JP2015159335A - 酸化ケイ素及び酸窒化ケイ素膜、それらの形成方法、並びに化学気相成長用組成物 - Google Patents
酸化ケイ素及び酸窒化ケイ素膜、それらの形成方法、並びに化学気相成長用組成物 Download PDFInfo
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- JP2015159335A JP2015159335A JP2015106450A JP2015106450A JP2015159335A JP 2015159335 A JP2015159335 A JP 2015159335A JP 2015106450 A JP2015106450 A JP 2015106450A JP 2015106450 A JP2015106450 A JP 2015106450A JP 2015159335 A JP2015159335 A JP 2015159335A
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- silicon oxide
- chemical vapor
- vapor deposition
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 43
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 28
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052710 silicon Inorganic materials 0.000 title claims description 15
- 239000010703 silicon Substances 0.000 title claims description 15
- 239000000203 mixture Substances 0.000 title claims description 11
- 239000002243 precursor Substances 0.000 claims abstract description 52
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 18
- 239000007800 oxidant agent Substances 0.000 claims abstract description 16
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 125000003282 alkyl amino group Chemical group 0.000 claims abstract description 8
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 238000000151 deposition Methods 0.000 claims description 16
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- BIVNKSDKIFWKFA-UHFFFAOYSA-N N-propan-2-yl-N-silylpropan-2-amine Chemical compound CC(C)N([SiH3])C(C)C BIVNKSDKIFWKFA-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- -1 alkyl hydrazine Chemical compound 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 4
- 239000001272 nitrous oxide Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- NJZXXBCJVZNZOI-UHFFFAOYSA-N 1-[amino(propyl)silyl]propane Chemical group CCC[SiH](N)CCC NJZXXBCJVZNZOI-UHFFFAOYSA-N 0.000 claims 2
- CHADYUSNUWWKFP-UHFFFAOYSA-N 1H-imidazol-2-ylsilane Chemical compound [SiH3]c1ncc[nH]1 CHADYUSNUWWKFP-UHFFFAOYSA-N 0.000 claims 2
- USTUYCWNJZIRHP-UHFFFAOYSA-N 1H-pyrrol-2-ylsilane Chemical compound [SiH3]C1=CC=CN1 USTUYCWNJZIRHP-UHFFFAOYSA-N 0.000 claims 2
- SWNUAOAVNPPMOD-UHFFFAOYSA-N 2-methyl-N-(2-methylpropyl)-N-silylpropan-1-amine Chemical compound CC(C)CN([SiH3])CC(C)C SWNUAOAVNPPMOD-UHFFFAOYSA-N 0.000 claims 2
- LGMQYXBIQCWTMR-UHFFFAOYSA-N CN1CCNCC1[SiH3] Chemical compound CN1CCNCC1[SiH3] LGMQYXBIQCWTMR-UHFFFAOYSA-N 0.000 claims 2
- AEMCEFCSIVSRGO-UHFFFAOYSA-N [SiH3]C=1C=CNN=1 Chemical compound [SiH3]C=1C=CNN=1 AEMCEFCSIVSRGO-UHFFFAOYSA-N 0.000 claims 2
- YGTNKWDUDNNONJ-UHFFFAOYSA-N pyrrolidin-1-ylsilane Chemical compound [SiH3]N1CCCC1 YGTNKWDUDNNONJ-UHFFFAOYSA-N 0.000 claims 2
