TW201823257A - 用於緻密osg膜的橋接甲矽基之烷基化合物的用途 - Google Patents
用於緻密osg膜的橋接甲矽基之烷基化合物的用途 Download PDFInfo
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- TW201823257A TW201823257A TW106137662A TW106137662A TW201823257A TW 201823257 A TW201823257 A TW 201823257A TW 106137662 A TW106137662 A TW 106137662A TW 106137662 A TW106137662 A TW 106137662A TW 201823257 A TW201823257 A TW 201823257A
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- AZIOCGWAHZIFSU-UHFFFAOYSA-N 2-diethoxysilylpropan-2-yl(diethoxy)silane Chemical compound CC([SiH](OCC)OCC)([SiH](OCC)OCC)C AZIOCGWAHZIFSU-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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- JCIZYWSFVCTJDH-UHFFFAOYSA-N CC([Si](OCC)(OCC)C)([Si](OCC)(OCC)C)C Chemical compound CC([Si](OCC)(OCC)C)([Si](OCC)(OCC)C)C JCIZYWSFVCTJDH-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- WSTYNZDAOAEEKG-UHFFFAOYSA-N Mayol Natural products CC1=C(O)C(=O)C=C2C(CCC3(C4CC(C(CC4(CCC33C)C)=O)C)C)(C)C3=CC=C21 WSTYNZDAOAEEKG-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- HTLZVHNRZJPSMI-UHFFFAOYSA-N N-ethylpiperidine Chemical compound CCN1CCCCC1 HTLZVHNRZJPSMI-UHFFFAOYSA-N 0.000 description 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 1
- ODUCDPQEXGNKDN-UHFFFAOYSA-N Nitrogen oxide(NO) Natural products O=N ODUCDPQEXGNKDN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004200 TaSiN 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
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- CIBUDKJODXACBL-UHFFFAOYSA-N [SiH3][SiH2]Br Chemical class [SiH3][SiH2]Br CIBUDKJODXACBL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 1
- 239000006117 anti-reflective coating Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- FXMNVBZEWMANSQ-UHFFFAOYSA-N chloro(silyl)silane Chemical class [SiH3][SiH2]Cl FXMNVBZEWMANSQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 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
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 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
- 238000005137 deposition process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- GDTLMYWGMGSRSA-UHFFFAOYSA-N dimethoxy-methyl-(1-trimethoxysilylethyl)silane Chemical compound CO[Si](C([Si](C)(OC)OC)C)(OC)OC GDTLMYWGMGSRSA-UHFFFAOYSA-N 0.000 description 1
- WMILIGJGOAOXNJ-UHFFFAOYSA-N dimethoxymethyl(methyl)silane Chemical compound COC(OC)[SiH2]C WMILIGJGOAOXNJ-UHFFFAOYSA-N 0.000 description 1
- CNMKFNVCPOVSIU-UHFFFAOYSA-N dimethoxymethyl-[2-(dimethoxymethylsilyl)ethyl]silane Chemical compound COC(OC)[SiH2]CC[SiH2]C(OC)OC CNMKFNVCPOVSIU-UHFFFAOYSA-N 0.000 description 1
