CN102187011B - Cvd前体 - Google Patents
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- Publication number
- CN102187011B CN102187011B CN200980141783.2A CN200980141783A CN102187011B CN 102187011 B CN102187011 B CN 102187011B CN 200980141783 A CN200980141783 A CN 200980141783A CN 102187011 B CN102187011 B CN 102187011B
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- Prior art keywords
- gas
- silacyclobutane
- film
- diamino
- silicon
- 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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- 239000002243 precursor Substances 0.000 title description 7
- 239000007789 gas Substances 0.000 claims abstract description 73
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000004065 semiconductor Substances 0.000 claims abstract description 10
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 13
- 238000004518 low pressure chemical vapour deposition Methods 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- -1 pyrrolidyl Chemical group 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- JUINSXZKUKVTMD-UHFFFAOYSA-N hydrogen azide Chemical compound N=[N+]=[N-] JUINSXZKUKVTMD-UHFFFAOYSA-N 0.000 claims description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000010408 film Substances 0.000 abstract 2
- 230000004888 barrier function Effects 0.000 abstract 1
- 239000003989 dielectric material Substances 0.000 abstract 1
- 238000002161 passivation Methods 0.000 abstract 1
- 125000006850 spacer group Chemical group 0.000 abstract 1
- 238000012719 thermal polymerization Methods 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- PASYEMKYRSIVTP-UHFFFAOYSA-N 1,1-dichlorosiletane Chemical compound Cl[Si]1(Cl)CCC1 PASYEMKYRSIVTP-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 0 CC=*(CN(C1)S2(CCC2)*2C=C2)C1(C1)C1C1CC1 Chemical compound CC=*(CN(C1)S2(CCC2)*2C=C2)C1(C1)C1C1CC1 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000012066 reaction slurry Substances 0.000 description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000012212 insulator Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- DVHMVRMYGHTALQ-UHFFFAOYSA-N silylhydrazine Chemical compound NN[SiH3] DVHMVRMYGHTALQ-UHFFFAOYSA-N 0.000 description 2
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- AUGGYPRPZNGWTM-UHFFFAOYSA-N CC[SiH2]NN(C)C Chemical compound CC[SiH2]NN(C)C AUGGYPRPZNGWTM-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- FCLZCOCSZQNREK-UHFFFAOYSA-N Pyrrolidine, hydrochloride Chemical compound Cl.C1CCNC1 FCLZCOCSZQNREK-UHFFFAOYSA-N 0.000 description 1