- FPNIXYNDTVFQNX-UHFFFAOYSA-N (2-methylpyrrolidin-1-yl)silane Chemical compound CC1CCCN1[SiH3] FPNIXYNDTVFQNX-UHFFFAOYSA-N 0.000 claims 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract description 9
- 229910000077 silane Inorganic materials 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 abstract 1
- WZUCGJVWOLJJAN-UHFFFAOYSA-N diethylaminosilicon Chemical compound CCN([Si])CC WZUCGJVWOLJJAN-UHFFFAOYSA-N 0.000 description 14
- 150000002431 hydrogen Chemical class 0.000 description 9
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910002808 Si–O–Si Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000000231 atomic layer deposition Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 4
- 238000005001 rutherford backscattering spectroscopy Methods 0.000 description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- CLQPEJKJHMMRRW-UHFFFAOYSA-N N-silylpropan-2-amine Chemical compound CC(C)N[SiH3] CLQPEJKJHMMRRW-UHFFFAOYSA-N 0.000 description 1
- 0 [*+]N([*+])C1CCCCC1 Chemical compound [*+]N([*+])C1CCCCC1 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 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
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- JTGAUXSVQKWNHO-UHFFFAOYSA-N ditert-butylsilicon Chemical compound CC(C)(C)[Si]C(C)(C)C JTGAUXSVQKWNHO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VYIRVGYSUZPNLF-UHFFFAOYSA-N n-(tert-butylamino)silyl-2-methylpropan-2-amine Chemical compound CC(C)(C)N[SiH2]NC(C)(C)C VYIRVGYSUZPNLF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000012686 silicon precursor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XVYIJOWQJOQFBG-UHFFFAOYSA-N triethoxy(fluoro)silane Chemical compound CCO[Si](F)(OCC)OCC XVYIJOWQJOQFBG-UHFFFAOYSA-N 0.000 description 1
- 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
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
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- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N 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
- C23C16/22—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
- C23C16/22—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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- 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
- 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
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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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- 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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
- H01L21/3145—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers formed by deposition from a gas or vapour
