WO2005121399A1 - Precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides - Google Patents
Precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides Download PDFInfo
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- WO2005121399A1 WO2005121399A1 PCT/GB2005/002095 GB2005002095W WO2005121399A1 WO 2005121399 A1 WO2005121399 A1 WO 2005121399A1 GB 2005002095 W GB2005002095 W GB 2005002095W WO 2005121399 A1 WO2005121399 A1 WO 2005121399A1
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- silicon oxynitride
- hnnme
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- 239000002243 precursor Substances 0.000 title claims abstract description 51
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 38
- 239000010703 silicon Substances 0.000 title claims abstract description 38
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 230000008021 deposition Effects 0.000 title claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 27
- 239000002184 metal Substances 0.000 title claims abstract description 27
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 22
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical group N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- RHUYHJGZWVXEHW-UHFFFAOYSA-N 1,1-Dimethyhydrazine Chemical compound CN(C)N RHUYHJGZWVXEHW-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000005229 chemical vapour deposition Methods 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 10
- 239000007924 injection Substances 0.000 claims description 10
- CEPICIBPGDWCRU-UHFFFAOYSA-N [Si].[Hf] Chemical compound [Si].[Hf] CEPICIBPGDWCRU-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 6
- 125000001339 silanediyl group Chemical group [H][Si]([H])(*)* 0.000 claims description 6
- 239000012702 metal oxide precursor Substances 0.000 claims description 5
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- YQZPXDARQGIHCT-UHFFFAOYSA-N 2-[1-(2,2-dimethylhydrazinyl)-2-silylethyl]-1,1-dimethylhydrazine Chemical group CN(NC(C[SiH3])NN(C)C)C YQZPXDARQGIHCT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- MXUXZWFVAPTPAG-UHFFFAOYSA-N 1-methoxy-2-methylpropan-2-ol Chemical compound COCC(C)(C)O MXUXZWFVAPTPAG-UHFFFAOYSA-N 0.000 claims description 3
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 claims description 3
- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 claims description 3
- RFSDQDHHBKYQOD-UHFFFAOYSA-N 6-cyclohexylmethyloxy-2-(4'-hydroxyanilino)purine Chemical compound C1=CC(O)=CC=C1NC1=NC(OCC2CCCCC2)=C(N=CN2)C2=N1 RFSDQDHHBKYQOD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001272 nitrous oxide Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 claims description 2
- ANEOQSDZHUAKPH-UHFFFAOYSA-N 2-[(2,2-dimethylhydrazinyl)-ethylsilyl]-1,1-dimethylhydrazine Chemical compound CN(C)N[SiH](CC)NN(C)C ANEOQSDZHUAKPH-UHFFFAOYSA-N 0.000 claims 1
- 125000000717 hydrazino group Chemical group [H]N([*])N([H])[H] 0.000 claims 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 30
- 229910052786 argon Inorganic materials 0.000 description 15
- 239000010408 film Substances 0.000 description 12
- 239000012159 carrier gas Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 4
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 3
- 238000004377 microelectronic Methods 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910020781 SixOy Inorganic materials 0.000 description 2
- 239000006117 anti-reflective coating Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- QKDIBALFMZCURP-UHFFFAOYSA-N 1-methyl-1$l^{3}-silinane Chemical compound C[Si]1CCCCC1 QKDIBALFMZCURP-UHFFFAOYSA-N 0.000 description 1
- 0 CN(C)N(*)[Si](C)C Chemical compound CN(C)N(*)[Si](C)C 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 101100023111 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mfc1 gene Proteins 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006388 chemical passivation reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- PFMKUUJQLUQKHT-UHFFFAOYSA-N dichloro(ethyl)silicon Chemical compound CC[Si](Cl)Cl PFMKUUJQLUQKHT-UHFFFAOYSA-N 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001912 gas jet deposition Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000009834 vaporization Methods 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
- H01L21/02104—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
-
- 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
- C23C16/308—Oxynitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/34—Nitrides
- C23C16/345—Silicon nitride
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- H—ELECTRICITY
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- 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
- H01L21/0214—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 the material being a silicon oxynitride, e.g. SiON or SiON:H
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- 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
- H01L21/02142—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02148—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing hafnium, e.g. HfSiOx or HfSiON
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- H—ELECTRICITY
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- 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
- H01L21/02142—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides
- H01L21/02159—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 silicon and at least one metal element, e.g. metal silicate based insulators or metal silicon oxynitrides the material containing zirconium, e.g. ZrSiOx
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- H—ELECTRICITY
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- 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
- H01L21/0217—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 nitride not containing oxygen, e.g. SixNy or SixByNz
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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
- H01L21/02214—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
- H01L21/02216—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
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- H—ELECTRICITY
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- 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
Definitions
- This invention concerns precursors for deposition, of silicon nitride, silicon oxynitride, and metal silicon oxynitrides, such as hafnium silicon oxynitride, methods of making precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, and methods of depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides.