- WFPZPJSADLPSON-UHFFFAOYSA-N dinitrogen tetraoxide Chemical compound [O-][N+](=O)[N+]([O-])=O WFPZPJSADLPSON-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-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
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- XUGPYSXPMMKZGO-UHFFFAOYSA-N iodo(silyl)silane Chemical class [SiH3][SiH2]I XUGPYSXPMMKZGO-UHFFFAOYSA-N 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
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000001035 methylating effect Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000005244 neohexyl group Chemical group [H]C([H])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- LMEKMHPYJBYBEV-UHFFFAOYSA-N triethoxy(2-triethoxysilylpropan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)(C)[Si](OCC)(OCC)OCC LMEKMHPYJBYBEV-UHFFFAOYSA-N 0.000 description 1
- JCGDCINCKDQXDX-UHFFFAOYSA-N trimethoxy(2-trimethoxysilylethyl)silane Chemical compound CO[Si](OC)(OC)CC[Si](OC)(OC)OC JCGDCINCKDQXDX-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000001039 wet etching Methods 0.000 description 1
- 238000010626 work up procedure 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
- H01L21/02107—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
-
- 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
- C23C16/308—Oxynitrides
-
- 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
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
-
- 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
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
-
- 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
- C23C16/448—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
-
- 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
- C23C16/46—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 characterised by the method used for heating the substrate
-
- 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
- C23C16/48—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 by irradiation, e.g. photolysis, radiolysis, particle radiation
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Abstract
一種低介電材料及包含其之膜,當其使用在積體電路中作為夾層(interlevel)介電質時,已經辨認出能改良性能;和其製造方法。
Description
本申請案在35 U.S.C.§119(e)下主張2016年11月2日提出的美國臨時專利申請案案號62/416,302之優先權,其全文以參考之方式併入本文。
本發明係關於一種用於緻密OSG膜的橋接甲矽基之烷基化合物的用途。
本發明廣泛關於一種介電膜之形成。更特別是,本發明係關於一種介電材料及包含其而具有低介電常數與提高的機械性質之膜;及其製造方法。
於本文中所引用之包括公告、專利申請案及專利的全部參考資料藉此以參考方式併入本文,至如若每篇參考資料各別及特別指示出以參考方式併入本文及其全文係於本文中提出般相同的程度。
微電子工業持續想要在諸如記憶體及邏輯晶片的多層積體電路元件中增加電路密度,以改良操作速度及減低電力消耗。為了持續減少在積體電路上的元件尺寸,防止於不同金屬化程度間之電容性串音的需求漸漸變重要。這些需求可由表示詞”RC”概述,其中”R”係導線的電阻及”C”係絕緣的層間介電質之電容。電容”C”係與線間隔呈反比及與層間介電質(ILD)的介電常數(k)呈正比。此低介電材料係想要例如使用作為金屬沈積前(premetal)介電層或夾層介電層。
