CN112969817A - 含硅膜的高温原子层沉积 - Google Patents
含硅膜的高温原子层沉积 Download PDFInfo
- Publication number
- CN112969817A CN112969817A CN201980073823.8A CN201980073823A CN112969817A CN 112969817 A CN112969817 A CN 112969817A CN 201980073823 A CN201980073823 A CN 201980073823A CN 112969817 A CN112969817 A CN 112969817A
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- China
- Prior art keywords
- reactor
- oxygen
- silicon oxide
- oxide film
- methylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052710 silicon Inorganic materials 0.000 title claims description 26
- 239000010703 silicon Substances 0.000 title claims description 25
- 238000000231 atomic layer deposition Methods 0.000 title abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 87
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 85
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000001301 oxygen Substances 0.000 claims abstract description 84
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 84
- 238000010926 purge Methods 0.000 claims abstract description 70
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000007789 gas Substances 0.000 claims abstract description 62
- 239000002243 precursor Substances 0.000 claims abstract description 60
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 60
- 238000000151 deposition Methods 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 11
- -1 (methyl) methylene Chemical group 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 29
- 229910001868 water Inorganic materials 0.000 claims description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 125000000217 alkyl group Chemical group 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 125000005647 linker group Chemical group 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- QMMPBNFUSOIFDC-UHFFFAOYSA-N ctk0b2378 Chemical compound Cl[Si](Cl)(Cl)N[Si](Cl)(Cl)Cl QMMPBNFUSOIFDC-UHFFFAOYSA-N 0.000 claims description 5
- 150000002978 peroxides Chemical class 0.000 claims description 5
- 238000004873 anchoring Methods 0.000 claims description 4
- VTDZAHJRMRMQNP-UHFFFAOYSA-N chloro-[[chloro(dimethyl)silyl]methyl]-dimethylsilane Chemical compound C[Si](C)(Cl)C[Si](C)(C)Cl VTDZAHJRMRMQNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- RNRQKQHZWFHUHS-UHFFFAOYSA-N trichloro-[[dichloro(trichlorosilylmethyl)silyl]methyl]silane Chemical compound Cl[Si](Cl)(Cl)C[Si](Cl)(Cl)C[Si](Cl)(Cl)Cl RNRQKQHZWFHUHS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims 4