- Silicon nitride has a number of attractive properties, such as high electrical resistivity, high dielectric breakdown field, high chemical stability, good diffusion barrier characteristics and superior mechanical strength. These properties render silicon nitride films useful in a wide range of applications, especially in the field of microelectronics.
- Silicon nitride is also used as a mask for selective oxidation of Si. Silicon nitride has applications in FRONT-END-OF-LINE (FEOL applications) as an advanced gate dielectric (k > 3.8) in metal-nitride-oxide-silicon (MNOS) structures, and as sidewall spacers. Silicon oxynitride, Si x O y N z , films have potential applications in microelectronics, for instance in shallow trench isolation (STI), antireflective coatings (ARCs) and DRA capacitors. Hafnium silicon oxynitride is a promising alternative to Si0 2 as the
- CMOS complementary metal-oxide-semiconductor
- LPCVD low pressure chemical vapour deposition techniques
- Silane and ammonia a hot wall reactor
- plasma enhanced CVD and jet vapour CVD R.F. Bundish, ed.
- An object of this invention is to provide alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures.
- Another object of the present invention is to provide a method for making alternative precursors for deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures.
- a further object of the invention is to provide methods for depositing silicon nitride, silicon oxynitride and metal silicon oxynitrides, such as hafnium silicon oxynitride at low temperatures using alternative precursors.
- precursors suitable for use in low temperature deposition of silicon nitride, silicon oxynitride and metal silicon oxynitrides have the following general formula:
- R 3 R 5 wherein R 1 , R 2 , R 3 , R 4 and R 5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
- R , R , R , R and R are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms comprising reacting a dichlorosilane of the formula R 1 R 2 SiCI 2 with a hydrazine of the formula R 3 HNNR 4 R 5 in appropriate molar quantities, R 1 to R 5 being as defined above.
- the reaction is preferably carried in a hydrocarbon solvent, such as hexane.
- R 1 , R 2 , R 3 , R 4 , R 5 are selected from H and alkyl groups having 1 to 6 carbon atoms, especially 1 to 4 carbon atoms.
- the precursors of the invention may be used alone or with the addition of another nitrogen source, such as ammonia, 1 ,1- dimethylhydrazine (Me 2 NNH 2 ) or tert-butylhydrazine (Bu t NHNH 2 ) for the deposition of silicon nitride.
- Another nitrogen source such as ammonia, 1 ,1- dimethylhydrazine (Me 2 NNH 2 ) or tert-butylhydrazine (Bu t NHNH 2 ) for the deposition of silicon nitride.
- the main effects of adding the other nitrogen source are to increase the amount of nitrogen incorporated in the deposited films and to reduce the level of oxygen and carbon contamination.
- an oxygen source needs to be present, such as oxygen or nitrous oxide, N 2 0.
- an oxygen and metal source needs to be present.
- a precursor according to the first aspect of the invention is combined with a suitable metal-oxide precursor.