已經使用一些方法來製備低介電常數膜。典型會使用化學氣相沈積(CVD)及旋壓介電質(SOD)方法來製備絕緣層的薄膜。亦已知有其它混雜方法,諸如液體聚合物前驅物之CVD及運送聚合(transport polymerization)CVD。一般會將藉由這些技術沈積之廣泛多種低k材料分類成數種種類,諸如純無機材料、陶瓷材料、二氧化矽基底的材料、純有機材料或無機-有機雜合物。同樣地,已經使用多種方法來硬化這些材料,諸如例如,以電漿、電子束或UV輻射來加熱、處理該材料以分解及/或移除揮發性組分及實質上交聯該膜。
工業上已試圖藉由在矽酸鹽晶格中併入有機物或其它材料來製造出具有較低介電常數之二氧化矽基底的材料。未摻雜的二氧化矽玻璃(SiO2)於本文中指為”USG”,其具有介電常數大約4.0。但是,可藉由將諸如氟或甲基之終端基團併入矽酸鹽晶格中將二氧化矽玻璃的介電常數值降低至2.7至3.5之範圍。典型使用類似於形成USG膜的那些製程步驟將這些材料沈積成緻密膜及整合在IC元件內。
已知二氧化矽(SiO2)膜具有硬度~7GPa,而且亦具有介電常數(k)3.8-4.2。材料的介電常數(k)降低通常無法沒有隨後的材料機械性質,即,彈性模數(Young’s模數)、硬度、韌度降低。隨後的加工步驟需要機械強度,諸如蝕刻、CMP(”化學機械平坦化”)及沈積額外層,諸如用於銅、銅金屬(”Cu”)的擴散障壁及在產物上的覆蓋層。為了挺過CMP,機械完整性或硬性、擠壓及剪切強度可特別重要。已發現挺過CMP的能力可與材料之彈性模數和其它因素一起相互相關,包括研磨參數,諸如向下力量及平台速度。參見,例如,Wang等人,”Advanced processing:CMP of CU/low-.kappa.and Cu/ultralow-k layers”,Solid State Technology,September,2001;Lin等人,”Low-k Dielectrics Characterization for Damascene Integration”,International Interconnect Technology Conference,Burlingame,Calif.,June,2001。這些機械性質亦在最後產物之封裝時重要。因為權衡機械性質,使用某些多孔低介電質組成物會不切實際。
改良如所沈積的矽酸鹽膜之機械性質的方法已知。例如,美國專利案號7,932,188揭示出一種在多孔OSG上進行UV退火的步驟,其中該膜於曝光後在其硬度及彈性模數上具有至少10%改良。雖然已知可沈積出具有介電常數在2.8至3.1之範圍內的OSG膜,尚無法沈積出甚至在UV退火後具有硬度接近4.0GPa之這些膜。此外,在技藝中,對能形成具有介電常數2.8至3.1且具有如以千兆巴斯卡(GPa)測量硬度增加之緻密OSG膜的OSG前驅物化合物種類有所需求。
於本文中所描述的組成物或調配物及使用其之方法係藉由在至少一部分的基材表面上沈積一提供想要的膜性質之含矽膜來克服先述技藝的問題。
在一個態樣中,本開發提供一種用以將有機矽酸鹽膜沈積在至少一部分的基材上之方法,該方法其步驟包括:將一基材提供在真空艙中;將一包含至少一種選自於由式(I)及式(II)所組成之群的有機矽前驅物之含矽氣體前驅物組成物引進該真空艙中:
其中R1、R2、R3、R4、R5及R6各者各自獨立地選自於由-CH3及-OR8所組成之群,其中R8係C1-C4烷基,R7係H或-CH3,x係1或2,及n係1、2、3或4,其中當n係1時,至少一個R7係-CH3;及在該真空艙中,對該氣體結構形成組成物施加能量以引發該至少一種有機矽前驅物反應而在該基材之至少一部分上沈積一膜。
於此之後,本發明將與附加的圖形連起來進行描述,其中類似的數字被用於標示類似的元件:圖1係一曲線圖,其闡明藉由以Si-CxHy-Si橋取代來改變 Si-O-Si橋的分量之多種前驅物的分子動力學模擬及在機械性質上的衝擊。
在描述本發明的上下文中(特別是,在下列申請專利範圍的上下文中),用語”一”及”一種”及”該”及類似指示對象之使用欲解釋為涵蓋單數及複數二者,除非其它方面於本文中有指示出或上下文有清楚地矛盾。除非其它方面有提到,否則用語”包含”、”具有”及”包括”欲解釋為開放式用語(即,意謂著”包括但不限於”)。於本文中所列舉的值範圍全然意欲提供作為各別指出每個分別值係落在該範圍內的速記方法,除非其它方面於本文中有指示出,及每個分別值係如若其各別於本文中敘述般併入專利說明書中。於本文中所描述的全部方法可以任何合適的順序進行,除非其它方面於本文中有指示出或其它方面於上下文中有清楚地矛盾。於本文中所提供的任何及全部實施例或範例性文字(例如,”諸如”)之使用僅意欲較好地闡釋本發明而不在本發明之範圍上引起限制,除非其它方面有所主張。在專利說明書中的文字不應該解釋為指示出任何未主張的元件作為實行本發明之基本。
於本文中描述出本發明的較佳具體實例,包括由發明家已知用以進行本發明的最好模式。一般熟知此技藝之人士可在讀取前述說明後明瞭那些較佳具體實例的變化。本發明家預計熟練人士能如適當地使用此變化,及發明家意欲與如本文特別描述者不同般實施本發明。此外,本發明包括 在附加至此如由合適的法律准許之申請專利範圍中所敘述的主題之全部改質及同等物。再者,本發明包括上述元素其全部可能的變化之任何組合,除非其它方面於本文中有指示出或其它方面於上下文中有清楚地矛盾。
在申請專利範圍中,可使用字母來辨認所主張的製程步驟(例如,a、b及c)。這些字母係使用來輔助指出該等製程步驟及不意欲指示出所主張的步驟之進行順序,除非及僅有至此順序係在申請專利範圍中有特別敘述的程度。
在一個態樣中,本開發提供一種用以在至少一部分的基材上沈積一有機矽酸鹽膜之方法,該方法其步驟包括:將一基材提供在真空艙中;將一包含至少一種選自於由式(I)及式(II)所組成之群的有機矽前驅物之含矽氣體組成物引進該真空艙中:
