TW201403715A - 用於形成含氧化矽之薄膜的方法 - Google Patents
用於形成含氧化矽之薄膜的方法 Download PDFInfo
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- TW201403715A TW201403715A TW102133860A TW102133860A TW201403715A TW 201403715 A TW201403715 A TW 201403715A TW 102133860 A TW102133860 A TW 102133860A TW 102133860 A TW102133860 A TW 102133860A TW 201403715 A TW201403715 A TW 201403715A
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- 238000000034 method Methods 0.000 title claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title abstract description 14
- 229910052814 silicon oxide Inorganic materials 0.000 title abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000000758 substrate Substances 0.000 claims abstract description 43
- 238000010926 purge Methods 0.000 claims abstract description 32
- 239000011261 inert gas Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 89
- 229910052760 oxygen Inorganic materials 0.000 claims description 83
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 81
- 239000001301 oxygen Substances 0.000 claims description 81
- 150000001875 compounds Chemical class 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 41
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 24
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 19
- 238000000231 atomic layer deposition Methods 0.000 claims description 16
- 238000002347 injection Methods 0.000 claims description 16
- 239000007924 injection Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- GFUVGQUFNPGKRQ-UHFFFAOYSA-N 1-N,1-N,1-N',1-N'-tetraethyldecane-1,1-diamine Chemical compound C(C)N(CC)C(CCCCCCCCC)N(CC)CC GFUVGQUFNPGKRQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 150000003377 silicon compounds Chemical class 0.000 abstract 4
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- 150000003304 ruthenium compounds Chemical class 0.000 description 9
- -1 alkoxy decane Chemical compound 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
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- 101100023111 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfc1 gene Proteins 0.000 description 6
- 238000001784 detoxification Methods 0.000 description 6
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 5
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- 239000011733 molybdenum Substances 0.000 description 4
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 4
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- XWBTWKLPOWCMEX-UHFFFAOYSA-N 10,10-dimethylundecan-1-amine Chemical compound CC(C)(C)CCCCCCCCCN XWBTWKLPOWCMEX-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
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- 239000001307 helium Substances 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