- the precursors of the invention it is believed that deposition of SiN and SiON layers may be achieved at growth temperatures in the range of 400 to 600°C.
- R 1 to R 5 be selected from H, Me, Et, 'Pr and l Bu groups.
- Preferred precursors according to the invention have R 3 as H and have both R4 and R 5 as Me or R 4 as'Bu and R 5 as H. Examples of preferred precursors according to the invention include
- the invention is suitable for deposition of a number of metal silicon oxynitrides, such as hafnium silicon oxynitride, HfSiON, and Zirconium silicon oxynitride, ZrSiON.
- the precursors of the invention may be used in any type of CVD process but they are believed to be particularly suitable for liquid injection chemical vapour deposition.
- This invention will now be further described by means of the following Examples and with reference to the accompanying drawing, which shows a reactor used in the deposition of silicon nitride and silicon oxynitride described in Example 2 below.
- Example 1 Preparation of bis(2,2-dimethylhydrazino)ethylsilane The following procedure assumes that all solvents and starting materials have been dried.
- This reaction may be carried out in other solvents.
- the precursor/solvent vapour is then carried by argon or argon/oxygen mixture over the heated substrate (20) in the reactor chamber.
- Oxygen can be added to the argon flow as required.
- a single supply of high purity argon acts as the carrier gas while safety purges at the exhaust are nitrogen. The same supply of nitrogen is used to control the vacuum level. Nitrogen is also used continuously to purge the exhaust line from the
- the argon flows to the reactor through the injector assembly via two mass flow controllers (MFC1 0-11/min range or MFC2 0-5lmin range).
- the argon is used as a carrier gas, to purge the reactor and to bring the reactor up to argon when the vacuum processes are complete.
- the oxygen flow cannot be obtained unless the argon is flowing.
- Oxygen when in use, also flows through the injector assembly and is controlled by a single MFC (0- 0.51/min range).
- Deposition chamber The deposition chamber (16) consists of a horizontal quartz tube with stainless steel door assembly and exhaust outlet.
- the reactor substrate susceptor (22) is heated using IR radiation (24) and can achieve
- reactor tube is sized for one IR lamp, however, two lamps can be used either alongside each other to allow increased susceptor size or above and below to increase the temperature.
- the reactor tube is connected to the injector assembly via a heated gas line (26) to prevent the possible condensation of the precursor or solvent.
- injector assembly The method used to introduce precursor into the deposition chamber is to dissolve the precursor in a compatible solvent and inject this solution into a hot zone immediately before the reactor. This results in both solvent and precursor vaporising and being carried by the carrier gas (argon and oxygen when required) into the reactor chamber.
- the injector assembly comprises a reservoir (30), where the precursor/solvent mixture is stored at room temperature prior to injection, a liquid flow meter, so the actual flow of precursor/solvent to the injector can be measured, a BOSCH car fuel injector, through which the precursor/solvent mixture flows, a hot zone, heated by four cartridge heaters, where the precursor/solvent mixture is vaporised and mixed with the carrier gas and oxygen and a gas preheat to heat the carrier gas and oxygen before the injection zone.
- the fuel injector is also water cooled to prevent premature solvent vaporisation in the fuel injector.
- Oxygen levels found in the above samples are probably due to residual oxygen either in the precursor or the reactor.
- HfSiON hafnium silicon oxynitride
- Typical growth conditions are given in Table 3, and Auger Electron Spectroscopic (AES) data for the HfSiON films are given in Table 4.