- XDESNYGGKKUBOV-UHFFFAOYSA-N dichloro-[[chloro-[[dichloro(methyl)silyl]methyl]-methylsilyl]methyl]-methylsilane Chemical class C[Si](Cl)(Cl)C[Si](C)(Cl)C[Si](C)(Cl)Cl XDESNYGGKKUBOV-UHFFFAOYSA-N 0.000 claims 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 3
- 238000005259 measurement Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 9
- 210000002381 plasma Anatomy 0.000 description 36
- 230000008021 deposition Effects 0.000 description 32
- 239000000377 silicon dioxide Substances 0.000 description 12
- 235000012239 silicon dioxide Nutrition 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 8
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N hydrofluoric acid Substances F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000005137 deposition process Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 5
- 239000012686 silicon precursor Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- QHAHOIWVGZZELU-UHFFFAOYSA-N trichloro(trichlorosilyloxy)silane Chemical compound Cl[Si](Cl)(Cl)O[Si](Cl)(Cl)Cl QHAHOIWVGZZELU-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 229960001730 nitrous oxide Drugs 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 235000012431 wafers Nutrition 0.000 description 4
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000005049 silicon tetrachloride Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910003910 SiCl4 Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 235000013842 nitrous oxide Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- DPRGLQDKUYYXRR-UHFFFAOYSA-N Cl[Si](O[Si](Cl)(Cl)Cl)(Cl)Cl.[Si] Chemical compound Cl[Si](O[Si](Cl)(Cl)Cl)(Cl)Cl.[Si] DPRGLQDKUYYXRR-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001627 detrimental effect 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
- 238000000605 extraction Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KAHVZNKZQFSBFW-UHFFFAOYSA-N n-methyl-n-trimethylsilylmethanamine Chemical compound CN(C)[Si](C)(C)C KAHVZNKZQFSBFW-UHFFFAOYSA-N 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000005389 semiconductor device fabrication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0896—Compounds with a Si-H linkage
-
- 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
- C23C16/02—Pretreatment of the material to be coated
- C23C16/0209—Pretreatment of the material to be coated by heating
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- 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
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4408—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber by purging residual gases from the reaction chamber or gas lines