其中R1、R2、R3、R4、R5及R6各者各自獨立地選自於由-CH3及-OR8所組成之群,其中R8係C1-C4烷基,R7係H或-CH3,x係1或2,及n係1、2、3或4,其中當n係1時,至少一個R7係-CH3;及在該真空艙中,對該氣體結構形成組成物施加能量以引發該至少一種有機矽前驅物反應以在該基材之至少一部分上沈積一膜。
使用分子模擬來評估橋接碳(Si-CxHy-Si)在緻密 氧化矽之機械性質上的預計衝擊。為了評估以Si-CxHy-Si橋取代不同分量的Si-O-Si橋之衝擊,以橋接碳隨機置換O原子進行類似的分子動力學模擬。圖1顯示出對這些MD模擬來說,與Si-CH2-Si橋及所研究的其它Si-CxHy-Si橋比較,Si-CH(CH3)-Si及Si-C(CH3)2-Si橋之總體模數明顯增加。值得注意的是,Si-C(CH3)2-Si橋顯示出最高的總體模數增加,如為相對於Si-CH2-Si橋之O置換分量的函數。再者,亦模擬Si-O-Si鍵斷裂以形成終端甲基(Si-CH3CH3-Si),及這些取代顯示出在機械強度上的降低最強,如為Si-O-Si橋置換分量增加之函數。
不想要由任何特別的理論界限,從此模型咸信將甲基加入至連接二個矽原子的碳鏈將移除橋接碳的移動自由度,因為該橋將無法自由地轉動或容易地搖晃。已假定此自由度移除會適當地”鎖住”橋及增加機械性質。
藉由本發明之方法沈積的有機矽酸鹽膜係選自於由摻雜碳的氧化矽膜所組成之群。該組成物可係預混合的組成物、預混合物(在使用於沈積方法前混合)或就地混合物(在沈積方法期間混合)。因此,在此揭示中,用語”混合物”、”調配物”及”組成物”可互換。
在本開發的方法中,典型來說,第一步驟為將一包含至少一種表面特徵的基材放進溫度約-20℃至約600℃之反應器中。合適的基材包括但不限於半導體材料,諸如砷化鎵(”GaAs”)、氮化硼(”BN”);矽及包含矽組成物,諸如結晶矽、多晶矽、非晶矽、磊晶矽、二氧化矽(”SiO2”)、碳化矽(”SiC”)、氧碳化矽(”SiOC”)、氮化矽(”SiN”)、碳氮化矽(”SiCN”)、有機 矽酸鹽玻璃(”OSG”)、有機氟矽酸鹽玻璃(”OFSG”)、氟矽酸鹽玻璃(”FSG”)及其它適當的基材或其混合物。該基材可進一步包含多種層且對其施加該膜,其中該層有諸如例如抗反射塗層、光阻、有機聚合物、多孔有機及無機材料;金屬,諸如銅、鈷、釕、鎢、銠及鋁;或擴散障蔽層,例如,TiN、Ti、Ti(C)N、TaN、Ta(C)N、Ta、W、WN、TiSiN、TaSiN、SiCN、TiSiCN、TaSiCN或W(C)N。該基材可係單晶矽晶圓、碳化矽晶圓、氧化鋁(藍寶石)晶圓、玻璃薄片、金屬箔、有機聚合物膜;或可係聚合物、玻璃、矽或金屬的3維物件。該基材可塗佈有多種在技藝中熟知的材料,包括氧化矽、氮化矽、非晶相碳、氧碳化矽、氧氮化矽、碳化矽、砷化鎵、氮化鎵膜及其類似膜。這些塗層可完全被覆該基材、可呈多種材料的多重層及可經部分蝕刻以曝露出下面材料層。該表面亦可在其上面具有一已經進行圖案曝光及顯影而部分被覆該基材的光阻材料。
合適於本文所揭示的方法之沈積方法的實施例包括但不限於熱化學氣相沈積(CVD)、電漿輔助CVD(PECVD)、原子層沈積(ALD)或電漿輔助循環CVD(PECCVD)方法。在一個具體實例中,該膜係使用電漿基底(例如,遠程產生或就地)的CVD方法進行沈積。如於本文中所使用,用語”反應器”包括但不限於反應艙或沈積艙。
在某些具體實例中,該基材可曝露至一或多種前沈積處理,諸如但不限於電漿處理、熱處理、化學處理、紫外光曝光、電子束曝光、及其組合,以影響該膜的一或多種 性質。這些前沈積處理可在選自於惰性、氧化及/或還原之環境下進行。
雖然於本文中所使用的化學試劑有時可描述為”氣體”,要了解的是,該化學試劑可以氣體直接傳遞至反應器、以來自蒸發的液體或使用諸如氮、氦或氬之載劑氣體吹泡的液體蒸氣、來自昇華的固體及/或由惰性載劑氣體運送之蒸氣傳遞進反應器中。
在較佳的具體實例中,藉由本方法沈積之有機矽酸鹽膜係具有介電常數約2.8至約3.1之緻密有機矽酸鹽玻璃(OSG)膜,其具有硬度約3.2至約4.5千兆巴斯卡(GPa),如使用MTS Nano Indenter測量。此介電常數明顯降低而超過典型具有介電常數約3.8至約4.2與硬度約7GPa的二氧化矽膜。
本開發之方法包括將一包含至少一種選自於由式(I)及式(II)所組成之群的有機矽前驅物之氣體結構形成組成物引進該真空艙中的步驟:
其中R1、R2、R3、R4、R5及R6各者各自獨立地選自於由-CH3及-OR8所組成之群,其中R8係C1-C4烷基,R7係H或-CH3,x係1或2,及n係1、2、3或4,其中當n係1時,至少一個R7係-CH3;及在該真空艙中,對該氣體結構形成組成物施加能量以引發該至少一種有機矽前驅物反應以在該基材的至少一部分上沈 積一膜。
在上述式及遍及該說明中,用語”烷基”指示為具有1至10、3至10或1至6個碳原子的線性或分枝官能基。範例性線性烷基包括但不限於甲基、乙基、丙基、丁基、戊基及己基。範例性分枝烷基包括但不限於異丙基、異丁基、二級丁基、三級丁基、異戊基、三級戊基、環戊基、異己基、環己基及新己基。在某些具體實例中,該烷基可具有一或多個經取代的官能基接附於此,諸如但不限於烷氧基、二烷基胺基或其組合。在其它具體實例中,該烷基不具有一或多個官能基接附於此。該烷基可係飽和,或任擇地,不飽和。如於本文中所使用,用語”經取代”指為一或多個原子或原子基團進行取代置換例如氫原子。
在某些具體實例中,於上述式中的任何一或多個取代基R1、R2、R3、R4、R5及R6當其非為氫時,可與在上述式中之C-C鍵連結以形成一環結構。如熟練人士將了解,該取代基可選自於線性或分枝的C1至C10伸烷基部分;C2至C12伸烯基部分;C2至C12伸炔基部分;C4至C10環烷基部分;及C6至C10伸芳基部分。在這些具體實例中,該環結構可不飽和,諸如例如,環烷基環;或飽和,例如,芳基環。再者,在這些具體實例中,該環結構亦可經取代或未經取代。在其它具體實例中,該取代基R1、R2、R3、R4、R5及R6的任何一或多個未進行連結。
式I之化合物的實施例包括:1,1,1,3,3-五甲氧基-2-甲基-1,3-二矽丁烷(PMOM-DSB)