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- 229910052715 tantalum Inorganic materials 0.000 description 3
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- WJMXTYZCTXTFJM-UHFFFAOYSA-N 1,1,1,2-tetraethoxydecane Chemical compound C(C)OC(C(OCC)(OCC)OCC)CCCCCCCC WJMXTYZCTXTFJM-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- LOLANUHFGPZTLQ-UHFFFAOYSA-N 1-ethoxydecane Chemical compound CCCCCCCCCCOCC LOLANUHFGPZTLQ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
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- 125000006850 spacer group Chemical group 0.000 description 2
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- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PUNXVEAWLAVABA-UHFFFAOYSA-N 1,2,3,4-tetrahydroanthracene;1,2,5,6-tetrahydroanthracene Chemical compound C1=CC=C2C=C(CCCC3)C3=CC2=C1.C1=CCCC2=C1C=C1CCC=CC1=C2 PUNXVEAWLAVABA-UHFFFAOYSA-N 0.000 description 1
- WYDCLGLWAMNKTO-UHFFFAOYSA-N 1-N,1-N,1-N',1-N',1-N",1-N"-hexamethyldecane-1,1,1-triamine Chemical compound CN(C)C(CCCCCCCCC)(N(C)C)N(C)C WYDCLGLWAMNKTO-UHFFFAOYSA-N 0.000 description 1
- RSKFXZJLEFGMQK-UHFFFAOYSA-N 1-n,1-n,1-n',1-n'-tetramethyldecane-1,1-diamine Chemical compound CCCCCCCCCC(N(C)C)N(C)C RSKFXZJLEFGMQK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- DJPHKBWVUHIFGP-UHFFFAOYSA-N N(=C=O)C(C(N=C=O)(N=C=O)N=C=O)CCCCCCCC Chemical compound N(=C=O)C(C(N=C=O)(N=C=O)N=C=O)CCCCCCCC DJPHKBWVUHIFGP-UHFFFAOYSA-N 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical class CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
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- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- 239000007800 oxidant agent Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
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- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
- H01L21/02164—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 being a silicon oxide, e.g. SiO2
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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
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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
- C23C16/402—Silicon dioxide
-
- 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]
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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
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- 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
- H01L21/02219—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 nitrogen
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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
- H01L21/02205—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