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- 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
- C23C16/4486—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 producing an aerosol and subsequent evaporation of the droplets or particles
-
- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45531—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making ternary or higher compositions
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- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45534—Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
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- 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
- C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
- C23C16/45536—Use of plasma, radiation or electromagnetic fields
- C23C16/45542—Plasma being used non-continuously during the ALD reactions
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Abstract
提供了一种用于在600℃或更高的一个或多个温度下在原子层沉积工艺中沉积氧化硅膜的方法和组合物。在一个方面,提供了一种在约600℃至1000℃的一个或多个温度下在反应器中的衬底上沉积氧化硅膜或材料的方法,包括以下步骤:向反应器中引入至少一种选自具有本文所述式I和式II的化合物的卤代碳硅烷前体;用吹扫气体吹扫反应器;将含氧源引入反应器中;和用吹扫气体吹扫反应器;并且其中重复这些步骤直至沉积所需厚度的氧化硅。
Description
本申请要求2018年10月5日提交的美国临时申请62/742,056的优先权。本申请进一步要求2018年10月10日提交的美国临时申请62/743,887的优先权。
技术领域
本文描述了用于形成含硅膜的组合物和方法。更具体地,本文描述了一种用于在约600℃或更高的一个或多个沉积温度下并使用原子层沉积(ALD)工艺形成氧化硅膜的组合物和方法。
背景技术
热氧化是半导体应用中通常用于沉积高纯度和高保形氧化硅膜如二氧化硅(SiO2)的工艺。然而,热氧化工艺具有非常低的沉积速率,例如,在700℃下低于(参见B.E.Deal和A.S.Grove"General Relationship for the ThermalOxidation of Silicon."Journal of Applied Physics,Vol 36,3770页(1965)),这使得其对于商业上采用的大批量制造工艺不切实际。
原子层沉积(ALD)和等离子体增强原子层沉积(PEALD)是用于在低温(<500℃)下沉积二氧化硅(SiO2)保形膜的工艺。在ALD和PEALD工艺中,前体和反应性气体(例如氧气或臭氧)在一定数量的循环中分别脉冲以用每个循环形成单层二氧化硅(SiO2)。然而,使用这些工艺在低温下沉积的二氧化硅(SiO2)可能含有对半导体应用有害的水平的杂质如氢(H)、碳(C)、氮(N)或其组合。为了弥补这一点,一种可能的解决方案是将沉积温度提高至高于500℃的温度。然而,在这些较高的温度下,半导体工业采用的常规前体倾向于自身反应、热分解和以化学气相沉积(CVD)模式而非ALD模式沉积。与ALD沉积相比,CVD模式沉积具有降低的保形性,尤其是对于具有高纵横比结构的半导体应用如NAND和V-NAND。另外,CVD模式沉积工艺比ALD模式沉积对膜或材料厚度的控制更少。
US公开第2014/0170858号描述了一种通过执行预定次数的循环在衬底上形成包含预定元素、氧和至少一种选自氮、碳和硼的元素的膜的方法,该循环包括向衬底供应源气体(其中源气体包含预定元素、氯和氧,具有该预定元素和氧的化学键),以及向衬底供应反应性气体(其中反应性气体包含至少一种选自氮、碳和硼的元素)。
US公开第2007/0111545号描述了一种在半导体器件制造中使用ALD形成二氧化硅层以提高沉积速率和改善阶梯覆盖率的方法。
US专利第7,498,273号描述了一种在PECVD中使用硅氧烷在形成于衬底上的间隙中沉积低κ介电层的方法,其得到具有低孔隙率、高蚀刻选择性和较少裂纹的膜。该方法包括将有机Si前体和O前体引入到沉积室。有机Si前体具有小于8的C:Si原子比,并且O前体包含在沉积室外生成的原子氧。
US专利第7,084,076号描述了一种使用原子层沉积(ALD)形成二氧化硅膜的方法,其中使用卤素-或NCO-取代的硅氧烷作为Si源。
US公开第2013/0295779号描述了用于在约500℃或更高的一个或多个沉积温度下形成含氧化硅的膜的组合物和ALD。
前述专利和专利申请在此引入作为参考。