- 229910004014 SiF4 Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- XWBDWHCCBGMXKG-UHFFFAOYSA-N ethanamine;hydron;chloride Chemical compound Cl.CCN XWBDWHCCBGMXKG-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000006038 hexenyl group Chemical group 0.000 description 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000005891 transamination reaction Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Chemical group 0.000 description 1
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
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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
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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
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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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
- C23C16/36—Carbonitrides
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- 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
- C23C16/42—Silicides
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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
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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]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02126—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
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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
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Abstract
一种通过热聚合反应性气体混合物二氨基硅杂环丁烷和选自供氮气体、供氧气体及其混合物的源气体而生产含硅薄膜的方法。沉积的薄膜可以是氮化硅、碳氮化硅、二氧化硅或碳掺杂二氧化硅。这些薄膜适用于作为半导体器件中的介电层,钝化涂层,防护涂层,隔板,衬里和/或应激体。
Description
相关申请的交叉引用
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背景技术
二氧化硅和碳掺杂氧化硅的薄膜是制作半导体器件中所用的普通介电质。这些材料薄膜在低温下的沉积一般采用等离子体增强的化学汽相沉积(PECVD)工艺方法。然而,由于考虑到等离子体潜在地损坏晶体管,在某些情况下优选低温工艺方法。
热氮化硅或碳氮化硅已经用作半导体器件的介电质、钝化涂层、防护涂层、隔板、衬里或应激体。由于受限于器件中紧紧的热预算和热敏组分,半导体制作工业正寻求容许在降低的温度下沉积这些膜的新前体。据预计,当大规模生产开始时膜沉积温度在22nm的技术节可能低至400至450℃。容许膜在如此低温下沉积,这种前体要求在接近200℃下分解并,同时,仍能满足货架稳定性的条件。或许仅仅已经证实的硅烷前体远远地具有如此低的热分解温度和良好的货架寿命,是通过Air Products开发的肼基硅烷。已经公开,二(1,1-二甲基肼基)乙基硅烷,HEtSi(NH-NMe2)2,在氨中于370℃下提供了的膜生长速率。含微弱N-N键的1,1-二甲基肼基配体已知在硅表面上低于200℃下分解。然而,由肼基硅烷沉积的碳氮化硅膜具有低密度的问题。
二氨基硅杂环丁烷已被人提出作为新一类低温沉积含硅膜的前体。这些分子具有在低温下可能分解的应变四员硅杂环丁烷环。然而,因为二氨基硅杂环丁烷通过不同于肼基硅烷的机理分解,则二氨基硅杂环丁烷预期提供超级的薄膜性能。二氨基硅杂环丁烷已经可以制备99+%的纯度,并已经发现在200至250℃下发生分解。