- H01L21/02219—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 nitrogen
- H01L21/02222—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 nitrogen the compound being a silazane
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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
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/0228—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
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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
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
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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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31604—Deposition from a gas or vapour
- H01L21/31608—Deposition of SiO2
- H01L21/31612—Deposition of SiO2 on a silicon body
Abstract
一種用於形成含氧化矽薄膜之方法係包括下列步驟:-提供一處理基板到反應室中,-於減壓下,在50到400℃的基板溫度下,將惰性氣體導入反應室中以清洗反應室內的氣體,-在相同溫度及減壓下,藉由脈衝導入氣態矽化合物到反應室中,以吸附矽化合物到處理基板上,-在相同溫度及減壓下,使用惰性氣體來清洗反應室中未經吸附的矽化合物-在相同溫度及減壓下,導入含臭氧的混合氣體的脈衝到反應室中,並藉由與吸附在處理基板上之矽化合物氧化反應以產生氧化矽;及-若必要時,重複步驟1)到4),直到在基板上獲得所欲的厚度。
Description
本發明係關於一種使用矽前驅物及氧化劑氣體形成含氧化矽之薄膜之方法。
在CMOS半導體裝置的前端製造中,被動薄膜,如SiN是形成於每個MOS電晶體之閘極上。為了要增加每個電晶體之崩潰電壓,在閘極(例如多晶矽或金屬層)的上表面和側表面上會沉積SiN薄膜。
已經有嘗試要將SiN的沉積溫度降低到不高於400℃的溫度。然而,在低於400℃的溫度下沉積SiN薄膜通常具有較差的薄膜品質。為了要克服這個問題,已經建議了使用SiO2薄膜來增強SiN薄膜性質(“雙重間隙壁(dual spacer)”),並因此產生有效的電子障壁層(electrical barrier layers),以明顯改良元件的性質。同時,SiO2薄膜可被用來作為STI(淺溝槽絕緣)、內層介電層(ILD)、被動層、終止蝕刻層,而且也有嘗試要找出在低溫、亦即低於400℃的溫度下沉積這些SiO2層的方法。在雙重間隙壁應用之特定例子中,在低沉積溫度(最多為300℃)時所進行的非常薄(20-50埃厚)的薄膜沉積不應該導致金屬電極的氧化且較佳應該為沿著閘極均呈現均勻的,並且原子層沉積方法是最適合於這類的需求。只要是關於STI應用,保形薄膜應該使用低於500℃的高沉積速率(每分鐘數百埃)來沉積。
使用PECVD反應器以在低溫下由矽烷和氧來製成的氧化矽薄膜沉積,因為在導入作為前驅物氣體的矽烷氣體中存在有氫氣所引起的Si-H鍵併入所得之SiOx薄膜的緣故,該薄膜沉積已經在現今的應用中失效了。然後,Si-H鍵可能在環境中與氧氣來源立即反應以產生Si-OH鍵。
這類Si-OH鍵的存在增加了電晶體具有增加的漏電流的風險,及因此降低的電晶體之崩潰電壓。
本發明人相信為生成SiO2薄膜,在Si前驅物中存在有大量氫原子鍵結到的矽原子且存在著氧氣或含氧氣體之下,也可能會發生水分(H2O)的生成,水分然後會與Si反應以產生SiOH。
本發明人亦相信含矽化合物應較佳在含氫殘餘物方面具有高的純度,以限制H2O的生成,較佳為包含小於100ppm H2或含H化合物。
本發明之一主要目的為提供一種於400℃或低於400℃的溫度下在基板上形成氧化矽薄膜之方法,上述溫度避免或限制在SiO2薄膜生成期間生成OH鍵。
根據本發明,提供一種形成含氧化矽薄膜之方法,其包括下列步驟:
a)提供一基板到反應室中,
b)將至少一種含矽化合物注射到反應室中,上述含矽化合物為選自下列所組成之族群中:
-具有通式(R1R2N)x SiH4-x的胺基矽烷,其中R1及R2各自獨立為H,C1-C6
線型、分枝或環狀的碳鏈,且x是由1到4之間所組成;
-具有下式之烷氧基矽烷或乙醯氧基矽烷:Si(OR1)(OR2)(OR3)(OR4),或(OR1)(OR2)(OR3)SiSi(OR4)(OR5)(OR6),或(OR1)(OR2)(OR3)SiRSi(OR4)(OR5)(OR6),或Si(O-C(=O)-R1)(O-C(=O)-R2)(O-C(=O)-R3)(O-C(=O)-R4),較佳地,四(乙醯氧基)矽烷Si(O-C(=O)-Me)4其中R,R1,R2 ,R3,R4,R5,R6各自獨立為H,O,C1-C6線型、分枝或環狀的碳鏈;
-具有通式(SiH3)nR之矽烷,其中n是由1到4之間所組成,R為選自由H,N,O,CH2,C2H4,SiH2,SiH,Si所組成之族群中。
-四(異氰酸)矽烷Si(NCO)4
c)將至少一種含氧氣體,較佳為臭氧及/或氧氣及/或水分(水)注射到反應室中。
d)在反應室中,於低於500℃的溫度下,將至少一種含矽化合物與至少一種含氧氣體反應,以獲得沉積於基板上的含氧化矽薄膜。
e)重複步驟b)到d),直到獲得所欲的SiO2薄膜厚度。
較佳地,在進行步驟b)、c)、d)及/或e)之前,於基板導入反應室後,將基板於反應室中加熱到較佳為高至反應室的溫度。