因此,需要开发一种使用原子层沉积(ALD)工艺或ALD样工艺(例如但不限于循环化学气相沉积工艺)来形成高质量、低杂质、高保形的氧化硅膜的方法,以替代在高于600℃的温度下的基于热的沉积工艺而用于垂直NAND(V-NAND)存储器技术。此外,可能希望的是开发高温沉积(例如,在600℃或更高的一个或多个温度下的沉积)以在用于制造V-NAND存储器的ALD或ALD样工艺中改善一种或多种膜性质如纯度和/或密度。
发明内容
本文描述了一种在高温下(例如,在约600℃或更高的一个或多个温度下)在原子层沉积(ALD)或ALD样工艺中沉积氧化硅材料或膜的方法。使用本文所述的组合物或方法沉积的氧化硅膜包含至少一种或多种以下属性:约2.1g/cm3或更高的密度;相对于热氧化物在0.5wt.%dHF中约6或更低,优选约4或更低,最优选约3或更低的湿蚀刻速率(WER);通过二次离子质谱(SIMS)测量的2x1019原子/cm3或更低的碳含量。
在一个方面,提供了一种沉积氧化硅膜或材料的方法,包括以下步骤:
a.在反应器中提供衬底并将衬底加热至所需温度;
b.向反应器中引入至少一种选自具有下式I和II的化合物的卤代碳硅烷(halidocarbosilane)前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2;
c.用吹扫气体吹扫反应器;
d.将含氧源引入反应器中;和
e.用吹扫气体吹扫反应器;
其中重复步骤b至e直至沉积所需厚度的氧化硅;并且其中该方法在约600至850℃范围的一个或多个温度下进行。在该实施方案或其他实施方案中,该方法在约50毫托(mTorr)至约760托范围的一个或多个压力下进行。在该实施方案或其他实施方案中,含氧源是至少一个选自氧、过氧化物、氧等离子体、二氧化碳等离子体、一氧化碳等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含二氧化碳和氧的组合物、包含水和氧的组合物、包含氮和氧的组合物(即一氧化二氮N2O或一氧化氮,NO)、水蒸气、水蒸气等离子体、包含水和臭氧的组合物、过氧化氢、臭氧源及其组合的成员。
在另一方面,提供了一种沉积氧化硅膜或材料的方法,包括以下步骤:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2;
c.用吹扫气体吹扫反应器;
d.将含氧源引入反应器中;
e.用吹扫气体吹扫反应器;
f.向反应器中引入水蒸气或羟基源;和
g.用吹扫气体吹扫反应器;
其中重复步骤b至g直至沉积所需厚度的氧化硅;并且其中该方法在600至850℃范围的一个或多个温度下进行。
在上述方法的一个或多个实施方案中,该方法在约50毫托(mTorr)至约760托范围的一个或多个压力下进行。
在上述方法的一个或多个实施例方案中,吹扫气体选自氮气、氦气、氩气及其组合。
在上述方法的一个或多个实施方案中,含氧源包含至少一个选自氧、过氧化物、氧等离子体、二氧化碳等离子体、一氧化碳等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含二氧化碳和氧的组合物、包含水和氧的组合物、包含氮和氧的组合物(即一氧化二氮N2O或一氧化氮,NO)、水蒸气、水蒸气等离子体、包含水和臭氧的组合物、过氧化氢、臭氧源及其组合的成员。
在进一步的方面,提供了一种用于沉积氧化硅膜的组合物,其包含至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2。这些卤代碳硅烷前体的例子显示于如下表I中:
表I
本发明的一个实施方案涉及用于沉积含硅膜的组合物,其包含至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2。
本发明的另一实施方案涉及通过任何前述方法产生的含硅膜。本发明的另一个实施方案涉及密度约2.1g/cm3或更高;相对于热氧化物在0.5wt.%dHF中约6或更低的湿蚀刻速率(WER);和碳含量2x1019原子/cm3或更低的含硅膜。
本发明的各个方面和实施方案可以单独使用或相互组合使用。
具体实施方式
本文描述了用于形成氧化硅膜的方法和组合物。术语氧化硅膜或材料包括但不限于化学计量或非化学计量的氧化硅膜、氮氧化硅膜、碳氧化硅膜、氮碳氧化硅膜及其组合。在一个特定实施方案中,氧化硅膜在约600℃或更高的一个或多个温度下以原子层沉积(ALD)或ALD样沉积工艺(例如但不限于循环化学气相沉积工艺(CCVD))进行沉积。在整个说明书中,术语“ALD或ALD样”表示包括但不限于以下过程的工艺:a)将包括卤代硅烷前体和反应性气体的各种反应物顺序引入反应器如单晶片ALD反应器、半分批ALD反应器或批式炉ALD反应器中;b)通过将衬底移动或旋转至反应器的不同区段使包括卤代硅烷前体和反应性气体的各种反应物暴露于衬底,并且每个区段通过惰性气体帘幕分隔开(即空间ALD反应器或卷对卷ALD反应器)。在整个说明书中,术语“C1连接体”指与两个硅原子键合的一个碳原子,例如Si-CH2-Si(即,C1连接体是亚甲基)或Si-CH(Me)-Si(即,C1连接体是(甲基)亚甲基),或Si-CMe2-Si(即,C1连接体是(二甲基)亚甲基),或Si-CH(Et)-Si(即,C1连接体是(乙基)亚甲基)。
本文所述方法在循环工艺中,在约600℃至约950℃或约650℃至约750℃或约700℃至850℃的一个或多个沉积温度下使用至少一种卤代碳硅烷前体和含氧源以提供氧化硅膜。在本文所述的沉积方法的一个实施方案中,该方法包括以下步骤:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2;
c.用吹扫气体吹扫反应器;
d.将含氧源引入反应器中;和
e.用吹扫气体吹扫反应器。
其中重复步骤b至e,直至至少在衬底的表面上沉积所需厚度的氧化硅膜。