1,2-雙(甲基二甲氧基甲矽基)乙烷、1,2-雙(三甲氧基甲矽基)乙烷、1,2-雙(二甲氧基甲矽基)乙烷、1,1-雙(三甲氧基甲矽基)乙烷、1,1-雙(甲基二甲氧基甲矽基)乙烷、1,1-雙(二甲氧基甲矽基)乙烷、二甲基雙(三甲氧基甲矽基)甲烷、二甲基雙(甲基二甲氧基甲矽基)甲烷、二甲基雙(二甲氧基甲矽基)甲烷、1,1,1,3,3-五乙氧基-2-甲基-1,3-二矽丁烷、1,2-雙(甲基二乙氧基甲矽基)乙烷、1,2-雙(三乙氧基甲矽基)乙烷、1,2-雙(二乙氧基甲矽基)乙烷、1,1-雙(三乙氧基甲矽基)乙烷、1,1-雙(甲基二乙氧基甲矽基)乙烷、1,1-雙(二乙氧基甲矽基)乙烷、二甲基雙(三乙氧基甲矽基)甲烷、二甲基雙(甲基二乙氧基甲矽基)甲烷及二甲基雙(二乙氧基甲矽基)甲烷。
式2之化合物的實施例包括;1,1,3,3-四甲氧基-1,3-二矽環丁烷、1,3-二甲氧基-1,3-二甲基-1,3-二矽環丁烷、1,3-二甲氧基-1,3-二矽環丁烷、1,3,3-三甲氧基-1-甲基-1,3-二矽環丁烷、1,3-二甲氧基-1-甲基-二矽環丁烷、1,1-二甲氧基-1,3-二矽環丁烷、1,1,4,4-四甲氧基-1,4-二矽環己烷、1,4-二甲氧基-1,4-二甲基-1,4-二矽環己烷、1,4-二甲氧基-1,4-二矽環己烷、1,4,4-三甲氧基-1-甲基-1,4-二矽環己烷、1,4-二甲氧基-1-甲基-二矽環己烷、1,1-二甲氧基-1,4-二矽環己烷、1,1,3,3-四乙氧基-1,3-二矽環丁烷、1,3-二乙氧基-1,3-二甲基-1,3-二矽 環丁烷、1,3-二乙氧基-1,3-二矽環丁烷、1,3,3-三乙氧基-1-甲基-1,3-二矽環丁烷、1,3-二乙氧基-1-甲基-二矽環丁烷、1,1-二乙氧基-1,3-二矽環丁烷、1,1,4,4-四乙氧基-1,4-二矽環己烷、1,4-二乙氧基-1,4-二甲基-1,4-二矽環己烷、1,4-二乙氧基-1,4-二矽環己烷、1,4,4-三乙氧基-1-甲基-1,4-二矽環己烷、1,4-二乙氧基-1-甲基-二矽環己烷及1,1-二乙氧基-1,4-二矽環己烷。
在某些具體實例中,組合著使用不同有機矽前驅物之混合物。
可以多種方式將本文所描述的有機矽前驅物化合物傳遞至反應艙,諸如CVD或ALD反應器。在一個具體實例中,可使用液體傳遞系統。在任擇的具體實例中,可使用一結合液體傳遞及閃蒸方法的單元,諸如例如,由MSP Corporation of Shoreview,MN製造的渦輪蒸發器,以便能夠容積地傳遞低揮發性材料,此導致可再生性運送及沈積而沒有前驅物熱分解。在液體傳遞調配物中,於本文中所描述的前驅物可以純淨液體形式傳遞,或任擇地,可以包含其之溶劑調配物或組成物使用。因此,在某些具體實例中,該前驅物調配物可包括溶劑組分,其具有如可於所提供的末端使用應用中想要及優良以在基材上形成膜之合適特徵。
該有機矽前驅物化合物較佳為實質上無鹵化物離子,諸如氯化物;或金屬離子,諸如Al。如於本文中所使用,當與鹵化物離子(或鹵化物),諸如例如,氯化物及氟化物、溴化物、碘化物;Al3+離子、Fe2+、Fe3+、Ni2+、Cr3+相關時, 用語”實質上無”意謂著少於5ppm(以重量計),較佳為少於3ppm,及更佳為少於1ppm,及最佳為0ppm。如於本文中所使用,當與此等鹵化物離子相關時,用語”無”意謂著0ppm。已知氯化物或金屬離子作用為矽前驅物的分解觸媒。在最後產物中,明顯的氯化物程度可造成有機矽前驅物降解。有機矽前驅物逐步降解可直接衝擊該膜沈積方法,使得半導體製造商難以滿足膜規格。此外,較高的有機矽前驅物降解速率會負面衝擊閑置壽命或穩定性,因此難以保證1-2年的閑置壽命。再者,已知有機矽前驅物會在分解後形成易燃及/或發火性氣體,諸如氫及矽烷。因此,該有機矽前驅物之加速分解存在有與這些易燃及/或發火性氣體副產物之形成相關的安全性及性能關心。
可藉由下列方式達成根據本發明之實質上無鹵化物的有機矽前驅物:(1)減少或消除在化學合成期間的氯化物來源;及/或(2)執行有效的純化方法從粗產物移除氯化物,使得最後經純化的產物實質上無氯化物。該氯化物來源可藉由在合成期間使用不包括諸如氯二矽烷類、溴二矽烷類或碘二矽烷類的鹵化物試劑,因此避免產生包括鹵化物離子之副產物而減少。此外,前述提及的試劑應該實質上無氯化物雜質,使得所產生的粗產物實質上無氯化物雜質。以類似的方式,該合成應該不使用鹵化物基底的溶劑、觸媒或包括無法接受的高程度鹵化物污染物之溶劑。該粗產物亦可藉由多種純化方法進行處理以提供最後產物實質上無鹵化物,諸如氯化物。此等方法在先述技藝中有充分描述,及可包括但不限 於純化方法,諸如蒸餾或吸附。通常使用蒸餾,利用沸點差異來分離雜質與想要的產物。亦可使用吸附,利用該等組分的不同吸附性質實現分離,使得最後產物實質上無鹵化物。可使用吸附劑來移除諸如氯化物之鹵化物,諸如例如,可商業購得的MgO-Al2O3摻合物。
對與包含溶劑及至少一種於本文中所描述的有機矽前驅物化合物之組成物相關的那些具體實例來說,所選擇的溶劑或其混合物不會與該有機矽化合物反應。在該組成物中,該溶劑之量範圍以重量百分比計係0.5重量%至99.5%或10重量%至75%。在此或其它具體實例中,該溶劑具有沸點(b.p.)類似於式I及II之前驅物的b.p.,或在該溶劑的b.p.與式I及II之有機矽前驅物的b.p.間之差異係40℃或較少,30℃或較少,或20℃或較少,10℃或較少,或5℃或較少。任擇地,在沸點間的差異範圍係下列終點之任何一或多個:0、10、20、30或40℃。合適的b.p.差異範圍之實施例包括但不限於0℃至40℃,20℃至30℃,或10℃至30℃。在該組成物中,合適的溶劑實施例包括但不限於醚(諸如1,4-二氧六圜、二丁基醚)、三級胺(諸如吡啶、1-甲基哌啶、1-乙基哌啶、N,N’-二甲基哌ㄋ、N,N,N’,N’-四甲基乙二胺)、腈(諸如苯甲腈)、烷基烴(諸如辛烷、壬烷、十二烷、乙基環己烷)、芳香烴(諸如甲苯、均三甲苯)、三級胺基醚(諸如雙(2-二甲基胺基乙基)醚)或其混合物。