发明内容
本发明涉及通过热聚合含二氨基硅杂环丁烷和选自供氮气体、供氧气体及其混合物的源气体的反应性气体混合物而生产含硅薄膜的方法。沉积的膜可以是氮化硅、碳氮化硅、二氧化硅或碳掺杂二氧化硅。这些膜适用于作为半导体器件中的介电质、钝化涂层、防护涂层、隔板、衬里和/或应激体。
附图说明
图1显示了在低压CVD反应器中采用二(叔丁氨基)硅杂环丁烷(BTBSCB)沉积碳氮化硅膜的工艺方法。
具体实施方式
本发明涉及一种在基底上生产含硅薄膜的方法,其中所述薄膜可以是氮化硅、碳氮化硅、二氧化硅或碳掺杂二氧化硅。典型的基底包括但不限于,半导体基底,液晶器件,发光二极管显示器器件和有机发光显示器器件。对于“半导体基底”是指包括但不限于预想用于生产包括焦平面阵列的半导体组件的硅基器件和砷化镓基器件,光电器件,光伏电池,光学器件,晶体管型器件,3-D器件,绝缘体上外延硅器件(silicon-on-insulatordevices),超晶格器件等。半导体基底可以包含一层或多层布线。半导体基底也可以是在形成任何布线层之前的那些基底。
本文中有用的二氨基硅杂环丁烷选自具有以下结构式的化合物及其混合物:
其中每一R1,R2,R3,R4,R5和R6独立选自氢或具有1至6个碳的单价烃基(直链的,支链的或环状的;饱和的或不饱和的)而m,n具有0至10的值。每一R1,R2,R3,R4,R5和R6可以通过但不限于甲基,乙基,丙基,异丙基,正丁基,仲丁基,叔丁基,环己基,环丙基,苯基,乙烯基,己烯基等而示例性说明。
本文中有用的二氨基硅杂环丁烷通过具有以下结构式的化合物示例性说明
用于生产膜的反应性气体混合物也可以包含用量受控的选自供氮气体、供氧气体或其混合物的源气体。源气体的用量可以通过所用的气体类型,或通过膜沉积工艺条件而进行控制。
供氮气体包括,但不限于氮气N2,氨气NH3,肼N2H4,叠氮酸HN3,及其混合物。典型地供氮气体是氨,但是肼和叠氮酸可以用于低温沉积。供氮气体的用量典型地为每体积份的二氨基硅杂环丁烷0.1至50体积份的供氮气体,可替代地为每体积份的二氨基硅杂环丁烷0.2至7体积份的供氮气体。本领域内的技术人员将能够基于供氮气体的类型和沉积条件而易于确定供氮气体的用量。
供氧气体包括但不限于,氧气,空气,一氧化二氮,氧化一氮,一氧化碳,过氧化物,二氧化硫及其混合物。供氧气体的用量典型地为每体积份的二氨基硅杂环丁烷0.1至50体积份的供氧气体可替代地每体积份的二氨基硅杂环丁烷0.2至7体积份的供氧气体。本领域内的技术人员将能够基于供氧气体的类型和沉积条件而易于确定供氮气体的用量。
其它材料可以存在于反应性气体混合物中。例如,载体气体如氦、氮气或氩气,掺杂剂如膦或乙硼烷,卤素如氟,含卤素气体如SiF4,CF4,C3F6和C4F8,或其它任何对膜提供附加所需的性质的材料都可以存在。
反应性气体混合物引入到含基底,优选半导体基底的沉积室中,其中二氨基硅杂环丁烷的聚合作用被引发而导致膜沉积于所述基底上。热化学汽相沉积如低压化学汽相沉积(LPCVD)或原子层沉积(ALD)是优选的,因为能够低温使用并广泛地应用于工业中。等离子体辅助CVD也可以用于采用或不采用供氧气体由二氨基硅杂环丁烷沉积二氧化硅或碳掺杂氧化硅膜,或采用或不采用供氮气体由二氨基硅杂环丁烷沉积氮化硅或碳氮化硅膜。
在PECVD中,气体混合物通过将其传递通过等离子体场而进行反应。在工艺过程中使用的等离子体包含衍生于各种源如放电、处于射频或微波范围的电磁场、激光或粒子束的能量。一般在等离子体沉积工艺过程中优选使用射频(10kHz至102MHz)或微波(1.0至10GHz)能量以中等功率密度(0.1至5w/cm2)。特定的频率、功率和压力,然而,一般都适应于设备。优选膜采用功率20至1000W;压力0.13至1333Pa;和温度25至500℃进行沉积。限于低压(0.13-0.65Pa)微波频率等离子体,经常称之为高密度等离子体,能够与RF频率激发结合而在工艺过程中有助于CVD生长期间平面化一直变化的表面形貌。
本文中可以沉积的一种类型的膜是碳氮化硅膜。这些膜典型地具有化学式SiwCχHyNz,其中C∶Si比率能够处于约约0∶1至约10∶1的范围而N∶Si的比率能够处于约0∶1至约1.5∶1范围,其余的是氢。为了沉积碳氮化硅膜,共反应物是供氮气体。理论上而言,当膜由二氨基硅杂环丁烷和供氮气体沉积时,氨基用氮气源气体通过转氨作用而取代,而硅杂环丁烷基团分解释放气态有机物种。因此,预期在膜中的C∶Si比率将是不同于前体中的C∶Si比率的。二氨基硅杂环丁烷相对供氮气体的用量处于1份二氨基硅杂环丁烷对100份供氮气体,可替代地1份二氨基硅杂环丁烷对10份供氮气体的范围。
本文中可以沉积的一种类型的膜是氮化硅膜。这些膜典型地具有化学式SibHcNd,其中H∶Si比率能够处于约0∶1至约5∶1的范围而N∶Si比率能够处于约0∶1至约1.5∶1。这些膜典型地采用供氮气体作为共反应物进行沉积。二氨基硅杂环丁烷相对供氮气体的用量处于1份二氨基硅杂环丁烷对100份供氮气体,可替代地1份二氨基硅杂环丁烷对10份供氮气体的范围。
本文中可以沉积的一种类型的膜是氧化硅膜。这些膜典型地具有化学式SiOx,其中x为0至3。这些膜典型地采用供氧气体作为共反应物进行沉积。二氨基硅杂环丁烷相对供氧气体的用量处于1份二氨基硅杂环丁烷对100份供氧气体,可替代地1份二氨基硅杂环丁烷对10份供氧气体的范围。
本文中可以沉积的第四种类型的膜是碳掺杂二氧化硅膜。这种沉积的膜典型地具有SieCfOgHh的组成,其中e具有10至33,可替代地18至20原子%的值,f具有1至66,可替代地18至21原子%的值,g具有1至66,可替代地31至38原子%而h具有0.1至60,可替代地25至32原子%的值;而e+f+g+h=100原子%。这些膜典型地采用供氧气体作为共反应物进行沉积。二氨基硅杂环丁烷相对供氧气体的用量处于1份二氨基硅杂环丁烷对100份供氧气体,可替代地1份二氨基硅杂环丁烷对10份供氧气体的范围。