尽管不希望局限于理论或解释,据信与仅具有一个硅原子的常规硅前体(例如四氯化硅或二甲基氨基三甲基硅烷)相比,本文所述的至少一种卤代碳硅烷前体应具有至少一种锚定官能团以及预先存在的Si-C-Si连接(即,C1连接体),其与衬底表面上的某些反应性位点反应以锚定Si-C-Si物质的单层,该单层可用作屏障层以防止含氧源和衬底之间的任何不需要的相互作用,特别是在形成前几层氧化硅期间。锚定官能团可选自卤(Cl、Br、I)基团。钝化官能团选自烷基,优选甲基。然后,表面上的其余基团可被氧化以形成更多的Si-O-Si连接以及羟基。另外,也可以将羟基源(如H2O或水等离子体)引入反应器中以形成更多的羟基作为用于下一ALD循环的反应性位点。
如前所述,提供了一种用于沉积氧化硅膜的组合物,其包含至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2。具有式I或式II的前体的例子包括但不限于:1,1,1,3,3,3-六氯二硅杂丙烷、1,1,1,3,3-五卤代-1,3-二硅杂丁烷、1,1,1,3,3,3-六氯-2-甲基-1,3-二硅杂丙烷、1,1,1,3,3-五卤代-2-甲基-1,3-二硅杂丁烷、2,2,4,4-四氯-2,4-二硅杂戊烷、1,1,3,3-四氯-1,3-二硅杂丙烷、2,4-二氯-2,4-二甲基-2,4-二硅杂戊烷、1,1,1,3,3,5,5,5-八氯-1,3,5-三硅杂戊烷、2,2,4,6,6-五氯-2,4,6-三甲基-2,4,6-三硅杂庚烷及其混合物。
在一个特定实施方案中,卤代碳硅烷前体包含至少一个锚定官能团(例如,Si-Cl)和至少一个钝化官能团(例如,Si-Me,其中Me是甲基)。下表II提供了这类前体的实例:
表II:
在某些实施方案中,使用本文所述方法沉积的氧化硅膜使用含氧源、含氧的试剂或前体在氧的存在下形成的。含氧源可以以至少一种含氧源气体的形式引入反应器中和/或可以附带存在于沉积工艺中使用的其他前体中。合适的含氧源气体可包括例如氧、过氧化物、氧等离子体、二氧化碳等离子体、一氧化碳等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含二氧化碳和氧的组合物、包含水和氧的组合物、包含氮和氧的组合物(即一氧化二氮N2O或一氧化氮,NO)、水蒸气、水蒸气等离子体、包含水和臭氧的组合物、过氧化氢、臭氧源及其组合。在某些实施方案中,含氧源包含以约1至约10000标准立方厘米(sccm)或约1至约2000标准立方厘米(sccm)或约1至约1000sccm的流速引入反应器中的含氧源气体。含氧源可以引入约0.1至约100秒范围的时间。在一个特定实施方案中,含氧源包括温度为10℃或更高的水。在其中通过ALD或循环CVD工艺沉积膜的实施方案中,前体脉冲可具有大于0.01秒的脉冲持续时间,并且含氧源可具有小于0.01秒的脉冲持续时间,而水脉冲持续时间可为小于0.01秒的脉冲持续时间。在又一个实施方案中,脉冲之间的吹扫持续时间可以低至0秒,或者连续地脉冲而没有之间的吹扫。
在某些实施方案中,氧化硅膜进一步包含氮。在这些实施方案中,膜使用本文所述的方法沉积,并在含氮源的存在下形成。含氮源可以以至少一种氮源气体的形式引入反应器中和/或可以附带地存在于沉积工艺中使用的其他前体中。合适的含氮源气体可包括例如氨、肼、单烷基肼、二烷基肼、氮、氮/氢、氨等离子体、氮等离子体、氮/氢等离子体及其混合物。在某些实施方案中,含氮源包括以约1至约2000标准立方厘米(square cubiccentimeter)(sccm)或约1至约1000sccm的流速引入反应器中的氨等离子体或氢/氮等离子体源气体。含氮源可以引入约0.1至约100秒范围的时间。在其中通过ALD或循环CVD工艺沉积膜的实施方案中,前体脉冲可具有大于0.01秒的脉冲持续时间,并且含氮源可具有小于0.01秒的脉冲持续时间,而水脉冲持续时间可为小于0.01秒的脉冲持续时间。在又一个实施方案中,脉冲之间的吹扫持续时间可以低至0秒,或者连续地脉冲而没有之间的吹扫。
本文公开的沉积方法可涉及一种或多种吹扫气体。用于吹扫掉未消耗的反应物和/或反应副产物的吹扫气体是不与前体反应的惰性气体。示例性吹扫气体包括但不限于氩气(Ar)、氮气(N2)、氦气(He)、氖气、氢气(H2)及其混合物。在某些实施方案中,以约10至约6000sccm的流速向反应器中供应吹扫气体如Ar,持续约0.1至1000秒,从而吹扫反应器中可能残留的未反应材料和任何副产物。
供应前体、含氧源、含氮源和/或其他前体、源气体和/或试剂的相应步骤可通过改变供应它们的时间来进行以改变所得介电膜的化学计量组成。
吹扫气体可与前一步骤的残留气体组合以形成组合物。例如,该组合物可包含吹扫气体和至少一种本发明的前体。吹扫气体将占该组合物的约1%至约95%。
能量向卤代碳硅烷前体、含氧源、含氮源或其组合中的至少一种施加以诱导反应并在衬底上形成含硅膜或涂层。这种能量可通过但不限于热、等离子体、脉冲等离子体、螺旋波等离子体、高密度等离子体、电感耦合等离子体、X射线、电子束、光子、远程等离子体方法及其组合来提供。在某些实施方案中,二次RF射频源可用于改变衬底表面处的等离子体特性。在其中沉积涉及等离子体的实施方案中,等离子体发生工艺可包括直接等离子体发生工艺(其中等离子体在反应器中直接生成),或者可选地,远程等离子体发生工艺(其中等离子体在反应器外部生成并供应到反应器中)。
该至少一种卤代碳硅烷前体可通过多种方式输送至反应室如循环CVD或ALD反应器。在一个实施方案中,可以使用液体输送系统。在替代实施方案中,可采用组合液体输送和闪蒸处理单元,例如由Shoreview,MN的MSP Corporation制造的涡轮气化器,以使低挥发性材料能够定量地输送,这导致可重复的输送和沉积而没有前体的热分解。在液体输送方式中,本文所述的前体可以纯净液体形式递送,或者可选择地,可以在包含该前体的溶剂制剂或组合物中使用。因此,在某些实施方案中,前体制剂可包括具有在给定的最终用途应用中可能是期望的和有利的合适性质的溶剂组分,以在衬底上形成膜。