根據本發明之一較佳具體實例,至少一個步驟b)及/或c)是藉由間斷地注射至少一種化合物及/氣體來進行的。例如,在反應室中進行脈衝CVD或ALD。
儘管同時注射至少一種化合物及至少一種含氧氣體可以在
反應室中進行,較佳為提供至少一種化合物及至少一種含氧氣體在反應室中的另一種類型的注射。
根據另一具體實例,在注射另一種化合物及/或至少一種含氧氣體之前,至少一種化合物或至少一種含氧氣體是在基板的表面上。
較佳地,每次化合物及/或含氧氣體的注射係接續著注射純氣體,例如惰性氣體,到反應室中,同時,更佳為重複化合物及/或氣體的注射,直到獲得所欲的含SiO2薄膜厚度。在反應室外殼內的壓力較佳應低於100Torr,更佳為低於2Torr。較佳地,在含SiO2薄膜中的H含量是低於8×1021原子/cc。
根據另一具體實例,含臭氧氣體為一種包括具有O3/O2比例為低於30體積%(較佳為介於5%到20體積%之間)的氧氣和臭氧之氣體混合物。
較佳地,氧氣/臭氧之氣體混合物被稀釋到惰性氣體中,較佳為氮氣。
含矽化合物應包含低於100ppm H2,且較佳為選自由下列所組成之族群中:
本發明亦提供一種形成氧化矽薄膜之方法,該方法可在不高於500℃的低溫下形成薄膜期間抑制或避免OH鍵的導入,其中氧化矽薄膜的厚度被容易地控制,且氧化矽薄膜是具高度可靠度,例如當施加電流到閘極側表面上時降低漏電流。
本發明之方法也提供一種SiO2薄膜,尤其是當在每次注射之間使用具有氮氣清除的ALD方法沉積時,該方法具有非常高的保形度(亦即,在溝槽頂部和底部中沉積均勻薄膜的能力),而適用於填縫應用中或適用於DRAM的電容電極中,亦即適用於填滿表面上所有孔隙之薄膜,並且還可提供均勻SiO2層的薄膜。
11‧‧‧反應室
12‧‧‧氮氣筒
13‧‧‧Si化合物氣體筒
14‧‧‧氧氣筒
15‧‧‧除毒裝置
16‧‧‧臭氧生成器
V1-V7‧‧‧停止閥
V1’-V7’‧‧‧停止閥
L1-L7‧‧‧管線
L4’,L6’‧‧‧分枝管線
MFC1,MFC2,MFC3‧‧‧質量流量控制器
BV‧‧‧蝴蝶閥
PG1,PG2,PG3‧‧‧壓力計
PMP‧‧‧真空泵
OCS‧‧‧臭氧濃度感測器
101‧‧‧閘極
102‧‧‧金屬電極
103‧‧‧氧化矽薄膜
104‧‧‧氮化矽
105‧‧‧汲極
106‧‧‧源極
本發明係參照下列圖式來更詳細的說明。
圖1是在根據本發明具體實例之形成薄膜方法中所使用的薄膜形成裝置的概要圖(在惰性氣體清洗注射期間時)。
圖2是在Si化合物氣體注射期間,圖1之薄膜形成裝置的概要圖。
圖3是在臭氧/氧氣的氣體脈衝注射期間,圖1之薄膜形成裝置的概要圖。
圖4是具有根據本發明所沉積的SiO2薄膜的MOS電晶體之金屬閘極。
根據本發明之用於形成氧化矽薄膜之方法係詳細描述在下文中。其包括:
-使用氧源及具有通式(R1R2N)xSiH4-x之胺基矽烷(其中x是由1到4之間所組成,其中R1和R2各自獨立為H或C1-C6線型、分枝或環狀的碳鏈)來各自獨立地連續或以脈衝方式導入反應器中。較佳地,經由ALD方法注射。
較佳地,烷基胺基矽烷為雙(二乙基胺基)矽烷(BDEAS),雙(二甲基胺基)矽烷(BDMAS),或三(二甲基胺基)矽烷(三DMAS)。烷基胺基矽烷係吸附到基板表面上(在初始階段時,此步驟避免在導入氧氣源期間時底層金屬電極的可能氧化)。在一段使用惰性氣體排空來自反應器的胺基矽烷之清洗時間後,可能由氧氣/臭氧的氣體混合物(典型地:5-20體積%臭氧溶於氧氣中),氧氣,水分及/或過氧化氫(H2O2)或其組合所組成之氧氣源係經由脈衝導入。然後,循環是由一次脈衝的胺基矽烷,一次脈衝的清洗氣體,一次脈衝的含氧氣體,一次脈衝的清洗氣體所組成。循環次數是由目標厚度,以及考慮在所給定實驗條件下所得到之每次循環的沉積速率而定。沉積溫度在操作壓力為0.1-100Torr(13到13300Pa)時可以低至室溫且高至500℃。具有非常低的碳及氫含量之高品質薄膜較佳地是在0.1-10Torr(13到1330Pa)之間的壓力、於200到400℃之間的溫度下沉積的。
-使用氧源及烷氧基矽烷或乙醯氧基矽烷,彼等具有通式Si(OR1)(OR2)(OR3)(OR4),或(OR1)(OR2)(OR3)SiSi(OR4)(OR5)(OR6),或(OR1)(OR2)(OR3)SiRSi(OR4)(OR5)(OR6),或
Si(O-C(=O)-R1)(O-C(=O)-R2)(O-C(=O)-R3)(O-C(=O)-R4),較佳地四(乙醯氧基)矽烷Si(O-C(=O)-Me)4(其中R,R1,R2,R3,R4,R5,R6各自獨立為H,O,C1-C6線型、分枝或環狀的碳鏈),來各自獨立地以連續方式或脈衝方式導入反應器中。較佳地,乃經由ALD方法注射。較佳地,烷氧基矽烷為(EtO)3Si-CH2-CH2-Si(OEt)3(BTESE)。烷氧基矽烷係吸附在基板的表面(在初始階段時,此步驟避免在導入氧氣源期間時底層金屬電極的可能氧化))。在使用惰性氣體來從反應器排空胺基矽烷的清洗時間之後,氧氣源係藉由脈衝方式來導入,該氧氣源可能由氧氣/臭氧的氣體混合物(典型地:5-20體積%臭氧溶於氧氣中)、氧氣、水分及/或過氧化氫(H2O2)或其組合。循環是由一次脈衝的矽氧基矽烷,一次脈衝的清洗氣體,一次脈衝的含氧氣體,一次脈衝的清洗氣體所組成。循環次數是由目標厚度,以及考慮在所給定實驗條件下所得到之每次循環的沉積速率而定。沉積溫度在操作壓力為0.1-100Torr(13到13300Pa)時,可以低至室溫及高至500℃。具有非常低的碳及氫含量之高品質薄膜較佳地是在0.1-10Torr(13到1330Pa)之間的壓力下、於200到400℃之間的溫度下沉積的。
-使用氧源及具有通式Si(NCO)4之四(異氰酸)矽烷來以連續方式或脈衝方式分別地導入反應器中。較佳地,係經由脈衝式-CVD方法注射。異氰酸矽烷被吸附在基板表面(在初始步驟時,該步驟避免了在導入氧源期間底層金屬電極之可能氧化)。在一段使用惰性氣體排空來自反應器的矽烷化合物之清洗時間後,可能由氧氣/臭氧混合物(典型為5-20體積%之臭氧於氧氣中)、氧氣、水分及/或過氧化氫(H2O2)或其組合所組成之氧源被經由脈衝導入。然後,循環是由一次脈衝的異氰酸矽烷、一次脈衝的清洗氣