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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 potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table 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
- H01L21/31633—Deposition of carbon doped silicon oxide, e.g. SiOC
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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
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Abstract
【解決手段】以下の式によって表されるアミノシラン前駆体を使用することを含む、酸化剤との反応によるシラン酸化物前駆体の化学気相成長によって基材上に酸化ケイ素膜を形成するための方法:RR1NSiH3(式A)、RN(SiH3)2(式B)、SiH3RN(R2)NR1SiH3(式C)・式中、R及びR1は、直鎖、分枝又は環状の飽和又は不飽和のC2〜C10のアルキル基、芳香族、アルキルアミノ基からなる群より選択され;式A及び式C中において、RとR1は、環状基(CH2)nになっていてもよく(nは1〜6、好ましくは4及び5)、且つR2は、一重結合、(CH2)n鎖、環、SiR2又はSiH2を表す。
【選択図】なし
Description
R及びR1は、直鎖、分枝又は環状の飽和又は不飽和のC2〜C10のアルキル基、芳香族、アルキルアミノ基からなる群より選択され;
式A及び式C中において、RとR1は、環状基(CH2)nになっていてもよく(nは1〜6、好ましくは4及び5)、且つ
R2は、一重結合、(CH2)m鎖(mは1〜6)、環、SiR2又はSiH2を表す)。
低温条件での誘電体膜の形成を促進できること;
低い酸エッチ速度を有する膜を製造できること;
前駆体と酸素含有源との比を変化させることにより、得られる酸化ケイ素膜の炭素含有量を調整できること;
前駆体と窒素含有源との比を変化させることにより、得られる酸化ケイ素膜の窒素含有量を調整できること;
優れた堆積速度で酸化ケイ素膜を形成できること;及び
種々のシラン前駆体を使用した場合に過度の分解速度によって一般に生じる多くの製造上の問題を克服できること。
酸化ケイ素堆積物のための実験用前駆体を評価するのに用いられる低圧化学気相成長(LPCVD)反応器において、前駆体を試験した。前駆体を脱ガスし、低圧マスフローコントローラ(MFC)を通じて、反応器に計量供給した。化学物質の質量損失と流れ時間に対して、マスフローコントローラ(MFC)流量を較正した。酸素などの追加の反応体、及び窒素及びヘリウムなどの希釈剤も同様に、較正されたマスフローコントローラ(MFC)を通じて反応器に計量供給した。10−4Torr(0.013Pa)未満に反応器を排気できるルーツブロワー/ドライポンプの組合せに、反応器を連結した。堆積中にシリコンウェハの装填物にわたる温度は、設定点の1℃以内にした。
[ジエチルアミノシラン前駆体を用いた酸化ケイ素膜の形成]
以下の反応体及び流量条件を用いて、上で概説した一般的手順に従った。ジエチルアミノシラン(DEAS)11.7sccmを、O25.9sccmとともに、0.6Torrで、74分の堆積時間にわたって、500℃で、LPCVD反応器に流した。
[ジエチルアミノシラン前駆体を用いた酸化ケイ素膜の形成]
プロセス条件を除いて例1の手順に従った。この目的は、より高い温度と短い反応時間の効果を決定することであった。この例では、ジエチルアミノシラン(DEAS)11.7sccmを、O25.9sccmとともに、0.6Torrで、33分の堆積時間にわたって、600℃で、反応器に流した。
[ジイソプロピルアミノシラン前駆体を用いた酸化ケイ素膜の形成]
プロセス条件及び前駆体を除いて本質的に例1の手順に従った。この例では、ジイソプロピルアミノシラン(DIPAS)10.5sccmを、O25.0sccmとともに、0.6Torrで、74分の堆積時間にわたって、500℃で、反応器に流した。
[ジイソプロピルアミノシラン前駆体を用いた酸化ケイ素膜の形成]
プロセス条件及び前駆体を除いて例2の手順に従った。この例では、ジイソプロピルアミノシラン(DIPAS)10.5sccmを、O25.0sccmとともに、0.6Torrで、33分の堆積時間にわたって、600℃で、反応器に流した。
まとめると、例1〜4は、式Aで示されるタイプの有機アミノシランが、半導体基材上に酸化ケイ素膜を製造するための前駆体として使用できることを示している。ジイソプロピルアミノシラン(DIPAS)は、低エッチ速度の酸化物のプロセスにおいて、前駆体としてのジエチルアミノシラン(DEAS)の使用に対する利点をもたらす。ジエチルアミノシラン(DEAS)は、室温でジイソプロピルアミノシラン(DIPAS)よりも不安定である。ジエチルアミノシラン(DEAS)の不安定な性質は、多くのEH&Sマネジメント、製造、供給ライン(倉庫保管及び船積みを含む)及びエンドユーザプロセスの問題を引き起こす場合がある。例3及び4(本発明)は、ジイソプロピルアミノシラン(DIPAS)から形成された酸化物膜が、同様のプロセス条件下で例1及び2(参考例)においてジエチルアミノシラン(DEAS)から形成された酸化物膜と同じエッチ速度、誘電率、屈折率及び定性的組成(FTIRによる)を一般に有することを示している。したがって、化学及びプロセス両方の観点から、ジイソプロピルアミノシラン(DIPAS)は、低エッチ速度の酸化ケイ素膜を製造するための好ましい前駆体である。
Claims (24)