在本文所述方法的一个实施方案中,可以使用循环沉积工艺,如ALD样、ALD或PEALD,其中使用至少一种卤代碳硅烷前体和含氧源进行沉积。ALD样工艺被定义为循环CVD工艺,但仍提供高保形氧化硅膜。
在某些实施方案中,从前体罐连接至反应室的气体管线加热至取决于工艺要求的一个或多个温度,并且将至少一种卤代碳硅烷前体的容器保持在用于鼓泡的一个或多个温度下。在其他实施方案中,包含至少一种卤代碳硅烷的溶液注入保持在用于直接液体注射的一个或多个温度下的气化器中。
氩气和/或其他气体的流可用作载气以帮助在前体脉冲期间将至少一种卤代碳硅烷的蒸气输送至反应室。在某些实施方案中,反应室工艺压力为约1托。
在典型的ALD或ALD样工艺(如CCVD工艺)中,在反应室中的加热台上加热衬底(如氧化硅衬底),该反应室最初暴露于硅前体以允许复合物化学吸附到衬底表面上。
吹扫气体(如氩气)从处理室吹扫掉未吸收的过量复合物。在充分吹扫后,可将含氧源引入反应室中以与吸收的表面反应,随后进行另一次气体吹扫以从反应室去除反应副产物。工艺循环可重复进行以达到所需的膜厚度。在一些情况下,泵送可以替代用惰性气体的吹扫,或者可以使用两者以去除未反应的硅前体。
本发明的ALD工艺可实现的膜生长速率可以在约/循环至约/循环、约/循环至约/循环,和在一些优选情况下,约/循环至约/循环的范围内。沉积的膜的折射率(RI)可在约1.35至约1.55、约1.40至约1.50以及在一些情况下,约1.44至约1.48的范围内。所沉积膜相对于热氧化物在稀HF(去离子水中的约0.5wt.%HF)相对蚀刻速率可在约0.5至约8.0、约1.0至约6.0,并且在一些优选情况下,约1.0至约4.0的范围内。
在该实施方案或其他实施方案中,应当理解,本文描述的方法的步骤可以以多种顺序执行,可以顺序执行,可以同时执行(例如,在另一步骤的至少一部分期间),以及它们的任何组合方式。供应前体和含氧源气体的相应步骤可通过改变供应它们的持续时间来进行以改变所得介电膜的化学计量组成。所沉积膜的介电常数(k)可在约3.0至约6.0、约3.5至约5.0,和在一些优选情况下,约3.8至约4.2的范围内。
本文所述的在约600℃或更高的一个或多个沉积温度下在衬底上沉积氧化硅膜的方法的一个特定实施方案包括以下步骤:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入至少一种具有式I和式II的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2;
c.用吹扫气体吹扫反应器;
d.将含氧源引入反应器中;和
e.用吹扫气体吹扫反应器
其中重复步骤b至e直至沉积所需厚度的氧化硅膜。
本文所述方法的另一个实施方案在将含氧源引入反应器中后引入包含羟基的含氧源(例如,在沉积过程中形成的OH片段),如H2O蒸气或H2O等离子体。在该实施方案中,据信羟基重新填充表面以产生用于锚定在表面上以形成单层的卤代碳硅烷前体的反应性位点。沉积步骤包括:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入上述至少一种具有式I或II的卤代碳硅烷;
c.用吹扫气体吹扫反应器;
d.将包含选自水、过氧化氢和包含水的等离子体中的至少一种的含氧源引入反应器中;
e.用吹扫气体吹扫反应器;
f.将含氧源引入反应器中;和
g.用吹扫气体吹扫反应器
其中重复步骤b至g,直至沉积所需厚度的氧化硅膜。
在本文所述方法的替代实施方案中,沉积步骤包括:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入本文所述至少一种具有式I或II的卤代碳硅烷前体;
c.用吹扫气体吹扫反应器;
d.将含氧源引入反应器中;
e.用吹扫气体吹扫反应器;
f.将含OH源引入反应器中;和
g.用吹扫气体吹扫反应器,
其中重复步骤b至g直至沉积所需厚度的氧化硅膜。
又一个实施方案使用过氧化氢、臭氧、包含氢和氧的组合物或氧等离子体来去除钝化官能团或基团如甲基或氯。沉积步骤如下:
a.在反应器中提供衬底并将该衬底加热至所需温度;
b.向反应器中引入本文所述至少一种具有式I或II的卤代碳硅烷前体;
c.用吹扫气体吹扫反应器;
d.将包含选自臭氧、过氧化氢、包含氢和氧的组合物和氧等离子体中的至少一种的源引入反应器中;和
e.用吹扫气体吹扫反应器,
其中重复步骤b至e直至沉积所需厚度的氧化硅膜。
在本文所述的方法中,一个或多个沉积温度在以下任一或多个端点的范围内:600、650、675、600、700、725、750、775、800、825、850、875、900、925、950、975或1000℃。在某些实施方案中,至少一个沉积温度在约600℃至约1000℃;或从约600℃至约750℃;或从700℃到850℃;或约750℃至约850℃的范围内。
在整个说明书中,本文中使用的术语“阶梯覆盖率”被定义为在具有通孔或沟槽或两者的结构化或特征化衬底中沉积的含硅膜的两种厚度的百分比,其中底部阶梯覆盖为以下比率(以%计):特征底部处的厚度除以特征顶部处的厚度,和中间阶梯覆盖率为以下比率(以%计):特征侧壁上的厚度除以特征顶部处的厚度。使用本文所述方法沉积的膜呈现约60%或更大、约70%或更大、约80%或更大或约90%或更大的台阶覆盖率,这表明膜是保形的。
在整个说明书中,本文中使用的术语“含羟基源”指具有羟基的含氧源。实例包括但不限于水、水等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含水和氧的组合物、包含水和二氧化碳的组合物、包含水和氧的组合物、包含水和臭氧的组合物、包含水和一氧化二氮的组合物、包含水和一氧化氮的组合物、过氧化氢(H2O2)、由氢和氧生成的等离子体及其组合。
沉积压力为50毫托(mT)至760托或500mT至100托范围的一个或多个压力。
