEt)2及BCHD或(HC=CH2)(EtO)3Si及BCHD所獲得之膜的最佳介電常數。
應瞭解,熟習此項技術者可在如隨附申請專利範圍所表示之本發明之原理及範疇內對本文中已描述及說明以解釋本發明本質之詳情、材料、步驟及零件配置作出多種其他改變。因此,本發明並不意欲侷限於上文及/或隨附圖式中給出之實施例中的特定具體實例。
Claims (10)
- 一種於基板上形成SiCOH膜層之方法,該方法包含以下步驟:提供安置有至少一個基板之反應腔室;向該反應腔室中引入由Me2(OEt)Si-CH2-Si(OEt)2H與(EtO)2HSi-CH2-SiH(OEt)2組成之群之前驅體;向該反應腔室中引入乙烯基三乙氧基矽烷;及向該反應腔室中引入經取代或未經取代之雙環[2.2.1]庚-2,5-二烯;及使該前驅體、乙烯基三乙氧基矽烷、經取代或未經取代之雙環[2.2.1]庚-2,5-二烯及該基板接觸以使用沈積方法在該基板之至少一表面上形成SiCOH膜。
- 如申請專利範圍第1項之方法,其中該沈積方法為單頻率PECVD。
- 如申請專利範圍第1項之方法,其進一步包含使該SiCOH膜變得多孔之步驟。
- 如申請專利範圍第2項之方法,其進一步包含使該SiCOH膜變得多孔之步驟。
- 如申請專利範圍第1項之方法,其中該SiCOH膜具有低於以下兩者之介電常數:(1)由Me2(OEt)Si-CH2-Si(OEt)2H與(EtO)2HSi-CH2-SiH(OEt)2組成之群之前驅體及經取代或未經取代之雙環[2.2.1]庚-2,5-二烯形成之SiCOH膜的介電常數;及(2)由乙烯基三乙氧基矽烷及經取代或未經取代之雙環[2.2.1]庚-2,5-二烯形成 之SiCOH膜的介電常數。
- 如申請專利範圍第1項之方法,其中該沈積方法為化學氣相沈積。
- 一種膜,其係由如申請專利範圍第1項至第6項中任一項之方法形成。
- 如申請專利範圍第7項之膜,其中該膜具有在2.0至2.7範圍內的介電常數,及在4GPa至10GPa範圍內的楊氏模數(Young's Modulus)。
- 如申請專利範圍第8項之膜,其中該膜具有在2.0至2.5範圍內的介電常數。
- 如申請專利範圍第8項之膜,其中該膜具有在5GPa至10GPa範圍內的楊氏模數。
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EP2536867A4 (en) | 2013-07-10 |
TW201134976A (en) | 2011-10-16 |
SG183291A1 (en) | 2012-09-27 |
WO2011103282A2 (en) | 2011-08-25 |
EP2536867A2 (en) | 2012-12-26 |
CN102762763A (zh) | 2012-10-31 |
JP2013520030A (ja) | 2013-05-30 |
US20130042790A1 (en) | 2013-02-21 |
US8932674B2 (en) | 2015-01-13 |
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