體、一次脈衝的含氧氣體、一次脈衝的清洗氣體所組成。循環的次數是目標厚度以及考慮在所給定實驗條件下所得到之每次循環之沉積速率來決定之。沉積溫度在操作壓力為0.1-100Torr(13到13300Pa)時可以低至室溫及高至500℃。具有非常低的碳及氫含量之高品質薄膜較佳地是在0.1-10Torr(13到1330Pa)之間的壓力下時、於200到400℃之間的溫度下沉積的。
-使用氧源,具有通式(SiH3)xR之矽烷(矽烷,二矽烷,三矽烷,三甲矽烷基胺),其中x可從1變化到4,且其中R為選自包括H,N,O,CH2,CH2-CH2,SiH2,SiH,Si,及在ALD機制中可能使用的觸媒。較佳地,矽烷為不含C之矽烷。最佳地,矽烷為三甲矽烷基胺。非常少量(<1%)觸媒可被導入反應器中。上述矽烷係難以用於ALD環境中,因為它們在矽晶圓上的吸附式不利的。使用觸媒係有助於矽烷吸附在基板上或底層中。在使用惰性氣體排空來自反應器的矽烷的清洗循環時間之後,可能由氧氣/臭氧的氣體混合物(典型地:5-20體積%臭氧溶於氧氣中),氧氣,水分及/或過氧化氫(H2O2)及其組合所組成之氧氣源係經由脈衝方式來導入。然後,循環是由一次脈衝的觸媒,一次脈衝的清洗氣體,一次脈衝的矽烷,一次脈衝的清洗氣體,一次脈衝的氧氣源,更多的清洗時間所組成。可能地,觸媒係同時與矽烷導入,因此降低在循環及其後持續期間步驟的數目。觸媒為胺或含金屬的分子,較佳地為含過渡金屬的分子,最佳地為含鉿分子,例如Hf(NEt2)4。在一些應用中,觸媒應為不含C。因此建議使用鹵化物或硝酸鹽,例如HfCl4或Hf(NO3)4。循環次數是由目標厚度,以及考慮在所給定實驗條件下所得到之每次循環的沉積速率而定。沉積溫度在操作壓力為0.1-100Torr(13到13300Pa)時可以低至室溫及高至400℃。具有非常低的碳及
氫含量之高品質薄膜較佳地是在0.1-10Torr(13到1330Pa)之間的壓力下時、於200到500℃之間的溫度下沉積的。
較佳地,根據本發明之方法係如下所進行:在基板已經導入反應室後,於反應室中氣體是在50到400℃的基板溫度下、於減壓下,藉由供應惰性氣體到反應室中來清洗的。然後,儘管在相同溫度及減壓下,氣態矽化合物之脈衝被傳送到反應室中,且非常薄的矽化合物層係藉由吸附作用而形成在處理基板上。接著係供應惰性氣體到反應室中,以清洗未反應的(未經吸附)矽化合物,在此之後,含氧氣體的脈衝係傳送到反應室中。含臭氧的氣體將吸附到基板上之非常薄的矽化合物層氧化,藉此形成非常薄的氧化矽層,再注射惰性氣體到反應室中以清洗未經反應的產物。藉由重複惰性氣體清洗、氣態矽化合物脈衝、惰性氣體清洗及含氧的混合氣體脈衝的順序來在基板上形成所欲厚度的氧化矽薄膜。
較佳地,基板應為用於製造半導體裝置之矽晶圓(或SOI),或沉積於其上的層,或用於製造液晶顯示器裝置的玻璃基板,或者為沉積於其上的層。在閘極已經形成於其上的半導體基板是用來作為基板,尤其當氧化矽薄膜係用於改良閘極崩潰電壓的目的時。
在反應室中的減壓較佳地是介於0.1到1000torr(13到1330kPa)之間,且較佳地為1到10torr(133到1330Pa)。
基板溫度應較佳地為至少50℃且最多為500℃,較佳地是在200到400℃之間,同時甚至更佳為250到350℃。
用於本發明方法中的惰性氣體較佳為氮氣,氬氣及/或氦氣。
上述矽化合物的例示為矽烷類,如四氫化矽[SiH4],二矽烷[(SiH3)2],三矽烷[(SiH3)2SiH2],烷基矽烷[(SiH3)nR,其中R代表C1到C6直鏈、分枝或環狀的烷類],三甲矽基胺[(SiH3)3N],及二矽氧烷[(SiH3)2O];矽氧化物如TEOS[Si(OC2H5)4],TMOS[Si(OCH3)4],雙三乙氧基甲矽烷基乙烷,及三烷基甲矽烷基烷類[(RO)3Si-Alk-Si(OR)3,其中R為C1到C6烷基],乙醯氧基矽烷(Si(-O-C(=O)-CH3)4及BDEAS(SiH2(NEt2)2)。
矽化合物較佳於室溫下為氣體時從例如圓筒中脈衝進入反應室中。當矽化合物在室溫為液態時,如TEOS之例子,其可使用起泡技術來脈衝入反應室中。特定地,矽化合物之溶液被放入反應室中,視情況需要加熱,並藉由使用置放於容器內之惰性氣體起泡管來使惰性氣體起泡以夾帶在惰性氣體(例如,氮氣,氬氣,氦氣)中,接著再導入反應室中。可使用液體質量流量控制器及蒸發器之組合。
含氧的混合氣體氧化矽化合物並將其轉化成氧化矽。混合氣體的例子為臭氧和氧氣的混合氣體,及臭氧加上氧氣加上惰性氣體(如氮氣,氬氣或氦氣)之混合氣體。在混合氣體中的臭氧濃度較佳為0.1到20體積%。小於0.1體積%之臭氧濃度具有在低溫下影響矽化合物之單原子層徹底氧化的可能性問題。另一方面,因為與臭氧相關的毒性、不安定性及危險性,高於20%之臭氧濃度具有處理方面的可能問題。
氣態矽化合物之脈衝是以1.0到100sccm之流速,歷時0.1到10秒的時間傳送到反應室中。含氧氣體的脈衝是以例如10到1000sccm之流速,歷時0.1到10秒的時間傳送到反應室中。
本發明將參照所附圖式來做更詳細的說明。
在圖1中,薄膜形成裝置具有反應室11;為惰性氣體(例如氮氣)進料來源之氮氣筒12;為氣態Si化合物進料來源之Si化合物氣體筒13;及為氧氣進料來源之氧氣筒14。在單一晶圓裝置中,基座(未示出)被置於反應室11中,且一個半導體基板(未示出),例如,矽基板,被置於基座上。在基座內提供一加熱器,以加熱半導體基板到一特定的反應溫度。在批次型式裝置的例子中,5到200個半導體基板係支持於反應室11內。在批次型式裝置中的加熱器可具有與單一晶圓裝置中的加熱器不同的結構。
氮氣筒12係經由管線L1連接到反應室11中。停止閥(shut valve)V1及流速控制器,例如質量流量控制器MFC1是以從上游側所給予的順序來提供在管線L1上。停止閥V2亦提供在鄰近於反應室11的管線L1上。
延伸到真空泵PMP的廢氣管線L2係提供在反應室11的底部。壓力計PG1,用於回壓控制之蝴蝶閥BV,以及停止閥V3是以從上游側所給予的順序來提供在管線L2上。真空泵PMP係經由管線L3連接到除毒裝置15。除毒裝置15例如可為相對應於氣體物種及含量的燃燒型式的除毒裝置或乾燥型式的除毒裝置。
Si化合物氣體筒13係經由管線L4連接到停止閥V2上游的管線L1上,亦即位在停止閥V2和質量流量控制器MFC1之間。停止閥V4,質量流量控制器MFC2,壓力計PG2及停止閥V5是以從上游側所給予的順序來置於管線L4上。管線L4是在壓力計PG2上游處來分枝的,且導致分枝管線L4'係連接到真空泵PMP上游的廢氣管線L2上,亦即位在真空泵PMP和停止閥V3之間。停止閥V5'係提供在分枝管線L4'上。停止閥V5和V5'