在一個特別的具體實例中,該引進步驟係將該至少一種有機矽前驅物化合物引進反應器中,此係在範圍-20℃ 至1000℃,或約400℃至約1000℃,或約400℃至約600℃,或約-20℃至約400℃之一或多種溫度下進行。在這些或其它具體實例中,該基材包括一包含表面特徵的半導體基材。
可選擇性加入氧化劑,諸如氧(O2)、臭氧(O3)、一氧化二氮(N2O)、氧化氮(NO)、二氧化氮(NO2)、四氧化二氮(N2O4)及/或過氧化氫(H2O2),但是若該有機矽前驅物包括氧及SiO鍵時,此可不需要。
可在該反應或後處理中使用一或多種氟提供氣體作為添加劑。該氟提供氣體之實施例有NF3、F2、CF4、C2F6、C4F6及C6F6。
除了該有機矽前驅物及選擇性氧提供氣體及氟提供氣體外,可在沈積反應前、期間及/或後將額外的材料充入真空艙中。此等材料包括反應性物質,諸如氣體或液體有機物質、NH3、H2、CO2、CO或碳氟化合物。該有機物質的實施例有CH4、C2H6、C2H4、C2H2、C3H8、環戊烷、環辛烷、丙二烯、丙烯、α-萜品烯、對-傘花烴、苯、萘、甲苯及苯乙烯。
可分別地從不同來源或如為混合物將該等試劑(即,有機矽前驅物、氧化劑等等)帶進反應器中。該等試劑可藉由任何數目的設備傳遞至該反應器系統,較佳為使用安裝有適合的閥及配件之可加壓不銹鋼容器以允許將液體傳遞至該製程反應器。
在某些具體實例中,組合著使用不同有機矽前驅物之混合物,諸如例如,至少一種式I及至少一種式II。
對該氣體試劑施加能量以引發氣體反應及在該 基材的至少一部分上形成膜。此能量可藉由例如熱、電漿、脈衝電漿、螺旋電漿、高密度電漿、誘導耦合電漿及遠程電漿方法提供。可使用二次RF頻率來源修改在基材表面處的電漿特徵。較佳的是,該膜係藉由電漿輔助化學氣相沈積形成。特別佳的是,在頻率13.56MHz下產生電容性耦合電漿。以該基材的表面積為基準,電漿功率較佳為0.02至7瓦/平方公分,更佳為0.3至3瓦/平方公分。可優良地使用擁有低離子化能量之載劑氣體以降低在電漿中的電子溫度,此依次將在OSG前驅物及多孔質(porogen)中造成較少碎片。此型式的低離子化氣體之實施例包括CO2、NH3、CO、CH4、Ar、Xe及Kr。
在該能量係電漿能量的某些具體實例中,該電漿來源係選自於由碳來源電漿所組成之群,包括但不限於:烴電漿、包含烴及氦的電漿、包含烴及氬的電漿、二氧化碳電漿、一氧化碳電漿、包含烴及氫的電漿、包含烴及氮來源的電漿、包含烴及氧來源的電漿及其混合物。
每種氣體試劑的流速範圍較佳為每單片200毫米晶圓10至5000sccm,更佳為30至1000sccm。選擇各別的速率,以便在該膜中提供想要的結構形成劑及孔洞形成劑之量。所需要的實際流速可依晶圓尺寸及艙組態而定,及決不限於200毫米晶圓或單片晶圓艙。
在某些具體實例中,該膜係以50-250奈米/分鐘之速率進行沈積。
在沈積期間,於真空艙中的壓力較佳為0.01至600托耳,更佳為1至15托耳。
該膜的較佳沈積厚度為0.002至10微米,然而可如需要般改變厚度。沈積在未圖形化表面上之毯覆膜具有優良的均勻度,其遍及該基材於1個標準偏差內與合理的邊緣排除之厚度變化係少於2%,其中例如在均勻度的統計計算時不包括基材之最外邊5毫米邊緣。
不意欲由任何特別的理論界限,已認為可能使用諸如具有亞甲基或/伸乙基橋之式I及式II那些二矽氧烷前驅物,以碳橋置換橋接Si-O-Si基團將可降低純SiO2網狀物之介電常數,同時保留硬度。
可使用就地或沈積後處理來提高材料性質,如硬度、穩定性(對收縮、對空氣曝露、對蝕刻、對溼式蝕刻等等)、完整性、均勻度及黏附力。可在使用與使用於多孔質移除相同或不同的方法來移除多孔質前、期間及/或後,將此等處理施加至該膜。因此,如於本文中所使用,用語”後處理”指示為以能量(例如,熱、電漿、光子、電子、微波等等)或化學物質處理該膜,以移除多孔質及選擇性提高材料性質。
後處理之進行條件可大大地變化。例如,可在高壓下或在真空環境下進行後處理。
於下列條件下進行熱退火。該環境可係惰性(例如,氮、CO2、鈍氣(He、Ar、Ne、Kr、Xe)等等)、氧化(例如,氧、空氣、稀氧環境、富氧環境、臭氧、一氧化二氮等等)或還原(稀或濃氫、烴(飽和、不飽和、線性或分枝、芳香烴)等等)。壓力較佳為約1托耳至約1000托耳,更佳為大氣壓。但是,亦可對熱退火和任何其它後處理方法使用真空環境。溫度較 佳為200-500℃,及溫度傾斜速率係0.1至100℃/分鐘。總退火時間較佳為0.01分鐘至12小時。
亦可經由使用氟化(HF、SiF4、NF3、F2、COF2、CO2F2等等)、氧化(H2O2、O3等等)、化學乾燥、甲基化或提高最後材料的性質之其它化學處理來進行該OSG膜的化學處理。在此處理中所使用的化學物質可呈固體、液體、氣體及/或超臨界流體狀態。
在某些具體實例中,讓該OSG膜接受退火,較佳為藉由加熱或輻射(即,光退火)。在這些具體實例中,於下列條件下進行光退火。該環境可係惰性(例如,氮、CO2、鈍氣(He、Ar、Ne、Kr、Xe)等等)、氧化(例如,氧、空氣、稀氧環境、富氧環境、臭氧、一氧化二氮等等)或還原(例如,稀或濃烴、氫、氨等等)。功率範圍可係0至5000瓦。波長較佳為IR、可見光、UV或深UV(波長<200奈米)。溫度範圍可係週圍至500℃。壓力範圍可係10毫托耳至大氣壓。總硬化時間範圍可係0.01分鐘至12小時。
在下列條件下進行用於OSG膜之化學改質的電漿處理。該環境可係惰性(氮、CO2、鈍氣(He、Ar、Ne、Kr、Xe)等等)、氧化(例如,氧、空氣、稀氧環境、富氧環境、臭氧、一氧化二氮等等)或還原(例如,稀或濃氫、烴(飽和、不飽和、線性或分枝、芳香烴)、氨等等)。電漿功率較佳為0-5000瓦。溫度較佳為週圍至500℃。壓力較佳為10毫托耳至大氣壓。總硬化時間較佳為0.01分鐘至12小時。
在下列條件下進行後微波。該環境可係惰性(例 如,氮、CO2、鈍氣(He、Ar、Ne、Kr、Xe)等等)、氧化(例如,氧、空氣、稀氧環境、富氧環境、臭氧、一氧化二氮等等)或還原(例如,稀或濃烴、氫等等)。溫度較佳為週圍至500℃。可對特定鍵結改變及調整功率及波長。總硬化時間較佳為0.01分鐘至12小時。