在一个特定实施方案中,本文所述的方法在基本上不含催化剂,例如有机胺(例如,吡啶、三甲胺,参见美国专利第7,084,076号;在此引入作为参考)的情况下进行。在该实施方案或另一实施方案中,在不需要一个或多个退火步骤的情况下进行本文所述的方法。
提供以下实施例是为了说明本发明的某些实施方案,而不应限制所附权利要求的范围。
工作实施例
对比实施例1a:使用四氯化硅的氧化硅膜的原子层沉积
使用四氯化硅(SiCl4)前体进行氧化硅膜的原子层沉积。沉积在实验室规模的ALD处理设备上进行。硅前体通过蒸气抽取输送至反应室。所有气体(例如,吹扫和反应物气体或前体和含氧源)在进入沉积室之前被预热至100℃。气体和前体流速用具有高速致动的ALD隔膜阀控制。沉积中使用的衬底为12英寸长的硅条。热电偶连接到样品架上以确认衬底温度。使用臭氧作为含氧源气体进行沉积。表III提供了沉积参数,其中术语脉冲或进料是可互换的,代表将硅前体或含氧源引入反应器中的步骤。
表III:使用SiCl4的具有氧源的氧化硅膜原子层沉积的方法
重复步骤b至e直至达到所需厚度。通过将膜的反射数据与预设物理模型(例如洛仑兹振子模型)进行拟合,使用FilmTek 2000SE椭偏仪测量膜的厚度和折射率。使用1%的去离子水中49%氢氟酸(HF)的溶液(约0.5wt.%HF)进行湿蚀刻。对于每一批次使用热氧化物晶片作为参考以确认溶液浓度。对于去离子水中的0.5wt.%HF溶液,典型的热氧化物晶片湿蚀刻速率(WER)为/s。使用蚀刻之前和之后的膜厚度计算湿蚀刻速率。表IV总结了在800℃的晶片温度下使用SiCl4前体的12秒前体暴露及作为含氧源的臭氧沉积的SiO2膜的性质。生长速率或每循环生长(GPC)定义为以埃计的氧化硅的厚度除以循环数。
表IV.用SiCl4和作为氧源的臭氧沉积的氧化硅膜的性质
对比实施例1b:在高于600℃的衬底温度下使用六氯二硅氧烷的氧化硅膜的原子层沉积
使用对比实施例1a的表III中所列的步骤用硅六氯二硅氧烷(HCDSO)及作为含氧源气体的臭氧进行氧化硅膜的原子层沉积。表V总结了在700℃到800℃范围的温度下沉积的氧化硅的沉积条件和物理性质,表明在类似的ALD条件下,HCDSO的生长速率远高于SiCl4。
表V.用HCDSO和臭氧方法沉积的氧化硅膜的沉积速率和膜性质
实施例2:在高于600℃的衬底温度下用1,1,1,3,3,3-六氯二硅杂丙烷的氧化硅膜的原子层沉积
使用对比实施例1a的表III中列出的步骤用硅1,1,1,3,3,3-六氯二硅杂丙烷及作为含氧源的臭氧进行氧化硅膜的原子层沉积。表VI总结了在700℃到800℃范围的温度下沉积的氧化硅的沉积条件和物理性质,表明在类似的ALD条件下1,1,1,3,3,3-六氯二硅杂丙烷的生长速率远高于SiCl4和HCDSO。表VI还显示了在各种不同的衬底温度下用1,1,1,3,3,3-六氯二硅杂丙烷和臭氧沉积的氧化硅膜对于热氧化物的相对WER,表明温度越高,WER越低。
表VI.用1,1,1,3,3,3-六氯二硅杂丙烷和臭氧沉积的氧化硅膜的沉积速率和膜性质
通过二次离子质谱(SIMS)分析膜杂质,且膜杂质显示于表VII中。该膜显示出低C、N和氯杂质。
表VII.用1,1,1,3,3,3-六氯二硅杂丙烷和臭氧沉积的氧化硅膜的膜杂质
尽管本发明已经参照某些优选实施方案进行了描述,但是本领域技术人员应当理解,在不脱离本发明范围的情况下,可以进行各种改变,并且可以用等同物替代本发明的元素。另外,在不脱离本发明实质范围的情况下,可以进行许多修改以使特定情况或材料适应本发明的教导。因此,意图的是本发明不限于特定实施方案,而是本发明包括所有落入所附权利要求范围内的实施方案。
Claims (22)
1.一种沉积氧化硅膜的方法,该方法包括以下步骤:
a.在反应器中提供包含表面的衬底,并将所述反应器加热至约600℃至约1000℃范围的温度,
b.向所述反应器中引入至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2,其中所述至少一种卤代碳硅烷前体在所述衬底的表面的至少一部分上反应以提供化学吸附层;
c.用第一吹扫气体吹扫所述反应器中来自步骤b的任何未消耗的前体和/或反应副产物;
d.向所述反应器中引入含氧源以与所述化学吸附膜反应而形成氧化硅膜;和
e.用与所述第一吹扫气体相同或不同的第二吹扫气体吹扫所述反应器中来自步骤d的任何未消耗的含氧源和/或反应副产物;和
其中重复步骤b至e直至沉积所需厚度的所述氧化硅膜。
2.根据权利要求1所述的方法,其中所述至少一种卤代碳硅烷前体选自:1,1,1,3,3,3-六氯二硅杂丙烷、1,1,1,3,3-五卤代-1,3-二硅杂丁烷、1,1,1,3,3,3-六氯-2-甲基-1,3-二硅杂丙烷、1,1,1,3,3-五卤代-2-甲基-1,3-二硅杂丁烷、2,2,4,4-四氯-2,4-二硅杂戊烷、1,1,3,3-四氯-1,3-二硅杂丙烷、2,4-二氯-2,4-二甲基-2,4-二硅杂戊烷、1,1,1,3,3,5,5,5-八氯-1,3,5-三硅杂戊烷、2,2,4,6,6-五氯-4-甲基-2,4,6-三硅杂庚烷及其混合物。
3.根据权利要求1所述的方法,其中所述第一和第二吹扫气体各自选自氮气、氦气、氩气及其组合。
4.根据权利要求1所述的方法,其中所述含氧源包含至少一个选自以下的成员:氧、过氧化物、氧等离子体、二氧化碳等离子体、一氧化碳等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含二氧化碳和氧的组合物、包含水和氧的组合物、包含氮和氧的组合物、水蒸气、水蒸气等离子体、包含水和臭氧的组合物、过氧化氢、臭氧源及其组合。
5.一种沉积氧化硅膜的方法,包括以下步骤:
a.在反应器中提供衬底,并将所述反应器加热至约600℃至约1000℃范围的温度;