之狀態是以當其中一個為開啟,而另一個為關閉的方式來啟動的。
氧氣筒14係提供有管線L5,管線L5係延伸到臭氧生成器16;管線L5以從上游側考量的順序具有停止閥V6及質量流量控制器MFC3。臭氧生成器16係經由管線L6與停止閥V2上游的管線L1連接,亦即連接在停止閥V2及質量流量控制器MFC1之間。臭氧濃度感測器OCS,壓力計PG3及停止閥V7以從上游側考量的順序提供在管線L6上。管線L6係從壓力計PG3上游處分枝,且所得分枝管線L6'係連接到真空泵PMP上游的廢氣管線L2上,亦即連接到真空泵PMP及停止閥V3之間。停止閥V7'係提供在分枝管線L6'上。停止閥V7和V7'之狀態是以當其中一個為開啟,另一個為關閉的方式來操作的。
由臭氧生成器16所產生的氧和臭氧之混合氣體係流入管線L6中。在固定氧氣供給流速下,在混合氣體中的臭氧濃度之控制主要是取決於施加於臭氧生成器16的壓力和能量。結果,臭氧濃度的控制是藉由使用置於管線L6上的臭氧濃度感測器OCS來量測臭氧含量並基於所量測數值來對臭氧生成器16施以能量和容器壓力控制的回饋控制。
用於形成氧化矽薄膜方法之具體實例係使用在圖1到3中所描述的薄膜形成裝置以敘述。
1)氮氣清洗
一種處理基板,例如半導體晶圓(未示出)係安裝在反應室11的基座上,且晶圓係經由基座上的溫度調節器加熱到50到400℃。如圖1所示,關閉停止閥V5和V7,且其他停止閥V1到V4,V6,V5',及V7'均開啟。關閉的控制閥係在圖1中以填黑方式顯示,同時,開啟的控制閥是以空白顯示。
在下列敘述中,停止閥是以相同模式顯示。
然後,當藉由真空泵PMP之操作來使反應室11中的氣體經由管線L2來排出時,經由管線L1來從氮氣筒12引出氮氣,並藉由質量流量控制器MFC1控制進料流速而導入反應室11中。藉此,經由排出在反應室11內之氣體再供給氮氣到反應室11中,以在所欲真空(例如,0.1到1000torr)中進行氮氣清洗,再以氮氣來充滿反應室11之內部。
在開始及持續前述氮氣清洗步驟後,Si化合物氣體係持續地藉由質量流量控制器MFC2控制的進料氣體流速下來從Si化合物氣體筒13供應到管線L4中。然而,在前述氮氣清洗步驟期間,在管線L4(其與延伸到反應室11之管線L1連接)上的停止閥V5是關閉的,在與廢氣管線L2連接之分枝管線L4’上的停止閥V5’是開啟的,結果,該Si化合物在氮氣清洗步驟期間沒有供應到反應室11中,但是藉由管線L4及L4’供應到廢氣管線L2來排出。
此外,在開始及持續前述氮氣清洗步驟後,氧氣係持續地藉由質量流量控制器MFC3控制進料流速來從氧氣筒14供應到臭氧生成器16。將所欲能量施加於臭氧生成器16上,且將所欲濃度之含臭氧之氧氣(混合氣體)從臭氧生成器16供應到管線L6中,同時基於所得測量值,使用臭氧和氧之混合氣體流動經過之管線L6上的臭氧濃度感測器OCS來測量臭氧含量,並且對於臭氧生成器16所施加能量及容器壓力施加回饋控制。然而,在前述氮氣清洗步驟期間,停止閥V7(其是在與延伸到反應室11之管線L1連接之管線L6上面)被關閉,且停止閥V7'(其是在與排放管線L2連接之分枝管線L6上)係開啟,且結果臭氧+氧氣的混合氣體沒有在氮氣清洗步驟期
間供給到反應室11中,反而是在氮氣清洗步驟期間,經由管線L6和L6’供給到廢氣管線L2來排出。
2)Si化合物氣體脈衝
持續圖1顯示的狀態,關閉在分枝管線L4’上的停止閥V5',且相類似於這種操作,如圖2所示,開啟管線L4上的停止閥V5。在所欲時間後,使每個停止閥V5和V5'的狀態倒反過來。在開啟停止閥V5的期間內,來自Si化合物氣體筒13的Si化合物氣體、在控制的流速下從管線L4供給到管線L1,並且隨著氮氣脈衝進入反應室11中。此脈衝導致Si化合物於設置在反應室11內基座上的半導體晶圓之加熱表面上產生近乎單分子層的吸附。
3)氮氣清洗
在已經傳送Si化合物氣體脈衝後,如圖1所示進行氮氣清洗,即將於管線L4和分枝管線L4’上之停止閥V5和V5'之狀態從圖2所示的狀態中倒反過來。當如此進行時,保留在反應室11中的未反應Si化合物係藉由氮氣來排出,且反應室11內部係再次由氮氣取代。
4)臭氧+氧氣的混合氣體脈衝
持續圖1顯示的狀態,關閉在分枝管線L6’上的停止閥V7',且相類似於這種操作,如圖2所示,開啟管線L6上的停止閥V7。在所欲時間後,使每個停止閥V7和V7'倒反過來。在開啟停止閥V7的期間內,將臭氧和氧氣之混合氣體從管線L6供給到管線L1,並且隨著氮氣脈衝入反應室11中。由於此脈衝之緣故,吸附在設置在反應室11內基座上的半導體晶圓加熱表面上之Si化合物是藉由臭氧+氧氣之混合氣體氧化,導致形成近乎單分
子層的氧化矽薄膜半導體晶圓表面。
藉由重複1)氮氣清洗,2)Si化合物氣體脈衝,3)氮氣清洗,和4)臭氧+氧氣混合氣體脈衝之步驟,在半導體晶圓表面上形成所欲厚度之氧化矽薄膜。在傳送4)臭氧+氧氣的混合氣體脈衝之後,如圖1所示進行氮氣清洗,此乃藉由將管線L6和分枝管線L6'上之停止閥V7和V7'之狀態從圖3的狀態中倒反過來。當如此進行時,停留在反應室11中的反應副產物和未經反應的臭氧+氧氣之混合氣體係經由氮氣來排出,且反應室11內部則再次由氮氣取代。
在周圍溫度下為氣態之Si化合物被用來作為氣態Si化合物在使用圖1到3中所示之薄膜形成裝置來形成氧化矽膜的例子。然而,當使用在室溫下為液態的Si化合物,如TEOS時,氣態Si化合物仍然可使用起泡程序來導入反應室11。在特定術語中,起泡器係用來取代圖1到3所示之Si化合物氣筒13,且該起泡器係與攜有氮氣的管線L1上的閥V1上游處所分枝的分枝管線連接,使其可能重複步驟1)氮氣清洗,2)Si化合物氣體脈衝,3)氮氣清洗,及4)臭氧+氧的混合氣體的脈衝。
其中一個反應物可以連續方式導入,同時其它反應物可藉由脈衝方式導入(脈衝的-CVD機制)。
根據前述具體實施例,經由傳送Si化合物氣體脈衝,引發Si化合物單分子層吸附在被加熱到不大於400℃的低溫的處理基板表面上,且在惰性氣體(例如氮氣)清洗之後,傳送含臭氧的混合氣體(例如,臭氧+氧氣的混合氣體)之脈衝,藉由混合氣體中臭氧強烈的氧化作用來使吸附在處理基板表面上的Si化合物徹底氧化能使氧化矽薄膜以近乎單分子層的
形式生成。此外,在氧化反應後進行惰性氣體(例如,氮氣)的清洗,有可能避免在反應室內的水分被已經形成之氧化矽薄膜吸附。此能夠形成極佳的氧化矽薄膜,其中OH鍵結的導入已經被抑制或避免。這類氧化矽薄膜例如具有在低漏電流方面極佳的性能。