在下列條件下進行後電子束。該環境可係真空、惰性(例如,氮、CO2、鈍氣(He、Ar、Ne、Kr、Xe)等等)、氧化(例如,氧、空氣、稀氧環境、富氧環境、臭氧、一氧化二氮等等)或還原(例如,稀或濃烴、氫等等)。溫度較佳為週圍至500℃。可對特定鍵結改變及調整電子密度及能量。總硬化時間較佳為0.001分鐘至12小時,及可係連續或脈衝。可在下列公告中獲得與一般電子束之使用有關的額外指導,諸如:S.Chattopadhyay等人,Journal of Materials Science,36(2001)4323-4330;G.Kloster等人,Proceedings of IITC,June 3-5,2002,SF,CA;及美國專利案號6,207,555 B1、6,204,201 B1及6,132,814 A1。使用電子束處理可提供用於多孔質移除及透過在基質中的鍵結形成過程來提高膜機械性質。
將伴隨著參照下列實施例更詳細地闡明本發明,但是應瞭解的是,本發明不視作限制於此。
從OSG前驅物沈積緻密OSG-一般程序
經由電漿輔助CVD方法,使用Applied Materials Precision-5000系統,在安裝有Advance Energy 200 RF產生器 之200毫米DxZ真空艙中,從多種不同化學前驅物及製程條件形成範例性膜。該CVD方法通常包括下列基本步驟:初始建立及穩定氣體流、沈積及在晶圓移出前清洗/排空艙。使用具有寬帶UV電子管的Fusion UV系統進行UV退火,且將晶圓保持在<10托耳壓力之氦氣流及溫度<400℃下。
在SCI Filmtek 2000反射計上測量厚度及折射率。使用Hg探針技術,在中電阻率p-型晶圓(範圍8-12歐姆-公分)上決定介電常數。使用Nicholet Nexxus 470 FTIR光譜儀測量FTIR光譜。使用MTS Nano Indenter決定機械性質。藉由X射線光電子光譜(XPS),在Physical Electronics 5000LS上獲得組成物資料。在表中報導的原子%值不包括氫。
比較例1:從BDMMSM沈積緻密OSG膜
使用下列製作法沈積OSG膜:經由DLI,以1000毫克/分鐘將1,2-雙(二甲氧基甲基甲矽基)甲烷傳遞至該艙;200sccm He載劑氣體流,20sccm O2流,350毫英吋蓮蓬頭/晶圓間隔,350℃晶圓夾盤溫度,7托耳艙壓,對其施加800瓦電漿。然後,UV退火所產生的緻密OSG膜4分鐘以提高該膜的機械強度。所產生的膜具有下列性質:介電常數在1MHz下係3.09,模數23.6GPa,硬度3.93GPa,在632奈米處之折射率係1.476,如藉由XPS測量之元素組成物係23.0%C,43.7%O,33.3%Si。
實施例1:從PMOM-DSP沈積緻密OSG膜
使用下列製作法沈積OSG膜:經由DLI,以1200毫克/分鐘將1,1,1,3,3-五甲氧基-2-甲基-1,3-二矽丁烷(PMOM-DSB)傳遞至該艙;200sccm He載劑氣體流,20sccm O2流,350毫英吋蓮蓬頭/晶圓間隔,400℃晶圓夾盤溫度,7托耳艙壓,對其施加600瓦電漿。然後,UV退火所產生的緻密OSG膜4分鐘以提高該膜的機械強度。所產生的膜具有下列性質:介電常數在1MHz下係3.23,模數24.9GPa,硬度4.13GPa,折射率在632奈米處係1.451,如藉由XPS測量之元素組成物係17.6%C,48.4%O,34.2%Si。
實施例2:從1,2-雙(甲基二甲氧基甲矽基)乙烷(BDMMSE)沈積緻密OSG膜
使用下列製作法沈積OSG膜:經由DLI,以800毫克/分鐘將1,2-雙(二甲氧基甲基甲矽基)乙烷(BDMMSE)傳遞至該艙;200sccm He載劑氣體流,100sccm O2流,350毫英吋蓮蓬頭/晶圓間隔,325℃晶圓夾盤溫度,7托耳艙壓,對其施加600瓦電漿。然後,UV退火所產生的緻密OSG膜4分鐘以提高該膜的機械強度。所產生的膜具有下列性質:介電常數在1MHz下係3.15,模數27.7GPa,硬度4.62GPa,折射率在632奈米處係1.430。
使用分子模擬來評估於緻密氧化矽中的橋接碳(Si-CxHy-Si)在機械性質上的預計衝擊。在Biovia Materials Studio 7.0軟體中,使用Forcite模組,以週期邊界條件進行標準分子動力學(MD)模擬。使用COMPASS力場,從實驗用a-石 英X射線結晶結構(cr-SiO2)創建包含306 Si原子及612 O原子的週期單位晶胞。從此結晶結構移除鍵結,然後在一系列的固定溫度、壓力及原子數目之MD模擬下,使用NPT整體退火該系統,以產生非晶相SiO2基質(a-SiO2)。對該a-SiO2基質加回鍵結及使用MD模擬來計算平衡的密度。然後,使用MD模擬,以不同等向性壓力壓縮該經平衡的a-SiO2單位晶胞。使用三階Brich-Murnaghan狀態方程式及MD模擬的體積結果,以壓力之函數對該a-SiO2基質回歸該總體模數。
為了評估以Si-CxHy-Si橋取代不同分量的Si-O-Si橋之衝擊,以橋接碳隨機置換O原子進行類似的MD模擬。圖1顯示出對這些MD模擬來說,與所研究的Si-CH2-Si橋及其它Si-CxHy-Si橋比較,Si-CH(CH3)-Si及Si-C(CH3)2-Si橋之總體模數明顯增加。值得注意的是,Si-C(CH3)2-Si橋顯示出最高的總體模數增加,如為相對於Si-CH2-Si橋之O置換分量的函數。再者,亦模擬Si-O-Si鍵斷裂以形成終端甲基(Si-CH3CH3-Si),及這些取代顯示出機械強度的降低最強,如為Si-O-Si橋置換分量增加之函數。
雖然上述已經與較佳具體實例連接描述出本發明之原理,要清楚了解的是,此描述僅係以實施例說明及不作為本發明的範圍之限制。
Claims (28)
- 一種用以將有機矽酸鹽膜沈積在至少一部分的基材上之化學氣相沈積方法,該方法其步驟包括:將一基材提供在真空艙中;將一包含至少一種選自於由式(I)及式(II)所組成之群的有機矽前驅物之氣體結構形成組成物引進該真空艙中:
- 如請求項1之化學氣相沈積方法,其中該膜具有介電常數在2.8至3.5間。
- 如請求項1之化學氣相沈積方法,其中該能量係電漿能 量。
- 如請求項1之化學氣相沈積方法,更包含一讓該膜接受一包含UV輻射的後處理步驟。