- 下記の式によって表されるアミノシランからなる群より選択されるアミノシラン前駆体と酸化剤とを使用することを含む、化学気相成長によって基材上に酸化ケイ素膜を形成する方法[ただし、前記アミノシラン前駆体は、ジ(ノルマルプロピル)アミノシラン、ジイソプロピルアミノシラン、ジイソブチルアミノシラン、ピロリルシラン、イミダゾリルシラン、ピラゾリルシラン、1−メチルピペラジニルシラン、ピロリジニルシラン、又は2−メチルピロリジニルシランではない]:
R及びR1は、置換又は非置換の、直鎖、分枝又は環状の飽和又は不飽和のC3〜C10のアルキル基;芳香族基;アルキルアミノ基;複素環基;からなる群より選択され;
式A及び式C中において、RとR1は、環状基になっていてもよく、且つ
R2は、一重結合、(CH2)m鎖(mは1〜6)、環、SiR2又はSiH2を表し、
ただし、式A中のRとR1の双方が直鎖アルキル基ではない)。 - 前記アミノシラン前駆体が式Aによって表される、請求項1に記載の方法。
- R及びR1が3〜4個の炭素を有するアルキル基である、請求項2に記載の方法。
- R及びR1が環状である、請求項2に記載の方法。
- R及びR1が組み合わさって(CH2)nの形態の環になっており、且つnが4又は5である、請求項2に記載の方法。
- 前記アミノシラン前駆体が式Bによって表される、請求項1に記載の方法。
- 前記アミノシラン前駆体が式Cによって表される、請求項1に記載の方法。
- 前記酸化剤が、酸素、過酸化水素、オゾン及び亜酸化窒素からなる群より選択される、請求項1〜11のいずれかに記載の方法。
- 炭素及び水素でドープされた酸化ケイ素膜を形成するために、炭素及び水素源を堆積チャンバーに導入する、請求項1〜12のいずれかに記載の方法。
- 炭素、窒素及び水素でドープされた酸化ケイ素膜を形成するために、窒素源を堆積チャンバーに更に導入する、請求項13に記載の方法。
- 前記窒素源が、アンモニア、ヒドラジン、アルキルヒドラジン、ジアルキルヒドラジン及びそれらの混合物からなる群より選択される、請求項14に記載の方法。
- 前記化学気相成長が原子層成長である、請求項1〜15のいずれかに記載の方法。
- 下記の式によって表されるアミノシランからなる群より選択されるアミノシラン前駆体と酸化剤とが反応して基材上に酸化ケイ素の誘電体層が堆積する条件下で、前記アミノシラン前駆体と酸化剤とを化学気相成長チャンバーに導入することを含む、化学気相成長チャンバーおける化学気相成長によって基材上に酸化ケイ素の誘電体層を製造する方法[ただし、前記アミノシラン前駆体は、ジ(ノルマルプロピル)アミノシラン、ジイソプロピルアミノシラン、ジイソブチルアミノシラン、ピロリルシラン、イミダゾリルシラン、ピラゾリルシラン、1−メチルピペラジニルシラン、ピロリジニルシラン、又は2−メチルピロリジニルシランではない]:
R及びR1は、置換又は非置換の、直鎖、分枝又は環状の飽和又は不飽和のC3〜C10のアルキル基;芳香族基;アルキルアミノ基;複素環基;からなる群より選択され;
式A及び式C中において、RとR1は、環状基になっていてもよく、且つ
R2は、一重結合、(CH2)m鎖(mは1〜6)、環、SiR2又はSiH2を表し、
ただし、式A中のRとR1の双方が直鎖アルキル基ではない)。 - 前記酸化剤が、オゾン、酸素、亜酸化窒素及び過酸化水素からなる群より選択される、請求項17に記載の方法。
- 350〜700℃の温度と0.1〜500Torrの圧力を前記化学気相成長チャンバーにおいて用いる、請求項18に記載の方法。
- 下記の式によって表されるアミノシランからなる群より選択されるアミノシラン前駆体と窒素源及び酸化剤とが反応して基材上に酸化ケイ素の誘電体層が堆積する条件下で、前記アミノシラン前駆体、窒素源、及び酸化剤とを前記化学気相成長チャンバーに導入することを含む、化学気相成長チャンバーおける化学気相成長によって基材上に酸窒化ケイ素の誘電体層を製造する方法[ただし、前記アミノシラン前駆体は、ジ(ノルマルプロピル)アミノシラン、ジイソプロピルアミノシラン、ジイソブチルアミノシラン、ピロリルシラン、イミダゾリルシラン、ピラゾリルシラン、1−メチルピペラジニルシラン、ピロリジニルシラン、又は2−メチルピロリジニルシランではない]:
R及びR1は、置換又は非置換の、直鎖、分枝又は環状の飽和又は不飽和のC3〜C10のアルキル基;芳香族基;アルキルアミノ基;複素環基;からなる群より選択され;
式A及び式C中において、RとR1は、環状基になっていてもよく、且つ
R2は、一重結合、(CH2)m鎖(mは1〜6)、環、SiR2又はSiH2を表し、
ただし、式A中のRとR1の双方が直鎖アルキル基ではない)。 - 前記酸化剤が、オゾン、酸素、亜酸化窒素及び過酸化水素からなる群より選択される、請求項20に記載の方法。
- 前記窒素源が、アンモニア、ヒドラジン、アルキルヒドラジン、ジアルキルヒドラジン及びそれらの混合物からなる群より選択される、請求項20に記載の方法。
- 請求項1〜22のいずれかに記載の方法によって製造される、酸化ケイ素膜又は酸窒化ケイ素膜。
- 下記の式によって表されるアミノシランからなる群より選択されるアミノシラン前駆体を含有する、酸化剤とアミノシラン前駆体とを使用する化学気相成長によって基材上に酸化ケイ素膜を形成するための化学気相成長用組成物[ただし、前記アミノシラン前駆体は、ジ(ノルマルプロピル)アミノシラン、ジイソプロピルアミノシラン、ジイソブチルアミノシラン、ピロリルシラン、イミダゾリルシラン、ピラゾリルシラン、1−メチルピペラジニルシラン、ピロリジニルシラン、又は2−メチルピロリジニルシランではない]:
R及びR1は、置換又は非置換の、直鎖、分枝又は環状の飽和又は不飽和のC3〜C10のアルキル基;芳香族基;アルキルアミノ基;複素環基;からなる群より選択され;
式A及び式C中において、RとR1は、環状基になっていてもよく、且つ
R2は、一重結合、(CH2)m鎖(mは1〜6)、環、SiR2又はSiH2を表し、
ただし、式A中のRとR1の双方が直鎖アルキル基ではない)。
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