此外,因為吸附在處理基板表面上的Si化合物係藉由含合適數量的臭氧(例如,5到20%的濃度)之混合氣體脈衝來氧化,可以使在使用含臭氧混合氣體的CVD方法中已經被確認的對處理基板的氧化問題被避免掉。此對於處理基板只有微小影響,因為所需含臭氧混合氣體之數量是於低溫下以脈波方式導入。使得根據具體實例,提出能承受高溫之薄膜的處理基板或容易氧化之金屬薄膜或金屬矽化物薄膜以形成氧化矽薄膜是有可能的。
圖4係說明包括根據本發明之SiO2層的MOS電晶體側面圖。在基圓100上,於個別的汲極105和源極106上方係設置有閘極介電材料的閘極101,在101上方係具有金屬電極102。保護性氧化矽薄膜103係置於閘極101和金屬閘極102的側端。
SiO2薄膜103亦可沉積在源極106和汲極105的頂部。
下列參考圖1到4說明本發明之實施例:
使用顯示在上面圖1到3的薄膜形成裝置。矽晶圓係置於反應室11內的基座,且晶圓係加熱到100℃上。使用下列的條件,根據上述之具體實例來重複1)氮氣清洗,2)Si化合物氣體的脈衝,3)氮氣清洗,及4)臭氧+氧的混合氣體的脈衝等步驟,以形成氧化矽薄膜。
1)氮氣清洗
‧於反應室內的壓力:3torr
‧氮氣進料流速:130sccm
‧氮氣清洗時間:6秒
2)Si化合物氣體的脈衝
‧於反應室內的壓力:3torr
‧Si化合物氣體:三甲矽烷基胺(TSA)氣體
‧TSA氣體進料流速:2sccm
‧TSA脈衝時間:1秒
3)氮氣清洗
‧於反應室內的壓力:3torr
‧氮氣進料流速:130sccm
‧氮氣清洗時間:6秒
4)臭氧+氧的混合氣體的脈衝
‧於反應室內的壓力:3torr
‧臭氧+氧的混合氣體進料流速(5%的臭氧濃度):20sccm
‧混合氣體脈衝時間:2秒
氧化矽薄膜係藉由實施例1之相同方法來形成,但在本例中,置於反應室基座上的矽晶圓係加熱到200℃。
氧化矽薄膜係藉由實施例1之相同方法來形成,但在本例中,置於反
應室基座上的矽晶圓係加熱到300℃。
量測在實施例1到3中薄膜形成步驟的每一次循環時的氧化矽薄膜的厚度(實施例1係經歷50次的循環)。氧化矽薄膜可以在實施例1到3中,以每次循環約1.2-1.7埃的速率形成良好的厚度控制,而不需要孕核期(incubation period)。
此外,對於在200次循環後實施例3中所產生的氧化矽薄膜上進行FT-IR分析(晶圓溫度:300℃)。已經確認出在300℃的低溫下產生薄膜可以提供避免OH鍵導入的極佳氧化矽薄膜。
使用具有鉬薄膜在其表面上之矽晶圓作為樣本,使用如實施例1到3所述之相同方法來在鉬薄膜上形成氧化矽薄膜(100次循環)。此接續為測試形成氧化矽薄膜之底層的鉬薄膜之狀態。沒有觀察到鉬薄膜的氧化,即使臭氧+氧氣的混合氣體(臭氧濃度=5%)被用來作為氧化氣體時。
使用BDEAS及臭氧的SiO2薄膜之ALD的沉積:使用圖1到3的設置來藉由使用BDEAS及臭氧/氧之混合物的ALD方法,成功地在矽及銦上沉積薄膜。
該反應室是一種由傳統加熱器加熱的熱壁型反應器。臭氧器產生臭氧,且其濃度在-0.01MPaG時為大約150g/m3。BDEAS(雙(二乙基胺基)矽烷,SiH2(NEt2)2)係藉由將惰性氣體(氮氣)氣泡進入液態胺基矽烷來導入反應室11中。實驗條件為:
-7.0sccm O3
-93sccm O2
-BDEAS:1sccm[在1到7sccm的範圍內]
-N2:50sccm
-溫度範圍在200到400℃之間
-操作壓力:1Torr[在0.1到5Torr的範圍]
-清洗及脈衝時間係典型設定在每次5秒。
-循環次數係典型設置在600次循環。
進行實驗,以決定薄膜特性,如沉積速率,沉積溫度,薄膜品質和薄膜組成。
在Si晶圓上獲得SiO2薄膜。進行在200,250,300,350及400℃下的沉積。根據Auger的內縱深分析,所沉積的薄膜既不包括氮,也不包括碳。
改變SiO2薄膜的沉積循環次數(350,600及900次循環沉積測試)且所沉積SiO2薄膜檢驗出沒有或幾乎可忽略之孕核期。
進行在銦上的沉積,以觀察金屬電極的可能氧化。Auger分布顯示在ALD SiO2和銦基板之間有銳利的介面,且因此沒有觀察到金屬氧化作用。
使用BDMAS和臭氧的SiO2薄膜之ALD沉積:在如實施例4中的相同條件下進行相似的實驗。在每次循環0.3埃的沉積速率,於1Torr,250到300℃之間溫度下獲得高品質的薄膜。
使用三DMAS和臭氧的SiO2薄膜之ALD沉積:
在如實施例4中的相同條件下進行相似的實驗。在每次循環0.2埃的沉積速率,於1Torr,250到300℃之間溫度下獲得高品質的薄膜。
使用TSA,臭氧和觸媒[Hf(NEt2)4]的SiO2薄膜的ALD沉積:藉由另外導入稀釋於氮氣中的Hf(NEt2)4,TSA,N2,和臭氧/氧O3/O2的混合物,以ALD在矽上成功地沉積薄膜(經由質量流量控制器來氮氣起泡進入Hf(NEt2)4中提供了該觸媒和N2之混合物,其另外以相似方式導入反應器11中)。
反應器是一種由傳統加熱器加熱的熱壁型管狀反應器。藉由將惰性氣體(氮氣)起泡進入液態胺基矽烷中來將BDEAS導入爐內。典型實驗條件為:
-4sccm O3
-96sccm O2
-TSA:1sccm[在1到7sccm的範圍內]
-N2:100sccm
-溫度:400℃
-操作壓力:5Torr
-脈衝持續時間係典型設定為每次5秒且脈衝持續時間為10秒。
-循環次數為44次循環。
藉由Auger光譜儀觀察到氧化矽薄膜上沒有可偵測到的鉿。
11‧‧‧反應室
12‧‧‧氮氣筒
13‧‧‧Si化合物氣體筒
14‧‧‧氧氣筒
15‧‧‧除毒裝置
16‧‧‧臭氧生成器
V1-V7‧‧‧停止閥
V1’-V7’‧‧‧停止閥
L1-L7‧‧‧管線
L4’,L6’‧‧‧分枝管線
MFC1,MFC2,MFC3‧‧‧質量流量控制器
BV‧‧‧蝴蝶閥
PG1,PG2,PG3‧‧‧壓力計
PMP‧‧‧真空泵
OCS‧‧‧臭氧濃度感測器
Claims (13)
- 一種用於形成含氧化矽薄膜之方法,其包括下列步驟:a)提供一基板到反應室中,b)將至少一種含矽化合物注射到反應室中,上述至少一種含矽化合物為BDEAS雙(二乙基胺基)矽烷SiH2(NEt2)2;c)將具有臭氧對氧氣的比例為低於20體積%,較佳地為5到20體積%,之含氧氣及臭氧之氣體混合物注射到反應室中,及d)在反應室中,於低於400℃的溫度下,將至少一種含矽化合物與至少一種含臭氧氣體反應,以獲得沉積於基板上的含氧化矽薄膜,其中含氧化矽薄膜經由原子層沉積(ALD)方法或脈衝式-(CVD)方法沉積於基板上。