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GBGB0412790.8A GB0412790D0 (en) | 2004-06-08 | 2004-06-08 | Precursors for deposition of silicon nitride,silicon oxynitride and metal silicon oxynitrides |
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GB2432363B (en) | 2005-11-16 | 2010-06-23 | Epichem Ltd | Hafnocene and zirconocene precursors, and use thereof in atomic layer deposition |
TWI425110B (en) | 2007-07-24 | 2014-02-01 | Sigma Aldrich Co | Methods of forming thin metal-containing films by chemical phase deposition |
TWI382987B (en) | 2007-07-24 | 2013-01-21 | Sigma Aldrich Co | Organometallic precursors for use in chemical phase deposition processes |
EP2201149B1 (en) | 2007-09-14 | 2013-03-13 | Sigma-Aldrich Co. | Methods of preparing titanium containing thin films by atomic layer deposition using monocyclopentadienyl titanium-based precursors |
TWI467045B (en) | 2008-05-23 | 2015-01-01 | Sigma Aldrich Co | High-k dielectric films and methods of producing high-k dielectric films using cerium-based precursors |
EP3150614B1 (en) | 2009-08-07 | 2017-11-29 | Sigma-Aldrich Co. LLC | High molecular weight alkyl-allyl cobalttricarbonyl complexes and use thereof for preparing dielectric thin films |
KR101847953B1 (en) | 2010-08-27 | 2018-04-11 | 메르크 파텐트 게엠베하 | Molybdenum(iv) amide precursors and use thereof in atomic layer deposition |
US8927748B2 (en) | 2011-08-12 | 2015-01-06 | Sigma-Aldrich Co. Llc | Alkyl-substituted allyl carbonyl metal complexes and use thereof for preparing dielectric thin films |
WO2013112383A1 (en) | 2012-01-26 | 2013-08-01 | Sigma-Aldrich Co. Llc | Molybdenum allyl complexes and use thereof in thin film deposition |
JP7346430B2 (en) | 2018-02-12 | 2023-09-19 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツング | Ruthenium deposition method using oxygen-free co-reactants |
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US20020130340A1 (en) * | 2000-02-11 | 2002-09-19 | Yanjun Ma | Method of forming a multilayer dielectric stack |
US20030127640A1 (en) * | 2002-01-08 | 2003-07-10 | Kabushiki Kaisha Toshiba | Semiconductor device and method for manufacturing semiconductor device |
US20040043569A1 (en) * | 2002-08-28 | 2004-03-04 | Ahn Kie Y. | Atomic layer deposited HfSiON dielectric films |
EP1441042A1 (en) * | 2003-01-23 | 2004-07-28 | Air Products And Chemicals, Inc. | Precursors for depositing silicon containing films and processes thereof |
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US20020130340A1 (en) * | 2000-02-11 | 2002-09-19 | Yanjun Ma | Method of forming a multilayer dielectric stack |
US20030127640A1 (en) * | 2002-01-08 | 2003-07-10 | Kabushiki Kaisha Toshiba | Semiconductor device and method for manufacturing semiconductor device |
US20040043569A1 (en) * | 2002-08-28 | 2004-03-04 | Ahn Kie Y. | Atomic layer deposited HfSiON dielectric films |
EP1441042A1 (en) * | 2003-01-23 | 2004-07-28 | Air Products And Chemicals, Inc. | Precursors for depositing silicon containing films and processes thereof |
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DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 1963, SERGEEVA, S.I.; CHIEN, HSING-CHANG; TSITOVICH, D.D.: "Synthesis of alkyl- and dialkylbis(1,1-dialkylhydrazino)silanes", XP002278438, Database accession no. 61:4288 * |
DATABASE CAPLUS [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 2003, RAKHLIN, V. I.; FOMINA, A.N.; MIRSKOV, R.G.; KANAEV, V.G.: "Organosilicon derivatives of 1,1-dimethylhydrazine: novel precursors of thin-film dielectric coatings", XP002339520, Database accession no. 2003:151746 * |
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SMIRNOVA T P ET AL: "SiCN alloys obtained by remote plasma chemical vapour deposition from novel precursors", PREPARATION AND CHARACTERIZATION, ELSEVIER SEQUOIA, NL, vol. 429, no. 1-2, 1 April 2003 (2003-04-01), pages 144 - 151, XP004421425, ISSN: 0040-6090 * |
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