b.向所述反应器中引入至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2,以在所述衬底上形成层;
c.用第一吹扫气体吹扫所述反应器中来自步骤b的任何未消耗的前体和/或反应副产物;
d.向所述反应器中引入含氧源以与所述层反应而形成氧化硅膜;
e.用与所述第一吹扫气体相同或不同的第二吹扫气体吹扫所述反应器中来自步骤d的任何未消耗的含氧源和/或反应副产物;
f.向所述反应器中引入含羟基的源以与所述氧化硅膜反应;
g.用吹扫气体吹扫所述反应器以去除任何未反应的含羟基源和/或任何反应副产物;且
其中重复步骤b至g直至形成所需厚度的所述氧化硅膜。
6.根据权利要求5所述的方法,其中所述至少一种卤代碳硅烷前体选自:1,1,1,3,3,3-六氯二硅杂丙烷、1,1,1,3,3-五卤代-1,3-二硅杂丁烷、1,1,1,3,3,3-六氯-2-甲基-1,3-二硅杂丙烷、1,1,1,3,3-五卤代-2-甲基-1,3-二硅杂丁烷、2,2,4,4-四氯-2,4-二硅杂戊烷、1,1,3,3-四氯-1,3-二硅杂丙烷、2,4-二氯-2,4-二甲基-2,4-二硅杂戊烷、1,1,1,3,3,5,5,5-八氯-1,3,5-三硅杂戊烷、2,2,4,6,6-五氯-4-甲基-2,4,6-三硅杂庚烷及其混合物。
7.根据权利要求5所述的方法,其中所述第一和第二吹扫气体各自选自氮气、氦气、氩气及其组合。
8.根据权利要求5所述的方法,其中所述含氧源包含至少一个选自以下的成员:氧、过氧化物、氧等离子体、二氧化碳等离子体、一氧化碳等离子体、包含氢和氧的组合物、包含氢和臭氧的组合物、包含二氧化碳和氧的组合物、包含水和氧的组合物、包含氮和氧的组合物、水蒸气、水蒸气等离子体、包含水和臭氧的组合物、过氧化氢、臭氧源及其组合。
9.根据权利要求1所述的方法,其中步骤b进一步包括使所述反应器达到50毫托(mTorr)至760托范围的压力,并且其中所述至少一种卤代碳硅烷前体包含至少一个锚定官能团及包含Si-Me或Si-Cl基团或Si-Me和Si-Cl两者的钝化官能团。
10.根据权利要求9所述的方法,其中所述反应器温度范围为700-850℃。
11.根据权利要求9所述的方法,其中所述反应器压力范围为50毫托(mTorr)至100托。
12.一种用于沉积含硅膜的组合物,其包含至少一种选自具有下式I和II的化合物的卤代碳硅烷前体:
I R3-nXnSi-R1-SiXmR2 3-m
II R3-nXnSi-R1-SiXqR3 p-R1-SiXmR2 3-m
其中X=Cl、Br或I;R和R2各自独立地选自氢原子和C1-C3烷基;R1是与两个硅原子键合的C1连接体,且选自亚甲基、(甲基)亚甲基、(二甲基)亚甲基和(乙基)亚甲基;R3选自氢和C1-C3烷基;n=1、2或3;m=0、1、2或3;p=0、1或2,q=0、1或2,和p+q=2。
13.根据权利要求12所述的组合物,进一步包含至少一种吹扫气体。
14.根据权利要求12所述的组合物,其中所述至少一种卤代碳硅烷前体选自:1,1,1,3,3,3-六氯二硅杂丙烷、1,1,1,3,3-五卤代-1,3-二硅杂丁烷、1,1,1,3,3,3-六氯-2-甲基-1,3-二硅杂丙烷、1,1,1,3,3-五氯-2-甲基-1,3-二硅杂丁烷、2,2,4,4-四氯-2,4-二硅杂戊烷、1,1,3,3-四氯-1,3-二硅杂丙烷、2,4-二氯-2,4-二甲基-2,4-二硅杂戊烷、1,1,1,3,3,5,5,5-八氯-1,3,5-三硅杂戊烷、2,2,4,6,6-五氯-4-甲基-2,4,6-三硅杂庚烷及其混合物。
15.一种通过根据权利要求1所述的方法形成的氧化硅膜。
16.一种通过根据权利要求5所述的方法形成的氧化硅膜。
17.一种通过根据权利要求1所述的方法形成的氧化硅膜,其具有约2.1g/cm3或更高的密度;相对于热氧化物在0.5wt.%dHF中约4或更低的湿蚀刻速率(WER);和通过SIMS测量的2x1019原子/cm3或更低的碳含量。
18.根据权利要求17所述的氧化硅膜,其具有相对于热氧化物在0.5wt.%dHF中约3或更低的湿蚀刻速率(WER)。
19.根据权利要求17所述的氧化硅膜,其中存在碳,并且其量通过X射线光电子能谱(XPS)测量为小于5at.%。
20.一种通过根据权利要求5所述的方法形成的氧化硅膜,其具有约2.1g/cm3或更高的密度;相对于热氧化物在0.5wt.%dHF中约4或更低的湿蚀刻速率(WER);和通过SIMS测量的2x1019原子/cm3或更低的碳含量。
21.根据权利要求20所述的氧化硅膜,其中存在碳,并且其量通过X射线光电子能谱(XPS)测量为小于5at.%。
22.根据权利要求20所述的氧化硅膜,其中相对于热氧化物在0.5wt.%dHF中的所述湿蚀刻速率(WER)为约3或更低。
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TWI721588B (zh) | 2021-03-11 |
JP7256263B2 (ja) | 2023-04-11 |
KR20210055101A (ko) | 2021-05-14 |
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JP2022504232A (ja) | 2022-01-13 |
TW202018119A (zh) | 2020-05-16 |
CN118086873A (zh) | 2024-05-28 |
CN112969817B (zh) | 2024-04-19 |
US20210380418A1 (en) | 2021-12-09 |
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TW202134471A (zh) | 2021-09-16 |
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