本文中沉积的膜可以是不同厚度的。具有0.01至10μm厚度的膜可以通过本发明的方法进行沉积。另外,这些膜具有0.5至3.0μm的厚度。
本文中沉积的膜,尤其适用于作为半导体集成电路生产中的介电质或防护金属涂层,包括但不限于,栅介电质,前金属和间金属介电质和钝化涂层。
图1显示了由二氨基硅杂环丁烷沉积氮化硅或碳氮化硅薄膜的典型工艺方法。在该工艺方法中,晶片基底载入到低压CVD(LPCVD)反应器中而LPCVD反应器加热至目标温度,并排气低至10-4torr。氨气与稀释氮气混合,而混合的NH3-N2气体随后计量加入LPCVD的反应器中。氮气载气流过含液体BTBSCB的样品圆筒。氮气中承载的BTBSCB蒸气计量加入LPCVD反应器中。在膜沉积之后,LPCVD反应器冷却下来并反填充氮气直至达到大气压力。最后涂层的晶片从LPCVD反应器中移出。
实施例
以下所包括的实施例证明了本发明的实施方式。本领域的那些技术人员应该理解到,在以下实施例中所公开的技术代表了本发明人发明的技术而在本发明的实践中工作良好。然而,本领域内的那些技术人员,依据本公开内容,应该理解到,许多变化能够在公开的具体实施方式中作出,而仍获得相像或类似的结果,而不偏离本发明的精神和范围。所有的百分数都是以wt%计。
实施例1
二(叔丁氨基)硅杂环丁烷(BTBSCB)通过将1,1-二氯硅杂环丁烷与过量的叔丁胺反应(方程式1)而合成。为了实现此目的,向105mL(0.999mol)叔丁胺在1L己烷中的溶液中于0℃下加入19.7mL(0.166mol)1,1-二氯硅杂环丁烷。室温下稠化3天之后,反应料浆经过过滤而除去叔丁胺盐酸盐。滤液真空干燥而得到粗液体产品,其随后真空蒸馏。在71℃于50torr压力下分离出16g产品,纯度99.2%,收率45%。采用1H、13C和29Si NMR、FT-IR和GC-MS分析的产品结构,与二(叔丁氨基)硅杂环丁烷一致。
实施例2
二(乙氨基)硅杂环丁烷通过将1,1-二氯硅杂环丁烷与过量的乙胺反应(方程式2)而合成。为了实现此目的,向66.2mL(1.01mol)乙胺在1L戊烷中的溶液中于-10℃下加入20.0mL(0.169mol)1,1-二氯硅杂环丁烷。室温下稠化1天之后,反应料浆经过过滤而除去乙胺盐酸盐。滤液真空干燥而得到粗液体产品,其随后真空蒸馏。在42℃于30torr压力下分离出9.8g产品,纯度99%,收率36%。采用1H、13C和29Si NMR、FT-IR和GC-MS分析的产品结构,与二(乙氨基)硅杂环丁烷一致。
实施例3
二(吡咯烷基)硅杂环丁烷通过将1,1-二氯硅杂环丁烷与过量的吡咯烷反应(方程式3)而合成。为了实现此目的,向100.0mL(1.20mol)吡咯烷在1L己烷中的溶液中于-10℃下加入23.7mL(0.200mol)1,1-二氯硅杂环丁烷。室温下稠化2天之后,反应料浆经过过滤而除去吡咯烷盐酸盐。滤液真空干燥而得到粗液体产品,其随后真空蒸馏。在51℃于1torr压力下分离出15.4g产品,纯度99.7%,收率34%。采用1H、13C和29Si NMR、FT-IR和GC-MS分析的产品结构,与二(吡咯烷基)硅杂环丁烷一致。
实施例4:二氨基硅杂环丁烷热分解温度的测定
在实施例1至3中生产的二氨基硅杂环丁烷采用差示扫描量热仪(DSC)进行分析。在DSC谱图上放热曲线开始倾斜的温度下分子开始热分解。热分解温度对于二(叔丁氨基)硅杂环丁烷(BTBSCB),二(乙氨基)硅杂环丁烷和二(吡咯烷基)硅杂环丁烷分别测定为200℃,200℃和250℃。那已经经过热处理的DSC样品采用GC-MS分析而确证这些物质的分解作用。BTBSCB的分解采用顶空GC在200℃和295℃下测试而进行进一步检验。
Claims (15)
1.一种在基底上生产含硅薄膜的方法,所述方法包括热聚合反应性气体混合物,所述气体混合物包括二氨基硅杂环丁烷和选自供氮气体、供氧气体及其混合物的源气。
3.根据权利要求2所述的方法,其中所述二氨基硅杂环丁烷选自二(叔丁氨基)硅杂环丁烷,二(乙氨基)硅杂环丁烷和二(吡咯烷基)硅杂环丁烷。
4.根据权利要求1所述的方法,其中所述源气是选自氮气N2,氨气NH3,肼N2H4,叠氮酸HN3,及其混合物的供氮气体。
5.根据权利要求4所述的方法,其中每体积份的二氨基硅杂环丁烷混合0.1至50体积份的供氮气体。
6.根据权利要求4所述的方法,其中所述源气体是氨气。
7.根据权利要求1所述的方法,其中所述源气体是选自氧气,空气,一氧化二氮,一氧化氮,一氧化碳,过氧化物,二氧化硫及其混合物的供氧气体。
8.根据权利要求7所述的方法,其中每体积份的二氨基硅杂环丁烷混合0.1至50体积份的供氧气体。
9.根据权利要求1所述的方法,其中也存在选自载体气体,掺杂剂,卤素和含卤素的气体的物质。
10.根据权利要求1所述的方法,其中所述基底是半导体基底。
11.根据权利要求1所述的方法,其中通过低压化学汽相沉积或原子层沉积实施所述热聚合。
12.根据权利要求1所述的方法,其中所述沉积的膜是碳氮化硅膜,氮化硅膜,氧化硅膜或碳掺杂的二氧化硅膜。
13.根据权利要求1所述的方法,其中所述沉积的膜具有0.01至10μm的厚度。
14.一种用于生产含硅薄膜的热聚合反应性气体混合物,包括二(乙氨基)硅杂环丁烷和选自供氮气体、供氧气体及其混合物的源气。
15.一种用于生产含硅薄膜的热聚合反应性气体混合物,包括二(吡咯烷基)硅杂环丁烷和选自供氮气体、供氧气体及其混合物的源气。
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