- 根據申請專利範圍第1項之方法,其進一步包括重複步驟b)到d)直到獲得含所欲SiO2薄膜的厚度。
- 根據申請專利範圍第1或2項之方法,其中在導入基板後,於進行步驟b),c)及d)之前,基板在反應室中被加熱,較佳地加熱到高至反應室的溫度。
- 根據申請專利範圍第1或2項之方法,其中藉由間斷地注射至少一種化合物及/或氣體來進行至少一個步驟b)及/或c)。
- 根據申請專利範圍第1或2項之方法,其中在反應室中進行至少一種化合物和含氧氣及臭氧之氣體混合物的交替注射。
- 根據申請專利範圍第1或2項之方法,其中在注射另一種化合物及/或至少一種含氧氣之氣體之前,該至少一種化合物或含氧氣及臭氧之氣體混合物被吸附在基板的表面上。
- 根據申請專利範圍第1或2項之方法,其中每次的化合物及/或含氧氣及臭氧之氣體混合物的注射後,係接續著在反應室中清洗氣體的注射,例如惰性氣體的注射。
- 根據申請專利範圍第1或2項之方法,其中重複化合物及/或氣體的注射,直到獲得含所欲SiO2薄膜的厚度。
- 根據申請專利範圍第1或2項之方法,其中反應室的壓力最多為100Torr(133kPa),較佳地最多為5Torr(665Pa)。
- 根據申請專利範圍第1或2項之方法,其中在含SiO2的薄膜中氫鍵的含量小於8x1021原子/cc。
- 根據申請專利範圍第1或2項之方法,其中氧氣/臭氧的氣體混合物被稀釋到惰性氣體中,較佳地為氮氣中。
- 根據申請專利範圍第1或2項之方法,其中惰性氣體亦被導入到反應室中。
- 根據申請專利範圍第1或2項之方法,其中少量的觸媒,例如小於1%的Hf(NEt2)4或NHEt2被導入到反應室中。
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- 2006-03-17 KR KR1020127002046A patent/KR101248358B1/ko active IP Right Grant
- 2006-03-17 KR KR1020077023846A patent/KR100961805B1/ko active IP Right Grant
- 2006-03-17 AT AT06725128T patent/ATE482301T1/de not_active IP Right Cessation
- 2006-03-17 US US11/908,707 patent/US8227032B2/en active Active
- 2006-03-17 KR KR1020137004043A patent/KR20130027573A/ko not_active Application Discontinuation
- 2006-03-17 WO PCT/EP2006/060829 patent/WO2006097525A2/en active Application Filing
- 2006-03-17 JP JP2008501327A patent/JP5329218B2/ja active Active
- 2006-03-17 KR KR1020147010408A patent/KR20140069192A/ko not_active Application Discontinuation
- 2006-03-17 CN CNA2006800149039A patent/CN101171366A/zh active Pending
- 2006-03-17 EP EP06725128A patent/EP1861519B1/en active Active
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Also Published As
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WO2006097525A3 (en) | 2006-11-23 |
WO2006097525A2 (en) | 2006-09-21 |
JP2013070077A (ja) | 2013-04-18 |
ATE482301T1 (de) | 2010-10-15 |
TWI435387B (zh) | 2014-04-21 |
TWI515794B (zh) | 2016-01-01 |
US8613976B2 (en) | 2013-12-24 |
KR20090107090A (ko) | 2009-10-12 |
KR20120044992A (ko) | 2012-05-08 |
US20120276292A1 (en) | 2012-11-01 |
KR100961805B1 (ko) | 2010-06-08 |
DE602006017042D1 (de) | 2010-11-04 |
KR20150047631A (ko) | 2015-05-04 |
US20090232985A1 (en) | 2009-09-17 |
JP2006261434A (ja) | 2006-09-28 |
JP5631958B2 (ja) | 2014-11-26 |
KR20130027573A (ko) | 2013-03-15 |
KR101547093B1 (ko) | 2015-08-24 |
EP1861519B1 (en) | 2010-09-22 |
TW200707582A (en) | 2007-02-16 |
CN101171366A (zh) | 2008-04-30 |
EP1861519A2 (en) | 2007-12-05 |
US8227032B2 (en) | 2012-07-24 |
JP5329218B2 (ja) | 2013-10-30 |
KR20140069192A (ko) | 2014-06-09 |
JP2008533731A (ja) | 2008-08-21 |
KR101248358B1 (ko) | 2013-04-03 |
KR20070114393A (ko) | 2007-12-03 |
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