- 如請求項4之化學氣相沈積方法,其中該膜具有介電常數在2.8至3.5間。
- 如請求項1之化學氣相沈積方法,更包含一讓該膜接受一包含加熱的後處理步驟。
- 如請求項4之化學氣相沈積方法,其中在高溫下進行該UV處理,較佳為200-500℃。
- 如請求項4之化學氣相沈積方法,其中在反應性環境中進行該UV處理,諸如於O 2、H 2或NH 3存在下。
- 如請求項1之化學氣相沈積方法,其中該至少一種有機矽前驅物係式I的前驅物。
- 如請求項9之化學氣相沈積方法,其中該至少一種有機矽前驅物係至少一種選自於由下列所組成之群的前驅物:1,1,1,3,3-五甲氧基-2-甲基-1,3-二矽丁烷(PMOM-DSB)、1,2-雙(甲基二甲氧基甲矽基)乙烷、1,2-雙(三甲氧基甲矽基)乙烷、1,2-雙(二甲氧基甲矽基)乙烷、1,1-雙(三甲氧基甲矽基)乙烷、1,1-雙(甲基二甲氧基甲矽基)乙烷、1,1-雙(二甲氧基甲矽基)乙烷、1,1-二甲基-1,1-雙(三甲氧基甲矽基)甲烷、1,1-二甲基-1,1-雙(甲基二甲氧基甲矽基)甲烷、1,1-二甲基-1,1-雙(二甲氧基甲矽基)甲烷、1,1,1,3,3-五乙氧基-2-甲基-1,3-二矽丁 烷、1,2-雙(甲基二乙氧基甲矽基)乙烷、1,2-雙(三乙氧基甲矽基)乙烷、1,2-雙(二乙氧基甲矽基)乙烷、1,1-雙(三乙氧基申矽基)乙烷、1,1-雙(甲基二乙氧基甲矽基)乙烷、1,1-雙(二乙氧基甲矽基)乙烷、1,1-二甲基-1,1-雙(三乙氧基甲矽基)甲烷、1,1-二甲基-1,1-雙(甲基二乙氧基甲矽基)甲烷及1,1-二甲基-1,1-雙(二乙氧基甲矽基)甲烷。
- 如請求項1之化學氣相沈積方法,其中該至少一種有機矽前驅物係式2的前驅物。
- 如請求項11之化學氣相沈積方法,其中該至少一種有機矽前驅物係至少一種選自於由下列所組成之群的前驅物:1,1,3,3-四甲氧基-1,3-二矽環丁烷、1,3-二甲氧基-1,3-二甲基-1,3-二矽環丁烷、1,3-二甲氧基-1,3-二矽環丁烷、1,3,3-三甲氧基-1-甲基-1,3-二矽環丁烷、1,3-二甲氧基-1-甲基-二矽環丁烷、1,1-二甲氧基-1,3-二矽環丁烷、1,1,4,4-四甲氧基-1,4-二矽環己烷、1,4-二甲氧基-1,4-二甲基-1,4-二矽環己烷、1,4-二甲氧基-1,4-二矽環己烷、1,4,4-三甲氧基-1-甲基-1,4-二矽環己烷、1,4-二甲氧基-1-甲基-二矽環己烷、1,1-二甲氧基-1,4-二矽環己烷、1,1,3,3-四乙氧基-1,3-二矽環丁烷、1,3-二乙氧基-1,3-二甲基-1,3-二矽環丁烷、1,3-二甲氧基-1,3-二矽環丁烷、1,3,3-三乙氧基-1-甲基-1,3-二矽環丁烷、1,3-二乙氧基-1-甲基-二矽環丁烷、1,1-二乙氧基-1,3-二矽環丁烷、1,1,4,4-四乙氧基-1,4-二矽環己烷、1,4-二乙氧基-1,4-二甲基-1,4-二矽環己 烷、1,4-二甲氧基-1,4-二矽環己烷、1,4,4-三乙氧基-1-甲基-1,4-二矽環己烷、1,4-二乙氧基-1-甲基-二矽環己烷及1,1-二乙氧基-1,4-二矽環己烷。
- 如請求項1之化學氣相沈積方法,其中該至少一種有機矽前驅物係無鹵化物離子、Al 3+離子、Fe 2+離子、Fe 3+離子、Ni 2+離子及Cr 3+離子。
- 如請求項13之化學氣相沈積方法,其中該鹵化物離子包括氯化物、氟化物、溴化物及碘化物。
- 如請求項1之化學氣相沈積方法,其中該化學氣相沈積條件係電漿輔助化學氣相沈積條件。
- 如請求項1之化學氣相沈積方法,其中該化學氣相沈積條件係熱化學氣相沈積條件。
- 如請求項1之化學氣相沈積方法,其中該基材係矽晶圓。
- 如請求項1之化學氣相沈積方法,其中該有機矽酸鹽膜具有一或多種選自於Si--O--C、Si--O--Si、Si--C、Si--F、Si--H、C--O、C--H及C--F之鍵結型式。
- 如請求項1之化學氣相沈積方法,其中該化學氣相沈積條件包括使用選自於由下列所組成之群的氧化劑:O 2、O 3、H 2O 2、N 2O及其混合物。
- 如請求項1之化學氣相沈積方法,其中該化學氣相沈積條件排除使用氧化劑。
- 如請求項1之化學氣相沈積方法,其中該化學氣相沈積條件包括使用一或多種選自於由下列所組成之群的惰性氣體:氦、氖、氬、氪、氙、氮。
- 如請求項1之化學氣相沈積方法,其中在該沈積反應前、期間及/或後,將一或多種反應性物質充入該真空艙中,其中該一或多種反應性物質係選自於由下列所組成之群:氣體或液體有機物質、氨、氫、二氧化碳、一氧化碳、碳氟化合物及其混合物。
- 一種膜,其係藉由如請求項1之方法形成。
- 如請求項23之膜,其中該膜具有密度1.8克/立方公分或較大。
- 如請求項24之膜,其中該膜具有密度2.0或較大。
- 如請求項25之膜,其中該膜具有介電常數2.5至3.5及Young’s模數大於20GPa及/或奈米壓痕硬度大於3.5GPa。
- 如請求項2之化學氣相沈積方法,其中該膜具有Young’s模數大於20GPa及/或奈米壓痕硬度大於3.5GPa。
- 如請求項4之化學氣相沈積方法,其中該膜具有Young’s模數大於20GPa及/或奈米壓痕硬度大於3.5GPa。
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JP6959334B2 (ja) | 2021-11-02 |
EP3535438B1 (en) | 2024-01-10 |
KR20190067929A (ko) | 2019-06-17 |
CN110073030A (zh) | 2019-07-30 |
EP3535438A1 (en) | 2019-09-11 |
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US10249489B2 (en) | 2019-04-02 |
WO2018085117A1 (en) | 2018-05-11 |
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